Investigation of the interaction of copper(II) oxide and electron beam irradiation crosslinkable polyethylene

International Nuclear Information System (INIS)

Bee, Soo-Tueen; Sin, Lee Tin; Ratnam, C.T.; Haraveen, K.J.S.; Tee, Tiam-Ting; Rahmat, A.R.

2015-01-01

In this study, the effects of electron beam irradiation on the properties of copper(II) oxide when added to low-density polyethylene (LDPE) blends were investigated. It was found that the addition of low loading level of copper(II) oxide (⩽2 phr) to LDPE results in significantly poorer gel content and hot set results. However, the incorporation of higher loading level of copper(II) oxide (⩾3 phr) could slightly increase the degree of crosslinking in all irradiated LDPE composites. This is due to the fact that higher amounts of copper(II) oxide could slightly induce the formation of free radicals in LDPE matrix. Besides, increasing irradiation doses was also found to gradually increase the gel content of LDPE composites by generating higher amounts of free radicals. As a consequence, these higher amounts of free radicals released in the LDPE matrix could significantly increase the degree of crosslinking. The addition of copper(II) oxide could reduce the tensile strength and fracture strain (elongation at break) of LDPE composites because of poorer interfacial adhesion effect between copper(II) oxide particles and LDPE matrix. Meanwhile, increasing irradiation doses on all copper(II) oxide added LDPE composites could marginally increase the tensile strength. In addition, increasing irradiation dose could enhance the thermal stability of LDPE composites by increasing the decomposition temperature. The oxidation induction time (OIT) analysis showed that, because of the crosslinking network in the copper(II) oxide added LDPE composites, oxidation reaction is much delayed.

Investigation of the interaction of copper(II) oxide and electron beam irradiation crosslinkable polyethylene

Energy Technology Data Exchange (ETDEWEB)

Bee, Soo-Tueen, E-mail: direct.beest@gmail.com [Department of Chemical Engineering, Lee Kong Chian Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Jalan Sungai Long, Bandar Sungai Long, Cheras, 43000 Kajang, Selangor (Malaysia); Sin, Lee Tin, E-mail: direct.tinsin@gmail.com [Department of Chemical Engineering, Lee Kong Chian Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Jalan Sungai Long, Bandar Sungai Long, Cheras, 43000 Kajang, Selangor (Malaysia); Ratnam, C.T. [Radiation Processing Technology Division, Malaysian Nuclear Agency, Bangi, 43000 Kajang, Selangor (Malaysia); Haraveen, K.J.S.; Tee, Tiam-Ting [Department of Chemical Engineering, Lee Kong Chian Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Jalan Sungai Long, Bandar Sungai Long, Cheras, 43000 Kajang, Selangor (Malaysia); Rahmat, A.R. [Department of Polymer Engineering, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia)

2015-10-01

In this study, the effects of electron beam irradiation on the properties of copper(II) oxide when added to low-density polyethylene (LDPE) blends were investigated. It was found that the addition of low loading level of copper(II) oxide (⩽2 phr) to LDPE results in significantly poorer gel content and hot set results. However, the incorporation of higher loading level of copper(II) oxide (⩾3 phr) could slightly increase the degree of crosslinking in all irradiated LDPE composites. This is due to the fact that higher amounts of copper(II) oxide could slightly induce the formation of free radicals in LDPE matrix. Besides, increasing irradiation doses was also found to gradually increase the gel content of LDPE composites by generating higher amounts of free radicals. As a consequence, these higher amounts of free radicals released in the LDPE matrix could significantly increase the degree of crosslinking. The addition of copper(II) oxide could reduce the tensile strength and fracture strain (elongation at break) of LDPE composites because of poorer interfacial adhesion effect between copper(II) oxide particles and LDPE matrix. Meanwhile, increasing irradiation doses on all copper(II) oxide added LDPE composites could marginally increase the tensile strength. In addition, increasing irradiation dose could enhance the thermal stability of LDPE composites by increasing the decomposition temperature. The oxidation induction time (OIT) analysis showed that, because of the crosslinking network in the copper(II) oxide added LDPE composites, oxidation reaction is much delayed.

A review on bis-hydrazonoyl halides: Recent advances in their synthesis and their diverse synthetic applications leading to bis-heterocycles of biological interest

Directory of Open Access Journals (Sweden)

Ahmad Sami Shawali

2016-11-01

Full Text Available This review covers a summary of the literature data published on the chemistry of bis-hydrazonoyl halides over the last four decades. The biological activities of some of the bis-heterocyclic compounds obtained from these bis-hydrazonoyl halides are also reviewed and discussed.

Halide based MBE of crystalline metals and oxides

Energy Technology Data Exchange (ETDEWEB)

Greenlee, Jordan D.; Calley, W. Laws; Henderson, Walter; Doolittle, W. Alan [Georgia Institute of Technology, School of Electrical and Computer Engineering, Atlanta, Georgia (United States)

2012-02-15

A halide based growth chemistry has been demonstrated which can deliver a range of transition metals using low to moderate effusion cell temperatures (30-700 C) even for high melting point metals. Previously, growth with transition metal species required difficult to control electron beam or impurity inducing metal organic sources. Both crystalline oxide and metal films exhibiting excellent crystal quality are grown using this halide-based growth chemistry. Films are grown using a plasma assisted Molecular Beam Epitaxy (MBE) system with metal-chloride precursors. Crystalline niobium, cobalt, iron, and nickel were grown using this chemistry but the technology can be generalized to almost any metal for which a chloride precursor is available. Additionally, the oxides LiNbO{sub 3} and LiNbO{sub 2} were grown with films exhibiting X-ray diffraction (XRD) rocking curve full-widths at half maximum of 150 and 190 arcseconds respectively. LiNbO{sub 2} films demonstrate a memristive response due to the rapid movement of lithium in the layered crystal structure. The rapid movement of lithium ions in LiNbO{sub 2} memristors is characterized using impedance spectroscopy measurements. The impedance spectroscopy measurements suggest an ionic current of.1 mA for a small drive voltage of 5 mV AC or equivalently an ionic current density of {proportional_to}87 A/cm{sup 2}. This high ionic current density coupled with low charge transfer resistance of {proportional_to}16.5 {omega} and a high relaxation frequency (6.6 MHz) makes this single crystal material appealing for battery applications in addition to memristors. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Correlated linear response calculations of the C6 dispersion coefficients of hydrogen halides

Czech Academy of Sciences Publication Activity Database

Sauer, S. P. A.; Paidarová, Ivana

2007-01-01

Roč. 3, 2-4 (2007), s. 399-421 ISSN 1574-0404 R&D Projects: GA AV ČR IAA401870702 Institutional research plan: CEZ:AV0Z40400503 Keywords : hydrogen halides * C6 dospersion coefficients * van der Waals coefficients * polarizability at imaginary frequences * SOPPA Subject RIV: CF - Physical ; Theoretical Chemistry

Template Syntheses, Crystal Structures and Supramolecular Assembly of Hexaaza Macrocyclic Copper(II) Complexes

International Nuclear Information System (INIS)

Kim, Taehyung; Kim, Ju Chang; Lough, Alan J.

2013-01-01

Two new hexaaza macrocyclic copper(II) complexes were prepared by a template method and structurally characterized. In the solid state, they were self-assembled by intermolecular interactions to form the corresponding supramolecules 1 and 2, respectively. In the structure of 1, the copper(II) macrocycles are bridged by a tp ligand to form a macrocyclic copper(II) dimer. The dimer extends its structure by intermolecular forces such as hydrogen bonds and C-H···π interactions, resulting in the formation of a double stranded 1D supramolecule. In 2, the basic structure is a monomeric copper(II) macrocycle with deprotonated imidazole pendants. An undulated 1D hydrogen bonded array is achieved through hydrogen bonds between imidazole pendants and secondary amines, where the imidazole pendants act as a hydrogen bond acceptor. The 1D hydrogen bonded supramolecular chain is supported by C-H···π interactions between the methyl groups of acetonitrile ligands and imidazole pendants of the copper(II) macrocycles. In both complexes, the introduction of imidazoles to the macrocycle as a pendant plays an important role for the formation of supramolecules, where they act as intermolecular hydrogen bond donors and/or acceptors, C-H···π and π-π interactions

Chemistry of alkali cation exchanged faujasite and mesoporous NaX using alkyl halides and phosphates

Science.gov (United States)

Lee, Min-Hong

The purpose of this work was to increase the reactivity of Faujasite X (NaX) zeolite toward the reactive decontamination of materials subject to nucleophilic attack by means of zeolite cation optimization and by means of the synthesis of mesoporous Faujasite X. Primary alkyl halides and trialkyl phosphates have been the test materials on which the cation-optimized and mesoporous zeolites have been tested. In the alkali cation optimization work, reactions of methyl iodide and 1-chloropropane with alkali metal cation exchanged Faujasite zeolite X were investigated at room temperature. The reactivity of the framework and the product formation were shown to depend on zeolite framework counter-cation. A quantitative study of zeolite product formation has been carried out, primarily using solid-state NMR spectroscopy. Large alkali cations showed preference toward substitution chemistry. In contrast, alkyl halide exposed LiX and NaX zeolites underwent both substitution and elimination. Subsequently introduced water molecules led to hydrolysis of framework species that was sensitive to framework counter-cation. The mesoporous NaX zeolites work undertakes to test whether an improvement in surface chemical reactivity can be achieved by introducing mesopores into the already reactive nucleophilic microporous NaX zeolite. Incorporation of the polydiallyl dimethyl ammonium chloride (PDADMAC) template and the formation of mesopores in Faujasite X zeolite (NaX) were successful and well-characterized. The mesopores are proposed to have occurred from incorporation of the cationic PDADMAC polymer into the zeolite by compensating zeolite framework charge. Subsequent sodium cation exchange of calcined mesoporous NaX was shown to restore the chemical reactivity characteristic of as-synthesized NaX. Trialkyl organophosphorous compounds underwent substitution reactions. The reactivity of both microporous and mesoporous Faujasite zeolite X and the product formation was shown to depend on

A model for additive transport in metal halide lamps containing mercury and dysprosium tri-iodide

NARCIS (Netherlands)

Beks, M.L.; Haverlag, M.; Mullen, van der J.J.A.M.

2008-01-01

The distribution of additives in a metal halide lamp is examined through numerical modelling. A model for a lamp containing sodium iodide additives has been modified to study a discharge containing dysprosium tri-iodide salts. To study the complex chemistry the method of Gibbs minimization is used

Double Charged Surface Layers in Lead Halide Perovskite Crystals

KAUST Repository

Sarmah, Smritakshi P.

2017-02-01

Understanding defect chemistry, particularly ion migration, and its significant effect on the surface’s optical and electronic properties is one of the major challenges impeding the development of hybrid perovskite-based devices. Here, using both experimental and theoretical approaches, we demonstrated that the surface layers of the perovskite crystals may acquire a high concentration of positively charged vacancies with the complementary negatively charged halide ions pushed to the surface. This charge separation near the surface generates an electric field that can induce an increase of optical band gap in the surface layers relative to the bulk. We found that the charge separation, electric field, and the amplitude of shift in the bandgap strongly depend on the halides and organic moieties of perovskite crystals. Our findings reveal the peculiarity of surface effects that are currently limiting the applications of perovskite crystals and more importantly explain their origins, thus enabling viable surface passivation strategies to remediate them.

A novel trinuclear copper(II) complex containing a symmetric tetradentate N.sub.2./sub.O.sub.2./sub. Schiff base ligand: synthesis, characterization, crystal structure and its usage as a new precursor for the preparation of CuO particles

Czech Academy of Sciences Publication Activity Database

Khalaji, A.D.; Ghorbani, M.; Feizi, N.; Akbari, A.; Eigner, Václav; Dušek, Michal

2017-01-01

Roč. 121, Jan (2017), s. 9-12 ISSN 0277-5387 R&D Projects: GA ČR(CZ) GA15-12653S; GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : trinuclear complex * copper(II) complex * Schiff base * crystal structure * thermal decomposition Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 1.926, year: 2016

Biosorption of copper(II) and lead(II) onto potassium hydroxide treated pine cone powder.

Science.gov (United States)

Ofomaja, A E; Naidoo, E B; Modise, S J

2010-08-01

Pine cone powder surface was treated with potassium hydroxide and applied for copper(II) and lead(II) removal from solution. Isotherm experiments and desorption tests were conducted and kinetic analysis was performed with increasing temperatures. As solution pH increased, the biosorption capacity and the change in hydrogen ion concentration in solution increased. The change in hydrogen ion concentration for lead(II) biosorption was slightly higher than for copper(II) biosorption. The results revealed that ion-exchange is the main mechanism for biosorption for both metal ions. The pseudo-first order kinetic model was unable to describe the biosorption process throughout the effective biosorption period while the modified pseudo-first order kinetics gave a better fit but could not predict the experimentally observed equilibrium capacities. The pseudo-second order kinetics gave a better fit to the experimental data over the temperature range from 291 to 347 K and the equilibrium capacity increased from 15.73 to 19.22 mg g(-1) for copper(II) and from 23.74 to 26.27 for lead(II). Activation energy was higher for lead(II) (22.40 kJ mol(-1)) than for copper(II) (20.36 kJ mol(-1)). The free energy of activation was higher for lead(II) than for copper(II) and the values of DeltaH* and DeltaS* indicate that the contribution of reorientation to the activation stage is higher for lead(II) than copper(II). This implies that lead(II) biosorption is more spontaneous than copper(II) biosorption. Equilibrium studies showed that the Langmuir isotherm gave a better fit for the equilibrium data indicating monolayer coverage of the biosorbent surface. There was only a small interaction between metal ions when simultaneously biosorbed and cation competition was higher for the Cu-Pb system than for the Pb-Cu system. Desorption studies and the Dubinin-Radushkevich isotherm and energy parameter, E, also support the ion-exchange mechanism. Copyright 2010 Elsevier Ltd. All rights reserved.

Synthesis, Characterization and DNA Cleavage of Copper(II ...

African Journals Online (AJOL)

Keywords: DNA shearing, Copper(II) complex, Dithiothreitol, Attenuated total reflectance-Fourier transform .... confirm the fragmentation of DNA by the newly .... sperm. Biochem Biophys Acta 1986; 884: 124-134. 7. Cornell NW, Crivaro KE.

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

Science.gov (United States)

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.

The ligational behavior of an isatinic quinolyl hydrazone towards copper(II- ions

Directory of Open Access Journals (Sweden)

Mousa Marwa A

2011-04-01

Full Text Available Abstract Background The importance of the isatinic quinolyl hydrazones arises from incorporating the quinoline ring with the indole ring. Quinoline ring has therapeutic and biological activities whereas, the indole ring occurs in Jasmine flowers and Orange blossoms. As a ligand, the isatin moiety is potentially ambidentate and can coordinate the metal ions either through its lactam or lactim forms. In a previous study, the ligational behavior of a phenolic quinolyl hydrazone towards copper(II- ions has been studied. As continuation of our interest, the present study is planned to check the ligational behavior of an isatinic quinolyl hydrazone. Results New homo- and heteroleptic copper(II- complexes were obtained from the reaction of an isatinic quinolyl hydrazone (HL with several copper(II- salts viz. Clˉ, Brˉ, NO3ˉ, ClO4-, SO42- and AcO-. The obtained complexes have Oh, Td and D4h- symmetry and fulfill the strong coordinating ability of Clˉ, Brˉ, NO3ˉ and SO42- anions. Depending on the type of the anion, the ligand coordinates the copper(II- ions either through its lactam (NO3ˉ and ClO4- or lactim (the others forms. Conclusion The effect of anion for the same metal ion is obvious from either the geometry of the isolated complexes (Oh, Td and D4h or the various modes of bonding. Also, the obtained complexes fulfill the strong coordinating ability of Clˉ, Brˉ, NO3ˉ and SO42- anions in consistency with the donor ability of the anions. In case of copper(II- acetate, a unique homoleptic complex (5 was obtained in which the AcO- anion acts as a base enough to quantitatively deprotonate the hydrazone. The isatinic hydrazone uses its lactim form in most complexes.

Methods for producing single crystal mixed halide perovskites

Science.gov (United States)

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.

Photofragmentation of metal halides

International Nuclear Information System (INIS)

Veen, N.J.A. van.

1980-01-01

The author deals with photodissociation of molecules of alkali halides. It is shown that the total absorption cross section consists of two contributions arising from transitions to excited states of total electronic angular momentum Ω=0 + and Ω=1. From the inversion of the absorption continua potential energy curves of the excited states can be constructed in the Franck-Condon region. It is found that for all alkali halides the 0 + state is higher in energy than the Ω=1 state. Extensive studies are reported on three thallium halides, TlI, TlBr and TlCl at various wavelengths covering the near ultraviolet region. (Auth.)

Interactions between copper(II) and DOM in the urban stormwater runoff: modeling and characterizations.

Science.gov (United States)

Zhao, Chen; Wang, Chong-Chen; Li, Jun-Qi; Wang, Peng; Ou, Jia-Qi; Cui, Jing-Rui

2018-01-01

Dissolved organic matter (DOM) can strongly interact with both organic and inorganic contaminants to influence their transportation, transformation, bioavailability, toxicity and even their ultimate fate. Within this work, DOM was extracted from urban stormwater runoff samples collected from a regular sampling site of a typical residential area in Beijing, China. Copper(II) ions were selected as model to investigate the interactions between DOM and typical heavy metals. Both ultraviolet (UV) absorbance and fluorescence titration methods were introduced to determine the complex capacities (C L ) and conditional stability constants (log K M ) of bonding between DOM and copper (II) ions, which revealed that the values of C L were 85.62 and 87.23 μmol mg -1 and the log K M values were 5.37 and 5.48, respectively. The results suggested the successful complexation between DOM and copper(II) ions. Furthermore, morphology of the DOM binding to copper(II) ions was confirmed by both energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS), which can facilitate to clarify the corresponding mechanism. The Cu 2p 3/2 peak at 933.7 eV and the characteristic shake-up peaks of Cu-O were found in the XPS spectra, implying that copper(II) ions might coordinate with hydroxyl (aliphatic or phenolic) or carboxyl groups. With these profitable results, it can be concluded that DOM in urban stormwater runoff has a strong binding affinity with copper(II) ions, which may further lead to potentially significant influence on their migration and transformation.

Binuclear trivalent and tetravalent uranium halides and cyanides supported by cyclooctatetraene ligands

International Nuclear Information System (INIS)

Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Shi, Wei-Qun; Gibson, John K.

2017-01-01

Although the first organoactinide chloride Cp_3UCl (Cp = η"5-C_5H_5) was synthesized more than 50 years ago, binuclear uranium halides remain very rare in organoactinide chemistry. Herein, a series of binuclear trivalent and tetravalent uranium halides and cyanides with cyclooctatetraene ligands, (COT)_2U_2X_n (COT = η"8-C_8H_8; X=F, Cl, CN; n=2, 4), have been systematically studied using scalar-relativistic density functional theory (DFT). The structures with bridging halide or cyanide ligands were predicted to be the most stable complexes of (COT)_2U_2X_n, and all the complexes show weak antiferromagnetic interactions between the uranium centers. However, for each species, there is no significant uranium-uranium bonding interaction. The bonding between the metal and the ligands shows some degree of covalent character, especially between the metal and terminal halide or cyanide ligands. The U-5f and 6d orbitals are predominantly involved in the metal-ligand bonding. All the (COT)_2U_2X_n species were predicted to be more stable compared to the mononuclear half-sandwich complexes at room temperature in the gas phase such that (COT)_2U_2X_4 might be accessible through the known (COT)_2U complex. The tetravalent derivatives (COT)_2U_2X_4 are more energetically favorable than the trivalent (COT)_2U_2X_2 analogs, which may be attributed to the greater number of strong metal-ligand bonds in the former complexes.

Radiation chemistry of hydrocarbon and alkyl halide systems. Progress report, August 1, 1977--August 1, 1978

International Nuclear Information System (INIS)

Hanrahan, R.J.

1978-01-01

Progress of experimental work is reported on pulse radiolysis of simple alkyl halides in the gas phase, gas phase radiolysis of CHF 3 -CH 3 I mixtures, gamma radiolysis of the system CO/H 2 , and improvements in equipment and facilities

Preconcentration and extraction of copper(II) on activated carbon ...

African Journals Online (AJOL)

Activated carbon modified method was used for the preconcentration and ... in real samples such as tap water, wastewater and a synthetic water sample by flame ... KEY WORDS: Copper(II), Solid phase extraction, Activated carbon, Flame ...

Study of the interaction mechanism in the biosorption of copper(II) ions onto posidonia oceanica and peat

Energy Technology Data Exchange (ETDEWEB)

Izquierdo, Marta; Marzal, Paula; Gabaldon, Carmen [Departamento de Ingenieria Quimica, Escuela Tecnica Superior de Ingenieria, Universitat de Valencia, Valencia (Spain); Silvetti, Margherita; Castaldi, Paola [Dipartimento di Scienze Ambientali e Agrarie e Biotecnologie Agro-Alimentari, Sez. Chimica Agraria ed Ambientale, University of Sassari, Sassari (Italy)

2012-04-15

A systematic approach was used to characterize the biosorption of copper(II) onto two biosorbents, Posidonia oceanica and peat, focusing on the interaction mechanisms, the copper(II) sorption-desorption process and the thermal behavior of the biosorbents. Sorption isotherms at pH 4-6 were obtained and the experimental data were fitted to the Langmuir model with a maximum uptake (q{sub max}) at pH 6 of 85.78 and 49.69 mg g{sup -1}, for P. oceanica and peat, respectively. A sequential desorption (SD) with water, Ca(NO{sub 3}){sub 2}, and EDTA was applied to copper-saturated biosorbents. Around 65-70% copper(II) were desorbed with EDTA, indicating that this heavy metal was strongly bound. The reversibility of copper(II) sorption was obtained by desorption with HCl and SD. Fourier transform IR spectroscopy (FTIR) analysis detected the presence of peaks associated with OH groups in aromatic and aliphatic structures, CH, CH{sub 2}, and CH{sub 3} in aliphatic structures, COO{sup -} and COOH groups and unsaturated aromatic structures on the surface of both biosorbents, as well as peaks corresponding to Si-O groups on the surface of peat. The results of SEM-EDX and FTIR analysis of copper-saturated samples demonstrated that ion exchange was one of the mechanisms involved in copper(II) retention. Thermal analysis of biosorbent samples showed that copper(II) sorption-desorption processes affected the thermal stability of the biosorbents. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

The crystal structure of paramagnetic copper(ii) oxalate (CuC2O4):

DEFF Research Database (Denmark)

Christensen, Axel Nørlund; Lebech, Bente; Andersen, Niels Hessel

2014-01-01

Synthetic copper(ii) oxalate, CuC2O4, was obtained in a precipitation reaction between a copper(ii) solution and an aqueous solution of oxalic acid. The product was identified from its conventional X-ray powder patterns which match that of the copper mineral Moolooite reported to have...... the composition CuC2O4·0.44H2O. Time resolved in situ investigations of the thermal decomposition of copper(ii) oxalate using synchrotron X-ray powder diffraction showed that in air the compound converts to Cu2O at 215 °C and oxidizes to CuO at 345 °C. Thermo gravimetric analysis performed in an inert Ar....... The crystal structure consists of a random stacking of CuC2O4 micro-crystallites where half the Cu-atoms are placed at (2a) and the other half at (2b) positions with the corresponding oxalate molecules centred around the corresponding (2b) and (2a) site positions, respectively. The diffraction patterns...

Copper(II) Complexes of Phenanthroline and Histidine Containing Ligands: Synthesis, Characterization and Evaluation of their DNA Cleavage and Cytotoxic Activity.

Science.gov (United States)

Leite, Sílvia M G; Lima, Luís M P; Gama, Sofia; Mendes, Filipa; Orio, Maylis; Bento, Isabel; Paulo, António; Delgado, Rita; Iranzo, Olga

2016-11-21

Copper(II) complexes have been intensely investigated in a variety of diseases and pathological conditions due to their therapeutic potential. The development of these complexes requires a good knowledge of metal coordination chemistry and ligand design to control species distribution in solution and tailor the copper(II) centers in the right environment for the desired biological activity. Herein we present the synthesis and characterization of two ligands HL1 and H 2 L2 containing a phenanthroline unit (phen) attached to the amino group of histidine (His). Their copper(II) coordination properties were studied using potentiometry, spectroscopy techniques (UV-vis and EPR), mass spectrometry (ESI-MS) and DFT calculations. The data showed the formation of single copper complexes, [CuL1] + and [CuL2], with high stability within a large pH range (from 3.0 to 9.0 for [CuL1] + and from 4.5 to 10.0 for [CuL2]). In both complexes the Cu 2+ ion is bound to the phen unit, the imidazole ring and the deprotonated amide group, and displays a distorted square pyramidal geometry as confirmed by single crystal X-ray crystallography. Interestingly, despite having similar structures, these copper complexes show different redox potentials, DNA cleavage properties and cytotoxic activity against different cancer cell lines (human ovarian (A2780), its cisplatin-resistant variant (A2780cisR) and human breast (MCF7) cancer cell lines). The [CuL2] complex has lower reduction potential (E pc = -0.722 V vs -0.452 V for [CuL1] + ) but higher biological activity. These results highlight the effect of different pendant functional groups (carboxylate vs amide), placed out of the coordination sphere, in the properties of these copper complexes.

FEATURES OF INITIATION OF STYRENE POLYMERIZATION BY CUMENE HYDROPEROXIDE IN PRESENCE OF ACETULACETONATE OF COPPER(II

Directory of Open Access Journals (Sweden)

A. V. Grekova

2016-04-01

Full Text Available Kinetics of sectional styrene polymerization initiated by cumene hydroperoxide, acetylacetonate of copper(II and by the system of cumene hydroperoxide — acetylacetonate of copper(II in a temperature range 333-363 K is studied. Kinetic parameters of polymerization process are determined. It is shown, that system of cumene hydroperoxide — acetylacetonate of copper(II is in 5-6 times more effective on the initiating ability comparatively to application of its individual components. From findings ensues that decline of energy of activating of initiation from 110 kdzh/mol’ to 87 kdzh/mol’ for cumene hydroperoxide at the use of the studied system is caused with participating of monomer in preliminary complexation facilitating formation of free radicals.

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

International Nuclear Information System (INIS)

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

2014-01-01

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

Surface Structures Formed by a Copper(II Complex of Alkyl-Derivatized Indigo

Directory of Open Access Journals (Sweden)

Akinori Honda

2016-10-01

Full Text Available Assembled structures of dyes have great influence on their coloring function. For example, metal ions added in the dyeing process are known to prevent fading of color. Thus, we have investigated the influence of an addition of copper(II ion on the surface structure of alkyl-derivatized indigo. Scanning tunneling microscope (STM analysis revealed that the copper(II complexes of indigo formed orderly lamellar structures on a HOPG substrate. These lamellar structures of the complexes are found to be more stable than those of alkyl-derivatized indigos alone. Furthermore, 2D chirality was observed.

Synthesis, spectroscopic and thermal studies of the copper(II) aspartame chloride complex

Science.gov (United States)

Çakır, S.; Coşkun, E.; Naumov, P.; Biçer, E.; Bulut, İ.; İçbudak, H.; Çakır, O.

2002-08-01

Aspartame adduct of copper(II) chloride Cu(Asp) 2Cl 2·2H 2O (Asp=aspartame) is synthesized and characterized by elemental analysis, FT IR, UV/vis, ESR spectroscopies, TG, DTG, DTA measurements and molecular mechanics calculations. Aqueous solution of the green solid absorbs strongly at 774 and 367 nm. According to the FT IR spectra, the aspartame moiety coordinates to the copper(II) ion via its carboxylate ends, whereas the ammonium terminal groups give rise to hydrogen bonding network with the water, the chloride ions or neighboring carboxylate groups. The results suggest tetragonally distorted octahedral environment of the copper ions.

Structural, optical, and electronic studies of wide-bandgap lead halide perovskites

KAUST Repository

Comin, Riccardo; Walters, Grant; Thibau, Emmanuel Sol; Voznyy, Oleksandr; Lu, Zheng-Hong; Sargent, Edward H.

2015-01-01

© The Royal Society of Chemistry 2015. We investigate the family of mixed Br/Cl organolead halide perovskites which enable light emission in the blue-violet region of the visible spectrum. We report the structural, optical and electronic properties of this air-stable family of perovskites, demonstrating full bandgap tunability in the 400-550 nm range and enhanced exciton strength upon Cl substitution. We complement this study by tracking the evolution of the band levels across the gap, thereby providing a foundational framework for future optoelectronic applications of these materials.

RECOVERY OF COPPER(II) AND CHROMIUM(III) FROM NITRATE ...

African Journals Online (AJOL)

Guerdouh A and Barkat D

2016-05-01

May 1, 2016 ... The ionic strength of the aqueous medium was ... phases were separated completely, concentrations of the copper(II) and chromium(III) ..... [18] Huff M M, Otu E O. Solvent Extraction and Ion Exchange, 2004, 22(4), 695-712.

Binuclear trivalent and tetravalent uranium halides and cyanides supported by cyclooctatetraene ligands

Energy Technology Data Exchange (ETDEWEB)

Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Shi, Wei-Qun [Chinese Academy of Sciences, Beijing (China). Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety; Chai, Zhi-Fang [Chinese Academy of Sciences, Beijing (China). Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety; Soochow Univ., Suzhou (China). School of Radiological and Interdisciplinary Sciences (RAD-X); Gibson, John K. [Lawrence Berkeley National Laboratory, CA (United States). Chemical Sciences Division

2017-03-01

Although the first organoactinide chloride Cp{sub 3}UCl (Cp = η{sup 5}-C{sub 5}H{sub 5}) was synthesized more than 50 years ago, binuclear uranium halides remain very rare in organoactinide chemistry. Herein, a series of binuclear trivalent and tetravalent uranium halides and cyanides with cyclooctatetraene ligands, (COT){sub 2}U{sub 2}X{sub n} (COT = η{sup 8}-C{sub 8}H{sub 8}; X=F, Cl, CN; n=2, 4), have been systematically studied using scalar-relativistic density functional theory (DFT). The structures with bridging halide or cyanide ligands were predicted to be the most stable complexes of (COT){sub 2}U{sub 2}X{sub n}, and all the complexes show weak antiferromagnetic interactions between the uranium centers. However, for each species, there is no significant uranium-uranium bonding interaction. The bonding between the metal and the ligands shows some degree of covalent character, especially between the metal and terminal halide or cyanide ligands. The U-5f and 6d orbitals are predominantly involved in the metal-ligand bonding. All the (COT){sub 2}U{sub 2}X{sub n} species were predicted to be more stable compared to the mononuclear half-sandwich complexes at room temperature in the gas phase such that (COT){sub 2}U{sub 2}X{sub 4} might be accessible through the known (COT){sub 2}U complex. The tetravalent derivatives (COT){sub 2}U{sub 2}X{sub 4} are more energetically favorable than the trivalent (COT){sub 2}U{sub 2}X{sub 2} analogs, which may be attributed to the greater number of strong metal-ligand bonds in the former complexes.

COPPER(II) COMPLEXES OF o -VANILLIN ACETYLHYDRAZONE ...

African Journals Online (AJOL)

A hydrazonic ligand, o-vanillin acetylhydrazone (H2L) has been prepared and used as chelating agent towards copper(II) ion. The ligand acts like a tridentate ligand in the monodeprotonated (HL-) and dideprotonated (L2-) states. Monoanionic complexes [{Cu(HL)(H2O)}2]•2BF4 and [{Cu(HL)(Hpz)(H2O)}]•NO3 have been ...

Synthesis, Characterization and DNA Cleavage of Copper(II ...

African Journals Online (AJOL)

Purpose: To study deoxyribonucleic acid (DNA) shearing capability of copper(II) complex of dithiothreitol (DTT) and to fevaluate its potential application in cancer therapy. Methods: A parrot green complex was synthesized by grinding copper acetate monohydrate and DTT in 1:2 molar ratio in a mortar until no fumes of acetic ...

Structure of polyvalent metal halide melts

International Nuclear Information System (INIS)

Tosi, M.P.

1990-12-01

A short review is given of recent progress in determining and understanding the structure of molten halide salts involving polyvalent metal ions. It covers the following three main topics: (i) melting mechanisms and types of liquid structure for pure polyvalent-metal chlorides; (ii) geometry and stability of local coordination for polyvalent metal ions in molten mixtures of their halides with alkali halides; and (iii) structure breaking and electron localization on addition of metal to the melt. (author). 28 refs, 3 figs, 1 tab

Halide-Dependent Electronic Structure of Organolead Perovskite Materials

KAUST Repository

Buin, Andrei; Comin, Riccardo; Xu, Jixian; Ip, Alexander H.; Sargent, Edward H.

2015-01-01

-based perovskites, in line with recent experimental data. As a result, the optimal growth conditions are also different for the distinct halide perovskites: growth should be halide-rich for Br and Cl, and halide-poor for I-based perovskites. We discuss stability

Standard molar enthalpies of formation of copper(II) β-diketonates and monothio-β-diketonates

International Nuclear Information System (INIS)

Ribeiro da Silva, Manuel A.V.; Santos, Luis M.N.B.F.

2006-01-01

The standard (p o =0.1MPa) molar enthalpies of formation of the crystalline complexes of dibenzoylmethane (Hdbm), thenoyltrifluoroacetone (Httfa), monothiodibenzoylmethane (HdbmS), and monothiothenoyltrifluoroacetone (HttfaS) of copper(II) were determined, at T=298.15K, by high precision solution-reaction calorimetry. The standard molar enthalpies of sublimation of the copper(II) β-diketonate complexes were measured by high-temperature Calvet microcalorimetry. From the standard molar enthalpies of formation of the complexes in the gaseous state, the mean molar dissociation enthalpies copper(II)-ligand, m >(Cu-L), were derived. Δ f H m o (cr)Δ cr g H m o kJ.mol -1 kJ.mol -1 Bis(dibenzoylmethanate)copper(II), Cu(dbm) 2 -364.0+/-3.9230.7+/-8.2Bis(thenoyltrifluoroacetonate)copper(II), Cu(ttfa) 2 -1824.3+/-8.3167.9+/-7.4Bis(monothiodibenzoylmethanate)copper(II), Cu(dbmS) 2 35.6+/-7.7[241+/-15]Bis(monothiothenoyltrifluoroacetonate) copper(II), Cu(ttfaS) 2 -1405.7+/-8.3[177+/-15

Development of Halide and Oxy-Halides for Isotopic Separations

Energy Technology Data Exchange (ETDEWEB)

Martin, Leigh R. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Johnson, Aaron T. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Pfeiffer, Jana [Idaho National Lab. (INL), Idaho Falls, ID (United States); Finck, Martha R. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2014-10-01

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

Critical review of the chemistry and thermodynamics of technetium and some of its inorganic compounds and aqueous species

International Nuclear Information System (INIS)

Rard, J.A.

1983-01-01

Chemical and thermodynamic data for Technetium (Tc) and some of its inorganic compounds and aqueous species are reviewed here. Major emphasis is given to systems with potential geochemical applications, especially the geochemistry of radioactive waste disposal. Compounds considered include oxides, hydroxides, hydrates oxides, halides, oxyhalides, double halides, and sulfides. The aqueous species considered include those in both noncomplexing media (pertechnetates, technetates, aquo-ions, and hydrolyzed cations) and complexing media (halides, sulfates, and phosphates). Thermodynamic values are recommended for specific compounds and aqueous ions when reliable experimental data are available. Where thermodynamic data are inadequate or unavailable, the chemistry is still discussed to provide information about what needs to be measured, and which chemistry needs to be clarified. A major application of these thermodynamic data will be for chemical equilibrium modeling and for construction of potential-pH diagrams for aqueous solutions. Unfortunately, the present lack of data precludes such calculations for complexing aqueous media. The situation is much better for noncomplexing aqueous media, but the chemistry and thermodynamics of cationic Tc(V) species and hydrolyzed Tc(III) species are poorly understood. 240 references, 6 tables

Fluorescent copper(II complexes: The electron transfer mechanism, interaction with bovine serum albumin (BSA and antibacterial activity

Directory of Open Access Journals (Sweden)

Madhumita Hazra

2017-01-01

Full Text Available Dinuclear copper(II complexes with formula [Cu2(L2(N32] (1 and [Cu2(L2(NCS2] (2 HL = (1-[(3-methyl-pyridine-2-ylimino-methyl]-naphthalen-2-ol were synthesized by controlling the molar ratio of Cu(OAC2·6H2O, HL, sodium azide (1 and ammonium thiocyanate (2. The end on bridges appear exclusively in azide and thiocyanate to copper complexes. The electron transfer mechanism of copper(II complexes is examined by cyclic voltammetry indicating copper(II complexes are Cu(II/Cu(I couple. The interactions of copper(II complexes towards bovine serum albumin (BSA were examined with the help of absorption and fluorescence spectroscopic tools. We report a superficial solution-based route for the synthesis of micro crystals of copper complexes with BSA. The antibacterial activity of the Schiff base and its copper complexes were investigated by the agar disc diffusion method against some species of pathogenic bacteria (Escherichia coli, Vibrio cholerae, Streptococcus pneumonia and Bacillus cereus. It has been observed that the antibacterial activity of all complexes is higher than the ligand.

CFD simulation of copper(II) extraction with TFA in non-dispersive hollow fiber membrane contactors.

Science.gov (United States)

Muhammad, Amir; Younas, Mohammad; Rezakazemi, Mashallah

2018-04-01

This study presents computational fluid dynamics (CFD) simulation of dispersion-free liquid-liquid extraction of copper(II) with trifluoroacetylacetone (TFA) in hollow fiber membrane contactor (HFMC). Mass and momentum balance Navier-Stokes equations were coupled to address the transport of copper(II) solute across membrane contactor. Model equations were simulated using COMSOL Multiphysics™. The simulation was run to study the detailed concentration distribution of copper(II) and to investigate the effects of various parameters like membrane characteristics, partition coefficient, and flow configuration on extraction efficiency. Once-through extraction was found to be increased from 10 to 100% when partition coefficient was raised from 1 to 10. Similarly, the extraction efficiency was almost doubled when porosity to tortuosity ratio of membrane was increased from 0.05 to 0.81. Furthermore, the study revealed that CFD can be used as an effective optimization tool for the development of economical membrane-based dispersion-free extraction processes.

Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

Science.gov (United States)

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.

Standard molar enthalpies of formation of copper(II) {beta}-diketonates and monothio-{beta}-diketonates

Energy Technology Data Exchange (ETDEWEB)

Ribeiro da Silva, Manuel A.V. [Centro de Investigacao em Quimica, Departamento de Quimica, Faculdade de Ciencias, Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal)]. E-mail: risilva@fc.up.pt; Santos, Luis M.N.B.F. [Centro de Investigacao em Quimica, Departamento de Quimica, Faculdade de Ciencias, Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal)

2006-07-15

The standard (p{sup o}=0.1MPa) molar enthalpies of formation of the crystalline complexes of dibenzoylmethane (Hdbm), thenoyltrifluoroacetone (Httfa), monothiodibenzoylmethane (HdbmS), and monothiothenoyltrifluoroacetone (HttfaS) of copper(II) were determined, at T=298.15K, by high precision solution-reaction calorimetry. The standard molar enthalpies of sublimation of the copper(II) {beta}-diketonate complexes were measured by high-temperature Calvet microcalorimetry. From the standard molar enthalpies of formation of the complexes in the gaseous state, the mean molar dissociation enthalpies copper(II)-ligand, (Cu-L), were derived. {delta}{sub f}H{sub m}{sup o} (cr){delta}{sub cr}{sup g}H{sub m}{sup o} kJ.mol{sup -1}kJ.mol{sup -1}Bis(dibenzoylmethanate)copper(II), Cu(dbm){sub 2}-364.0+/-3.9230.7+/-8.2Bis(thenoyltrifluoroacetonate)copper(II), Cu(ttfa){sub 2}-1824.3+/-8.3167.9+/-7.4Bis(monothiodibenzoylmethanate)copper(II), Cu(dbmS){sub 2}35.6+/-7.7[241+/-15]Bis(monothiothenoyltrifluoroacetonate) copper(II), Cu(ttfaS){sub 2}-1405.7+/-8.3[177+/-15].

Manhattan Project Technical Series: The Chemistry of Uranium (I)

International Nuclear Information System (INIS)

Rabinowitch, E. I.; Katz, J. J.

1947-01-01

This constitutes Chapters 11 through 16, inclusive, of the Survey Volume on Uranium Chemistry prepared for the Manhattan Project Technical Series. Chapters are titled: Uranium Oxides, Sulfides, Selenides, and Tellurides; The Non-Volatile Fluorides of Uranium; Uranium Hexafluoride; Uranium-Chlorine Compounds; Bromides, Iodides, and Pseudo-Halides of Uranium; and Oxyhalides of Uranium.

Manhattan Project Technical Series: The Chemistry of Uranium (I)

Energy Technology Data Exchange (ETDEWEB)

Rabinowitch, E. I. [Argonne National Lab. (ANL), Argonne, IL (United States); Katz, J. J. [Argonne National Lab. (ANL), Argonne, IL (United States)

1947-03-10

This constitutes Chapters 11 through 16, inclusive, of the Survey Volume on Uranium Chemistry prepared for the Manhattan Project Technical Series. Chapters are titled: Uranium Oxides, Sulfides, Selenides, and Tellurides; The Non-Volatile Fluorides of Uranium; Uranium Hexafluoride; Uranium-Chlorine Compounds; Bromides, Iodides, and Pseudo-Halides of Uranium; and Oxyhalides of Uranium.

TRANSURANIC METAL HALIDES AND A PROCESS FOR THE PRODUCTION THEREOF

Science.gov (United States)

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.

Performance Evaluation of Monolith Based Immobilized Acetylcholinesterase Flow-Through Reactor for Copper(II Determination with Spectrophotometric Detection

Directory of Open Access Journals (Sweden)

Parawee Rattanakit

2014-01-01

Full Text Available A monolith based immobilized acetylcholinesterase (AChE flow-through reactor has been developed for the determination of copper(II using flow injection spectrophotometric system. The bioreactor was prepared inside a microcapillary column by in situ polymerization of butyl methacrylate, ethylene dimethacrylate, and 2,2-dimethoxy-1,2-diphynyletane-1-one in the presence of 1-decanol, followed by vinyl azlactone functionalization and AChE immobilization. The behavior of AChE before and after being immobilized on the monolith was evaluated by kinetic parameters from Lineweaver and Burk equation. The detection was based on measuring inhibition effect on the enzymatic activity of AChE by copper(II using Ellman’s reaction with spectrophotometric detection at 410 nm. The linear range of the calibration graph was obtained over the range of 0.02–3.00 mg L−1. The detection limit, defined as 10% inhibition (I10, was found to be 0.04 mg L−1. The repeatability was 3.35 % (n=5 for 1.00 mg L−1 of copper(II. The proposed method was applied to the determination of copper(II in natural water samples with sampling rate of 4 h−1.

Structural and magnetic characterization of a tetranuclear copper(II) cubane stabilized by intramolecular metal cation-π interactions.

Science.gov (United States)

Papadakis, Raffaello; Rivière, Eric; Giorgi, Michel; Jamet, Hélène; Rousselot-Pailley, Pierre; Réglier, Marius; Simaan, A Jalila; Tron, Thierry

2013-05-20

A novel tetranuclear copper(II) complex (1) was synthesized from the self-assembly of copper(II) perchlorate and the ligand N-benzyl-1-(2-pyridyl)methaneimine (L(1)). Single-crystal X-ray diffraction studies revealed that complex 1 consists of a Cu4(OH)4 cubane core, where the four copper(II) centers are linked by μ3-hydroxo bridges. Each copper(II) ion is in a distorted square-pyramidal geometry. X-ray analysis also evidenced an unusual metal cation-π interaction between the copper ions and phenyl substituents of the ligand. Calculations based on the density functional theory method were used to quantify the strength of this metal-π interaction, which appears as an important stabilizing parameter of the cubane core, possibly acting as a driving parameter in the self-aggregation process. In contrast, using the ligand N-phenethyl-1-(2-pyridyl)methaneimine (L(2)), which only differs from L(1) by one methylene group, the same synthetic procedure led to a binuclear bis(μ-hydroxo)copper(II) complex (2) displaying intermolecular π-π interactions or, by a slight variation of the experimental conditions, to a mononuclear complex (3). These complexes were studied by X-ray diffraction techniques. The magnetic properties of complexes 1 and 2 are reported and discussed.

The creation of defects in ammonium halides by excitons

International Nuclear Information System (INIS)

Kim, L.M.

2002-01-01

The ammonium halides crystals and alkali halides crystals are analogous by kind chemical bonds and crystalline lattices. The anionic sublattice is identical in this crystals. It is known the main mechanism of defect creation by irradiation is radiationless decay of excitons in alkali halides crystals. The F-, H-centers are formation in this processes. However, F, H-centres are not detected in ammonium halides. The goal of this work is investigation the creation of defects in ammonium halides by excitons. We established that excitons in ammonium chlorides and bromides are similar to excitons in alkali halides. It is known excitons are self-trapped and have identical parameters of the exciton-phonon interaction in both kind crystals. It is supposed, that processes of radiationless disintegration of excitons are identical in ammonium and alkali halides. It is necessary to understand why F-, H-centers are absent in ammonium halides. V k -centres are created by the excitation of the ammonium halides crystals in the absorption band of excitons. It was established by thermoluminescence and spectrums of absorption. The V k -centers begin to migrate at 110-120 K in ammonium chlorides and bromides. The curve of thermoluminescence have peak with maximum at this temperatures. It is known V k -centers in ammonium chlorides have the absorption band at 380 nm. We discovered this absorption band after irradiation of crystals by ultra-violet. In alkali halides F-center is anionic vacancy with electron. The wave function of electron are spread ed at the cations around anionic vacancy. We established the cation NH 4 + in ammonium halides can to capture electron. The ion NH 4 2+ is unsteady. It is disintegrated to NH 3 + and H + . We suppose that excitons in ammonium and alkali halides are disintegrated identically. When cation NH 4 + capture electron, in the anionic sublattice the configuration are created in a direction (100) The indicated configuration is unsteady in relation to a

Immobilized copper(II) macrocyclic complex on MWCNTs with antibacterial activity

Energy Technology Data Exchange (ETDEWEB)

Tarlani, Aliakbar, E-mail: Tarlani@ccerci.ac.ir [Inorganic Nanostructures and Catalysts Research Lab., Chemistry & Chemical Engineering Research Center of Iran, Pajoohesh Blvd., km 17, Karaj Hwy, Tehran 14968-13151 (Iran, Islamic Republic of); Narimani, Khashayar [Inorganic Nanostructures and Catalysts Research Lab., Chemistry & Chemical Engineering Research Center of Iran, Pajoohesh Blvd., km 17, Karaj Hwy, Tehran 14968-13151 (Iran, Islamic Republic of); Mohammadipanah, Fatemeh; Hamedi, Javad [Department of Microbial Biotechnology, School of Biology and Center of Excellence in Phylogeny of Living Organisms, College of Science, University of Tehran, Tehran 14155-6455 (Iran, Islamic Republic of); University of Tehran Biocompound Collection (UTBC), Microbial Technology and Products Research Center, University of Tehran, Tehran (Iran, Islamic Republic of); Tahermansouri, Hasan [Department of Chemistry, Ayatollah Amoli Branch, Islamic Azad University, Amol (Iran, Islamic Republic of); Amini, Mostafa M. [Department of Chemistry, Shahid Behshti University, 1983963113, Tehran (Iran, Islamic Republic of)

2015-06-30

Graphical abstract: In an antibacterial test, grafted copper(II) macrocyclic complex on the surface of MWCNT showed higher antibacterial activity against Bacillus subtilis compared to the individual MWCNT-COOH and the complex. - Highlights: • Copper(II) tetraaza macrocyclic complex covalently bonded to modified MWCNT. • Grafting of the complex carried out via an interaction between −C(=O)Cl group and NH of the ligand. • The samples were subjected in an antibacterial assessment to compare their activity. • Immobilized complex showed higher antibacterial activity against Bacillus subtilis ATCC 6633 compared to separately MWCNT-C(C=O)-OH and CuTAM. - Abstract: In a new approach, a copper(II) tetraaza macrocyclic complex (CuTAM) was covalently bonded on modified multi-walled carbon nanotubes (MWCNTs). To achieve this purpose, MWCNTs were converted to MWCNT-COCl and then reacted to NH groups of TAM ligand. The prepared material was characterized by Fourier Transform Infrared (FT-IR), X-ray diffraction (XRD), Raman spectroscopy, thermal gravimetric analysis (TGA), and FESEM (field emission scanning electron microscopy). FT-IR and TGA demonstrated the presence of the organic moieties, and XRD proved that the structure of MWCNTs remained intact during the three modification steps. An increase in the I{sub D}/I{sub G} ratio in Raman spectra confirmed the surface modifications. Finally, the samples were subjected to an antibacterial assessment to compare their biological activity. The antibacterial test showed that the grafted complex on the surface of the nanotube (MWCNT-CO-CuTAM) has higher antibacterial activity against Bacillus subtilis ATCC 6633 than the MWCNT-COOH and CuTAM with 1000 and 2000 μg/mL.

Efficient electron-induced removal of oxalate ions and formation of copper nanoparticles from copper(II oxalate precursor layers

Directory of Open Access Journals (Sweden)

Kai Rückriem

2016-06-01

Full Text Available Copper(II oxalate grown on carboxy-terminated self-assembled monolayers (SAM using a step-by-step approach was used as precursor for the electron-induced synthesis of surface-supported copper nanoparticles. The precursor material was deposited by dipping the surfaces alternately in ethanolic solutions of copper(II acetate and oxalic acid with intermediate thorough rinsing steps. The deposition of copper(II oxalate and the efficient electron-induced removal of the oxalate ions was monitored by reflection absorption infrared spectroscopy (RAIRS. Helium ion microscopy (HIM reveals the formation of spherical nanoparticles with well-defined size and X-ray photoelectron spectroscopy (XPS confirms their metallic nature. Continued irradiation after depletion of oxalate does not lead to further particle growth giving evidence that nanoparticle formation is primarily controlled by the available amount of precursor.

Muonium centers in the alkali halides

International Nuclear Information System (INIS)

Baumeler, H.; Kiefl, R.F.; Keller, H.; Kuendig, W.; Odermatt, W.; Patterson, B.D.; Schneider, J.W.; Savic, I.M.

1986-01-01

Muonium centers (Mu) in single crystals and powdered alkali halides have been studied using the high-timing-resolution transverse field μSR technique. Mu has been observed and its hyperfine parameter (HF) determined in every alkali halide. For the rocksalt alkali halides, the HF parameter A μ shows a systematic dependence on the host lattice constant. A comparison of the Mu HF parameter with hydrogen ESR data suggests that the Mu center is the muonic analogue of the interstitial hydrogen H i 0 -center. The rate of Mu diffusion can be deduced from the motional narrowing of the nuclear hyperfine interaction. KBr shows two different Mu states, a low-temperature Mu I -state and a high-temperature Mu II -state. (orig.)

The thermal decomposition of copper(II) oxalate revisited

International Nuclear Information System (INIS)

Lamprecht, Emmanuel; Watkins, Gareth M.; Brown, Michael E.

2006-01-01

DSC, TG and TG-FT-IR, and XRPD have been used to examine the effects of supposedly inert atmospheres of argon and nitrogen on the mechanism of the thermal decomposition of copper(II) oxalate. The DSC curves in pure argon at 10 deg. C min -1 show a broad endotherm with onset at about 280 deg. C and maximum at about 295 deg. C. In mixtures of argon and nitrogen, as the proportion of argon gas is decreased, the endothermic character of the decomposition decreases until, when nitrogen is the main component, the decomposition exhibits a complex broad exothermic character. XRPD studies showed that, regardless of the proportions of nitrogen and argon, the DSC residues consisted of mainly copper metal with small amounts of copper(I) oxide (cuprite) and, under some conditions, traces of copper(II) oxide (tenorite). Various explanations for this behaviour are discussed and a possible answer lies in the disproportionation of CO 2 (g) to form small quantities of O 2 (g) or monatomic oxygen. The possibility exists that the exothermicity in nitrogen could be explained by reaction of the nitrogen with atomic oxygen to form N 2 O(g), but this product could not be detected using TG-FT-IR

The thermal decomposition of copper(II) oxalate revisited

Energy Technology Data Exchange (ETDEWEB)

Lamprecht, Emmanuel [Chemistry Department, Rhodes University, Grahamstown 6140 (South Africa); Watkins, Gareth M. [Chemistry Department, Rhodes University, Grahamstown 6140 (South Africa); Brown, Michael E. [Chemistry Department, Rhodes University, Grahamstown 6140 (South Africa)]. E-mail: m.brown@ru.ac.za

2006-07-01

DSC, TG and TG-FT-IR, and XRPD have been used to examine the effects of supposedly inert atmospheres of argon and nitrogen on the mechanism of the thermal decomposition of copper(II) oxalate. The DSC curves in pure argon at 10 deg. C min{sup -1} show a broad endotherm with onset at about 280 deg. C and maximum at about 295 deg. C. In mixtures of argon and nitrogen, as the proportion of argon gas is decreased, the endothermic character of the decomposition decreases until, when nitrogen is the main component, the decomposition exhibits a complex broad exothermic character. XRPD studies showed that, regardless of the proportions of nitrogen and argon, the DSC residues consisted of mainly copper metal with small amounts of copper(I) oxide (cuprite) and, under some conditions, traces of copper(II) oxide (tenorite). Various explanations for this behaviour are discussed and a possible answer lies in the disproportionation of CO{sub 2}(g) to form small quantities of O{sub 2}(g) or monatomic oxygen. The possibility exists that the exothermicity in nitrogen could be explained by reaction of the nitrogen with atomic oxygen to form N{sub 2}O(g), but this product could not be detected using TG-FT-IR.

Investigation of surface halide modification of nitrile butadiene rubber

Science.gov (United States)

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.

Cluster harvesting by successive reduction of a metal halide with a nonconventional reduction agent: a benefit for the exploration of metal-rich halide systems.

Science.gov (United States)

Ströbele, Markus; Mos, Agnieszka; Meyer, Hans-Jürgen

2013-06-17

The preparation of thermally labile compounds is a great temptation in chemistry which requires a careful selection of reaction media and reaction conditions. With a new scanning technique denoted here as Cluster Harvesting, a whole series of metal halide compounds is detected by differential thermal analysis (DTA) in fused silica tubes and structurally characterized by X-ray powder diffraction. Experiments of the reduction of tungsten hexahalides with elemental antimony and iron are presented. A cascade of six compounds is identified during the reduction with antimony, and five compounds or phases are monitored following the reduction with iron. The crystal structure of Fe2W2Cl10 is reported, and two other phases in the Fe-W-Cl system are discussed.

The alkali halide disk technique in infra-red spectrometry : Anomalous behaviour of some samples dispersed in alkali halide disks

NARCIS (Netherlands)

Tolk, A.

1961-01-01

Some difficulties encountered in the application of the alkali halide disk technique in infra-red spectrometry are discussed. Complications due to interaction of the sample with the alkali halide have been studied experimentally. It was found that the anomalous behaviour of benzoic acid, succinic

Copper(II) complexes of methimazole, an anti Grave's disease drug. Synthesis, characterization and its potential biological behavior as alkaline phosphatase inhibitor.

Science.gov (United States)

Urquiza, Nora M; Manca, Silvia G; Moyano, María A; Dellmans, Raquel Arrieta; Lezama, Luis; Rojo, Teófilo; Naso, Luciana G; Williams, Patricia A M; Ferrer, Evelina G

2010-04-01

Methimazole (MeimzH) is an anti-thyroid drug and the first choice for patients with Grave's disease. Two new copper(II) complexes of this drug: [Cu(MeimzH)(2)(NO(3))(2)]*0.5H(2)O and [Cu(MeimzH)(2)(H(2)O)(2)](NO(3))(2)*H(2)O were synthesized and characterized by elemental analysis, dissolution behavior, thermogravimetric analysis and UV-vis, diffuse reflectance, FTIR and EPR spectroscopies. As it is known that copper(II) cation can act as an inhibitor of alkaline phosphatase (ALP), the inhibitory effect of methimazole and its copper(II) complexes on ALP activity has also been investigated.

The chemistry of positronium. Part VI: inhibition and enhancement of positronium formation in aqueous solutions of halides, sulfide and thiocyanate

International Nuclear Information System (INIS)

Duplatre, G.; Abbe, J.C.; Maddock, A.G.; Haessler, A.

1977-01-01

The formation of positronium in aqueous solutions of halides, sulfide and thiocyanate has been investigated. Inhibiting and enhancing reactions of positronium formation are found. The results are discussed in terms of the spur model

Far IR spectra of Th(IV) halide complexes of some heterocyclic bases

International Nuclear Information System (INIS)

Srivastava, A.K.; Agarwal, R.K.; Srivastava, M.; Kapoor, V.; Srivastava, T.N.

1981-01-01

The synthesis and IR spectra of Th(IV) perchlorato, nitrato and thiocyanato complexes of some heterocyclic bases have been reported. Halogens are common ligands in coordination chemistry forming coordinate bonds with metals readily. Metal halogen (M-X) stretching bands show a strong absorption in the far-IR region. Very little information is available on Th-X stretching frequencies. In the present communication, adducts of Th(IV) halide with certain nitrogen heterocyclic bases such as pyridine, α-picoline, 2-amino pyridine, 2:4-lutidine, 2:6-lutidine, quinoline, 2,2'-bipyridine and 1,10-phenanthroline were synthesised and characterised. Experimental details are given. Results are presented and discussed. (author)

Treatment of alcaline metals halides for developing crystals

International Nuclear Information System (INIS)

Spurney, R.W.

1974-01-01

A process is described whereby crystals of an alkaline metal halide may be dried and placed in a crucible for development by the Bridgeman-Stockbarger method. Purified alkaline halides from a suspension are dried and formed into dense cakes of transverse section slightly smaller than that of the crucible, where they are packed, melted and grown into crystals according to the Bridgeman-Stockbarger technique. This method applies to the preparation of alkaline halide crystals, particularly sodium iodide for optical elements or scintillation counters [fr

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

Science.gov (United States)

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.

Spectroscopic and molecular docking studies on the interaction of human serum albumin with copper(II) complexes

Science.gov (United States)

Guhathakurta, Bhargab; Pradhan, Ankur Bikash; Das, Suman; Bandyopadhyay, Nirmalya; Lu, Liping; Zhu, Miaoli; Naskar, Jnan Prakash

2017-02-01

Two osazone based ligands, butane-2,3-dione bis(2‧-pyridylhydrazone) (BDBPH) and hexane-3,4-dione bis(2‧-pyridylhydrazone) (HDBPH), were synthesized out of the 2:1 M Schiff base condensation of 2-hydrazino pyridine respectively with 2,3-butanedione and 3,4-hexanedione. The X-ray crystal structures of both the ligands have been determined. The copper(II) complex of HDBPH has also been synthesized and structurally characterized. HDBPH and its copper(II) complex have thoroughly been characterized through various spectroscopic and analytical techniques. The X-ray crystal structure of the copper complex of HDBPH shows that it is a monomeric Cu(II) complex having 'N4O2' co-ordination chromophore. Interaction of human serum albumin (HSA) with these ligands and their monomeric copper(II) complexes have been studied by various spectroscopic means. The experimental findings show that the ligands as well as their copper complexes are good HSA binders. Molecular docking investigations have also been done to unravel the mode of binding of the species with HSA.

Chemistry of gaseous lower halides of uranium. Technical progress report, 1 September 1979-1 April 1980

International Nuclear Information System (INIS)

Hildenbrand, D.L.

1980-01-01

The gaseous uranium species UF, UF 2 , UF 3 , and UF 4 were generated in effusion cell beams by vaporization of UF 4 (s) under reducing conditions, and they were identified and studied by mass spectrometry. From extensive second-law studies of reaction equilibria involving these species and several reaction partners used as reference standards, the individual bond dissociation energies and standard enthalpies of formation of the U-F species were derived. Reaction entropies derived from the slope data indicate that the electronic entropies of the U-F species are substantial, and are comparable to or larger than that of atomic uranium. Additional thermochemical measurements were made to establish the properties of several Ag and Cu monohalides that have been or will be used as reference standards in the uranium halide measurements. From studies of the sublimation and decomposition of uranyl fluoride, UO 2 F 2 (s), the enthalpy of sublimation of UO 2 F 2 (g), has been determined, and another gaseous oxyfluoride, UOF 4 (g), has been tentatively identified. The gaseous products of decomposition of UO 2 F 2 (s) observed by mass spectrometry differ from those postulated by other investigators, indicating that the mechanism of decomposition has not been clearly established. A search of the thermochemical literature on uranium halides has been completed

Recovery of copper(II) and chromium(III) from nitrate medium with ...

African Journals Online (AJOL)

The solvent extraction of copper(II) and chromium(III) from nitrate medium with salicylideneaniline (HL) is studied as a function of various parameters: pH, concentration of salicylideneaniline, contact time and the nature of anoin (nitrate and sulfate) in aqueous phase. Chromium(III) is not extracted by salicylideneaniline ...

Organic Iodine(I, III, and V Chemistry: 10 Years of Development at the Medical University of Warsaw, Poland

Directory of Open Access Journals (Sweden)

Lech Skulski

2000-12-01

Full Text Available This review reports some novel (or considerably improved methods for the synthesis of aromatic iodides, (dichloroiodoarenes, (diacetoxyiodoarenes, iodylarenes and diaryliodonium salts, as well as some facile, oxidative anion metatheses in crude diaryliodonium halides and, for comparison, potassium halides. All these new results were obtained in our laboratory over the past decade (1990-2000. A full list of our papers dealing with the organic iodine(I, III and V chemistry, covering exlusively the aromatic derivatives, is also provided.

Formability of ABX3 (X=F,Cl,Br,I) halide perovskites

International Nuclear Information System (INIS)

Li Chonghea; Lu Xionggang; Ding Weizhong; Feng Liming; Gao Yonghui; Guo Ziming

2008-01-01

In this study a total of 186 complex halide systems were collected; the formabilities of ABX 3 (X = F, Cl, Br and I) halide perovskites were investigated using the empirical structure map, which was constructed by Goldschmidt's tolerance factor and the octahedral factor. A model for halide perovskite formability was built up. In this model obtained, for all 186 complex halides systems, only one system (CsF-MnF 2 ) without perovskite structure and six systems (RbF-PbF 2 , CsF- BeF 2 , KCl-FeCl 2 , TlI-MnI 2 , RbI-SnI 2 , TlI-PbI 2 ) with perovskite structure were wrongly classified, so its predicting accuracy reaches 96%. It is also indicated that both the tolerance factor and the octahedral factor are a necessary but not sufficient condition for ABX 3 halide perovskite formability, and a lowest limit of the octahedral factor exists for halide perovskite formation. This result is consistent with our previous report for ABO 3 oxide perovskite, and may be helpful to design novel halide materials with the perovskite structure. (orig.)

Synthesis, Reactivity and Stability of Aryl Halide Protecting Groups towards Di-Substituted Pyridines

Directory of Open Access Journals (Sweden)

Ptoton Mnangat Brian

2016-03-01

Full Text Available This paper reports the synthesis and reactivity of different Benzyl derivative protecting groups. The synthesis and stability of Benzyl halides, 4-methoxybenzyl halides, 3,5-dimethoxybenzyl halides, 3,4-dimethoxybenzyl halides, 3,4,5-trimethoxybenzyl halide protecting groups and their reactivity towards nitrogen atom of a di-substituted pyridine ring in formation of pyridinium salts is also reported.

Interesting properties of some iron(II), copper(I) and copper(II ...

Indian Academy of Sciences (India)

Administrator

Tridendate ligands with nitrogen centers, generally well-known as the tripod ligands, have been of considerable interest to inorganic chemists dealing with the preparation of model compounds for hemocyanin, tyrosinase etc. We have found that such ligands when complexed with iron(II) and copper(II) and copper(I) ions ...

High temperature reactions between molybdenum and metal halides

International Nuclear Information System (INIS)

Boeroeczki, A.; Dobos, G.; Josepovits, V.K.; Hars, Gy.

2006-01-01

Good colour rendering properties, high intensity and efficacy are of vital importance for high-end lighting applications. These requirements can be achieved by high intensity discharge lamps doped with different metal halide additives (metal halide lamps). To improve their reliability, it is very important to understand the different failure processes of the lamps. In this paper, the corrosion reactions between different metal halides and the molybdenum electrical feed-through electrode are discussed. The reactions were studied in the feed-through of real lamps and on model samples too. X-ray photoelectron spectroscopy (XPS) was used to establish the chemical states. In case of the model samples we have also used atomic absorption spectroscopy (AAS) to measure the reaction product amounts. Based on the measurement results we were able to determine the most corrosive metal halide components and to understand the mechanism of the reactions

Halide-Dependent Electronic Structure of Organolead Perovskite Materials

KAUST Repository

Buin, Andrei

2015-06-23

© 2015 American Chemical Society. Organometal halide perovskites have recently attracted tremendous attention both at the experimental and theoretical levels. These materials, in particular methylammonium triiodide, are still limited by poor chemical and structural stability under ambient conditions. Today this represents one of the major challenges for polycrystalline perovskite-based photovoltaic technology. In addition to this, the performance of perovskite-based devices is degraded by deep localized states, or traps. To achieve better-performing devices, it is necessary to understand the nature of these states and the mechanisms that lead to their formation. Here we show that the major sources of deep traps in the different halide systems have different origin and character. Halide vacancies are shallow donors in I-based perovskites, whereas they evolve into a major source of traps in Cl-based perovskites. Lead interstitials, which can form lead dimers, are the dominant source of defects in Br-based perovskites, in line with recent experimental data. As a result, the optimal growth conditions are also different for the distinct halide perovskites: growth should be halide-rich for Br and Cl, and halide-poor for I-based perovskites. We discuss stability in relation to the reaction enthalpies of mixtures of bulk precursors with respect to final perovskite product. Methylammonium lead triiodide is characterized by the lowest reaction enthalpy, explaining its low stability. At the opposite end, the highest stability was found for the methylammonium lead trichloride, also consistent with our experimental findings which show no observable structural variations over an extended period of time.

Infrared losses from a Na/Sc metal-halide high intensity discharge arc lamp

International Nuclear Information System (INIS)

Smith, D J; Bonvallet, G A; Lawler, J E

2003-01-01

A study of the near-infrared (IR) emission from the arc of a metal-halide high intensity discharge (MH-HID) lamp with a sodium/scandium chemistry is reported. Radiometrically calibrated spectra from 0.7 to 2.5 μm were recorded as a function of position on the arc tube of a 250 W lamp. These spectra were analysed to determine the relative densities of Na and Sc atoms and the arc temperature as a function of radius. Information from these spectra, combined with absorption measurements in the companion paper (Bonvallet and Lawler 2003), were used to determine the absolute output power in the near-IR from the MH-HID lamp

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

Energy Technology Data Exchange (ETDEWEB)

Dou, Benjia [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Wheeler, Lance M [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Christians, Jeffrey A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Moore, David [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Harvey, Steven P [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Berry, Joseph J [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Van Hest, Marinus F [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Barnes, Frank S. [University of Colorado; Shaheen, Sean E. [University of Colorado

2018-03-02

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

Entropy in halide perovskites

Science.gov (United States)

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.

Effect of Phosphorylation and Copper(II or Iron(II Ions Enrichment on Some Physicochemical Properties of Spelt Starch

Directory of Open Access Journals (Sweden)

Jacek Rożnowski

Full Text Available ABSTRACT: This paper provides an assessment of the effect of saturation of spelt starch and monostarch phosphate with copper or iron ions on selected physicochemical properties of the resulting modified starches. Native and modified spelt starch samples were analyzed for selected mineral element content using Atomic Absorption Spectroscopy (AAS. Thermodynamic properties were measured using DSC, and pasting properties by RVA. Flow curves of 5% pastes were plotted and described using the Herschel-Bulkley model. The structure recovery ratio was measured. AAS analysis established the presence of iron(II and copper(II ions in the samples of modified starches and that potassium and magnesium ions had leached from them. In comparison to unfortified samples, enriching native starch with copper(II ions decreases value of all temperatures of phase transformation about 1.3-2.7 °C, but in case of monostarch phosphates bigger changes (2.8-3.7 °C were observed. Fortified native spelt starch with copper(II ions caused increasing the final viscosity of paste from 362 to 429 mPa·s. However, presence iron(II ions in samples caused reduced its final viscosity by 170 (spelt starch and 103 mPa·s (monostarch phosphate. Furthermore, enriching monostarch phosphate contributed to reduce degree of structure recovery of pastes from 70.9% to 66.6% in case of copper(II ions and to 59.9% in case of iron(II ions.

Development of pyridine-containing macrocyclic copper(II) complexes: potential role in the redox modulation of oxaliplatin toxicity in human breast cells.

Science.gov (United States)

Fernandes, Ana S; Costa, Judite; Gaspar, Jorge; Rueff, José; Cabral, M Fátima; Cipriano, Madalena; Castro, Matilde; Oliveira, Nuno G

2012-09-01

The unique redox and catalytic chemistry of Cu has justified the development of novel Cu complexes for different therapeutic uses including cancer therapy. In this work, four pyridine-containing aza-macrocyclic copper(II) complexes were prepared (CuL1-CuL4) varying in ring size and/or substituents and their superoxide scavenging activity evaluated. CuL3, the most active superoxide scavenger, was further studied as a modulator of the cytotoxicity of oxaliplatin in epithelial breast MCF10A cells and in MCF7 breast cancer cells. Our results show that CuL3 enhances the therapeutic window of oxaliplatin, by both protecting non-tumour cells and increasing its cytotoxic effect in breast carcinoma cells. CuL3 is thus a promising complex to be further studied and to be used as a lead compound for the optimization of novel chemotherapy sensitizers.

Determination of formal redox potentials in aqueous solution of copper(II) complexes with ligands having nitrogen and oxygen donor atoms and comparison with their EPR and UV-Vis spectral features.

Science.gov (United States)

Tabbì, Giovanni; Giuffrida, Alessandro; Bonomo, Raffaele P

2013-11-01

Formal redox potentials in aqueous solution were determined for copper(II) complexes with ligands having oxygen and nitrogen as donor atoms. All the chosen copper(II) complexes have well-known stereochemistries (pseudo-octahedral, square planar, square-based pyramidal, trigonal bipyramidal or tetrahedral) as witnessed by their reported spectroscopic, EPR and UV-visible (UV-Vis) features, so that a rough correlation between the measured redox potential and the typical geometrical arrangement of the copper(II) complex could be established. Negative values have been obtained for copper(II) complexes in tetragonally elongated pseudo-octahedral geometries, when measured against Ag/AgCl reference electrode. Copper(II) complexes in tetrahedral environments (or flattened tetrahedral geometries) show positive redox potential values. There is a region, always in the field of negative redox potentials which groups the copper(II) complexes exhibiting square-based pyramidal arrangements. Therefore, it is suggested that a measurement of the formal redox potential could be of great help, when some ambiguities might appear in the interpretation of spectroscopic (EPR and UV-Vis) data. Unfortunately, when the comparison is made between copper(II) complexes in square-based pyramidal geometries and those in square planar environments (or a pseudo-octahedral) a little perturbed by an equatorial tetrahedral distortion, their redox potentials could fall in the same intermediate region. In this case spectroscopic data have to be handled with great care in order to have an answer about a copper complex geometrical characteristics. © 2013.

Strong copper(II) species in estuarine and sea waters investigated by a method with high detection window.

Science.gov (United States)

Alberti, Giancarla; Biesuz, Raffaela; D'Agostino, Girolamo; Scarponi, Giuseppe; Pesavento, Maria

2007-02-15

The distribution of copper(II) in species of different stability in some estuarine and sea water samples (Adriatic Sea) was investigated by a method based on the sorption of the metal ion on a strongly sorbing resin, Chelex 100, whose sorbing properties have been previously characterized. From them, it is possible to predict very high values of detection windows at the considered conditions, for example side reaction coefficient as high as 10(10) at pH 7.5. Strong copper(II) species in equilibrium with Chelex 100 were detected, at concentration 2-20nM, with a reaction coefficient approximately 10(10.6) at pH 7.45 in sea water, strictly depending on the acidity. They represent 50-70% of the total metal ion and are the strongest copper(II) complexes found in sea water. Weak complexes too were detected in all the samples, with reaction coefficient lower than ca. 10(9) at the same pH. The method applied, named resin titration (RT), was described in a previous investigation, and is here modified in order to be carried out on oceanographic boat during a cruise in the Adriatic Sea.

Preconcentration and extraction of copper(II) on activated carbon using ethyl-2-quinolyl-β (p-carboxyphenyl hydrazone)dioxo propionate

OpenAIRE

Mehrorang Ghaedi; Farshid Ahmadi; M.R. Baezat; J. Safari

2008-01-01

Activated carbon modified method was used for the preconcentration and determination of copper content in real samples such as tap water, wastewater and a synthetic water sample by flame atomic absorption spectrometry. The copper(II) was adsorbed quantitatively on activated carbon due to its complexation with ethyl-2-quinolyl-β(p-carboxyphenyl hydrazone)dioxo propionate (EQCPDP). The adsorbed copper(II) ion on solid phase was eluted quantitatively by using nitric acid. The important parameter...

The coacervation of aqueous solutions of tetraalkylammonium halides

International Nuclear Information System (INIS)

Mugnier de Trobriand, Anne.

1979-09-01

The coacervation of aqueous solutions of tatraalkylammonium halides in the presence of not of inorganic halides and acids has been studied, considering thermodynamic and spectroscopic aspects. The importance of dispersion forces as well as forces resulting from hydrophobic hydration has been assessed. The analogy between these systems and anionic ion exchange resins has been shown especially for Uranium VI extraction [fr

Computational screening of mixed metal halide ammines

DEFF Research Database (Denmark)

Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich

2013-01-01

Metal halide ammines, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, can reversibly store ammonia, with high volumetric hydrogen storage capacities. The storage in the halide ammines is very safe, and the salts are therefore highly relevant as a carbon-free energy carrier in future transportation infrastructure...... selection. The GA is evolving from an initial (random) population and selecting those with highest fitness, a function based on e.g. stability, release temperature and storage capacity. The search space includes all alkaline, alkaline earth, 3d and 4d metals and the four lightest halides. In total...... the search spaces consists of millions combinations, which makes a GA ideal, to reduce the number of necessary calculations. We are screening for a one step release from either a hexa or octa ammine, and we have found promising candidates, which will be further investigated ? both computationally...

Catalytic effect of halide additives ball milled with magnesium hydride

Energy Technology Data Exchange (ETDEWEB)

Malka, I.E.; Bystrzycki, J. [Department of Advanced Materials and Technologies, Military University of Technology, Kaliskiego 2, 00-908 Warsaw (Poland); Czujko, T. [Department of Advanced Materials and Technologies, Military University of Technology, Kaliskiego 2, 00-908 Warsaw (Poland); CanmetENERGY, Hydrogen Fuel Cells and Transportation Energy, Natural Resources (Canada)

2010-02-15

The influence of various halide additives milled with magnesium hydride (MgH{sub 2}) on its decomposition temperature was studied. The optimum amount of halide additive and milling conditions were evaluated. The MgH{sub 2} decomposition temperature and energy of activation reduction were measured by temperature programmed desorption (TPD) and differential scanning calorimetry (DSC). The difference in catalytic efficiency between chlorides and fluorides of the various metals studied is presented. The effects of oxidation state, valence and position in the periodic table for selected halides on MgH{sub 2} decomposition temperature were also studied. The best catalysts, from the halides studied, for magnesium hydride decomposition were ZrF{sub 4}, TaF{sub 5}, NbF{sub 5}, VCl{sub 3} and TiCl{sub 3}. (author)

Copper(II tetrafluoroborate as mild and versatile catalyst for the

Directory of Open Access Journals (Sweden)

Jihillu. S. Yadav

2008-12-01

Full Text Available A variety of -acetamido ketones and ketoesters are readily prepared in high yields under extremelymild conditions via a three component coupling of aromatic aldehydes, enolizable ketones or -ketoesters andnitriles in the presence of 10 mol% of copper(II tetrafluoroborate and a stoichiometric amount of acetylchloride. A solution of 10 mol% of Cu(BF42 in acetonitrile provides a convenient reaction medium to carry out athree component reaction under mild conditions

EPR studies on binuclear copper(II) complexes with N,N',N'',N'''-tetrakis(2-pyridylmethyl)-1,4,8,11-tetraaza-cyclotetradecane in solutions

International Nuclear Information System (INIS)

Jezierska, J.; Ozarowski, A.; Vuckovic, G.

1997-01-01

Binuclear copper(II) complexes of macrocyclic ligand TMPC (tetraazamacrocycle with four pendant 2-pirydylmethyl groups attached to the ring nitrogen atoms) with various anions forming bridge between copper ions, or coordinating to copper(II) ions at the apex, were prepared and their frozen solutions in DMF and NMF were investigated by EPR. The spectroscopic results have been interpreted in terms of molecular structure of investigated complexes

Alkali metal and alkali earth metal gadolinium halide scintillators

Science.gov (United States)

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.

Electrochemistry and Spectroelectrochemistry of Lead Halide Perovskite Films: Materials Science Aspects and Boundary Conditions

KAUST Repository

Samu, Gergely F.; Scheidt, Rebecca A; Kamat, Prashant V.; Janá ky, Csaba

2017-01-01

The unique optoelectronic properties of lead halide perovskites have triggered a new wave of excitement in materials chemistry during the past five years. Electrochemistry, spectroelectrochemistry, and photoelectrochemistry could be viable tools both for analyzing the optoelectronic features of these materials and to assemble their hybrid architectures (e.g., solar cells). At the same time, the instability of these materials limits the pool of solvents and electrolytes that can be employed in such experiments. The focus of our study is to establish a stability window for electrochemical tests for all-inorganic CsPbBr3 and hybrid organic-inorganic MaPbI3 perovskites. In addition, we aimed to understand the reduction and oxidation events that occur and to assess the damage done during these processes at extreme electrochemical conditions. In this vein, we demonstrated the chemical, structural, and morphological changes of the films in both reductive and oxidative environments. Taking all these results together as a whole, we propose a set of boundary conditions and protocols for how electrochemical experiments with lead halide perovskites should be carried out and interpreted. We believe that the presented results will contribute to the understanding of the electrochemical response of these materials and lead to a standardization of results in the literature so that easier comparisons can be made.

Electrochemistry and Spectroelectrochemistry of Lead Halide Perovskite Films: Materials Science Aspects and Boundary Conditions.

Science.gov (United States)

Samu, Gergely F; Scheidt, Rebecca A; Kamat, Prashant V; Janáky, Csaba

2018-02-13

The unique optoelectronic properties of lead halide perovskites have triggered a new wave of excitement in materials chemistry during the past five years. Electrochemistry, spectroelectrochemistry, and photoelectrochemistry could be viable tools both for analyzing the optoelectronic features of these materials and for assembling them into hybrid architectures (e.g., solar cells). At the same time, the instability of these materials limits the pool of solvents and electrolytes that can be employed in such experiments. The focus of our study is to establish a stability window for electrochemical tests for all-inorganic CsPbBr 3 and hybrid organic-inorganic MAPbI 3 perovskites. In addition, we aimed to understand the reduction and oxidation events that occur and to assess the damage done during these processes at extreme electrochemical conditions. In this vein, we demonstrated the chemical, structural, and morphological changes of the films in both reductive and oxidative environments. Taking all these results together as a whole, we propose a set of boundary conditions and protocols for how electrochemical experiments with lead halide perovskites should be carried out and interpreted. The presented results will contribute to the understanding of the electrochemical response of these materials and lead to a standardization of results in the literature so that comparisons can more easily be made.

Electrochemistry and Spectroelectrochemistry of Lead Halide Perovskite Films: Materials Science Aspects and Boundary Conditions

KAUST Repository

Samu, Gergely F.

2017-12-06

The unique optoelectronic properties of lead halide perovskites have triggered a new wave of excitement in materials chemistry during the past five years. Electrochemistry, spectroelectrochemistry, and photoelectrochemistry could be viable tools both for analyzing the optoelectronic features of these materials and to assemble their hybrid architectures (e.g., solar cells). At the same time, the instability of these materials limits the pool of solvents and electrolytes that can be employed in such experiments. The focus of our study is to establish a stability window for electrochemical tests for all-inorganic CsPbBr3 and hybrid organic-inorganic MaPbI3 perovskites. In addition, we aimed to understand the reduction and oxidation events that occur and to assess the damage done during these processes at extreme electrochemical conditions. In this vein, we demonstrated the chemical, structural, and morphological changes of the films in both reductive and oxidative environments. Taking all these results together as a whole, we propose a set of boundary conditions and protocols for how electrochemical experiments with lead halide perovskites should be carried out and interpreted. We believe that the presented results will contribute to the understanding of the electrochemical response of these materials and lead to a standardization of results in the literature so that easier comparisons can be made.

Electrochemistry and Spectroelectrochemistry of Lead Halide Perovskite Films: Materials Science Aspects and Boundary Conditions

Science.gov (United States)

2017-01-01

The unique optoelectronic properties of lead halide perovskites have triggered a new wave of excitement in materials chemistry during the past five years. Electrochemistry, spectroelectrochemistry, and photoelectrochemistry could be viable tools both for analyzing the optoelectronic features of these materials and for assembling them into hybrid architectures (e.g., solar cells). At the same time, the instability of these materials limits the pool of solvents and electrolytes that can be employed in such experiments. The focus of our study is to establish a stability window for electrochemical tests for all-inorganic CsPbBr3 and hybrid organic–inorganic MAPbI3 perovskites. In addition, we aimed to understand the reduction and oxidation events that occur and to assess the damage done during these processes at extreme electrochemical conditions. In this vein, we demonstrated the chemical, structural, and morphological changes of the films in both reductive and oxidative environments. Taking all these results together as a whole, we propose a set of boundary conditions and protocols for how electrochemical experiments with lead halide perovskites should be carried out and interpreted. The presented results will contribute to the understanding of the electrochemical response of these materials and lead to a standardization of results in the literature so that comparisons can more easily be made. PMID:29503507

Methyl halide emissions from greenhouse-grown mangroves

Science.gov (United States)

Manley, Steven L.; Wang, Nun-Yii; Walser, Maggie L.; Cicerone, Ralph J.

2007-01-01

Two mangrove species, Avicennia germinans and Rhizophora mangle, were greenhouse grown for nearly 1.5 years from saplings. A single individual of each species was monitored for the emission of methyl halides from aerial tissue. During the first 240 days, salinity was incrementally increased with the addition of seawater, and was maintained between 18 and 28‰ for the duration of the study. Exponential growth occurred after 180 days. Methyl halide emissions normalized to leaf area were measured throughout the study and varied dramatically. Emission rates normalized to land area (mg m-2 y-1), assuming a LAI = 5, yielded 82 and 29 for CH3Cl, 10 and 1.6 for CH3Br, and 26 and 11 for CH3I, for A. germinans and R. mangle, respectively. From these preliminary determinations, only CH3I emissions emerge as being of possible global atmospheric significance. This study emphasizes the need for field studies of methyl halide emissions from mangrove forests.

Complexes in polyvalent metal - Alkali halide melts

International Nuclear Information System (INIS)

Akdeniz, Z.; Tosi, M.P.

1991-03-01

Experimental evidence is available in the literature on the local coordination of divalent and trivalent metal ions by halogens in some 140 liquid mixtures of their halides with alkali halides. After brief reference to classification criteria for main types of local coordination, we focus on statistical mechanical models that we are developing for Al-alkali halide mixtures. Specifically, we discuss theoretically the equilibrium between (AlF 6 ) 3- and (AlF 4 ) - complexes in mixtures of AlF 3 and NaF as a function of composition in the NaF-rich region, the effect of the alkali counterion on this equilibrium, the possible role of (AlF 5 ) 2- as an intermediate species in molten cryolite, and the origin of the different complexing behaviours of Al-alkali fluorides and chlorides. We also present a theoretical scenario for processes of structure breaking and electron localization in molten cryolite under addition of sodium metal. (author). 26 refs, 2 tabs

Review of technetium chemistry research conducted at the University of Nevada Las Vegas

International Nuclear Information System (INIS)

Poineau, F.; Weck, P.F.; Forster, P.; Hartmann, T.; Mausolf, E.; Silva, G.W.C.; Czerwinski, K.R.; Rodriguez, E.E.; Sattelberger, A.P.; Jarvinen, G.D.; Cheetham, A.K.

2009-01-01

The chemistry of technetium is being explored at the University of Nevada Las Vegas. Our goal is to investigate both the applied and fundamental aspects of technetium chemistry, with a special emphasis on synthesis, separations, and materials science. The synthetic chemistry focuses on metal-metal multiple bonding, oxides and halides. Synthesis and characterizations of (n-Bu 4 N) 2 Tc 2 X 8 , Tc 2 (O 2 CCH 3 ) 4 X 2 (X = Cl, Br), TcO 2 , Bi 2 Tc 2 O 7 , Bi 3 TcO 8 , TcBr 3 and TcBr 4 have been performed. The applied chemistry is related to the behavior of Tc in the UREX process. Separation of U/Tc has been conducted using anion exchange resin and metallic Tc waste form synthesized and characterized. (author)

Synthesis and characterization of mononuclear copper(II complex of tetradentate N2S2 donor set and the study of DNA and bovine serum albumin binding

Directory of Open Access Journals (Sweden)

Sandipan Sarkar

2014-12-01

Full Text Available One mononuclear copper(II complex, containing neutral tetradentate NSSN-type ligands, of formulation [Cu II(L 1Cl]ClO 4 (1, was synthesized and isolated in pure form [where L 1˭ 1,3-bis(3-pyridylmethylthiopropane]. Green-colored copper(II complex was characterized by physicochemical, spectroscopic methods and conductivity measurement. These experimental data matched well with the proposed structure of the complex. Biological activity of the complex (1 toward calf thymus DNA and bovine serum albumin has been examined systematically and groove-binding behavior of the Copper(II complex 1 with calf thymus DNA has been observed from the spectral study.

Release of Halide Ions from the Buried Active Site of the Haloalkane Dehalogenase LinB Revealed by Stopped-Flow Fluorescence Analysis and Free Energy Calculations

Czech Academy of Sciences Publication Activity Database

Hladílková, Jana; Prokop, Z.; Chaloupková, R.; Damborský, J.; Jungwirth, Pavel

2013-01-01

Roč. 117, č. 46 (2013), s. 14329-14335 ISSN 1520-6106 R&D Projects: GA ČR GBP208/12/G016 Grant - others:GA ČR(CZ) GAP207/12/0775 Program:GA Institutional support: RVO:61388963 Keywords : access tunnel * buried active site * catalytic activity * enzyme mechanism * haloalkane dehalogenase * halide ions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.377, year: 2013

Lamp-Ballast Compatibility Index for Efficient Ceramic Metal Halide Lamp Operation

OpenAIRE

Sourish Chatterjee

2013-01-01

Development of energy efficient products and exploration of energy saving potential are major challenges for present day’s technology. Ceramic Metal Halide lamp is the latest improved version of metal halide lamp that finds its wide applications in indoor commercial lighting especially in retail shop lighting. This lamp shows better performance in terms of higher lumen per watt and colour constancy in comparison to conventional metal halide lamp. The inherent negative incremental impedance of...

Preconcentration and extraction of copper(II on activated carbon using ethyl-2-quinolyl-β (p-carboxyphenyl hydrazonedioxo propionate

Directory of Open Access Journals (Sweden)

Mehrorang Ghaedi

2008-12-01

Full Text Available Activated carbon modified method was used for the preconcentration and determination of copper content in real samples such as tap water, wastewater and a synthetic water sample by flame atomic absorption spectrometry. The copper(II was adsorbed quantitatively on activated carbon due to its complexation with ethyl-2-quinolyl-β(p-carboxyphenyl hydrazonedioxo propionate (EQCPDP. The adsorbed copper(II ion on solid phase was eluted quantitatively by using nitric acid. The important parameters such as pH, amount of carrier, flow rate, amount of activated carbon and type and concentration of eluting agent for obtaining maximum recovery were optimized. The method at optimum conditions gives linear concentration range of 0.05-1.0 μg mL-1 of copper(II with correlation coefficient of 0.9994 and the detection limit of 0.99 ng mL-1. The preconcentration leads to enrichment factor of 175 and break through volume of 1750 mL. The method has good tolerance limit of interfering ions and selectivity and it has been successfully applied for determination of copper content in real sample such as blood, wastewater and river sample.

Green chemistry: solvent- and metal-free Prins cyclization. Application to sequential reactions.

Science.gov (United States)

Clarisse, Damien; Pelotier, Béatrice; Piva, Olivier; Fache, Fabienne

2012-01-04

Prins cyclization between a homoallylic alcohol and an aldehyde, promoted by trimethylsilyl halide, afforded 4-halo-tetrahydropyrans with good to excellent yields. Thanks to the absence of the solvent and metal, the THP thus obtained have been implicated without purification in several other reactions, in a sequential way, affording in particular new indole derivatives. This journal is © The Royal Society of Chemistry 2012

Miscellaneous Lasing Actions in Organo-Lead Halide Perovskite Films.

Science.gov (United States)

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.

Single Crystals of Organolead Halide Perovskites: Growth, Characterization, and Applications

KAUST Repository

Peng, Wei

2017-04-01

With the soaring advancement of organolead halide perovskite solar cells rising from a power conversion efficiency of merely 3% to more than 22% shortly in five years, researchers’ interests on this big material family have been greatly spurred. So far, both in-depth studies on the fundamental properties of organolead halide perovskites and their extended applications such as photodetectors, light emitting diodes, and lasing have been intensively reported. The great successes have been ascribed to various superior properties of organolead halide hybrid perovskites such as long carrier lifetimes, high carrier mobility, and solution-processable high quality thin films, as will be discussed in Chapter 1. Notably, most of these studies have been limited to their polycrystalline thin films. Single crystals, as a counter form of polycrystals, have no grain boundaries and higher crystallinity, and thus less defects. These characteristics gift single crystals with superior optical, electrical, and mechanical properties, which will be discussed in Chapter 2. For example, organolead halide perovskite single crystals have been reported with much longer carrier lifetimes and higher carrier mobilities, which are especially intriguing for optoelectronic applications. Besides their superior optoelectronic properties, organolead halide perovskites have shown large composition versatility, especially their organic components, which can be controlled to effectively adjust their crystal structures and further fundamental properties. Single crystals are an ideal platform for such composition-structure-property study since a uniform structure with homogeneous compositions and without distraction from grain boundaries as well as excess defects can provide unambiguously information of material properties. As a major part of work of this dissertation, explorative work on the composition-structure-property study of organic-cation-alloyed organolead halide perovskites using their single

Local Polar Fluctuations in Lead Halide Perovskite Crystals

Science.gov (United States)

Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z.; Egger, David A.; Hull, Trevor; Stoumpos, Constantinos C.; Zheng, Fan; Heinz, Tony F.; Kronik, Leeor; Kanatzidis, Mercouri G.; Owen, Jonathan S.; Rappe, Andrew M.; Pimenta, Marcos A.; Brus, Louis E.

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 (CH3 NH3 PbBr3 ) and all-inorganic (CsPbBr3 ) 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. MD simulations indicate 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 CsPbBr3 .

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

Science.gov (United States)

Martinson, Alex B.; Kim, In Soo

2017-09-26

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. 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.

Methyl halide emission estimates from domestic biomass burning in Africa

Science.gov (United States)

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

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

Distinctive EPR signals provide an understanding of the affinity of bis-(3-hydroxy-4-pyridinonato) copper(II) complexes for hydrophobic environments.

Science.gov (United States)

Rangel, Maria; Leite, Andreia; Silva, André M N; Moniz, Tânia; Nunes, Ana; Amorim, M João; Queirós, Carla; Cunha-Silva, Luís; Gameiro, Paula; Burgess, John

2014-07-07

In this work we report the synthesis and characterization of a set of 3-hydroxy-4-pyridinone copper(ii) complexes with variable lipophilicity. EPR spectroscopy was used to characterize the structure of copper(ii) complexes in solution, and as a tool to gain insight into solvent interactions. EPR spectra of solutions of the [CuL2] complexes recorded in different solvents reveal the presence of two copper species whose ratio depends on the nature of the solvent. Investigation of EPR spectra in the pure solvents methanol, dimethylsulfoxide, dichloromethane and their 50% (v/v) mixtures with toluene allowed the characterization of two types of copper signals (gzz = 2.30 and gzz = 2.26) whose spin-Hamiltonian parameters are consistent with solvated and non-solvated square-planar copper(ii) complexes. Regarding the potential biological application of ligands and complexes and to get insight into the partition properties in water-membrane interfaces, EPR spectra were also obtained in water-saturated octanol, an aqueous solution buffered at pH = 7.4 and liposome suspensions, for three compounds representative of different hydro-lipophilic balances. Analysis of the EPR spectra obtained in liposomes allowed establishment of the location of the complexes in the water and lipid phases. In view of the results of this work we put forward the use of EPR spectroscopy to assess the affinity of copper(ii) complexes for a hydrophobic environment and also to obtain indirect information about the lipophilicity of the ligands and similar EPR silent complexes.

Solar cells, structures including organometallic halide perovskite monocrystalline films, and methods of preparation thereof

KAUST Repository

Bakr, Osman M.

2017-03-02

Embodiments of the present disclosure provide for solar cells including an organometallic halide perovskite monocrystalline film (see fig. 1.1B), other devices including the organometallic halide perovskite monocrystalline film, methods of making organometallic halide perovskite monocrystalline film, and the like.

Definition of a high intensity metal halide discharge reference lamp

NARCIS (Netherlands)

Stoffels, W.W.; Baede, A.H.F.M.; Mullen, van der J.J.A.M.; Haverlag, M.; Zissis, G.

2006-01-01

The design of a ref. metal halide discharge lamp is presented. This lamp is meant as a common study object for researchers working on metal halide discharge lamps, who by using the same design will be able to compare results between research groups, diagnostic techniques and numerical models. The

An efficient, cost effective, sensing behaviour liquid-liquid extraction and spectrophotometric determination of copper(II) incorporated with 4-(4'-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole: Analysis of food samples, leafy vegetables, fertilizers and environmental samples.

Science.gov (United States)

Barache, Umesh B; Shaikh, Abdul B; Lokhande, Tukaram N; Kamble, Ganesh S; Anuse, Mansing A; Gaikwad, Shashikant H

2018-01-15

The aim of the present work is to develop an efficient, simple and selective moreover cost-effective method for the extractive spectrophotometric determination of copper(II) by using the Schiff base 4-(4'-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole [CBIMMT]. This chromogenic reagent forms a yellow coloured complex with copper(II) in acetate buffer at pH4.2. The copper(II) complex with ligand is instantly extracted into chloroform and shows a maximum absorbance at 414nm which remains stable for >48h. The composition of extracted complex is found to be 1:2 [copper(II): reagent] which was ascertained using Job's method of continuous variation, mole ratio method and slope ratio method. Under optimal conditions, the copper(II) complex in chloroform adheres to Beer's law up to 17.5μgmL -1 of copper(II). The optimum concentration range obtained from Ringbom's plot is from 5μgmL -1 to 17.5μgmL -1 . The molar absorptivity, Sandell's sensitivity and enrichment factor of the extracted copper(II) chelate are 0.33813×10 4 Lmol -1 cm -1 , 0.01996μgcm -2 and 2.49 respectively. In the extraction of copper(II), several affecting factors including the solution pH, ligand concentration, equilibrium time, effect of foreign ions are optimized. The interfering effects of various cations and anions were also studied and use of masking agents enhances the selectivity of the method. The chromogenic sulphur containing reagent, 4-(4'-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole has been synthesized in a single step with high purity and yield. The synthesized reagent has been successfully applied first time for determination of copper(II). The reagent forms stable chelate with copper(II) in buffer medium instantly and quantitatively extracted in chloroform within a minute. The method is successfully applied for the determination of copper(II) in various synthetic mixtures, complexes, fertilizers, environmental samples such as food samples, leafy

Unraveling halide hydration: A high dilution approach.

Science.gov (United States)

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.

78 FR 51463 - Energy Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures

Science.gov (United States)

2013-08-20

... merging the metal halide lamp fixture and the high-intensity discharge (HID) lamp rulemakings. This NOPR... Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures; Proposed Rule #0;#0;Federal...: Energy Conservation Standards for Metal Halide Lamp Fixtures AGENCY: Office of Energy Efficiency and...

Development of halide copper vapor laser (the characteristics of using Cul)

International Nuclear Information System (INIS)

Oouti, Kazumi; Wada, Yukio; Sasao, Nobuyuki

1990-01-01

We are developing halide copper vapor laser that is high efficiency and high reputation rate visible laser. Halide copper vapor laser uses halide copper of copper vapor source. It melts low temperature in comporison with metal copper, because laser tube structure is very simple and it can operate easy. This time, we experiment to use Cul for copper vapor source. We resulted maximum output energy 17.8 (W) and maximum efficiency 0.78 (%) when operate condition was reputation rate 30 (kHz), gas pressure 90 (Torr), charging voltage 13 (kV). (author)

Broadly tunable metal halide perovskites for solid-state light-emission applications

NARCIS (Netherlands)

Adjokatse, Sampson; Fang, Hong-Hua; Loi, Maria Antonietta

2017-01-01

The past two years have witnessed heightened interest in metal-halide perovskites as promising optoelectronic materials for solid-state light emitting applications beyond photovoltaics. Metal-halide perovskites are low-cost solution-processable materials with excellent intrinsic properties such as

Systemic analysis of thermodynamic properties of lanthanide halides

International Nuclear Information System (INIS)

Mirsaidov, U.; Badalov, A.; Marufi, V.K.

1992-01-01

System analysis of thermodynamic characteristics of lanthanide halides was carried out. A method making allowances for the influence of spin and orbital moments of momentum of the main states of lanthanide trivalent ions in their natural series was employed. Unknown in literature thermodynamic values were calculated and corrected for certain compounds. The character of lanthanide halide thermodynamic parameter change depending on ordinal number of the metals was ascertained. Pronouncement of tetrad-effect in series of compounds considered was pointed out

RECOVERY OF COPPER(II AND CHROMIUM(III FROM NITRATE MEDIUM WITH SALICYLIDENEANILINE DISSOLVED IN 1-OCTANOL

Directory of Open Access Journals (Sweden)

A. Guerdouh

2016-05-01

Full Text Available The solvent extraction of copper(II and chromium(III from nitrate medium with salicylideneaniline (HL is studied as a function of various parameters: pH, concentration of salicylideneaniline, contact time and the nature of anoin (nitrate and sulfate in aqueous phase. Chromium(III is not extracted by salicylideneaniline  diluted in 1-octanol. Copper(II is only extracted by salicylideneaniline and it was found that the highest extractability achieved to 95% at pH 4.9, The stoichiometry of the extracted species was determined by using the method of slope analysis. Elemental analysis, UV–vis and IR-spectra were used to confirm the structure. It is found that the copper (II is extracted as CuL2.2H2O Their equilibrium constant, distribution coefficient, percentage extraction (%E and free energy are also calculated.

Two-Dimensional Halide Perovskites for Emerging New- Generation Photodetectors

DEFF Research Database (Denmark)

Tang, Yingying; Cao, Xianyi; Chi, Qijin

2018-01-01

Compared to their conventional three-dimensional (3D) counterparts, two-dimensional (2D) halide perovskites have attracted more interests recently in a variety of areas related to optoelectronics because of their unique structural characteristics and enhanced performances. In general, there are two...... distinct types of 2D halide perovskites. One represents those perovskites with an intrinsic layered crystal structure (i.e. MX6 layers, M = metal and X = Cl, Br, I), the other defines the perovskites with a 2D nanostructured morphology such as nanoplatelets and nanosheets. Recent studies have shown that 2D...... halide perovskites hold promising potential for the development of new-generation photodetectors, mainly arising from their highly efficient photoluminescence and absorbance, color tunability in the visible-light range and relatively high stability. In this chapter, we present the summary and highlights...

An efficient, cost effective, sensing behaviour liquid-liquid extraction and spectrophotometric determination of copper(II) incorporated with 4-(4‧-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole: Analysis of food samples, leafy vegetables, fertilizers and environmental samples

Science.gov (United States)

Barache, Umesh B.; Shaikh, Abdul B.; Lokhande, Tukaram N.; Kamble, Ganesh S.; Anuse, Mansing A.; Gaikwad, Shashikant H.

2018-01-01

The aim of the present work is to develop an efficient, simple and selective moreover cost-effective method for the extractive spectrophotometric determination of copper(II) by using the Schiff base 4-(4‧-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole [CBIMMT]. This chromogenic reagent forms a yellow coloured complex with copper(II) in acetate buffer at pH 4.2. The copper(II) complex with ligand is instantly extracted into chloroform and shows a maximum absorbance at 414 nm which remains stable for > 48 h. The composition of extracted complex is found to be 1:2 [copper(II): reagent] which was ascertained using Job's method of continuous variation, mole ratio method and slope ratio method. Under optimal conditions, the copper(II) complex in chloroform adheres to Beer's law up to 17.5 μg mL- 1 of copper(II). The optimum concentration range obtained from Ringbom's plot is from 5 μg mL- 1 to 17.5 μg mL- 1. The molar absorptivity, Sandell's sensitivity and enrichment factor of the extracted copper(II) chelate are 0.33813 × 104 L mol- 1 cm- 1, 0.01996 μg cm- 2 and 2.49 respectively. In the extraction of copper(II), several affecting factors including the solution pH, ligand concentration, equilibrium time, effect of foreign ions are optimized. The interfering effects of various cations and anions were also studied and use of masking agents enhances the selectivity of the method. The chromogenic sulphur containing reagent, 4-(4‧-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole has been synthesized in a single step with high purity and yield. The synthesized reagent has been successfully applied first time for determination of copper(II). The reagent forms stable chelate with copper(II) in buffer medium instantly and quantitatively extracted in chloroform within a minute. The method is successfully applied for the determination of copper(II) in various synthetic mixtures, complexes, fertilizers, environmental samples such as food samples

Halogen-bonded network of trinuclear copper(II 4-iodopyrazolate complexes formed by mutual breakdown of chloroform and nanojars

Directory of Open Access Journals (Sweden)

Stuart A. Surmann

2016-11-01

Full Text Available Crystals of bis(tetrabutylammonium di-μ3-chlorido-tris(μ2-4-iodopyrazolato-κ2N:N′tris[chloridocuprate(II] 1,4-dioxane hemisolvate, (C16H36N2[Cu3(C3H2IN23Cl5]·0.5C4H8O or (Bu4N2[CuII3(μ3-Cl2(μ-4-I-pz3Cl3]·0.5C4H8O, were obtained by evaporating a solution of (Bu4N2[{CuII(μ-OH(μ-4-I-pz}nCO3] (n = 27–31 nanojars in chloroform/1,4-dioxane. The decomposition of chloroform in the presence of oxygen and moisture provides HCl, which leads to the breakdown of nanojars to the title trinuclear copper(II pyrazolate complex, and possibly CuII ions and free 4-iodopyrazole. CuII ions, in turn, act as catalyst for the accelerated decomposition of chloroform, ultimately leading to the complete breakdown of nanojars. The crystal structure presented here provides the first structural description of a trinuclear copper(II pyrazolate complex with iodine-substituted pyrazoles. In contrast to related trinuclear complexes based on differently substituted 4-R-pyrazoles (R = H, Cl, Br, Me, the [Cu3(μ-4-I-pz3Cl3] core in the title complex is nearly planar. This difference is likely a result of the presence of the iodine substituent, which provides a unique, novel feature in copper pyrazolate chemistry. Thus, the iodine atoms form halogen bonds with the terminal chlorido ligands of the surrounding complexes [mean length of I...Cl contacts = 3.48 (1 Å], leading to an extended two-dimensional, halogen-bonded network along (-110. The cavities within this framework are filled by centrosymmetric 1,4-dioxane solvent molecules, which create further bridges via C—H...Cl hydrogen bonds with terminal chlorido ligands of the trinuclear complex not involved in halogen bonding.

Electrochemistry of plutonium in molten halides

International Nuclear Information System (INIS)

McCurry, L.E.; Moy, G.M.M.; Bowersox, D.F.

1987-01-01

The electrochemistry of plutonium in molten halides is of technological importance as a method of purification of plutonium. Previous authors have reported that plutonium can be purified by electrorefining impure plutonium in various molten haldies. Work to eluciate the mechanism of the plutonium reduction in molten halides has been limited to a chronopotentiometric study in LiCl-KCl. Potentiometric studies have been carried out to determine the standard reduction potential for the plutonium (III) couple in various molten alkali metal halides. Initial cyclic voltammetric experiments were performed in molten KCL at 1100 K. A silver/silver chloride (10 mole %) in equimolar NaCl-KCl was used as a reference electrode. Working and counter electrodes were tungsten. The cell components and melt were contained in a quartz crucible. Background cyclic voltammograms of the KCl melt at the tungsten electrode showed no evidence of electroactive impurities in the melt. Plutonium was added to the melt as PuCl/sub 3/, which was prepared by chlorination of the oxide. At low concentrations of PuCl/sub 3/ in the melt (0.01-0.03 molar), no reduction wave due to the reduction of Pu(III) was observed in the voltammograms up to the potassium reduction limit of the melt. However on scan reversal after scanning into the potassium reduction limit a new oxidation wave was observed

Synthesis, X-ray crystal structures, and phosphate ester cleavage properties of bis(2-pyridylmethyl)amine copper(II) complexes with guanidinium pendant groups.

Science.gov (United States)

Belousoff, Matthew J; Tjioe, Linda; Graham, Bim; Spiccia, Leone

2008-10-06

Three new derivatives of bis(2-pyridylmethyl)amine (DPA) featuring ethylguanidinium (L (1)), propylguanidinium (L (2)), or butylguanidinium (L (3)) pendant groups have been prepared by the reaction of N, N- bis(2-pyridylmethyl)alkane-alpha,omega-diamines with 1 H-pyrazole-1-carboxamidine hydrochloride. The corresponding mononuclear copper(II) complexes were prepared by reacting the ligands with copper(II) nitrate and were isolated as [Cu(LH (+))(OH 2)](ClO 4) 3. xNaClO 4. yH 2O ( C1: L = L (1), x = 2, y = 3; C2: L = L (2), x = 2, y = 4; C3: L = L (3), x = 1, y = 0) following cation exchange purification. Recrystallization yielded crystals of composition [Cu(LH (+))(X)](ClO 4) 3.X ( C1': L = L (1), X = MeOH; C2': L = L (2), X = H 2O; C3': L = L (3), X = H 2O), which were suitable for X-ray crystallography. The crystal structures of C1', C2', and C3' indicate that the DPA moieties of the ligands coordinate to the copper(II) centers in a meridional fashion, with a water or methanol molecule occupying the fourth basal position. Weakly bound perchlorate anions located in the axial positions complete the distorted octahedral coordination spheres. The noncoordinating, monoprotonated guanidinium groups project away from the Cu(II)-DPA units and are involved in extensive charge-assisted hydrogen-bonding interactions with cocrystallized water/methanol molecules and perchlorate anions within the crystal lattices. The copper(II) complexes were tested for their ability to promote the cleavage of two model phosphodiesters, bis( p-nitrophenyl)phosphate (BNPP) and uridine-3'- p-nitrophenylphosphate (UpNP), as well as supercoiled plasmid DNA (pBR 322). While the presence of the guanidine pendants was found to be detrimental to BNPP cleavage efficiency, the functionalized complexes were found to cleave plasmid DNA and, in some cases, the model ribose phosphate diester, UpNP, at a faster rate than the parent copper(II) complex of DPA.

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

KAUST Repository

Moore, David T.

2014-08-01

The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material.Despite recent advances, however, there are still a number of fundamental aspects of their formation as well as their physical and electronic behavior that are not well understood. In this letter we explore the mechanism by which these materials crystallize by testing the outcome of each of the reagent halide salts. We find that components of both salts, lead halide and methylammonium halide, are relatively mobile and can be readily exchanged during the crystallization process when the reaction is carried out in solution or in the solid state. We exploit this fact by showing that the perovskite structure is formed even when the lead salt\\'s anion is a non-halide, leading to lower annealing temperature and time requirements for film formation. Studies into these behaviors may ultimately lead to improved processing conditions for photovoltaic films. © 2014 Author(s).

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

Directory of Open Access Journals (Sweden)

David T. Moore

2014-08-01

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

Changes in magnetic properties from solid state to solution in a trinuclear linear copper(II) complex

NARCIS (Netherlands)

Koval, I.A.; Akhideno, H.; Tanase, S.; Belle, C.; Duboc, C.; Saint-Aman, E.; Gamez, P.; Tooke, D.M.; Spek, A.L.; Pierre, J.-L.; Reedijk, J.

2007-01-01

A linear trinuclear copper(II) complex containing phenoxido- and alkoxido-bridges between the metal centers has been isolated and structurally characterized. The complex cation consists of a linear array of three copper ions, assembled by means of two doubly deprotonated ligands. The octahedral

Observation of vapor pressure enhancement of rare-earth metal-halide salts in the temperature range relevant to metal-halide lamps

Energy Technology Data Exchange (ETDEWEB)

Curry, J. J.; Henins, A.; Hardis, J. E. [National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); Estupinan, E. G. [Osram Sylvania Inc., Beverly, Massachusetts 01915 (United States); Lapatovich, W. P. [Independent Consultant, 51 Pye Brook Lane, Boxford, Massachusetts 01921 (United States); Shastri, S. D. [Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

2012-02-20

Total vapor-phase densities of Dy in equilibrium with a DyI{sub 3}/InI condensate and Tm in equilibrium with a TmI{sub 3}/TlI condensate have been measured for temperatures between 900 K and 1400 K. The measurements show strong enhancements in rare-earth vapor densities compared to vapors in equilibrium with the pure rare-earth metal-halides. The measurements were made with x-ray induced fluorescence on the sector 1-ID beam line at the Advanced Photon Source. The temperature range and salt mixtures are relevant to the operation of metal-halide high-intensity discharge lamps.

Preparation of CuO nanoparticles by thermal decomposition of double-helical dinuclear copper(II Schiff-base complexes

Directory of Open Access Journals (Sweden)

Aliakbar Dehno Khalaji

2015-12-01

Full Text Available In this paper, two double helical dinuclear copper(II complexes of bis-N,O-bidentate Schiff base ligands bis(3-methoxy-N-salicylidene-4,4'-diaminodiphenylsulfone (L1 and bis(5-bromo-N-salicylidene-4,4'-diaminodiphenylsulfone (L2 were prepared and characterized by elemental analyses (CHN, as well as thermal analysis. Elemental analyses (CHN suggested that the reaction between ligands and copper salt has been occurred in 1:1 molar ratio. In these complexes the Schiff base ligands behaves as an anionic and bis-bidentate chelate and is coordinated to the copper(II ion via two phenolic oxygen and two iminic nitrogen atoms. In these double helical dinuclear complexes, each copper(II center has a pseudo-tetrahedral coordination sphere two-wrapped ligands. Thermal analysis of ligands and their complexes were studied in the range of room temperature to 750 °C with a heating rate of 10 °C min-1. TG plots show that the ligands and their complexes are thermally decomposed via 2 and 3 thermal steps, respectively. In addition, the complexes thermally decomposed in air at 520 °C for 3 h. The obtained solids characterized by Fourier transform infrared spectroscopy (FT-IR, X-ray powder diffraction (XRD and transmission electron microscopy (TEM. The X-ray pattern result shows that the CuO nanoparticles are pure and single phase. The TEM result shows the as prepared CuO nanoparticles were very small and similar shape with particle size about

Ultrafast time-resolved spectroscopy of lead halide perovskite films

Science.gov (United States)

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.

Lanthanide doped strontium-barium cesium halide scintillators

Science.gov (United States)

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.

A novel aggregation induced emission active cyclometalated Ir(III) complex as a luminescent probe for detection of copper(II) ion in aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Shen, Wei; Yan, Liqiang; Tian, Wenwen; Cui, Xia; Qi, Zhengjian, E-mail: qizhengjian@seu.edu.cn; Sun, Yueming, E-mail: sun@seu.edu.cn

2016-09-15

We report the synthesis and characterization of a novel aggregation induced emission (AIE) active cyclometalated Ir(III) complex, namely [Ir(dfppy){sub 2}(phen-DPA)]PF{sub 6}, where dfppy and phen-DPA represent 2-(2,4-difluorophenyl)pyridine and 2-(bis(pyridin-2-ylmethyl)amino)-N-(1,10-phenanthrolin-5-yl)acetamide, respectively. The complex showed remarkable selectivity for copper(II) in aqueous solution over other competitive ions. Furthermore, this sensor showed a rapid and reversible response to copper(II) in aqueous solution with a detection limit of 65 nM.

Photocleavage of DNA by copper (II) complexes

Indian Academy of Sciences (India)

The chemistry of ternary and binary copper(II) complexes showing efficient visible lightinduced DNA cleavage activity is summarized in this article. The role of the metal in photo-induced DNA cleavage reactions is explored by designing complex molecules having a variety of ligands. Ternary copper(II) complexes with amino ...

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

Science.gov (United States)

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.

Current developments in radiation chemistry

International Nuclear Information System (INIS)

Cooper, R.

2000-01-01

Full text: The theme of the 2000 Gordon Conference on Radiation Chemistry was 'diversity'. The range of topics covered was heralded by the opening presentations which went from the galactic to molecular biology, radiation chemistry and non thermal surface processes in the outer solar system to achievements and open challenges in DNA research. The rest of the conference reflected the extended usage of radiation chemistry -its processes and techniques - applied to a panorama of topics. The ability to generate either oxidising or reducing free radicals in known quantities has been the foundation stone on which all applications are based. In particular it is noticeable that biological systems have been attempted by an increasing number of workers, such as studies of biological ageing and also reactions of nitric oxide in biological environments. Electron transfer processes in proteins are straightforward applications of solvated electron chemistry even if the results are not straightforward in their interpretation. Other topics presented include, radiation chemical processes induced in: supercritical CO 2 , treatment of contaminated materials, 3-dimensional Fullerenes, zeolites and radiation catalysis. In material science, aspects of ions and excited states in polymers, conducting polymers, donor acceptor processes in photo curing, enhancement of photo-electron yields in doped silver halides- improvement of the photographic process, radiation chemistry in cages and bubbles are discussed. The fundamental aspects of radiation chemistry are not yet all worked out. Subpicosecond pulsed electron beam sources, some of them 'tabletop', are still being planned to probe the early events in radiation chemistry both in water and in organic solvents. There is still an interest in the chemistry produced by pre-solvated electrons and the processes induced by heavy ion radiolysis. The description of the relaxation of an irradiated system which contains uneven distributions of ions

luminescence in coloured alkali halide crystals

Indian Academy of Sciences (India)

have studied the effect of annealing in chlorine gas on the ML of X-rayed KCl crystals. ..... high temperature because of the thermal bleaching of the coloration in alkali halide ..... [31] J Hawkins, Ph.D. Thesis (University of Reading, 1976).

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

International Nuclear Information System (INIS)

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

2016-01-01

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

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

Science.gov (United States)

2010-01-01

... high intensity discharge fixture, the efficiency of a lamp and ballast combination, expressed as a... lamps. Metal halide lamp means a high intensity discharge lamp in which the major portion of the light... 10 Energy 3 2010-01-01 2010-01-01 false Definitions concerning metal halide lamp ballasts and...

Complexes of alkylphenols with aluminium halides

International Nuclear Information System (INIS)

Golounin, A.V.

1997-01-01

Interaction of aluminium halides with alkylphenols is studied through the NMR method. The peculiarity of complex formation of pentamethylphenol with AlI 3 is revealed. By AlI 3 action on the pentamethylphenol the complexes are formed both of keto- and oxy form [ru

Maximizing and stabilizing luminescence from halide perovskites with potassium passivation

Science.gov (United States)

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

Broadly tunable metal halide perovskites for solid-state light-emission applications

OpenAIRE

Adjokatse, Sampson; Fang, Hong-Hua; Loi, Maria Antonietta

2017-01-01

The past two years have witnessed heightened interest in metal-halide perovskites as promising optoelectronic materials for solid-state light emitting applications beyond photovoltaics. Metal-halide perovskites are low-cost solution-processable materials with excellent intrinsic properties such as broad tunability of bandgap, defect tolerance, high photoluminescence quantum efficiency and high emission color purity (narrow full-width at half maximum). In this review, the photophysical propert...

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

OpenAIRE

Sutter-Fella, CM; Ngo, QP; Cefarin, N; Gardener, K; Tamura, N; Stan, CV; Drisdell, WS; Javey, A; Toma, FM; Sharp, ID

2018-01-01

© 2018 American Chemical Society. 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 photo-induced halide demixing using in-situ photoluminescence spectroscopy and in-situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of comp...

Refined global methyl halide budgets with respect to rapeseed (Brassica napus) by life-cycle measurements

Science.gov (United States)

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.

Solar cells, structures including organometallic halide perovskite monocrystalline films, and methods of preparation thereof

KAUST Repository

Bakr, Osman; Peng, Wei; Wang, Lingfei

2017-01-01

Embodiments of the present disclosure provide for solar cells including an organometallic halide perovskite monocrystalline film (see fig. 1.1B), other devices including the organometallic halide perovskite monocrystalline film, methods of making

Photography: enhancing sensitivity by silver-halide crystal doping

International Nuclear Information System (INIS)

Belloni, Jacqueline

2003-01-01

The physical chemistry of the silver photography processes, exposure, development and fixing, is briefly summarized. The mechanism of the autocatalytic development by the developer of the clusters produced in silver bromide crystals during the exposure which is controlled by the critical nuclearity of these clusters was understood from pulse radiolysis studies. The effective quantum yield PHI eff of photoinduced silver cluster formation in silver halide microcrystals is usually much lower than the photoionization theoretical limit PHI theor =1 electron-hole pair per photon absorbed, owing to a subsequent very fast intra-crystal recombination of a part of the electron-hole pairs. In order to inhibit this recombination and favor the silver reduction by photo-electrons, the AgX crystals were doped with the formate HCO 2 - as a specific hole scavenger. First, the dopant scavenges the photoinduced hole, thus enhancing the electron escape from the pair recombination. Second, the CO 2 ·- radical so formed transfers an electron to another silver cation, so that the PHI eff limit may be of 2Ag 0 per photon. This Photoinduced Bielectronic Transfer mechanism is strictly proportional to the light quanta absorbed and induces an exceptional efficiency for enhancing the radio- or photographic sensitivity insofar as it totally suppresses the electron-hole recombination

High stability and biological activity of the copper(II) complexes of alloferon 1 analogues containing tryptophan.

Science.gov (United States)

Kadej, Agnieszka; Kuczer, Mariola; Czarniewska, Elżbieta; Urbański, Arkadiusz; Rosiński, Grzegorz; Kowalik-Jankowska, Teresa

2016-10-01

Copper(II) complex formation processes between the alloferon 1 (Allo1) (HGVSGHGQHGVHG) analogues where the tryptophan residue is introducing in the place His residue H1W, H6W, H9W and H12W have been studied by potentiometric, UV-visible, CD and EPR spectroscopic, and MS methods. For all analogues of alloferon 1 complex speciation have been obtained for a 1:1 metal-to-ligand molar ratio and 2:1 of H1W because of precipitation at higher (2:1, 3:1 and 4:1) ratios. At physiological pH7.4 and a 1:1 metal-to-ligand molar ratio the tryptophan analogues of alloferon 1 form the CuH -1 L and/or CuH -2 L complexes with the 4N binding mode. The introduction of tryptophan in place of histidine residues changes the distribution diagram of the complexes formed with the change of pH and their stability constants compared to the respective substituted alanine analogues of alloferon 1. The CuH -1 L, CuH -2 L and CuH -3 L complexes of the tryptophan analogues are more stable from 1 to 5 log units in comparison to those of the alanine analogues. This stabilization of the complexes may result from cation(Cu(II))-π and indole/imidazole ring interactions. The induction of apoptosis in vivo, in Tenebrio molitor cells by the ligands and their copper(II) complexes at pH7.4 was studied. The biological results show that copper(II) ions in vivo did not cause any apparent apoptotic features. The most active were the H12W peptide and Cu(II)-H12W complex formed at pH7.4. Copyright © 2016 Elsevier Inc. All rights reserved.

Improving the Response of Copper(II) Selective PVC Membrane Electrode by Modification of N2S2 Donor Ligand.

Science.gov (United States)

Brinić, Slobodan; Buzuk, Marijo; Generalić, Eni; Bralić, Marija

2010-06-01

S,S'-bis(2-aminophenyl)ethanebis(thioate), (APhET), is reported as N2S2 ligand which form chelate with copper of high stability as compared to the other metals. Two modification of APhET, simpler 1,2-di-(o-aminophenylthio)ethane (DAPhTE), and the complex one 1,2-di-(o-salicylaldiminophenylthio)ethane (SAPhTE), were examined as the active material for copper(II) ion selective PVC membrane electrodes, and observed results are correlated. The obtained results with DAPhTE based electrodes show that only coordination abilities of ligand are insufficient for preparing the efficient membrane material. On the other hand, the results that are achieved with electrodes based on SAPhTE actuate interaction of ligand with polymer membrane matrix and necessity of ionophore immobilization in membrane. Optimized SAPhTE based membrane electrode has a linear range down to 10-6 mol L-1, with slope of 27.0 mV per decade, very rapid response time (under 5 seconds) and detection limit of 5.1 × 10-7 mol L-1. Such electrode is suitable for determination of copper(II) in analytical measurements by direct potentiometry and in potentiometric titrations, within pH between 2 and 7. The electrode is selective for copper(II) ions over a large number of metal ions, with the exception on Hg2+ ion when is present in concentrations above 2 × 10-5 mol L-1.

Heterofacial alkylation of alkylenediamines by higher alkyl halides

International Nuclear Information System (INIS)

Semenov, V.A.; Kryshko, G.M.; Sokal'skaya, L.I.; Zhukova, N.G.

1985-01-01

A study of the physiochemical properties of alkylenediamines substituted by lower alkyls, showed that they possess increased complex-forming ability with respect to salts of different metals as titanium, niobium, zirconium, molybdenum, and zinc. To create a simpler method of synthesis of higher tetraaklyalkylalklyenediamines, based on the use of the accessible domestic raw material, the authors investigated the reaction of alkylenediamines with various alkyl halides. It was established that the best reagents can be obtained using alkyl bromides. It is concluded that the procedure of alkylation of alkylenediamines by higher alkyl halides in the presence of water developed permits the production of terraalkylalkylenediamines in one step with good yield and with purity acceptable for use as extraction reagents

Synthesis, characterization and catalytic oxidation properties of multi-wall carbon nanotubes with a covalently attached copper(II) salen complex

Science.gov (United States)

Salavati-Niasari, Masoud; Bazarganipour, Mehdi

2009-06-01

Hydroxyl functionalized copper(II) Schiff-base, N,N'-bis(4-hydroxysalicylidene)-ethylene-1,2-diaminecopper(II), [Cu((OH) 2-salen)], has been covalently anchored on modified MWCNTs. The new modified MWCNTs ([Cu((OH) 2-salen)]-MWCNTs) have been characterized by TEM, thermal analysis, XRD, XPS, UV-vis, DRS, FT-IR spectroscopy and elemental analysis. The modified copper(II) MWCNTs solid was used to affect the catalytic oxidation of ethylbenzene with tert-butylhydroperoxide as the oxidant at 333 K. The system is truly heterogeneous (no leaching observed) and reusable (no decrease in activity) in three consecutive runs. Acetophenone was the major product though small amounts of o- and p-hydroxyacetophenones were also formed revealing that C-H bond activation takes place both at benzylic and aromatic ring carbon atoms. Ring hydroxylation was more over the "neat" complexes than over the encapsulated complexes.

Lasing in robust cesium lead halide perovskite nanowires

Science.gov (United States)

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

Quantum confinement effect of two-dimensional all-inorganic halide perovskites

KAUST Repository

Cai, Bo; Li, Xiaoming; Gu, Yu; Harb, Moussab; Li, Jianhai; Xie, Meiqiu; Cao, Fei; Song, Jizhong; Zhang, Shengli; Cavallo, Luigi; Zeng, Haibo

2017-01-01

Quantum confinement effect (QCE), an essential physical phenomenon of semiconductors when the size becomes comparable to the exciton Bohr radius, typically results in quite different physical properties of low-dimensional materials from their bulk counterparts and can be exploited to enhance the device performance in various optoelectronic applications. Here, taking CsPbBr3 as an example, we reported QCE in all-inorganic halide perovskite in two-dimensional (2D) nanoplates. Blue shifts in optical absorption and photoluminescence spectra were found to be stronger in thinner nanoplates than that in thicker nanoplates, whose thickness lowered below ∼7 nm. The exciton binding energy results showed similar trend as that obtained for the optical absorption and photoluminescence. Meanwile, the function of integrated intensity and full width at half maximum and temperature also showed similar results, further supporting our conclusions. The results displayed the QCE in all-inorganic halide perovskite nanoplates and helped to design the all-inorganic halide perovskites with desired optical properties.

Quaternary oxide halides of group 15 with zinc and cadmium

International Nuclear Information System (INIS)

Rueck, Nadia

2014-01-01

The present thesis ''Quaternary oxide halides of group 15 with zinc and cadmium'' deals with the chemical class of oxide halides, which contain d-block element cations and pnicogens. Over the past few years compounds containing pnicogene cations are intensively investigated. The reason for this is the free electron pair of the Pn"3"+ cation, which is responsible for some interesting properties. Free electron pairs do not only impact the spatial structure of molecules but also the properties of materials. The object of this work was the synthesis and characterization of compounds containing Pn"3"+ cations with free electron pairs. Due to the structure-determining effect of these free electron pairs and in combination with halides it is possible to synthesize compounds with low-dimensional structures like chains and layers. In these compounds the structure is separated into halophilic and chalcophilic sub-structures, which are held together only by weak Van der Waals forces.

Quantum confinement effect of two-dimensional all-inorganic halide perovskites

KAUST Repository

Cai, Bo

2017-09-07

Quantum confinement effect (QCE), an essential physical phenomenon of semiconductors when the size becomes comparable to the exciton Bohr radius, typically results in quite different physical properties of low-dimensional materials from their bulk counterparts and can be exploited to enhance the device performance in various optoelectronic applications. Here, taking CsPbBr3 as an example, we reported QCE in all-inorganic halide perovskite in two-dimensional (2D) nanoplates. Blue shifts in optical absorption and photoluminescence spectra were found to be stronger in thinner nanoplates than that in thicker nanoplates, whose thickness lowered below ∼7 nm. The exciton binding energy results showed similar trend as that obtained for the optical absorption and photoluminescence. Meanwile, the function of integrated intensity and full width at half maximum and temperature also showed similar results, further supporting our conclusions. The results displayed the QCE in all-inorganic halide perovskite nanoplates and helped to design the all-inorganic halide perovskites with desired optical properties.

Thorium valency in molten alkali halides in equilibrium with metallic thorium

International Nuclear Information System (INIS)

Smirnov, M.V.; Kudyakov, V.Ya.

1983-01-01

Metallic thorium is shown to corrode in molten alkali halides even in the absence of external oxidizing agents, alkali cations acting as oxidizing agents. Its corrosion rate grows in the series of alkali chlorides from LiCl to CsCl at constant temperature. Substituting halide anions for one another exerts a smaller influence, the rate rising slightly in going from chlorides to bromides and iodides, having the same alkali cations. Thorium valency is determined coulometrically, the metal being dissolved anodically in molten alkali halides and their mixtures. In fluoride melts it is equal to 4 but in chloride, bromide and iodide ones, as a rule, it has non-integral values between 4 and 2 which diminish as the temperature is raised, as the thorium concentration is lowered, as the radii of alkali cations decrease and those of halide anions increase. The emf of cells Th/N ThHlsub(n) + (1-N) MHl/MHl/C, Hlsub(2(g)) where Hl is Cl, Br or I, M is Li, Na, K, Cs or Na + K, and N < 0.05, is measured as a function of concentration at several temperatures. Expressions are obtained for its concentration dependence. The emf grows in the series of alkali chlorides from LiCl to CsCl, other conditions being equal. (author)

Flotation of traces of silver and copper(II) ions with a methyl cellosolve solution of dithizone.

Science.gov (United States)

Hiraide, M; Mizuike, A

1975-06-01

Microgram quantities of silver and copper(II) ions in aqueous solutions are collected on dithizone precipitates, which are then floated with the aid of small nitrogen bubbles. This separation technique has been successfully applied to the atomic-absorption spectrophotometric determination of down to a tenth ppm of silver and copper in high-purity lead and zinc metals.

Fabrication of Semiconducting Methylammonium Lead Halide Perovskite Particles by Spray Technology

Science.gov (United States)

Ahmadian-Yazdi, Mohammad-Reza; Eslamian, Morteza

2018-01-01

In this "nano idea" paper, three concepts for the preparation of methylammonium lead halide perovskite particles are proposed, discussed, and tested. The first idea is based on the wet chemistry preparation of the perovskite particles, through the addition of the perovskite precursor solution to an anti-solvent to facilitate the precipitation of the perovskite particles in the solution. The second idea is based on the milling of a blend of the perovskite precursors in the dry form, in order to allow for the conversion of the precursors to the perovskite particles. The third idea is based on the atomization of the perovskite solution by a spray nozzle, introducing the spray droplets into a hot wall reactor, so as to prepare perovskite particles, using the droplet-to-particle spray approach (spray pyrolysis). Preliminary results show that the spray technology is the most successful method for the preparation of impurity-free perovskite particles and perovskite paste to deposit perovskite thin films. As a proof of concept, a perovskite solar cell with the paste prepared by the sprayed perovskite powder was successfully fabricated.

Fabrication of Semiconducting Methylammonium Lead Halide Perovskite Particles by Spray Technology.

Science.gov (United States)

Ahmadian-Yazdi, Mohammad-Reza; Eslamian, Morteza

2018-01-10

In this "nano idea" paper, three concepts for the preparation of methylammonium lead halide perovskite particles are proposed, discussed, and tested. The first idea is based on the wet chemistry preparation of the perovskite particles, through the addition of the perovskite precursor solution to an anti-solvent to facilitate the precipitation of the perovskite particles in the solution. The second idea is based on the milling of a blend of the perovskite precursors in the dry form, in order to allow for the conversion of the precursors to the perovskite particles. The third idea is based on the atomization of the perovskite solution by a spray nozzle, introducing the spray droplets into a hot wall reactor, so as to prepare perovskite particles, using the droplet-to-particle spray approach (spray pyrolysis). Preliminary results show that the spray technology is the most successful method for the preparation of impurity-free perovskite particles and perovskite paste to deposit perovskite thin films. As a proof of concept, a perovskite solar cell with the paste prepared by the sprayed perovskite powder was successfully fabricated.

Transfer Hydro-dehalogenation of Organic Halides Catalyzed by Ruthenium(II) Complex.

Science.gov (United States)

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 %.

Synthesis and spectral characterization of mono- and binuclear copper(II) complexes derived from 2-benzoylpyridine-N4-methyl-3-thiosemicarbazone: Crystal structure of a novel sulfur bridged copper(II) box-dimer

Science.gov (United States)

Jayakumar, K.; Sithambaresan, M.; Aiswarya, N.; Kurup, M. R. Prathapachandra

2015-03-01

Mononuclear and binuclear copper(II) complexes of 2-benzoylpyridine-N4-methyl thiosemicarbazone (HL) were prepared and characterized by a variety of spectroscopic techniques. Structural evidence for the novel sulfur bridged copper(II) iodo binuclear complex is obtained by single crystal X-ray diffraction analysis. The complex [Cu2L2I2], a non-centrosymmetric box dimer, crystallizes in monoclinic C2/c space group and it was found to have distorted square pyramidal geometry (Addison parameter, τ = 0.238) with the square basal plane occupied by the thiosemicarbazone moiety and iodine atom whereas the sulfur atom from the other coordinated thiosemicarbazone moiety occupies the apical position. This is the first crystallographically studied system having non-centrosymmetrical entities bridged via thiolate S atoms with Cu(II)sbnd I bond. The tridentate thiosemicarbazone coordinates in mono deprotonated thionic tautomeric form in all complexes except in sulfato complex, [Cu(HL)(SO4)]·H2O (1) where it binds to the metal centre in neutral form. The magnetic moment values and the EPR spectral studies reflect the binuclearity of some of the complexes. The spin Hamiltonian and bonding parameters are calculated based on EPR studies. In all the complexes g|| > g⊥ > 2.0023 and the g values in frozen DMF are consistent with the dx2-y2 ground state. The thermal stabilities of some of the complexes were also determined.

Bio-analytical applications of mid-infrared spectroscopy using silver halide fiber-optic probes

International Nuclear Information System (INIS)

Heise, H.M.; Kuepper, L.; Butvina, L.N.

2002-01-01

Infrared-spectroscopy has proved to be a powerful method for the study of various biomedical samples, in particular for in-vitro analysis in the clinical laboratory and for non-invasive diagnostics. In general, the analysis of biofluids such as whole blood, urine, microdialysates and bioreactor broth media takes advantage of the fact that a multitude of analytes can be quantified simultaneously and rapidly without the need for reagents. Progress in the quality of infrared silver halide fibers enabled us to construct several flexible fiber-optic probes of different geometries, which are particularly suitable for the measurement of small biosamples. Recent trends show that dry film measurements by mid-infrared spectroscopy could revolutionize analytical tools in the clinical chemistry laboratory, and an example is given. Infrared diagnostic tools show a promising potential for patients, and minimal-invasive blood glucose assays or skin tissue pathology in particular cannot be left out using mid-infrared fiber-based probes. Other applications include the measurement of skin samples including penetration studies of vitamins and constituents of cosmetic cream formulations. A further field is the micro-domain analysis of biopsy samples from bog mummified corpses, and recent results on the chemistry of dermis and hair samples are reported. Another field of application, for which results are reported, is food analysis and bio-reactor monitoring

Environmental Effects on the Photophysics of Organic-Inorganic Halide Perovskites.

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Metal induced gap states at alkali halide/metal interface

International Nuclear Information System (INIS)

Kiguchi, Manabu; Yoshikawa, Genki; Ikeda, Susumu; Saiki, Koichiro

2004-01-01

The electronic state of a KCl/Cu(0 0 1) interface was investigated using the Cl K-edge near-edge X-ray absorption fine structure (NEXAFS). A pre-peak observed on the bulk edge onset of thin KCl films has a similar feature to the peak at a LiCl/Cu(0 0 1) interface, which originates from the metal induced gap state (MIGS). The present result indicates that the MIGS is formed universally at alkali halide/metal interfaces. The decay length of MIGS to an insulator differs from each other, mainly due to the difference in the band gap energy of alkali halide

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

Science.gov (United States)

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

2018-04-01

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

Silver halide photographic material providing an image and an unsharp mask

International Nuclear Information System (INIS)

Broadhead, P.; Farnell, G.C.

1981-01-01

Desirable edge effects are produced by normal imagewise exposure and processing of a sensitive radiographic film comprising a transparent film support bearing a layer of a direct-positive silver halide emulsion and a layer of a negative silver halide emulsion and wherein the film comprises means to reduce crossover between the two emulsion layers, one of said emulsion layers being adapted to record a primary image and the other being adapted to record an unsharp mask image. (author)

Monocrystalline halide perovskite nanostructures for optoelectronic applications

NARCIS (Netherlands)

Khoram, P.

2018-01-01

Halide perovskites are a promising class of materials for incorporation in optoelectronics with higher efficiency and lower cost. The solution processability of these materials provides unique opportunities for simple nanostructure fabrication. In the first half of the thesis (chapter 2 and 3) we

Reactivity of halide and pseudohalide ligands

International Nuclear Information System (INIS)

Kukushkin, Yu.N.

1987-01-01

Reactivity of halide and pseudohalide (cyanide, azide, thiocyanate, cyanate) ligands tending to form bridge bonds in transition metal (Re, Mo, W) complexes is considered. Complexes where transition metal salts are ligands of other, complex-forming ion, are described. Transformation of innerspheric pseudohalide ligands is an important way of directed synthesis of these metal coordination compounds

Vibrational Spectra of Discrete UO22+ Halide Complexes in the Gas Phase

International Nuclear Information System (INIS)

Groenewold, G.S.; Van Stipdonk, Michael J.; Oomens, Jos; De Jong, Wibe A.; Gresham, Garold L.; Mcilwain, Michael

2010-01-01

The intrinsic binding of halide ions to the metal center in the uranyl molecule is a topic of ongoing research interest in both the actinide separations and theoretical communities. Investigations of structure in the condensed phases is frequently obfuscated by solvent interactions that can alter ligand binding and spectroscopic properties. The approach taken in this study is to move the uranyl halide complexes into the gas phase where they are free from solvent interactions, and then interrogate their vibrational spectroscopy using infrared multiple photon dissociation (IRMPD). The spectra of cationic coordination complexes having the composition (UO 2 (X)(ACO) 3 ) + (where X = F, Cl, Br and I; ACO = acetone) were acquired using electrospray for ion formation, and monitoring the ion signal from the photoelimination of ACO ligands. The studies showed that the asymmetric ν 3 UO 2 frequency was insensitive to halide identity as X was varied from Cl to I, suggesting that in these pseudo-octahedral complexes, changing the nucleophilicity of the halide did not appreciably alter its binding in the complex. The ν 3 peak in the spectrum of the F-containing complex was 9 cm -1 lower indicating stronger coordination in this complex. Similarly the ACO carbonyl stretches showed that the C=O frequency was relatively insensitive to the identity of the halide, although a modest shift to higher wavenumber was seen for the complexes with the more nucleophilic anions, consistent with the idea that they loosen solvent binding. Surprisingly, the ν 1 stretch was activated when the softer anions Cl, Br and I were present in the complexes. IR studies of the anionic complexes (UO 2 X 3 ) - (where X = Cl - , Br - and I - ) compared the ν 3 UO 2 modes versus halide, and showed that the ν 3 values decreased with increasing anion nucleophilicity. This observation was consistent with DFT calculations that indicated that (UO 2 X 2 ) - -X, and (UO 2 X 2 )·-X - dissociation energies

Synthesis, characterization, and antimicrobial activity of silver(I) and copper(II) complexes of phosphate derivatives of pyridine and benzimidazole.

Science.gov (United States)

Kalinowska-Lis, Urszula; Szewczyk, Eligia M; Chęcińska, Lilianna; Wojciechowski, Jakub M; Wolf, Wojciech M; Ochocki, Justyn

2014-01-01

Two silver(I) complexes--[Ag(4-pmOpe)]NO₃}(n) and [Ag(2-bimOpe)₂]NO₃--and three copper(II) complexes--[Cu₄Cl₆O(2-bimOpe)₄], [CuCl₂(4-pmOpe)₂], and [CuCl₂(2-bis(pm)Ope]--were synthesized by reaction of silver(I) nitrate or copper(II) chloride with phosphate derivatives of pyridine and benzimidazole, namely diethyl (pyridin-4-ylmethyl)phosphate (4-pmOpe), 1H-benzimidazol-2-ylmethyl diethyl phosphate (2-bimOpe), and ethyl bis(pyridin-2-ylmethyl)phosphate (2-bis(pm)Ope). These compounds were characterized by ¹H, ¹³C, and ³¹P NMR as well as IR spectroscopy, elemental analysis, and ESIMS spectrometry. Additionally, molecular and crystal structures of {[Ag(4-pmOpe)]NO₃}n and [Cu₄Cl₆O(2-bimOpe)₄] were determined by single-crystal X-ray diffraction analysis. The antimicrobial profiles of synthesized complexes and free ligands against test organisms from the ATCC and clinical sources were determined. Silver(I) complexes showed good antimicrobial activities against Candida albicans strains (MIC values of ∼19 μM). [Ag(2-bimOpe)₂]NO₃ was particularly active against Pseudomonas aeruginosa and methicillin-resistant Staphylococcus epidermidis, with MIC values of ∼5 and ∼10 μM, respectively. Neither copper(II) complexes nor the free ligands inhibited the growth of test organisms at concentrations below 500 μg mL⁻¹. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides

International Nuclear Information System (INIS)

Magdesieva, Tatiana V.; Graczyk, Magdalena; Vallat, Alain; Nikitin, Oleg M.; Demyanov, Petr I.; Butin, Kim P.; Vorotyntsev, Mikhail A.

2006-01-01

We have studied a reaction between the reduced form of titanocene dichloride (Cp 2 TiCl 2 ) and a group of organic halides: benzyl derivatives (4-X-C 6 H 4 CH 2 Cl, X = H, NO 2 , CH 3 ; 4-X-C 6 H 4 CH 2 Br, X = H, NO 2 , PhC(O); 4-X-C 6 H 4 CH 2 SCN, X = H, NO 2 ) as well as three aryl halides (4-NO 2 C 6 H 4 Hal, Hal = Cl, Br; 4-CH 3 O-C 6 H 4 Cl). It has been shown that the electrochemical reduction of Cp 2 TiCl 2 in the presence of these benzyl halides leads to a catalytic cycle resulting in the reductive dehalogenation of these organic substrates to yield mostly corresponding toluene derivatives as the main product. No dehalogenation has been observed for aryl derivatives. Based on electrochemical data and digital simulation, possible schemes of the catalytic process have been outlined. For non-substituted benzyl halides halogen atom abstraction is a key step. For the reaction of nitrobenzyl halides the complexation of Ti(III) species with the nitro group takes place, with the electron transfer from Ti(III) to this group (owing to its highest coefficient in LUMO of the nitro benzyl halide) followed by an intramolecular dissociative electron redistribution in the course of the heterolytic C-Hal bond cleavage. The results for reduced titanocene dichloride centers immobilized inside a polymer film showed that the catalytic reductive dehalogenation of the p-nitrobenzyl chloride does occur but with a low efficiency because of the partial deactivation of the film due to the blocking of the electron charge transport between the electrode and catalytic centers

Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides

Energy Technology Data Exchange (ETDEWEB)

Magdesieva, Tatiana V. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation)]. E-mail: tvm@org.chem.msu.ru; Graczyk, Magdalena [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France); Vallat, Alain [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France); Nikitin, Oleg M. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Demyanov, Petr I. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Butin, Kim P. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Vorotyntsev, Mikhail A. [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France)]. E-mail: MV@u-bourgogne.fr

2006-11-12

We have studied a reaction between the reduced form of titanocene dichloride (Cp{sub 2}TiCl{sub 2}) and a group of organic halides: benzyl derivatives (4-X-C{sub 6}H{sub 4}CH{sub 2}Cl, X = H, NO{sub 2}, CH{sub 3}; 4-X-C{sub 6}H{sub 4}CH{sub 2}Br, X = H, NO{sub 2}, PhC(O); 4-X-C{sub 6}H{sub 4}CH{sub 2}SCN, X = H, NO{sub 2}) as well as three aryl halides (4-NO{sub 2}C{sub 6}H{sub 4}Hal, Hal = Cl, Br; 4-CH{sub 3}O-C{sub 6}H{sub 4}Cl). It has been shown that the electrochemical reduction of Cp{sub 2}TiCl{sub 2} in the presence of these benzyl halides leads to a catalytic cycle resulting in the reductive dehalogenation of these organic substrates to yield mostly corresponding toluene derivatives as the main product. No dehalogenation has been observed for aryl derivatives. Based on electrochemical data and digital simulation, possible schemes of the catalytic process have been outlined. For non-substituted benzyl halides halogen atom abstraction is a key step. For the reaction of nitrobenzyl halides the complexation of Ti(III) species with the nitro group takes place, with the electron transfer from Ti(III) to this group (owing to its highest coefficient in LUMO of the nitro benzyl halide) followed by an intramolecular dissociative electron redistribution in the course of the heterolytic C-Hal bond cleavage. The results for reduced titanocene dichloride centers immobilized inside a polymer film showed that the catalytic reductive dehalogenation of the p-nitrobenzyl chloride does occur but with a low efficiency because of the partial deactivation of the film due to the blocking of the electron charge transport between the electrode and catalytic centers.

Characterisation of spin-waves in copper(II) deuteroformate tetradeuterate: A square ¤S¤=1/2 Heisenberg antiferromagnet

DEFF Research Database (Denmark)

Clarke, S.J.; Harrison, A.; Mason, T.E.

1999-01-01

Copper(II) formate tetrahydrate (CFTH) is a model square S = 1/2 Heisenberg antiferromagnet with T-N = 16.54 +/- 0.05 K. The dispersion of spin-waves in the magnetic layers of a fully deuterated sample of this material has been mapped at 4.3 K by inelastic neutron scattering from the zone centre ...

Direct ToF-SIMS analysis of organic halides and amines on TLC plates

Energy Technology Data Exchange (ETDEWEB)

Parent, Alexander A. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Anderson, Thomas M. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Michaelis, David J. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Jiang, Guilin [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Savage, Paul B. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Linford, Matthew R. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States)]. E-mail: mrlinford@chem.byu.edu

2006-07-30

It has been reported that: 'direct analysis of thin layer chromatography (TLC) plates with secondary ion mass spectrometry (SIMS) yields no satisfactory results' (J. Chromatogr. A 1084 (2005) 113-118). While this statement appears to be true in general, we have identified two important classes of compounds, organic halides and amines, that appear to yield to such direct analyses. For example, five organic halides with diverse structures were eluted on normal phase TLC plates. In all cases the halide signals in the negative ion time-of-flight secondary ion mass spectrometry (ToF-SIMS) spectra were notably stronger than the background signals. Similarly, a series of five organic amines with diverse structures were directly analyzed by positive ion ToF-SIMS. In all but one of the spectra characteristic, and sometimes even quasi-molecular ions, were observed. Most likely, the good halide ion yields are largely a function of the electronegativity of the halogens. We also propose that direct analysis of amines on normal phase silica gel is facilitated by the acidity, i.e., proton donation, of surface silanol groups.

Direct ToF-SIMS analysis of organic halides and amines on TLC plates

International Nuclear Information System (INIS)

Parent, Alexander A.; Anderson, Thomas M.; Michaelis, David J.; Jiang, Guilin; Savage, Paul B.; Linford, Matthew R.

2006-01-01

It has been reported that: 'direct analysis of thin layer chromatography (TLC) plates with secondary ion mass spectrometry (SIMS) yields no satisfactory results' (J. Chromatogr. A 1084 (2005) 113-118). While this statement appears to be true in general, we have identified two important classes of compounds, organic halides and amines, that appear to yield to such direct analyses. For example, five organic halides with diverse structures were eluted on normal phase TLC plates. In all cases the halide signals in the negative ion time-of-flight secondary ion mass spectrometry (ToF-SIMS) spectra were notably stronger than the background signals. Similarly, a series of five organic amines with diverse structures were directly analyzed by positive ion ToF-SIMS. In all but one of the spectra characteristic, and sometimes even quasi-molecular ions, were observed. Most likely, the good halide ion yields are largely a function of the electronegativity of the halogens. We also propose that direct analysis of amines on normal phase silica gel is facilitated by the acidity, i.e., proton donation, of surface silanol groups

Synthesis and characterization of iron(III), manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes of salicylidene-N-anilinoacetohydrazone (H2L1) and 2-hydroxy-1-naphthylidene-N-anilinoacetohydrazone (H2L2).

Science.gov (United States)

AbouEl-Enein, S A; El-Saied, F A; Kasher, T I; El-Wardany, A H

2007-07-01

Salicylidene-N-anilinoacetohydrazone (H(2)L(1)) and 2-hydroxy-1-naphthylidene-N-anilinoacetohydrazone (H(2)L(2)) and their iron(III), manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes have been synthesized and characterized by IR, electronic spectra, molar conductivities, magnetic susceptibilities and ESR. Mononuclear complexes are formed with molar ratios of 1:1, 1:2 and 1:3 (M:L). The IR studies reveal various modes of chelation. The electronic absorption spectra and magnetic susceptibility measurements show that the iron(III), nickel(II) and cobalt(II) complexes of H(2)L(1) have octahedral geometry. While the cobalt(II) complexes of H(2)L(2) were separated as tetrahedral structure. The copper(II) complexes have square planar stereochemistry. The ESR parameters of the copper(II) complexes at room temperature were calculated. The g values for copper(II) complexes proved that the Cu-O and Cu-N bonds are of high covalency.

Template synthesis of poly aza macrocyclic copper(II) and nickel(II) complexes: Spectral characterization and antimicrobial studies

Energy Technology Data Exchange (ETDEWEB)

Gurumoorthy, P.; Ravichandran, J.; Kaliur Rahiman, A. [The New College, Chennai (India); Karthikeyan, N.; Palani, P. [Univ. of Madras, Chennai (India)

2012-07-15

The template synthesis of copper(II) and nickel(II) complexes derived from 2,6-diformyl-4-methylphenol with diethylenetriamine or 1,2-bis(3-amino propylamino)ethane produce the 12-membered N{sub 3}O and 17-membered N{sub 4}O macrocyclic complexes, respectively. The geometry of the complexes has been determined with the help of electronic and EPR spectroscopic values and found to be five coordinated square pyramidal and, six coordinated distorted tetragonal for 12-membered and 17-membered macrocyclic complexes, respectively. Electrochemical studies of the mononuclear N{sub 3}O and N{sub 4}O copper(II) complexes show one irreversible one electron reduction wave at E{sup pc} = .1.35 and .1.15 V respectively, and the corresponding nickel(II) complexes show irreversible one-electron reduction wave at E{sup pc} = .1.25 and .1.22 V, respectively. The nickel(II) complexes show irreversible one-electron oxidation wave at Epa = +0.84 and +0.82 V, respectively. All the complexes were evaluated for in vitro antimicrobial activity against the human pathogenic bacteria and fungi.

Radiation damage in the alkali halide crystals

International Nuclear Information System (INIS)

Diller, K.M.

1975-10-01

A general review is given of the experimental data on radiation damage in the alkali halide crystals. A report is presented of an experimental investigation of irradiation produced interstitial dislocation loops in NaCl. These loops are found to exhibit the usual growth and coarsening behaviour during thermal annealing which operates by a glide and self-climb mechanism. It is shown that the recombination of defects in these crystals is a two stage process, and that the loss of interstitials stabilized at the loops is caused by extrinsic vacancies. The theoretical techniques used in simulating point defects in ionic crystals are described. Shell model potentials are derived for all the alkali halide crystals by fitting to bulk crystal data. The fitting is supplemented by calculations of the repulsive second neighbour interactions using methods based on the simple electron gas model. The properties of intrinsic and substitutional impurity defects are calculated. The HADES computer program is used in all the defect calculations. Finally the report returns to the problems of irradiation produced interstitial defects. The properties of H centres are discussed; their structure, formation energies, trapping at impurities and dimerization. The structure, formation energies and mobility of the intermediate and final molecular defects are then discussed. The thermodynamics of interstitial loop formation is considered for all the alklai halide crystals. The nucleation of interstitial loops in NaCl and NaBr is discussed, and the recombination of interstitial and vacancy defects. The models are found to account for all the main features of the experimental data. (author)

Synthesis and spectral characterization of mono- and binuclear copper(II) complexes derived from 2-benzoylpyridine-N⁴-methyl-3-thiosemicarbazone: crystal structure of a novel sulfur bridged copper(II) box-dimer.

Science.gov (United States)

Jayakumar, K; Sithambaresan, M; Aiswarya, N; Kurup, M R Prathapachandra

2015-03-15

Mononuclear and binuclear copper(II) complexes of 2-benzoylpyridine-N(4)-methyl thiosemicarbazone (HL) were prepared and characterized by a variety of spectroscopic techniques. Structural evidence for the novel sulfur bridged copper(II) iodo binuclear complex is obtained by single crystal X-ray diffraction analysis. The complex [Cu2L2I2], a non-centrosymmetric box dimer, crystallizes in monoclinic C2/c space group and it was found to have distorted square pyramidal geometry (Addison parameter, τ=0.238) with the square basal plane occupied by the thiosemicarbazone moiety and iodine atom whereas the sulfur atom from the other coordinated thiosemicarbazone moiety occupies the apical position. This is the first crystallographically studied system having non-centrosymmetrical entities bridged via thiolate S atoms with Cu(II)I bond. The tridentate thiosemicarbazone coordinates in mono deprotonated thionic tautomeric form in all complexes except in sulfato complex, [Cu(HL)(SO4)]·H2O (1) where it binds to the metal centre in neutral form. The magnetic moment values and the EPR spectral studies reflect the binuclearity of some of the complexes. The spin Hamiltonian and bonding parameters are calculated based on EPR studies. In all the complexes g||>g⊥>2.0023 and the g values in frozen DMF are consistent with the d(x2-y2) ground state. The thermal stabilities of some of the complexes were also determined. Copyright © 2014 Elsevier B.V. All rights reserved.

Green and selective synthesis of N-substituted amides using water soluble porphyrazinato copper(II) catalyst

International Nuclear Information System (INIS)

Ghodsinia, Sara S.E.; Akhlaghinia, Batool; Eshghi, Hossein; Safaei, Elham

2013-01-01

N, N',N , N ' -Tetramethyl tetra-2,3-pyridinoporphyrazinato copper(II) methyl sulfate ([Cu(2,3-tmtppa)](MeSO 4 ) 4 ) efficiently catalyzed the direct conversion of nitriles to N-substituted amides. The one pot selective synthesis of the N-substituted amides from nitriles and primary amines was performed in refluxing H 2 O. The catalyst was recovered and reused at least four times, maintaining its efficiency. (author)

Local coordination of polyvalent metal ions in molten halide mixtures

International Nuclear Information System (INIS)

Akdeniz, Z.; Tosi, M.P.

1989-07-01

Ample experimental evidence is available in the literature on the geometry and the stability of local coordination for polyvalent metal ions in molten mixtures of their halides with alkali halides. Recent schemes for classifying this evidence are discussed. Dissociation of tetrahedral halocomplexes in good ionic systems can be viewed as a classical Mott problem of bound-state stability in a conducting matrix. More generally, structural coordinates can be constructed from properties of the component elements, to separate out systems with long-lived fourfold or sixfold coordination and to distinguish between these. (author). 11 refs, 1 fig

Thallous and cesium halide materials for use in cryogenic applications

International Nuclear Information System (INIS)

Lawless, W.N.

1983-01-01

Certain thallous and cesium halides, either used alone or in combination with other ceramic materials, are provided 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 and cesium 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 or extruded onto substrates or wires. (author)

Development and melt growth of novel scintillating halide crystals

Science.gov (United States)

Yoshikawa, Akira; Yokota, Yuui; Shoji, Yasuhiro; Kral, Robert; Kamada, Kei; Kurosawa, Shunsuke; Ohashi, Yuji; Arakawa, Mototaka; Chani, Valery I.; Kochurikhin, Vladimir V.; Yamaji, Akihiro; Andrey, Medvedev; Nikl, Martin

2017-12-01

Melt growth of scintillating halide crystals is reviewed. The vertical Bridgman growth technique is still considered as very popular method that enables production of relatively large and commercially attractive crystals. On the other hand, the micro-pulling-down method is preferable when fabrication of small samples, sufficient for preliminary characterization of their optical and/or scintillation performance, is required. Moreover, bulk crystal growth is also available using the micro-pulling-down furnace. The examples of growths of various halide crystals by industrially friendly melt growth techniques including Czochralski and edge-defined film-fed growth methods are also discussed. Finally, traveling molten zone growth that in some degree corresponds to horizontal zone melting is briefly overviewed.

Alkali Halide Microstructured Optical Fiber for X-Ray Detection

Science.gov (United States)

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.

Formation of structured nanophases in halide crystals

Czech Academy of Sciences Publication Activity Database

Kulveit, Jan; Demo, Pavel; Polák, Karel; Sveshnikov, Alexey; Kožíšek, Zdeněk

2013-01-01

Roč. 5, č. 6 (2013), s. 561-564 ISSN 2164-6627 R&D Projects: GA ČR GAP108/12/0891 Institutional support: RVO:68378271 Keywords : halide crystals * nucleation Subject RIV: BM - Solid Matter Physics ; Magnetism http://www.aspbs.com/asem.html#v5n6

Determination of the structural phase and octahedral rotation angle in halide perovskites

Science.gov (United States)

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.

Solvation structures of lithium halides in methanol–water mixtures

International Nuclear Information System (INIS)

Sarkar, Atanu; Dixit, Mayank Kumar; Tembe, B.L.

2015-01-01

Highlights: • Potentials of mean force for Li + -halides are calculated in methanol–water mixtures. • Stable CIP for x methanol = 1.0 becomes unstable at and below x methanol = 0.75. • The Li + ion is preferentially solvated by methanol molecules. • The halide ions are preferentially solvated by water molecules. - Abstract: The potentials of mean force (PMFs) for the ion pairs, Li + −Cl − , Li + −Br − and Li + −I − have been calculated in five methanol–water compositions. The results obtained are verified by trailing the trajectories and calculating the ion pair distance residence times. Local structures around the ions are studied using the radial distribution functions, density profiles, orientational correlation functions, running coordination numbers and excess coordination numbers. The major change in PMF is observed as the methanol mole fraction (x methanol ) is changed from 1.0 to 0.75. The stable contact ion pair occurring for x methanol = 1.0 becomes unstable at and below x methanol = 0.75. The preferential solvation data show that the halide ions are always preferentially solvated by water molecules. Although the lithium ion is preferentially solvated by methanol molecules, there is significant affinity towards water molecules as well

trans-Bis(perchlorato-κOtetrakis(1H-pyrazole-κN2copper(II

Directory of Open Access Journals (Sweden)

Viktor Zapol'skii

2008-10-01

Full Text Available The title compound, [Cu(ClO42(C3H4N24], was obtained unexpectedly by the reaction of copper(II perchlorate hexahydrate with equimolar amounts of 1-chloro-1-nitro-2,2,2-tripyrazolylethane in methanol solution. The crystal structure comprises octahedrally coordinated Cu2+ ions, located on an inversion centre, with four pyrazole ligands in the equatorial plane. The average Cu—N distance is 2.000 (1 Å. Two perchlorate ions are coordinated to copper in trans positions [Cu—O = 2.4163 (11 Å].

Green and selective synthesis of N-substituted amides using water soluble porphyrazinato copper(II) catalyst

Energy Technology Data Exchange (ETDEWEB)

Ghodsinia, Sara S.E.; Akhlaghinia, Batool; Eshghi, Hossein, E-mail: akhlaghinia@um.ac.ir [Ferdowsi University of Mashhad (Iran, Islamic Republic of). Faculty of Sciences. Department of Chemistry; Safaei, Elham [Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan (Iran, Islamic Republic of). Department of Chemistry

2013-06-15

N, N',N{sup ,} N{sup '}-Tetramethyl tetra-2,3-pyridinoporphyrazinato copper(II) methyl sulfate ([Cu(2,3-tmtppa)](MeSO{sub 4}){sub 4}) efficiently catalyzed the direct conversion of nitriles to N-substituted amides. The one pot selective synthesis of the N-substituted amides from nitriles and primary amines was performed in refluxing H{sub 2}O. The catalyst was recovered and reused at least four times, maintaining its efficiency. (author)

Electron detachment energies in high-symmetry alkali halide solvated-electron anions

Science.gov (United States)

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.

Local Polar Fluctuations in Lead Halide Perovskite Crystals

Energy Technology Data Exchange (ETDEWEB)

Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z.; Egger, David A.; Hull, Trevor; Stoumpos, Constantinos C.; Zheng, Fan; Heinz, Tony F.; Kronik, Leeor; Kanatzidis, Mercouri G.; Owen, Jonathan S.; Rappe, Andrew M.; Pimenta, Marcos A.; Brus, Louis E.

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 coupled to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr3.

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

Science.gov (United States)

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

Thermoelectrical and thermal analyses of copper(II) acetate monohydrate ZnO-matrix composite powder obtained by freeze-drying

International Nuclear Information System (INIS)

Bellini, Jusmar Valentin; Pineda, Edgardo Alfonso Gomez; Rocha, Raquel de Almeida; Ponzoni, Andre Luis de Lima; Paesano, Andrea

2006-01-01

The thermal history of freeze-dried mixtures of composite powders containing ZnO-matrix and (CH 3 COO) 2 Cu.H 2 O (copper(II) acetate monohydrate) was undertaken by thermal analysis (TA) coupled to thermoelectrical analysis (TEA). Experiments were carried out on compacted samples, under non-isothermal conditions, in air, up to 350 deg. C, by measuring the electrical resistance during heating, called thermoelectrical resistometry (TER), and by differential scanning calorimetry (DSC). Activation energy (E a ) for exothermal events related to the decomposition of (CH 3 COO) 2 Cu (copper(II) acetate, CuAc 2 ), observed within the range 225-325 deg. C, was estimated according to ASTM E 698 method. Values of E a equal to 154 and 155 kJ/mol were obtained by TER and DSC, respectively. TER showed that the thermal decomposition of CuAc 2 involves the liberation of electrons. Results also indicated that TER may be used as an alternative or complementary method for the study of the thermal decomposition mechanisms of transition metal(II) acetates

Thermal battery. [solid metal halide electrolytes with enhanced electrical conductance after a phase transition

Science.gov (United States)

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.

Analysis and modeling of alkali halide aqueous solutions

DEFF Research Database (Denmark)

Kim, Sun Hyung; Anantpinijwatna, Amata; Kang, Jeong Won

2016-01-01

on calculations for various electrolyte properties of alkali halide aqueous solutions such as mean ionic activity coefficients, osmotic coefficients, and salt solubilities. The model covers highly nonideal electrolyte systems such as lithium chloride, lithium bromide and lithium iodide, that is, systems...

A study on the localized corrosion of cobalt in bicarbonate solutions containing halide ions

Energy Technology Data Exchange (ETDEWEB)

Gallant, Danick [Departement de Biologie, Chimie et Sciences de la Sante, Universite du Quebec a Rimouski, 300, Allee des Ursulines, Rimouski, Que., G5L 3A1 (Canada); Departement de Chimie, Universite Laval, Quebec, Que., G1K 7P4 (Canada); Simard, Stephan [Departement de Biologie, Chimie et Sciences de la Sante, Universite du Quebec a Rimouski, 300, Allee des Ursulines, Rimouski, Que., G5L 3A1 (Canada)]. E-mail: stephan_simard@uqar.qc.ca

2005-07-01

The localized attack of cobalt in bicarbonate aqueous solutions containing halide ions was investigated using electrochemical techniques, scanning electron microscopy, UV-visible and Raman spectroscopies. Rotating disc and rotating ring-disc electrodes were used to determine the effect of bicarbonate concentration, solution pH, nature and concentration of the halide ions, convection and potential sweep rate on the corrosion processes. These parameters were found to play a key role on the localized attack induced by halide ions by influencing the production of a Co(HCO{sub 3}){sub 2} precipitate on the pit surface. Potentiostatically generated cobalt oxide films (CoO and Co{sub 3}O{sub 4}) were found to be efficient to reduce pitting corrosion of cobalt.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Iodometric determination of peroxydiphosphate in the presence of copper(II) or iron(II) as catalyst.

Science.gov (United States)

Kapoor, S; Sharma, P D; Gupta, Y K

1975-09-01

Peroxydiphosphate can be determined iodometrically in the presence of a large excess of potassium iodide with copper(II) or iron(II) as catalyst through the operation of the Cu(II)/Cu(I) or Fe(II)/Fe(III) cycle. The method is applicable in HClO(4), H(2)SO(4), HCl and CH(3)COOH acid media in the range 0.1-1.0M studied. Nickel, manganese(II), cobalt(II), silver, chloride and phosphate are without effect.

Structures of butyl ions formed by electron impact ionization of isomeric butyl halides and alkanes

International Nuclear Information System (INIS)

Shold, D.M.; Ausloos, P.

1978-01-01

Using a pulsed ion cyclotron resonance (ICR) spectrometer, it is demonstrated that at pressures of about 10 -6 Torr and at observation times ranging from 10 -3 to 0.5 s, isobutane, neopentane, 2,2-dimethylbutane, isobutyl halides, and tert-butyl halides form C 4 H 9 + ions having the tertiary structure. In n-alkanes, 2-methylbutane, 3-methylpentane, n-butyl halides, and sec-butyl halides, both sec-C 4 H 9 + and t-C 4 H 9 + ions are observed, the sec-C 4 H 9 + ions surviving without rearrangement for at least 0.1 s. However, in the case of the halides, a collision-induced isomerization of the sec-C 4 H 9 + to the t-C 4 H 9 + ions occurs. The efficiency of this process increases with the basicity of the alkyl halide. Radiolysis experiments carried out at atmospheric pressures indicate, in agreement with ICR and solution experiments, that at times as short as 10 -10 s the majority of the i-C 4 H 9 + ions from isobutyl bromide rearrange to the t-C 4 H 9 + structure. On the other hand, in the radiolysis of both n-hexane and 3-methylpentane, the abundance of t-C 4 H 9 + relative to sec-C 4 H 9 + is substantially smaller than that observed in the ICR experiments, and decreases with decreasing collision interval. It is suggested that about 90% of the i-C 4 H 9 + can rearrange to t-C 4 H 9 + by simple 1,2-hydride shift without involving secondary or protonated methylcyclopropane structures as intermediates. 4 figures, 2 tables

Dipole-dipole van der Waals interaction in alkali halides

International Nuclear Information System (INIS)

Thakur, B.N.; Thakur, K.P.

1978-01-01

Values of van der Waals dipole-dipole constants and interaction energetics of alkali halides are reported using the recent data. The values obtained are somewhat larger than those of earlier workers. (orig.) [de

Lead Halide Perovskite Nanocrystals in the Research Spotlight: Stability and Defect Tolerance

Science.gov (United States)

2017-01-01

This Perspective outlines basic structural and optical properties of lead halide perovskite colloidal nanocrystals, highlighting differences and similarities between them and conventional II–VI and III–V semiconductor quantum dots. A detailed insight into two important issues inherent to lead halide perovskite nanocrystals then follows, namely, the advantages of defect tolerance and the necessity to improve their stability in environmental conditions. The defect tolerance of lead halide perovskites offers an impetus to search for similar attributes in other related heavy metal-free compounds. We discuss the origins of the significantly blue-shifted emission from CsPbBr3 nanocrystals and the synthetic strategies toward fabrication of stable perovskite nanocrystal materials with emission in the red and infrared parts of the optical spectrum, which are related to fabrication of mixed cation compounds guided by Goldschmidt tolerance factor considerations. We conclude with the view on perspectives of use of the colloidal perovskite nanocrystals for applications in backlighting of liquid-crystal TV displays. PMID:28920080

Preparation and testing of a tetra-amine copper(II) chitosan bead system for enhanced phosphate remediation.

Science.gov (United States)

Kumar, Ilango Aswin; Viswanathan, Natrayasamy

2018-03-01

A tetra-amine copper(II) chitosan bead system (TAC@CS composite beads) was developed by grafting tetra-amine copper(II) (TAC) with chitosan (CS) and utilized for phosphate removal. The prepared TAC@CS composite beads possess enhanced phosphate sorption capacity (SC) of 41.42 ± 0.071 mg/g than copper grafted chitosan (Cu@CS) composite, TAC and chitosan which were found to be 37.01 ± 0.803, 33.20 ± 0.650 and 7.24 ± 0.059 mg/g respectively. In batch mode, various adsorption influencing parameters like contact time, initial phosphate concentration, solution pH, co-anions and temperature were optimized for maximum phosphate sorption. The prepared adsorbents were characterized by FTIR, XRD, UV-Visible, SEM and EDAX analysis. The adsorption isotherms and thermodynamic parameters of the adsorbent were studied. The feasible phosphate uptake mechanism of TAC@CS biocomposite beads was reported. The reusability studies of TAC@CS composite beads were carried out using NaOH as elutant. The suitability of TAC@CS composite beads at field conditions was tested with phosphate contaminated field water samples collected from nearby areas of Dindigul district. Copyright © 2017 Elsevier Ltd. All rights reserved.

Calcium phosphate cements with strontium halides as radiopacifiers.

Science.gov (United States)

López, Alejandro; Montazerolghaem, Maryam; Engqvist, Håkan; Ott, Marjam Karlsson; Persson, Cecilia

2014-02-01

High radiopacity is required to monitor the delivery and positioning of injectable implants. Inorganic nonsoluble radiopacifiers are typically used in nondegradable bone cements; however, their usefulness in resorbable cements is limited due to their low solubility. Strontium halides, except strontium fluoride, are ionic water-soluble compounds that possess potential as radiopacifiers. In this study, we compare the radiopacity, mechanical properties, composition, and cytotoxicity of radiopaque brushite cements prepared with strontium fluoride (SrF2 ), strontium chloride (SrCl2 ·6H2 O), strontium bromide (SrBr2 ), or strontium iodide (SrI2 ). Brushite cements containing 10 wt % SrCl2 ·6H2 O, SrBr2 , or SrI2 exhibited equal to or higher radiopacity than commercial radiopaque cements. Furthermore, the brushite crystal lattice in cements that contained the ionic radiopacifiers was larger than in unmodified cements and in cements that contained SrF2 , indicating strontium substitution. Despite the fact that the strontium halides increased the solubility of the cements and affected their mechanical properties, calcium phosphate cements containing SrCl2 ·6H2 O, SrBr2 , and SrI2 showed no significant differences in Saos-2 cell viability and proliferation with respect to the control. Strontium halides: SrCl2 ·6H2 O, SrBr2 , and SrI2 may be potential candidates as radiopacifiers in resorbable biomaterials although their in vivo biocompatibility, when incorporated into injectable implants, is yet to be assessed. Copyright © 2013 Wiley Periodicals, Inc.

Synthesis, spectroscopy, magnetic and redox behaviors of copper(II) complexes with tert-butylated salen type ligands bearing bis(4-aminophenyl)ethane and bis(4-aminophenyl)amide backbones.

Science.gov (United States)

Kasumov, Veli T; Yerli, Yusuf; Kutluay, Aysegul; Aslanoglu, Mehmet

2013-03-01

New salen type ligands, N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-ethylenedianiline [(X=H (1), 5-tert-butyl (2)] and N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-amidedianiline [X=H (3), 5-tert (4)] and their copper(II) complexes 5-8, have been synthesized. Their spectroscopic (IR, (1)H NMR, UV/vis, ESR) properties, as well as magnetic and redox-reactivity behavior are reported. IR spectra of 7 and 8 indicate the coordination of amide oxygen atoms of 3 and 4 ligands to Cu(II). The solid state ESR spectra of 5-8 exhibits less informative exchange narrowed isotropic or anisotropic signals with weak unresolved low field patterns. The magnetic moments of 5 (2.92 μ(B) per Cu(II)) and 6 (2.79 μ(B) per Cu(II)) are unusual for copper(II) complexes and considerably higher than those for complexes 7 and 8. Cryogenic measurements (300-10 K) show weak antiferromagnetic exchange interactions between the copper(II) centers in complexes 6 and 8. The results of electrochemical and chemical redox-reactivity studies are discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

Sodium-metal halide and sodium-air batteries.

Science.gov (United States)

Ha, Seongmin; Kim, Jae-Kwang; Choi, Aram; Kim, Youngsik; Lee, Kyu Tae

2014-07-21

Impressive developments have been made in the past a few years toward the establishment of Na-ion batteries as next-generation energy-storage devices and replacements for Li-ion batteries. Na-based cells have attracted increasing attention owing to low production costs due to abundant sodium resources. However, applications of Na-ion batteries are limited to large-scale energy-storage systems because of their lower energy density compared to Li-ion batteries and their potential safety problems. Recently, Na-metal cells such as Na-metal halide and Na-air batteries have been considered to be promising for use in electric vehicles owing to good safety and high energy density, although less attention is focused on Na-metal cells than on Na-ion cells. This Minireview provides an overview of the fundamentals and recent progress in the fields of Na-metal halide and Na-air batteries, with the aim of providing a better understanding of new electrochemical systems. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Local polar fluctuations in lead halide perovskites

Science.gov (United States)

Tan, Liang; Yaffe, Omer; Guo, Yinsheng; Brus, Louis; Rappe, Andrew; Egger, David; Kronik, Leeor

The lead halide perovskites have recently attracted much attention because of their large and growing photovoltaic power conversion efficiencies. However, questions remain regarding the temporal and spatial correlations of the structural fluctuations, their atomistic nature, and how they affect electronic and photovoltaic properties. To address these questions, we have performed a combined ab initio molecular dynamics (MD) and density functional theory (DFT) study on CsPbBr3. We have observed prevalent anharmonic motion in our MD trajectories, with local polar fluctuations involving head-to-head motion of A-site Cs cations coupled with Br window opening. We calculate Raman spectra from the polarizability auto-correlation functions obtained from these trajectories and show that anharmonic A-site cation motion manifests as a broad central peak in the Raman spectrum, which increases in intensity with temperature. A comparison of the experimental Raman spectrum of hybrid organometallic MAPbBr3 and fully inorganic CsPbBr3 suggests that structural fluctuations in lead-halide perovskites is more general than rotation of polar organic cations and is intimately coupled to the inorganic framework.

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

Science.gov (United States)

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.

Abiotic Formation of Methyl Halides in the Terrestrial Environment

Science.gov (United States)

Keppler, F.

2011-12-01

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

The impact of alkali metal halide electron donor complexes in the photocatalytic degradation of pentachlorophenol

Energy Technology Data Exchange (ETDEWEB)

Khuzwayo, Z., E-mail: zack.khuzwayo@up.ac.za; Chirwa, E.M.N

2017-01-05

Highlights: • Facilitation of photocatalysis using simple metal-halides as VB hole scavengers. • Recombination prevention by coupled valence and conduction band approaches. • Determination of anions critical levels beyond which process retardation occurs. • Determination of the photocatalytic process rate of reaction kinetics. - Abstract: The performance of photocatalytic oxidation of chemical pollutants is subjected to the presence of anion complexes in natural waters. This study investigated the influence of alkali metal (Na{sup +} (sodium), K{sup +} (potassium)) halides (Cl{sup −} (chloride), Br{sup −} (bromide), F{sup −} (fluoride)) as inorganic ion sources in the photocatalytic degradation of pentachlorophenol (PCP) in batch systems. It was found that the exclusive presence of halides in the absence of an electron acceptor adequately facilitated the photocatalyst process below critical levels of anion populations, where beyond the critical point the process was significantly hindered. Below the determined critical point, the performance in some cases near matches that of the facilitation of the photocatalytic process by exclusive oxygen, acting as an electron scavenger. The coupling of halide ions and oxygenation presented significantly improved photo-oxidation of PCP, this was confirmed by the inclusion of formic acid as a comparative electron donor. The Langmuir-Hinshelwood kinetic expression was used to calculate the performance rate kinetics. The probable impact of the halide anions was discussed with regards to the process of electron hole pair recombination prevention.

Solution-Phase Synthesis of Cesium Lead Halide Perovskite Nanowires.

Science.gov (United States)

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.

Development of alkali halide-optics for high power-IR laser

International Nuclear Information System (INIS)

Pohl, L.

1989-01-01

In this work 'Development of Alkali Halide-Optics for High Power-IR Laser' we investigated the purification of sodiumchloride-, potassiumchloride- and potassiumbromide-raw materials. We succeeded to reduce the content of impurities like Cu, Pb, V, Cr, Mn, Fe, Co and Ni in these raw materials to the lower of ppb's by a Complex-Adsorption-Method (CAM). Crystals were grown from purified substances by 'Kyropoulos' method'. Windows were cur thereof, polished and measured by FTIR-spectroscopy. Analytical data showed, that the resulting crystals were of lower quality than the raw materials. Because of this fact crystal-growing-conditions have to undergo a special improvement. Alkali halide windows from other sources on the market had been tested. (orig.) [de

Spectroscopic investigation of indium halides as substitudes of mercury in low pressure discharges for lighting applications

Energy Technology Data Exchange (ETDEWEB)

Briefi, Stefan

2012-05-22

Low pressure discharges with indium halides as radiator are discussed as substitutes for hazardous mercury in conventional fluorescent lamps. In this work, the applicability of InBr and InCl in a low pressure discharge light source is investigated. The aim is to identify and understand the physical processes which determine the discharge characteristics and the efficiency of the generated near-UV emission of the indium halide molecule and of the indium atom which is created due to dissociation processes in the plasma. As discharge vessels sealed cylindrical quartz glass tubes which contain a defined amount of indium halide and a rare gas are used. Preliminary investigations showed that for a controlled variation of the indium halide density a well-defined cold spot setup is mandatory. This was realized in the utilized experimental setup. The use of metal halides raises the issue, that power coupling by internal electrodes is not possible as the electrodes would quickly be eroded by the halides. The comparison of inductive and capacitive RF-coupling with external electrodes revealed that inductively coupled discharges provide higher light output and much better long term stability. Therefore, all investigations are carried out using inductive RF-coupling. The diagnostic methods optical emission and white light absorption spectroscopy are applied. As the effects of absorption-signal saturation and reabsorption of emitted radiation within the plasma volume could lead to an underestimation of the determined population densities by orders of magnitude, these effects are considered in the data evaluation. In order to determine the electron temperature and the electron density from spectroscopic measurements, an extended corona model as population model of the indium atom has been set up. A simulation of the molecular emission spectra has been implemented to investigate the rovibrational population processes of the indium halide molecules. The impact of the cold spot

Fluorescence-based detection of nitric oxide in aqueous and methanol media using a copper(II) complex.

Science.gov (United States)

Mondal, Biplab; Kumar, Pankaj; Ghosh, Pokhraj; Kalita, Apurba

2011-03-14

The quenched fluorescent intensity of a copper(II) complex, 1, of a fluorescent ligand, in degassed methanol or aqueous (buffered at pH 7.2) solution, was found to reappear on exposure to nitric oxide. Thus, it can function as a fluorescence based nitric oxide sensor. It has been found that the present complex can be used to sense nanomolar quantities of nitric oxide in both methanol and pH 7.2 buffered-water medium.

Thermomechanical measurements of lead halide single crystals

Czech Academy of Sciences Publication Activity Database

Nitsch, Karel; Rodová, Miroslava

2002-01-01

Roč. 234, č. 2 (2002), s. 701-709 ISSN 0370-1972 R&D Projects: GA AV ČR IAA2010926 Institutional research plan: CEZ:AV0Z1010914 Keywords : PbX 2 (X=Cl, Br, I) * coefficients of linear thermal expansion * polymorphism in lead halides Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.930, year: 2002

Dislocation unpinning model of acoustic emission from alkali halide ...

Indian Academy of Sciences (India)

The present paper reports the dislocation unpinning model of acoustic emis- sion (AE) from ... Acoustic emission; dislocation; alkali halide crystals; plastic deformation. ..... [5] T Nishimura, A Tahara and T Kolama, Jpn. Metal Inst. 64, 339 (2000).

Scalable room-temperature conversion of copper(II) hydroxide into HKUST-1 (Cu3 (btc)2).

Science.gov (United States)

Majano, Gerardo; Pérez-Ramírez, Javier

2013-02-20

Copper(II) hydroxide is converted directly to HKUST-1 (Cu(3) (btc)(2) ) after only 5 min at room-temperature in aqueous ethanolic solution without the need of additional solvents. Scale up to the kilogram scale does not influence porous properties yielding pure-phase product with a remarkable total surface area exceeding 1700 m(2) g(-1) featuring aggregates of nanometer-sized crystals (<600 nm) and extremely high space-time yields. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

and copper(ii)

African Journals Online (AJOL)

DELL

Department of Chemistry, Obafemi Awolowo University, Ile-Ife Nigeria. Corresponding Author: Akinyele ... derivatives with aldehydes or ketones (Deepa and. Aravindakshan, 2005). ... used in organic synthesis, especially for the preparation of ...

Alternative route to metal halide free ionic liquids

International Nuclear Information System (INIS)

Takao, Koichiro; Ikeda, Yasuhisa

2008-01-01

An alternative synthetic route to metal halide free ionic liquids using trialkyloxonium salt is proposed. Utility of this synthetic route has been demonstrated by preparing 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid through the reaction between 1-methylimidazole and triethyloxonium tetra-fluoroborate in anhydrous ether. (author)

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

Science.gov (United States)

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.

Large polarons in lead halide perovskites

Science.gov (United States)

Miyata, Kiyoshi; Meggiolaro, Daniele; Trinh, M. Tuan; Joshi, Prakriti P.; Mosconi, Edoardo; Jones, Skyler C.; De Angelis, Filippo; Zhu, X.-Y.

2017-01-01

Lead halide perovskites show marked defect tolerance responsible for their excellent optoelectronic properties. These properties might be explained by the formation of large polarons, but how they are formed and whether organic cations are essential remain open questions. We provide a direct time domain view of large polaron formation in single-crystal lead bromide perovskites CH3NH3PbBr3 and CsPbBr3. We found that large polaron forms predominantly from the deformation of the PbBr3− frameworks, irrespective of the cation type. The difference lies in the polaron formation time, which, in CH3NH3PbBr3 (0.3 ps), is less than half of that in CsPbBr3 (0.7 ps). First-principles calculations confirm large polaron formation, identify the Pb-Br-Pb deformation modes as responsible, and explain quantitatively the rate difference between CH3NH3PbBr3 and CsPbBr3. The findings reveal the general advantage of the soft [PbX3]− sublattice in charge carrier protection and suggest that there is likely no mechanistic limitations in using all-inorganic or mixed-cation lead halide perovskites to overcome instability problems and to tune the balance between charge carrier protection and mobility. PMID:28819647

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

Science.gov (United States)

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

Resonant halide perovskite nanoparticles

Science.gov (United States)

Tiguntseva, Ekaterina Y.; Ishteev, Arthur R.; Komissarenko, Filipp E.; Zuev, Dmitry A.; Ushakova, Elena V.; Milichko, Valentin A.; Nesterov-Mueller, Alexander; Makarov, Sergey V.; Zakhidov, Anvar A.

2017-09-01

The hybrid halide perovskites is a prospective material for fabrication of cost-effective optical devices. Unique perovskites properties are used for solar cells and different photonic applications. Recently, perovskite-based nanophotonics has emerged. Here, we consider perovskite like a high-refractive index dielectric material, which can be considered to be a basis for nanoparticles fabrication with Mie resonances. As a result, we fabricate and study resonant perovskite nanoparticles with different sizes. We reveal, that spherical nanoparticles show enhanced photoluminescence signal. The achieved results lay a cornerstone in the field of novel types of organic-inorganic nanophotonics devices with optical properties improved by Mie resonances.

A Cluster-Bethe lattice treatment for the F-center in alkali-halides

International Nuclear Information System (INIS)

Queiroz, S.L.A. de; Koiller, B.; Maffeo, B.; Brandi, H.S.

1977-01-01

The electronic structure of the F-center in alkali-halides with the NaCl structure has been studied using the Cluster-Bethe lattice method. The central cluster has been taken as constituted by the vacancy and the nearest- and second- neighbors to it, respectively, cations and anions. The optical transitions have been calculated and compared to experimental data on the location of the peak of the F-absorption band. The agreement obtained indicates that this method may be used to study properties of this defect in alkali halides [pt

Electrochemical specific adsorption of halides on Cu 111, 100, and 211: A Density Functional Theory study

International Nuclear Information System (INIS)

McCrum, Ian T.; Akhade, Sneha A.; Janik, Michael J.

2015-01-01

The specific adsorption of ions onto electrode surfaces can affect electrocatalytic reactions. Density functional theory is used to investigate the specific adsorption of aqueous F − , Cl − , Br − , and I − onto Cu (111), (100), and (211) surfaces. The adsorption is increasingly favorable in the order of F − < Cl − < Br − < I − . The adsorption has a weak dependence on the surface facet, with adsorption most favorable on Cu (100) and least favorable on Cu (111). Potential ranges where specific adsorption would be expected on each facet are reported. The thermodynamics of bulk copper halide (CuX, CuX 2 ) formation are also investigated as a function of potential. CuX formation occurs at potentials slightly more positive of halide specific adsorption and of copper oxidation in aqueous electrolytes. Specifically adsorbed halides and bulk CuX may be present during a variety of electrochemical reactions carried out over a Cu electrode in halide containing electrolyte solutions

First-principles study of γ-ray detector materials in perovskite halides

Science.gov (United States)

Im, Jino; Jin, Hosub; Stoumpos, Constantinos; Chung, Duck; Liu, Zhifu; Peters, John; Wessels, Bruce; Kanatzidis, Mercouri; Freeman, Arthur

2013-03-01

In an effort to search for good γ-ray detector materials, perovskite halide compounds containing heavy elements were investigated. Despite the three-dimensional network of the corner shared octahedra and the extended nature of the outermost shell, its strong ionic character leads to a large band gap, which is one of the essential criteria for γ-ray detector materials. Thus, considering high density and high atomic number, these pervoskite halides are possible candidate for γ-ray detector materials. We performed first-principles calculations to investigate electronic structures and thermodynamic properties of intrinsic defects in the selected perovskite halide, CsPbBr3. The screened-exchange local density approximation scheme was employed to correct the underestimation of the band gap in the LDA method. As a result, the calculated band gap of CsPbBr3 is found to be suitable for γ-ray detection. Furthermore, defect formation energy calculations allow us to predict thermodynamic and electronic properties of possible intrinsic defects, which affect detector efficiency and energy resolution. Supported by the office of Nonproliferation and Verification R &D under Contract No. DE-AC02-06CH11357

Single Crystals of Organolead Halide Perovskites: Growth, Characterization, and Applications

KAUST Repository

Peng, Wei

2017-01-01

Despite their outstanding charge transport characteristics, organolead halide perovskite single crystals grown by hitherto reported crystallization methods are not suitable for most optoelectronic devices due to their small aspect ratios

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

Science.gov (United States)

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.

Correlations between entropy and volume of melting in halide salts

International Nuclear Information System (INIS)

Akdeniz, Z.; Tosi, M.P.

1991-09-01

Melting parameters and transport coefficients in the melt are collated for halides of monovalent, divalent and trivalent metals. A number of systems show a deficit of entropy of melting relative to the linear relationships between entropy change and relative volume change on melting that are found to be approximately obeyed by a majority of halides. These behaviours are discussed on the basis of structural and transport data. The deviating systems are classified into three main classes, namely (i) fast-ion conductors in the high-temperature crystal phase such as AgI, (ii) strongly structured network-like systems such as ZnCl 2 , and (iii) molecular systems melting into associated molecular liquids such as SbCl 3 . (author). 35 refs, 1 fig., 3 tabs

Influence of electrode, buffer gas and control gear on metal halide lamp performance

International Nuclear Information System (INIS)

Lamouri, A; Naruka, A; Sulcs, J; Varanasi, C V; Brumleve, T R

2005-01-01

In this paper the influence of electrode composition, buffer gas fill pressure and control gear on the performance of metal halide lamps is investigated. It is shown that pure tungsten electrodes improve lumen maintenance and reduce voltage rise over lamp life. An optimum buffer gas fill pressure condition is discovered which allows for reduced electrode erosion during lamp starting as well as under normal operating conditions. Use of electronic control gear is shown to improve the performance of metal halide lamps

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

Science.gov (United States)

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.

Electrical conductivity of solutions of copper(II) nitrate crystalohydrate in dimethyl sulfoxide

Science.gov (United States)

Mamyrbekova, Aigul K.; Mamitova, A. D.; Mamyrbekova, Aizhan K.

2016-06-01

Conductometry is used to investigate the electric conductivity of Cu(NO3)2 ṡ 3H2O solutions in dimethyl sulfoxide in the 0.01-2.82 M range of concentrations and at temperatures of 288-318 K. The limiting molar conductivity of the electrolyte and the mobility of Cu2+ and NO 3 - ions, the effective coefficients of diffusion of copper(II) ions and nitrate ions, and the degree and constant of electrolytic dissociation are calculated for different temperatures from the experimental results. It is established that solutions containing 0.1-0.6 M copper nitrate trihydrate in DMSO having low viscosity and high electrical conductivity can be used in electrochemical deposition.

Copper(II) Thiosemicarbazone Complexes and Their Proligands upon UVA Irradiation: An EPR and Spectrophotometric Steady-State Study.

Science.gov (United States)

Hricovíni, Michal; Mazúr, Milan; Sîrbu, Angela; Palamarciuc, Oleg; Arion, Vladimir B; Brezová, Vlasta

2018-03-21

X- and Q-band electron paramagnetic resonance (EPR) spectroscopy was used to characterize polycrystalline Cu(II) complexes that contained sodium 5-sulfonate salicylaldehyde thiosemicarbazones possessing a hydrogen, methyl, ethyl, or phenyl substituent at the terminal nitrogen. The ability of thiosemicarbazone proligands to generate superoxide radical anions and hydroxyl radicals upon their exposure to UVA irradiation in aerated aqueous solutions was evidenced by the EPR spin trapping technique. The UVA irradiation of proligands in neutral or alkaline solutions and dimethylsulfoxide (DMSO) caused a significant decrease in the absorption bands of aldimine and phenolic chromophores. Mixing of proligand solutions with the equimolar amount of copper(II) ions resulted in the formation of 1:1 Cu(II)-to-ligand complex, with the EPR and UV-Vis spectra fully compatible with those obtained for the dissolved Cu(II) thiosemicarbazone complexes. The formation of the complexes fully inhibited the photoinduced generation of reactive oxygen species, and only subtle changes were found in the electronic absorption spectra of the complexes in aqueous and DMSO solutions upon UVA steady-state irradiation. The dark redox activity of copper(II) complexes and proligand/Cu(II) aqueous solutions towards hydrogen peroxide which resulted in the generation of hydroxyl radicals, was confirmed by spin trapping experiments.

DNA binding, cytotoxicity and apoptosis induction activity of a mixed-ligand copper(II) complex with taurine Schiff base and imidazole

Science.gov (United States)

Li, Mei; kong, Lin Lin; Gou, Yi; Yang, Feng; Liang, Hong

2014-07-01

A novel binuclear copper(II) complex (complex 1) with taurine Schiff base and imidazole has been synthesized and structurally characterized by single crystal X-ray diffraction, elemental analysis, ESI-MS spectrometry, UV-vis and IR spectroscopy. Single-crystal analysis revealed that 1 displays the sulfonate-bridged dinuclear copper(II) centers. Both copper atoms are five-coordinated and exhibit slightly distorted square pyramidal geometries. Each of copper atom is surrounded by three oxygen atoms and one nitrogen atom from different taurine Schiff base ligands, and one nitrogen atom from one imidazole ligand. The interaction between 1 and calf thymus DNA (CT-DNA) was investigated by UV-vis, fluorescence, circular dichroism (CD) spectra and agarose gel electrophoresis. The experimental results indicated that 1 could bind to CT-DNA via an intercalative mode and show efficient cleavage activity. In addition, 1 showed an antitumor effect on cell cycle and apoptosis. Flow cytometric analysis revealed that MGC-803 cells were arrested in the S phase after treatment with 1. Fluorescence microscopic observation indicated that 1 could induce apoptosis of MGC-803 cells.

Coumarin-Based Fluorescent Probes for Dual Recognition of Copper(II and Iron(III Ions and Their Application in Bio-Imaging

Directory of Open Access Journals (Sweden)

Olimpo García-Beltrán

2014-01-01

Full Text Available Two new coumarin-based “turn-off” fluorescent probes, (E-3-((3,4-dihydroxybenzylideneamino-7-hydroxy-2H-chromen-2-one (BS1 and (E-3-((2,4-dihydroxybenzylideneamino-7-hydroxy-2H-chromen-2-one (BS2, were synthesized and their detection of copper(II and iron(III ions was studied. Results show that both compounds are highly selective for Cu2+ and Fe3+ ions over other metal ions. However, BS2 is detected directly, while detection of BS1 involves a hydrolysis reaction to regenerate 3-amino-7-hydroxycoumarin (3 and 3,4-dihydroxybenzaldehyde, of which 3 is able to react with copper(II or iron(III ions. The interaction between the tested compounds and copper or iron ions is associated with a large fluorescence decrease, showing detection limits of ca. 10−5 M. Preliminary studies employing epifluorescence microscopy demonstrate that Cu2+ and Fe3+ ions can be imaged in human neuroblastoma SH-SY5Y cells treated with the tested probes.

Physicochemical properties of mixed phosphorus halides

International Nuclear Information System (INIS)

Sladkov, I.B.; Tugarinova, N.S.

1996-01-01

Certain physicochemical properties (thermodynamic characteristics at boiling point, critical constants, density of liquid on the saturation line) of mixed phosphorus halides (PI 3 , PI 2 F, PIF 2 , PI 2 Cl, PICl 2 , PI 1 Br, PIBr 2 , PIClF, PIBrCl, etc.) are determined by means of approximate methods. Reliability of the results obtained is confirmed by comparison of calculated and experimental data for phosphorus compounds of the same type. 7 refs., 3 figs., 4 tabs

Effect of Non-Stoichiometric Solution Chemistry on Improving the Performance of Wide-Bandgap Perovskite Solar Cells

Energy Technology Data Exchange (ETDEWEB)

Zhu, Kai [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Yang, Mengjin [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Kim, Donghoe [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Li, Zhen [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Reid, Obadiah G [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Yu, Yue [University of Toledo; Song, Zhaoning [University of Toledo; Zhao, Dewei [University of Toledo; Wang, Changlei [University of Toledo; Li, Liwei [ENN Energy Research Institute; ENN Solar Energy Co., Ltd.; Meng, Yuan [ENN Energy Research Institute; ENN Solar Energy Co., Ltd.; Guo, Ted [ENN Energy Research Institute; ENN Solar Energy Co., Ltd.; Yan, Yanfa [University of Toledo

2017-10-18

A high-efficiency wide-bandgap (WBG) perovskite solar cell is critical for developing perovskite-related (e.g., all-perovskite, perovskite/Si, or perovskite/Cu(In,Ga)Se2) tandem devices. Here, we demonstrate the use of non-stoichiometric precursor chemistry with excess methylammonium halides (MAX; X = I, Br, or Cl) for preparing high-quality ~1.75-eV FA0.83Cs0.17Pb(I0.6Br0.4)3 perovskite solar cells. Among various methylammonium halides, using excess MABr in the non-stoichiometric precursor exhibits the strongest effect on improving perovskite crystallographic properties and device characteristics without affecting the perovskite composition. In contrast, using excess MAI significantly reduces the bandgap of perovskite due to the replacement of Br with I. Using 40% excess MABr, we demonstrate a single-junction WBG perovskite solar cell with stabilized efficiency of 16.4%. We further demonstrate a 20.3%-efficient 4-terminal tandem device by using a 14.7%-efficient semi-transparent WBG perovskite top cell and an 18.6%-efficient unfiltered (5.6%-efficient filtered) Si bottom cell.

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

Science.gov (United States)

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.

Photovoltaic Rudorffites: Lead-Free Silver Bismuth Halides Alternative to Hybrid Lead Halide Perovskites.

Science.gov (United States)

Turkevych, Ivan; Kazaoui, Said; Ito, Eisuke; Urano, Toshiyuki; Yamada, Koji; Tomiyasu, Hiroshi; Yamagishi, Hideo; Kondo, Michio; Aramaki, Shinji

2017-10-09

Hybrid CPbX 3 (C: Cs, CH 3 NH 3 ; X: Br, I) perovskites possess excellent photovoltaic properties but are highly toxic, which hinders their practical application. Unfortunately, all Pb-free alternatives based on Sn and Ge are extremely unstable. Although stable and non-toxic C 2 ABX 6 double perovskites based on alternating corner-shared AX 6 and BX 6 octahedra (A=Ag, Cu; B=Bi, Sb) are possible, they have indirect and wide band gaps of over 2 eV. However, is it necessary to keep the corner-shared perovskite structure to retain good photovoltaic properties? Here, we demonstrate another family of photovoltaic halides based on edge-shared AX 6 and BX 6 octahedra with the general formula A a B b X x (x=a+3 b) such as Ag 3 BiI 6 , Ag 2 BiI 5 , AgBiI 4 , AgBi 2 I 7 . As perovskites were named after their prototype oxide CaTiO 3 discovered by Lev Perovski, we propose to name these new ABX halides as rudorffites after Walter Rüdorff, who discovered their prototype oxide NaVO 2 . We studied structural and optoelectronic properties of several highly stable and promising Ag-Bi-I photovoltaic rudorffites that feature direct band gaps in the range of 1.79-1.83 eV and demonstrated a proof-of-concept FTO/c-m-TiO 2 /Ag 3 BiI 6 /PTAA/Au (FTO: fluorine-doped tin oxide, PTAA: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], c: compact, m: mesoporous) solar cell with photoconversion efficiency of 4.3 %. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and coordination chemistry of 1,1,1-tris-(pyrid-2-yl)ethane.

Science.gov (United States)

Santoro, Amedeo; Sambiagio, Carlo; McGowan, Patrick C; Halcrow, Malcolm A

2015-01-21

A new synthesis of 1,1,1-tris(pyrid-2-yl)ethane (L), and a survey of its coordination chemistry, are reported. The complexes [ML2](n+) (M(n+) = Fe(2+), Co(2+), Co(3+), Cu(2+) and Ag(+)), [PdCl2L] and [CuI(L)] have all been crystallographically characterised. Noteworthy results include an unusual square planar silver(i) complex [Ag(L)2]X (X(-) = NO3(-) and SbF6(-)); the oxidative fixation of aerobic CO2 by [CuI(L)] to yield [Cu2I(L)2(μ-CO3)]2[CuI3] and [Cu(CO3)(L)]; and, water/carbonato tape and water/iodo layer hydrogen bonding networks in hydrate crystals of two of the copper(ii) complexes. Cyclic voltammetric data on [Fe(L)2](2+) and [Co(L)2](2+/3+) imply that the peripheral methyl substituent has a weak influence on the ligand field exerted by L onto a coordinated metal ion.

Advances and Promises of Layered Halide Hybrid Perovskite Semiconductors

NARCIS (Netherlands)

Pedesseau, Laurent; Sapori, Daniel; Traore, Boubacar; Robles, Roberto; Fang, Hong-Hua; Loi, Maria Antonietta; Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean-Christophe; Neukirch, Amanda; Tretiak, Sergei; Mohite, Aditya D.; Katan, Claudine; Even, Jacky; Kepenekian, Mikael

2016-01-01

Layered halide hybrid organic inorganic perovskites (HOP) have been the subject of intense investigation before the rise of three-dimensional (3D) HOP and their impressive performance in solar cells. Recently, layered HOP have also been proposed as attractive alternatives for photostable solar cells

Strong Carrier-Phonon Coupling in Lead Halide Perovskite Nanocrystals

NARCIS (Netherlands)

Iaru, Claudiu M; Geuchies, Jaco J|info:eu-repo/dai/nl/370526090; Koenraad, Paul M; Vanmaekelbergh, Daniël|info:eu-repo/dai/nl/304829137; Silov, Andrei Yu

2017-01-01

We highlight the importance of carrier-phonon coupling in inorganic lead halide perovskite nanocrystals. The low-temperature photoluminescence (PL) spectrum of CsPbBr3 has been investigated under a nonresonant and a nonstandard, quasi-resonant excitation scheme, and phonon replicas of the main PL

Homocoupling of aryl halides in flow: Space integration of lithiation and FeCl3 promoted homocoupling

Directory of Open Access Journals (Sweden)

Aiichiro Nagaki

2011-08-01

Full Text Available The use of FeCl3 resulted in a fast homocoupling of aryllithiums, and this enabled its integration with the halogen–lithium exchange reaction of aryl halides in a flow microreactor. This system allows the homocoupling of two aryl halides bearing electrophilic functional groups, such as CN and NO2, in under a minute.

Self-trapped holes in alkali silver halide crystals

International Nuclear Information System (INIS)

Awano, T.; Ikezawa, M.; Matsuyama, T.

1995-01-01

γ-Ray irradiation at 77 K induces defects in M 2 AgX 3 (M=Rb, K and NH 4 ; X=Br and I) crystals. The irradiation induces self-trapped holes of the form of I 0 in the case of alkali silver iodides, and (halogen) 2 - and (halogen) 0 in the case of ammonium silver halides. The (halogen) 0 is weakly coupled with the nearest alkali metal ion or ammonium ion. It is able to be denoted as RbI + , KI + , NH 4 I + or NH 4 Br + . The directions of hole distribution of (halogen) 2 - and (halogen) 0 were different in each case of the alkali silver iodides, ammonium silver halides and mixed crystal of them. The (halogen) 0 decayed at 160 K in annealing process. The (halogen) 2 - was converted into another form of (halogen) 2 - at 250 K and this decayed at 310 K. A formation of metallic layers was observed on the crystal surface parallel with the c-plane of (NH 4 ) 2 AgI 3 irradiated at room temperature. (author)

Large polarons in lead halide perovskites

OpenAIRE

Miyata, Kiyoshi; Meggiolaro, Daniele; Trinh, M. Tuan; Joshi, Prakriti P.; Mosconi, Edoardo; Jones, Skyler C.; De Angelis, Filippo; Zhu, X.-Y.

2017-01-01

Lead halide perovskites show marked defect tolerance responsible for their excellent optoelectronic properties. These properties might be explained by the formation of large polarons, but how they are formed and whether organic cations are essential remain open questions. We provide a direct time domain view of large polaron formation in single-crystal lead bromide perovskites CH3NH3PbBr3 and CsPbBr3. We found that large polaron forms predominantly from the deformation of the PbBr3 ? framewor...

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

Science.gov (United States)

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

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

International Nuclear Information System (INIS)

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

2000-01-01

Characteristic features of the coordination chemistry of Cu(I) and mechanisms of catalytic conversions of alkynes in the CuCl-MCl-H 2 O-HC≡CR system (MCl is alkali metal or ammonium chloride or amine hydrochloride; R=H, CH 2 OH, CH=CH 2 , 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.

and copper(II)

Indian Academy of Sciences (India)

Unknown

(II) and copper(II)–zinc(II) complexes. SUBODH KUMAR1, R N PATEL1*, P V KHADIKAR1 and. K B PANDEYA2. 1 Department of Chemistry, APS University, Rewa 486 003, India. 2 CSJM University, Kanpur 208 016, India e-mail: (R N Patel) ...

Copper(II) and molybdenum(VI) complexes of a tridentate ONN donor isothiosemicarbazone: synthesis, characterization, X-ray, TGA and DFT

Czech Academy of Sciences Publication Activity Database

Fasihizad, A.; Akbari, A.; Ahmadi, M.; Dušek, Michal; Henriques, Margarida Isabel Sousa; Pojarová, Michaela

2016-01-01

Roč. 115, Sep (2016), s. 297-305 ISSN 0277-5387 R&D Projects: GA ČR(CZ) GA14-03276S; GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : isothiosemicarbazone * Copper(II) complex * molybdenum(VI) complex * crystal structure * DFT Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.926, year: 2016

Empirical formula for the parameters of metallic monovalent halides ...

African Journals Online (AJOL)

By collating the data on melting properties and transport coefficients obtained from various experiments and theories for certain halides of monovalent metals, allinclusive linear relationship has been fashioned out. This expression holds between the change in entropy and volume on melting; it is approximately obeyed by ...

Spectroscopy on metal-halide lamps under varying gravity conditions

NARCIS (Netherlands)

Flikweert, A.J.

2008-01-01

Worldwide, 20% of all electricity is used for lighting. For this reason, efficient lamps are economically and ecologically important. High intensity discharge (HID) lamps are efficient lamps. The most common HID lamp these days is the metal-halide (MH) lamp. MH lamps have a good colour rendering

Dislocation unpinning model of acoustic emission from alkali halide ...

Indian Academy of Sciences (India)

AE) from alkali halide crystals. Equations are derived for the strain dependence of the transient AE pulse rate, peak value of the AE pulse rate and the total number of AE pulse emitted. It is found that the AE pulse rate should be maximum for a ...

Halide Perovskites: New Science or ``only'' future Energy Converters?

Science.gov (United States)

Cahen, David

Over the years many new ideas and systems for photovoltaic, PV, solar to electrical energy conversion have been explored, but only a few have really impacted PV's role as a more sustainable, environmentally less problematic and safer source of electrical power than fossil or nuclear fuel-based generation. Will Halide Perovskites, HaPs, be able to join the very select group of commercial PV options? To try to address this question, we put Halide Perovskite(HaP) cells in perspective with respect to other PV cells. Doing so also allows to identify fundamental scientific issues that can be important for PV and beyond. What remains to be seen is if those issues lead to new science or scientific insights or additional use of existing models. Being more specific is problematic, given the fact that this will be 4 months after writing this abstract. Israel National Nano-initiative, Weizmann Institute of Science's Alternative sustainable Energy Research Initiative; Israel Ministries of -Science and of -Infrastructure, Energy & Water.

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

Science.gov (United States)

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.

The nature of dynamic disorder in lead halide perovskite crystals (Conference Presentation)

Science.gov (United States)

Yaffe, Omer; Guo, Yinsheng; Hull, Trevor; Stoumpos, Costas; Tan, Liang Z.; Egger, David A.; Zheng, Fan; Szpak, Guilherme; Semonin, Octavi E.; Beecher, Alexander N.; Heinz, Tony F.; Kronik, Leeor; Rappe, Andrew M.; Kanatzidis, Mercouri G.; Owen, Jonathan S.; Pimenta, Marcos A.; Brus, Louis E.

2016-09-01

We combine low frequency Raman scattering measurements with first-principles molecular dynamics (MD) to study the nature of dynamic disorder in hybrid lead-halide perovskite crystals. We conduct a comparative study between a hybrid (CH3NH3PbBr3) and an all-inorganic lead-halide perovskite (CsPbBr3). Both are of the general ABX3 perovskite formula, and have a similar band gap and structural phase sequence, orthorhombic at low temperature, changing first to tetragonal and then to cubic symmetry as temperature increases. In the high temperature phases, we find that both compounds show a pronounced Raman quasi-elastic central peak, indicating that both are dynamically disordered.

Organometallic halide perovskite single crystals having low deffect density and methods of preparation thereof

KAUST Repository

Bakr, Osman M.

2016-02-18

The present disclosure presents a method of making a single crystal organometallic halide perovskites, with the formula: AMX3, wherein A is an organic cation, M is selected from the group consisting of: Pb, Sn, Cu, Ni, Co, Fe, Mn, Pd, Cd, Ge, and Eu, and X is a halide. The method comprises the use of two reservoirs containing different precursors and allowing the vapor diffusion from one reservoir to the other one. A solar cell comprising said crystal is also disclosed.

Cuprous halides semiconductors as a new means for highly efficient light-emitting diodes

Science.gov (United States)

Ahn, Doyeol; Park, Seoung-Hwan

2016-01-01

In group-III nitrides in use for white light-emitting diodes (LEDs), optical gain, measure of luminous efficiency, is very low owing to the built-in electrostatic fields, low exciton binding energy, and high-density misfit dislocations due to lattice-mismatched substrates. Cuprous halides I-VII semiconductors, on the other hand, have negligible built-in field, large exciton binding energies and close lattice matched to silicon substrates. Recent experimental studies have shown that the luminescence of I-VII CuCl grown on Si is three orders larger than that of GaN at room temperature. Here we report yet unexplored potential of cuprous halides systems by investigating the optical gain of CuCl/CuI quantum wells. It is found that the optical gain and the luminescence are much larger than that of group III-nitrides due to large exciton binding energy and vanishing electrostatic fields. We expect that these findings will open up the way toward highly efficient cuprous halides based LEDs compatible to Si technology. PMID:26880097

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

Science.gov (United States)

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.

Third-order elastic moduli for alkali-halide crystals possessing the sodium chloride structure

International Nuclear Information System (INIS)

Ray, U.

2010-01-01

The values of third-order elastic moduli for alkali halides, having NaCl-type crystal structure are calculated according to the Born-Mayer potential model, considering the repulsive interactions up to the second nearest neighbours and calculating the values of the potential parameters for each crystal, independently, from the compressibility data. This work presents the first published account of the calculation of the third-order elastic moduli taking the actual value of the potential parameter unlike the earlier works. Third-order elastic constants have been computed for alkali halides at 0 and 300 K. The results of the third-order elastic constants are compared with the available experimental and theoretical data. Very good agreement between experimental and theoretical third-order elastic constant data (except C 123 ) is found. We have also computed the values of the pressure derivatives of second-order elastic constants and Anderson-Grueneisen parameter for alkali halides, which agree reasonably well with the experimental values, indicating the satisfactory nature of our computed data for third-order elastic constants.

Inhibition of mild steel corrosion in acidic medium using synthetic and naturally occurring polymers and synergistic halide additives

Energy Technology Data Exchange (ETDEWEB)

Umoren, S.A. [Department of Chemistry, Faculty of Science, University of Uyo, P.M.B 1017 Uyo (Nigeria)], E-mail: saviourumoren@yahoo.com; Ogbobe, O.; Igwe, I.O. [Department of Polymer and Textile Engineering, School of Engineering and Engineering Technology, Federal University of Technology, P.M.B. 1526 Owerri (Nigeria); Ebenso, E.E. [Department of Chemistry and Chemical Technology, National University of Lesotho, P. O. Roma180, Lesotho (South Africa)

2008-07-15

The corrosion inhibition of mild steel in H{sub 2}SO{sub 4} in the presence of gum arabic (GA) (naturally occurring polymer) and polyethylene glycol (PEG) (synthetic polymer) was studied using weight loss, hydrogen evolution and thermometric methods at 30-60 deg. C. PEG was found to be a better inhibitor for mild steel corrosion in acidic medium than GA. The effect of addition of halides (KCl, KBr and KI) was also studied. Results obtained showed that inhibition efficiency (I%) increased with increase in GA and PEG concentration, addition of halides and with increase in temperature. Increase in inhibition efficiency (I%) and degree of surface coverage ({theta}) was found to follow the trend Cl{sup -} < Br{sup -} < I{sup -} which indicates that the radii and electronegativity of the halide ions play a significant role in the adsorption process. GA and PEG alone and in combination with halides were found to obey Temkin adsorption isotherm. Phenomenon of chemical adsorption is proposed from the trend of inhibition efficiency with temperature and values {delta}G{sub ads}{sup 0} obtained. The synergism parameter, S{sub I} evaluated is found to be greater than unity indicating that the enhanced inhibition efficiency caused by the addition of halides is only due to synergism.

Preparation of gold microparticles using halide ions in bulk block copolymer phases via photoreduction

International Nuclear Information System (INIS)

Cha, Sang-Ho; Kim, Ki-Hyun; Lee, Won-Ki; Lee, Jong-Chan

2009-01-01

Gold microparticles were prepared from the gold salt in the solid bulk phase of a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer via a photoreduction process in the presence of halide ions. The shapes and sizes of the gold microparticles were found to be dependent on the types and amount of halide ions as well as the types of cations used due to the combined effects of the adsorption power and oxidative dissolution ability of the additives on gold surfaces. Gold nanorods were obtained when poly(ethylene oxide) was used instead of the block copolymer. This suggests that the poly(propylene oxide) (PPO) parts in the block copolymer are essential for the formation of gold microparticles, even though the degree of the direct interaction between the PPO blocks and gold salt is not significant. - Graphical abstract: Gold microparticles were successfully prepared using halide ions as additives in the polymeric bulk phase via photoreduction with the glow lamp irradiation.

Demixing in a metal halide lamp, results from modeling

NARCIS (Netherlands)

Beks, M.L.; Hartgers, A.; Mullen, van der J.J.A.M.; Veldhuizen, van E.M.

2005-01-01

Metal Halide (MH) lamps are high pressure discharge devices, containing a complex chemical mixture, to emit light on a broad spectrum while maintaining good efficacies. Lamps of this type were first exhibited by General Electric at the 1964 World Fair in New York [1]. They typically consist of an

Crystal growth, structure and phase studies on gold halides

NARCIS (Netherlands)

Janssen, Eugenius Maria Wilhelmus Janssen

1977-01-01

Only very corrosive substances attack gold, the most noble metal. In this study the reactivity and the phase diagrams of gold with the halogens chlorine, bromine and iodine have been investigated. owing to the noble behaviour of gold, its halides are sensitive to heat; on heating they decompose into

Growth and Characterization of PDMS-Stamped Halide Perovskite Single Microcrystals

NARCIS (Netherlands)

Khoram, P.; Brittman, S.; Dzik, W.I.; Reek, J.N.H.; Garneett, E.C.

2016-01-01

Recently, halide perovskites have attracted considerable attention for optoelectronic applications, but further progress in this field requires a thorough understanding of the fundamental properties of these materials. Studying perovskites in their single-crystalline form provides a model system for

Synergistic effect of halide ions on the corrosion inhibition of aluminium in H2SO4 using 2-acetylphenothiazine

International Nuclear Information System (INIS)

Ebenso, E.E.

2003-01-01

The corrosion inhibition of aluminium in H 2 SO 4 in the presence of 2-acetylphenothiazine (2APTZ) at temperature range of 30-60 deg. C was studied using the weight loss and thermometric techniques. The effect of addition of halides (KCl, KBr, KI) is also reported. The inhibition efficiency (I, %) increased with increase in concentration of 2APTZ. The addition of the halides increased the inhibition efficiency to a considerable extent. The temperature increased the corrosion rate and inhibition efficiency in the range 30-60 deg. C in the absence and presence of the inhibitor and halides. Phenomenon of chemical adsorption is proposed. Flory-Huggins adsorption isotherm equation was obeyed at all the concentrations studied. The decrease in inhibition efficiency (and surface coverage values) was found to be in the order I - >Br - >Cl - which clearly indicates that the radii and the electronegativity of halides play a significant role in the adsorption process. All the data acquired reveal that 2APTZ acts as an inhibitor in the acid environment from the two techniques used. The synergistic effect of 2APTZ and halide ions is discussed

Trap-Free Hot Carrier Relaxation in Lead–Halide Perovskite Films

KAUST Repository

Bretschneider, Simon A.; Laquai, Fré dé ric; Bonn, Mischa

2017-01-01

Photovoltaic devices that employ lead-halide perovskites as photoactive materials exhibit power conversion efficiencies of 22%. One of the potential routes to go beyond the current efficiencies is to extract charge carriers that carry excess energy, that is, nonrelaxed or

Trap-Free Hot Carrier Relaxation in Lead–Halide Perovskite Films

KAUST Repository

Bretschneider, Simon A.

2017-05-08

Photovoltaic devices that employ lead-halide perovskites as photoactive materials exhibit power conversion efficiencies of 22%. One of the potential routes to go beyond the current efficiencies is to extract charge carriers that carry excess energy, that is, nonrelaxed or

Halides of BET-TTF: novel hydrated molecular metals

Energy Technology Data Exchange (ETDEWEB)

Laukhina, E.; Ribera, E.; Vidal-Gancedo, J.; Canadell, E.; Veciana, J.; Rovira, C. [Universidad Autonoma de Barcelona, Bellaterra (Spain). Inst. de Ciencia de Materials; Khasanov, S.; Zorina, L.; Shibaeva, R. [Rossijskaya Akademiya Nauk, Chernogolovka (Russian Federation). Inst. Fiziki Tverdogo Tela; Laukhin, V. [Inst. of Problems of Chemical Physics, RAS, Chernogolovka (Russian Federation); Honold, M.; Nam, M.-S.; Singleton, J. [Clarendon Lab., Univ. of Oxford (United Kingdom)

2000-01-07

A hint of superconducting transition has been observed for the first time in a cation radical salt derived from bisethylenethio-tetrathiafulvalene (BET-TTF), the salt (BET-TTF){sub 2}Br.3H{sub 2}O. Here the synthesis, X-ray structure, and physical properties of two hydrated halides of BET-TTF that are isostructural and present stable metallic properties are described. (orig.)

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

KAUST Repository

Adinolfi, Valerio

2017-10-12

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.

Building up an electrocatalytic activity scale of cathode materials for organic halide reductions

International Nuclear Information System (INIS)

Bellomunno, C.; Bonanomi, D.; Falciola, L.; Longhi, M.; Mussini, P.R.; Doubova, L.M.; Di Silvestro, G.

2005-01-01

A wide investigation on the electrochemical activity of four model organic bromides has been carried out in acetonitrile on nine cathodes of widely different affinity for halide anions (Pt, Zn, Hg, Sn, Bi, Pb, Au, Cu, Ag), and the electrocatalytic activities of the latter have been evaluated with respect to three possible inert reference cathode materials, i.e. glassy carbon, boron-doped diamond, and fluorinated boron-doped diamond. A general electrocatalytic activity scale for the process is proposed, with a discussion on its modulation by the configuration of the reacting molecule, and its connection with thermodynamic parameters accounting for halide adsorption

Isolation of a new two-dimensional honeycomb carbonato-bridged copper(II) complex exhibiting long-range ferromagnetic ordering.

Science.gov (United States)

Majumder, Arpi; Choudhury, Chirantan Roy; Mitra, Samiran; Rosair, Georgina M; El Fallah, M Salah; Ribas, Joan

2005-04-28

Atmospheric CO2 fixation by an aqueous solution containing Cu(ClO4)2.6H2O and 4-aminopyridine (4-apy) yields a novel example of a two-dimensional mu3-CO3 bridged copper(II) complex {[Cu(4-apy)2]3(mu3-CO3)2(ClO4)2.(1/2)CH3OH}n that has been characterized by IR, UV and X-ray crystallography; preliminary magnetic measurements show that complex exhibits long-range ordered ferromagnetic coupling.

Demixing in a metal halide lamp, results from modelling

NARCIS (Netherlands)

Beks, M.L.; Hartgers, A.; Mullen, van der J.J.A.M.

2006-01-01

Convection and diffusion in the discharge region of a metal halide lamp is studied using a computer model built with the plasma modeling package Plasimo. A model lamp contg. mercury and sodium iodide is studied. The effects of the total lamp pressure on the degree of segregation of the light

Fullerenes doped with metal halides

International Nuclear Information System (INIS)

Martin, T.P.; Heinebrodt, M.; Naeher, U.; Goehlich, H.; Lange, T.; Schaber, H.

1993-01-01

The cage-like structure of fullerenes is a challenge to every experimental to put something inside - to dope the fullerenes. In fact, the research team that first identified C 60 as a football-like molecule quickly succeeded in trapping metal atoms inside and in shrinking the cage around this atom by photofragmentation. In this paper we report the results of ''shrink-wrapping'' the fullerenes around metal halide molecules. Of special interest is the critical size (the minimum number of carbon atoms) that can still enclose the dopant. A rough model for the space available inside a carbon cage gives good agreement with the measured shrinking limits. (author). 8 refs, 6 figs

Iron halide mediated atom transfer radical polymerization of methyl methacrylate with N-Alkyl-2-pyridylmethanimine as the ligand

NARCIS (Netherlands)

Zhang, H.; Schubert, U.S.

2004-01-01

The controlled atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) catalyzed by iron halide/N-(n-hexyl)-2-pyridylmethanimine (NHPMI) is described. The ethyl 2-bromoisobutyrate (EBIB)-initiated ATRP with [MMA]0/[EBIB]0/[iron halide]0/[NHPMI]0 = 150/1/1/2 was better controlled in

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

Science.gov (United States)

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.

Solution enthalpies of alkali metal halides in water and heavy water mixtures with dimethyl sulfoxide

International Nuclear Information System (INIS)

Egorov, G.I.

1994-01-01

Solution enthalpies of CsF, LiCl, NaI, CsI and some other halides of alkali metals and tetrabutylammonium have been measured by the method of calorimetry. Standard solution enthalpies of all alkali metals (except rubidium) halides in water and heavy water mixtures with dimethylsulfoxide at 298.15 K have been calculated. Isotopic effects in solvation enthalpy of the electrolytes mentioned in aqueous solutions of dimethylsulfoxide have been discussed. 29 refs., 2 figs., 4 tabs

Barium halide nanocrystals in fluorozirconate based glass ceramics for scintillation application

Energy Technology Data Exchange (ETDEWEB)

Selling, J.

2007-07-01

Europium (Eu)-activated barium halide nanocrystals in fluorozirconate based glass ceramics represent a promising class of Xray scintillators. The scintillation in these glass ceramics is mainly caused by the emission of divalent Eu incorporated in hexagonal BaCl{sub 2} nanocrystals which are formed in the glass matrix upon appropriate annealing. Experiments with cerium (Ce)-activated fluorozironate glass ceramics showed that Ce is an interesting alternative. In order to get a better understanding of the scintillation mechanism in Eu- or Ce-activated barium halide nanocrystals, an investigation of the processes in the corresponding bulk material is essential. The objective of this thesis is the investigation of undoped, Eu-, and Ce-doped barium halides by X-ray excited luminescence (XL), pulse height, and scintillation decay spectra. That will help to figure out which of these crystals has the most promising scintillation properties and would be the best nanoparticles for the glass ceramics. Furthermore, alternative dopants like samarium (Sm) and manganese (Mn) were also investigated. Besides the above-mentioned optical investigation electron paramagnetic resonance (EPR) and Moessbauer measurements were carried out in order to complete the picture of Eu-doped barium halides. The EPR data of Eu-doped BaI{sub 2} is anticipated to yield more information about the crystal field and crystal structure that will help to understand the charge carrier process during the scintillation process. The main focus of the Moessbauer investigations was set on the Eu-doped fluorochlorozirconate glass ceramics. The results of this investigation should help to improve the glass ceramics. The Eu{sup 2+}/Eu{sup 3+} ratio in the glass ceramics should be determined and optimize favor of the Eu{sup 2+}. We also want to distinguish between Eu{sup 2+} in the glass matrix and Eu{sup 2+} in the nanocrystals. For a better understanding of Moessbauer spectroscopy on Eu also measurements on Eu in a

Barium halide nanocrystals in fluorozirconate based glass ceramics for scintillation application

International Nuclear Information System (INIS)

Selling, J.

2007-01-01

Europium (Eu)-activated barium halide nanocrystals in fluorozirconate based glass ceramics represent a promising class of Xray scintillators. The scintillation in these glass ceramics is mainly caused by the emission of divalent Eu incorporated in hexagonal BaCl 2 nanocrystals which are formed in the glass matrix upon appropriate annealing. Experiments with cerium (Ce)-activated fluorozironate glass ceramics showed that Ce is an interesting alternative. In order to get a better understanding of the scintillation mechanism in Eu- or Ce-activated barium halide nanocrystals, an investigation of the processes in the corresponding bulk material is essential. The objective of this thesis is the investigation of undoped, Eu-, and Ce-doped barium halides by X-ray excited luminescence (XL), pulse height, and scintillation decay spectra. That will help to figure out which of these crystals has the most promising scintillation properties and would be the best nanoparticles for the glass ceramics. Furthermore, alternative dopants like samarium (Sm) and manganese (Mn) were also investigated. Besides the above-mentioned optical investigation electron paramagnetic resonance (EPR) and Moessbauer measurements were carried out in order to complete the picture of Eu-doped barium halides. The EPR data of Eu-doped BaI 2 is anticipated to yield more information about the crystal field and crystal structure that will help to understand the charge carrier process during the scintillation process. The main focus of the Moessbauer investigations was set on the Eu-doped fluorochlorozirconate glass ceramics. The results of this investigation should help to improve the glass ceramics. The Eu 2+ /Eu 3+ ratio in the glass ceramics should be determined and optimize favor of the Eu 2+ . We also want to distinguish between Eu 2+ in the glass matrix and Eu 2+ in the nanocrystals. For a better understanding of Moessbauer spectroscopy on Eu also measurements on Eu in a CaF 2 host lattice were carried

Metal Halide Perovskite Polycrystalline Films Exhibiting Properties of Single Crystals

NARCIS (Netherlands)

Brenes, Roberto; Guo, D.; Osherov, Anna; Noel, Nakita K.; Eames, Christopher; Hutter, E.M.; Pathak, Sandeep K.; Niroui, Farnaz; Friend, Richard H.; Islam, M. Saiful; Snaith, Henry J.; Bulović, Vladimir; Savenije, T.J.; Stranks, Samuel D.

2017-01-01

Metal halide perovskites are generating enormous excitement for use in solar cells and light-emission applications, but devices still show substantial non-radiative losses. Here, we show that by combining light and atmospheric treatments, we can increase the internal luminescence quantum

Non-covalent interactions in 2-methylimidazolium copper(II) complex (MeImH)2[Cu(pfbz)4]: Synthesis, characterization, single crystal X-ray structure and packing analysis

Science.gov (United States)

Sharma, Raj Pal; Saini, Anju; Kumar, Santosh; Kumar, Jitendra; Sathishkumar, Ranganathan; Venugopalan, Paloth

2017-01-01

A new anionic copper(II) complex, (MeImH)2 [Cu(pfbz)4] (1) where, MeImH = 2-methylimidazolium and pfbz = pentafluorobenzoate has been isolated by reacting copper(II) sulfate pentahydrate, pentafluorobenzoic acid and 2-methylimidazole in ethanol: water mixture in 1:2:2 molar ratio. This complex 1 has been characterized by elemental analysis, thermogravimetric analysis, spectroscopic techniques (UV-Vis, FT-IR) and conductance measurements. The complex salt crystallizes in monoclinic crystal system with space group C2/c. Single crystal X-ray structure determination revealed the presence of discrete ions: [Cu(pfbz)4]2- anion and two 2-methylimidazolium cation (C4H7N2)+. The crystal lattice is stabilized by strong hydrogen bonding and F⋯F interactions between cationic-anionic and the anionic-anionic moieties respectively, besides π-π interactions.

Melting and liquid structure of polyvalent metal halides

International Nuclear Information System (INIS)

Tosi, M.P.

1992-08-01

A short review is given of recent progress in determining and understanding liquid structure types and melting mechanisms for halides of polyvalent metals. The nature of the preferred local coordination for the polyvalent metal ion in the melt can usually be ascertained from data on liquid mixtures with halogen-donating alkali halides. The stability of these local coordination states and the connectivity that arises between them in the approach to the pure melt determines the character of its short-range and possible medium-range order. A broad classification of structural and melting behaviours can be given on the basis of measured melting parameters and transport coefficients for many compounds, in combination with the available diffraction data on the liquid structure of several compounds. Correlations have been shown to exist with a simple indicator of the nature of the chemical bond and also with appropriate parameters of ionic models, wherever the latter are usefully applicable for semiquantitative calculations of liquid structure. Consequences on the mechanisms for valence electron localization in solutions of metallic elements into strongly structured molten salts are also briefly discussed. (author). 46 refs, 4 figs, 2 tabs

Mechanoluminescence response to the plastic flow of coloured alkali halide crystals

International Nuclear Information System (INIS)

Chandra, B.P.; Bagri, A.K.; Chandra, V.K.

2010-01-01

The present paper reports the luminescence induced by plastic deformation of coloured alkali halide crystals using pressure steps. When pressure is applied onto a γ-irradiated alkali halide crystal, then initially the mechanoluminescence (ML) intensity increases with time, attains a peak value and later on it decreases with time. The ML of diminished intensity also appears during the release of applied pressure. The intensity I m corresponding to the peak of ML intensity versus time curve and the total ML intensity I T increase with increase in value of the applied pressure. The time t m corresponding to the ML peak slightly decreases with the applied pressure. After t m , initially the ML intensity decreases at a fast rate and later on it decreases at a slow rate. The decay time of the fast decrease in the ML intensity is equal to the pinning time of dislocations and the decay time for the slow decrease of ML intensity is equal to the diffusion time of holes towards the F-centres. The ML intensity increases with the density of F-centres and it is optimum for a particular temperature of the crystals. The ML spectra of coloured alkali halide crystals are similar to the thermoluminescence and afterglow spectra. The peak ML intensity and the total ML intensity increase drastically with the applied pressure following power law, whereby the pressure dependence of the ML intensity is related to the work-hardening exponent of the crystals. The ML also appears during the release of the applied pressure because of the movement of dislocation segments and movements of dislocation lines blocked under pressed condition. On the basis of the model based on the mechanical interaction between dislocation and F-centres, expressions are derived for the ML intensity, which are able to explain different characteristics of the ML. From the measurements of the plastico ML induced by the application of loads on γ-irradiated alkali halide crystals, the pinning time of dislocations

Manganese-Catalyzed Cross-Coupling of Aryl Halides and Grignard Reagents by a Radical Mechanism

DEFF Research Database (Denmark)

Antonacci, Giuseppe; Ahlburg, Andreas; Fristrup, Peter

2017-01-01

The substrate scope and the mechanism have been investigated for the MnCl2-catalyzed cross-coupling reaction between aryl halides and Grignard reagents. The transformation proceeds rapidly and in good yield when the aryl halide component is an aryl chloride containing a cyano or an ester group....... Two radical-clock experiments were carried out, and in both cases an intermediate aryl radical was successfully trapped. The cross-coupling reaction is therefore believed to proceed by an SRN1 mechanism, with a triorganomanganate complex serving as the most likely nucleophile and single-electron donor...

The electronic structure of the F-center in alkali-halides-The Bethe cluster - lattice

International Nuclear Information System (INIS)

Queiroz, S.L.A. de.

1977-07-01

The electronic structure of the F-center in alkali-halides with the NaCl structure has been studied using the Bethe Cluster lattice method. The central cluster has been taken as constituted by the vacancy and the nearest- and second-neighbors to it, respectively cations and anions. The optical transitions have been calculated and compared to experimental data on the location of the peak of the F-absorption band. The agreement obtained indicates that this method may be used to study properties of this defect in alkali halides. (Author) [pt

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

Science.gov (United States)

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).

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

Science.gov (United States)

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.

The first row anomaly and recoupled pair bonding in the halides of the late p-block elements.

Science.gov (United States)

Dunning, Thom H; Woon, David E; Leiding, Jeff; Chen, Lina

2013-02-19

The dramatic differences between the properties of molecules formed from the late p-block elements of the first row of the periodic table (N-F) and those of the corresponding elements in subsequent rows is well recognized as the first row anomaly. Certain properties of the atoms, such as the relative energies and spatial extents of the ns and np orbitals, can explain some of these differences, but not others. In this Account, we summarize the results of our recent computational studies of the halides of the late p-block elements. Our studies point to a single underlying cause for many of these differences: the ability of the late p-block elements in the second and subsequent rows of the periodic table to form recoupled pair bonds and recoupled pair bond dyads with very electronegative ligands. Recoupled pair bonds form when an electron in a singly occupied ligand orbital recouples the pair of electrons in a doubly occupied lone pair orbital on the central atom, leading to a central atom-ligand bond. Recoupled pair bond dyads occur when a second ligand forms a bond with the orbital left over from the initial recoupled pair bond. Recoupled pair bonds and recoupled pair bond dyads enable the late p-block elements to form remarkably stable hypervalent compounds such as PF(5) and SF(6) and lead to unexpected excited states in smaller halides of the late p-block elements such as SF and SF(2). Recoupled pair bonding also causes the F(n-1)X-F bond energies to oscillate dramatically once the normal valences of the central atoms have been satisfied. In addition, recoupled pair bonding provides a lower-energy pathway for inversion in heavily fluorinated compounds (PF(3) and PF(2)H, but not PH(2)F and PH(3)) and leads to unusual intermediates and products in reactions involving halogens and late p-block element compounds, such as (CH(3))(2)S + F(2). Although this Account focuses on the halides of the second row, late p-block elements, recoupled pair bonds and recoupled pair

Thermodynamics of Small Alkali Metal Halide Cluster Ions: Comparison of Classical Molecular Simulations with Experiment and Quantum Chemistry

Energy Technology Data Exchange (ETDEWEB)

Vlcek, Lukas [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Uhlik, Filip [Charles Univ., Prague (Czech Republic); Moucka, Filip [Purkinje Univ. (Czech Republic); Nezbeda, Ivo [Purkinje Univ. (Czech Republic); Academy of Sciences of the Czech Republic (ASCR), Prague (Czech Republic); Chialvo, Ariel A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2015-12-16

We evaluate the ability of selected classical molecular models to describe the thermodynamic and structural aspects of gas-phase hydration of alkali halide ions and the formation of small water clusters. To understand the effect of many-body interactions (polarization) and charge penetration effects on the accuracy of a force field, we perform Monte Carlo simulations with three rigid water models using different functional forms to account for these effects: (i) point charge non-polarizable SPC/E, (ii) Drude point charge polarizable SWM4- DP, and (iii) Drude Gaussian charge polarizable BK3. Model predictions are compared with experimental Gibbs free energies and enthalpies of ion hydration, and with microscopic structural properties obtained from quantum DFT calculations. We find that all three models provide comparable predictions for pure water clusters and cation hydration, but differ significantly in their description of anion hydration. None of the investigated classical force fields can consistently and quantitatively reproduce the experimental gas phase hydration thermodynamics. The outcome of this study highlights the relation between the functional form that describes the effective intermolecular interactions and the accuracy of the resulting ion hydration properties.

Coordination of different ligands to copper(II) and cobalt(III) metal centers enhances Zika virus and dengue virus loads in both arthropod cells and human keratinocytes.

Science.gov (United States)

Dutta, Shovan; Celestine, Michael J; Khanal, Supreet; Huddleston, Alexis; Simms, Colin; Arca, Jessa Faye; Mitra, Amlan; Heller, Loree; Kraj, Piotr J; Ledizet, Michel; Anderson, John F; Neelakanta, Girish; Holder, Alvin A; Sultana, Hameeda

2018-01-01

Trace elements such as copper and cobalt have been associated with virus-host interactions. However, studies to show the effect of conjugation of copper(II) or cobalt(III) metal centers to thiosemicarbazone ligand(s) derived from either food additives or mosquito repellent such as 2-acetylethiazole or citral, respectively, on Zika virus (ZIKV) or dengue virus (serotype 2; DENV2) infections have not been explored. In this study, we show that four compounds comprising of thiosemicarbazone ligand derived from 2-acetylethiazole viz., (E)-N-ethyl-2-[1-(thiazol-2-yl)ethylidene]hydrazinecarbothioamide (acetylethTSC) (compound 1), a copper(II) complex with acetylethTSC as a ligand (compound 2), a thiosemicarbazone ligand-derived from citral (compound 3) and a cobalt(III) complex with a citral-thiosemicarbazone ligand (compound 4) increased DENV2 and ZIKV replication in both mosquito C6/36 cells and human keratinocytes (HaCaT cells). Treatment of both cell lines with compounds 2 or 4 showed increased dengue viral titers at all three tested doses. Enhanced dengue viral plaque formation was also noted at the tested dose of 100μM, suggesting higher production of infectious viral particles. Treatment with the compounds 2 or 4 enhanced ZIKV and DENV2 RNA levels in HeLa cell line and primary cultures of mouse bone marrow derived dendritic cells. Also, pre- or post treatments with conjugated compounds 2 or 4 showed higher loads of ZIKV or DENV2 envelope (E) protein in HaCaT cells. No changes in loads of E-protein were found in ZIKV-infected C6/36 cells, when compounds were treated after infection. In addition, we tested bis(1,10-phenanthroline)copper(II) chloride ([Cu(phen) 2 ]Cl 2 , (compound 5) and tris(1,10-phenanthroline)cobalt(III) chloride ([Co(phen) 3 ]Cl 3 , (compound 6) that also showed enhanced DENV2 loads. Also, we found that copper(II) chloride dehydrate (CuCl 2 ·2H 2 O) or cobalt(II) chloride hexahydrate (CoCl 2 ·6H 2 O) alone had no effects as "free" cations

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

OpenAIRE

Pandey, Mohnish; Jacobsen, Karsten Wedel; Thygesen, Kristian Sommer

2016-01-01

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 (C4H9NH3)2MX2Y2, where M = Pb, Ge, Sn and X,Y = Cl, Br, I. The band gaps computed using the GLLB-SC ...

Sequential One-Pot Ruthenium-Catalyzed Azide−Alkyne Cycloaddition from Primary Alkyl Halides and Sodium Azide

KAUST Repository

Johansson, Johan R.

2011-04-01

An experimentally simple sequential one-pot RuAAC reaction, affording 1,5-disubstituted 1H-1,2,3-triazoles in good to excellent yields starting from an alkyl halide, sodium azide, and an alkyne, is reported. The organic azide is formed in situ by treating the primary alkyl halide with sodium azide in DMA under microwave heating. Subsequent addition of [RuClCp*(PPh 3) 2] and the alkyne yielded the desired cycloaddition product after further microwave irradiation. © 2011 American Chemical Society.

Ni(II

African Journals Online (AJOL)

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analytical chemistry, catalysis, electrochemistry, ring-opening metathesis ... Ethanol was dried over anhydrous copper(II) sulfate and distilled over metallic sodium. ... All bacteria were inoculated into Nutrient Broth (Difco) and incubated for 24 h ...

Analisa Teknis Pemakaian Kombinasi Lampu Metal Halide Dan Led Sebagai Pemikat Ikan Pada Kapal Pukat Cincin (Purse Seine Dan Pengaruhnya Terhadap Konsumsi Bahan Bakar Genset

Directory of Open Access Journals (Sweden)

Septian Ragil Wibisono

2017-01-01

Full Text Available Saat ini lampu Metal Halide dipakai sebagai pemikat ikan  oleh nelayan Purse Seine. Peggunaan lampu tersebut memerlukan daya Genset yang besar karena satu lampu Metal Halide berdaya 1500 Watt. Semakin banyak lampu Metal Halide yang digunakan semakin besar pula konsumsi bahan bakar Genset. Dalam upaya penghematan energi bahan bakar maka digunakan lampu LED sebagai alternatif pemikat ikan. Lampu LED dikenal sebagai lampu yang hemat energi. Penelitian ini ditujukan untuk mengetahui dan membandingkan konsumsi bahan bakar Genset saat menggunakan kombinasi lampu Metal Halide dan LED. Penelitian ini dilakukan dengan mengambil data konsumsi bahan bakar Genset untuk menyalakan sejumlah lampu Metal Halide dan lampu LED, kemudian dilakukan analisa regresi untuk mendapatkan model persaamaan konsumsi bahan bakar Genset. Selanjutnya dilakukan ekstrapolasi untuk memprediksi konsumsi bahan bakar saat Genset dengan jumlah lampu tertentu. Hasilnya dengan besar fluks cahaya yang hampir sama, saat penggunaan 6 lampu Metal Halide konsumsi bahan bakar sebesar 13.606,03 liter, dan saat menggunakan kombinasi lampu 1 Metal Halide dan 25 lampu LED konsumsi bahan bakar sebesar 13.255,63 liter, yang artinya terjadi penghematan bahan bakar sebesar 2,58%.

Finding New Perovskite Halides via Machine learning

Directory of Open Access Journals (Sweden)

Ghanshyam ePilania

2016-04-01

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

Finding New Perovskite Halides via Machine learning

Science.gov (United States)

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

2016-04-01

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

Conformational isomerism in mixed-ligand complexes of 2,2'-bipyridine and triphenylphosphine with copper(I) halides

International Nuclear Information System (INIS)

Barron, P.F.; Engelhardt, L.M.; Healy, P.C.; Kildea, J.D.; White, A.H.

1988-01-01

Mixed-ligand complexes of triphenylphosphine and 2,2'-bipyridine and copper(I) halides have been synthesized. The 31 P NMR spectra of the complexes were measured and are reported along with data for complete structural characterization of the complexes. The results indicate a novel dichotomy of conformational isomers to be present in the chloride lattice. The Cu-P bond length was found to not vary with different halides. 8 refs., 4 figs., 6 tabs

THERMODYNAMICS OF MICELLE FORMATION BY 1-METHYL-4-ALKYLPYRIDINIUM HALIDES

NARCIS (Netherlands)

BIJMA, K; ENGBERTS, JBFN; HAANDRIKMAN, G; VANOS, NM; BLANDAMER, MJ; BUTT, MD; CULLIS, PM

This paper reports enthalpies of micellization for a series of 1-methyl-4-alkylpyridinium halide surfactants at 303.2 K with different lengths and degrees of branching of the 4-alkyl chain and different sizes of counterions using two microcalorimeters (LKB 2277 and Omega Microcal). The standard

Halide salts accelerate degradation of high explosives by zerovalent iron

International Nuclear Information System (INIS)

Kim, Jong Sung; Shea, Patrick J.; Yang, Jae E.; Kim, Jang-Eok

2007-01-01

Zerovalent iron (Fe 0 , ZVI) has drawn great interest as an inexpensive and effective material to promote the degradation of environmental contaminants. A focus of ZVI research is to increase degradation kinetics and overcome passivation for long-term remediation. Halide ions promote corrosion, which can increase and sustain ZVI reactivity. Adding chloride or bromide salts with Fe 0 (1% w/v) greatly enhanced TNT, RDX, and HMX degradation rates in aqueous solution. Adding Cl or Br salts after 24 h also restored ZVI reactivity, resulting in complete degradation within 8 h. These observations may be attributed to removal of the passivating oxide layer and pitting corrosion of the iron. While the relative increase in degradation rate by Cl - and Br - was similar, TNT degraded faster than RDX and HMX. HMX was most difficult to remove using ZVI alone but ZVI remained effective after five HMX reseeding cycles when Br - was present in solution. - The addition of halide ions promotes the degradation of high explosives by zerovalent iron

Exciton-relaxation dynamics in lead halides

International Nuclear Information System (INIS)

Iwanaga, Masanobu; Hayashi, Tetsusuke

2003-01-01

We survey recent comprehensive studies of exciton relaxation in the crystals of lead halides. The luminescence and electron-spin-resonance studies have revealed that excitons in lead bromide spontaneously dissociate and both electrons and holes get self-trapped individually. Similar relaxation has been also clarified in lead chloride. The electron-hole separation is ascribed to repulsive correlation via acoustic phonons. Besides, on the basis of the temperature profiles of self-trapped states, we discuss the origin of luminescence components which are mainly induced under one-photon excitation into the exciton band in lead fluoride, lead chloride, and lead bromide

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

Energy Technology Data Exchange (ETDEWEB)

Sudheer,, E-mail: sudheer@rrcat.gov.in; Tiwari, P.; Rai, V. N.; Srivastava, A. K. [Indus Synchrotrons Utilization Division, Raja Ramanna Centre for Advanced Technology Indore, Madhya Pradesh 452013 (India); Varshney, G. K. [Laser Bio-medical Applications & Instrumentation Division, Raja Ramanna Centre for Advanced Technology Indore, Madhya Pradesh 452013 (India)

2016-05-23

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.

Crystal Structure and Magnetic Behavior of Two New Dinuclear Carbonato-Bridged Copper(II) Compounds. Superexchange Pathway for the Different Coordination Modes of the Carbonato Bridge in Polynuclear Copper(II) Compounds.

Science.gov (United States)

Escuer, Albert; Mautner, Franz A.; Peñalba, Evaristo; Vicente, Ramon

1998-08-24

Four new &mgr;-CO(3)(2-) copper(II) complexes with different coordination modes for the carbonato bridge have been obtained by fixation of atmospheric CO(2): {(&mgr;(3)-CO(3))[Cu(3)(ClO(4))(3)(Et(3)dien)(3)]}(ClO(4)) (1), Et(3)dien = N,N',N"-triethylbis(2-aminoethane)amine; {(&mgr;-CO(3))[Cu(2)(H(2)O)(Et(4)dien)(2)]}(ClO(4))(2).H(2)O (2), Et(4)dien = N,N,N",N"-tetraethyl-bis(2-aminoethane)amine; {(&mgr;-CO(3))[Cu(2)(H(2)O)(2)(EtMe(4)dien)(2)]} (ClO(4))(2).2H(2)O (3), EtMe(4)dien = N'-ethyl-N,N,N",N"-tetramethylbis(2-aminoethane)amine; and {(&mgr;-CO(3))[Cu(2)(H(2)O)(Me(5)dien)(2)]}(ClO(4))(2).H(2)O (4), Me(5)dien = N,N,N',N",N"-pentamethylbis(2-aminoethane)amine. The crystal structures have been solved for 2, monoclinic system, space group P2(1)/n, formula [C(25)H(62)Cl(2)Cu(2)N(6)O(13)] with a = 12.763(6) Å, b = 25.125(8) Å, c = 13.261(4) Å, beta = 111.85(3) degrees, Z = 4, and for 3, triclinic system, space group P&onemacr;, formula [C(21)H(58)Cl(2)Cu(2)N(6)O(15)] with a = 8.412(3) Å, b = 14.667(4) Å, c = 16.555(5) Å, alpha = 99.66(2) degrees, beta = 102.14(2) degrees, gamma = 104.72(2) degrees, Z = 2. Susceptibility measurements show ferromagnetic behavior (J = +6.7(6) cm(-)(1)) for the trinuclear compound 1 whereas 2-4 are antiferromagnetically coupled with J = -17.8(8), -125.5(9), and -21.2(3) cm(-)(1) respectively. Certain synthetic aspects that may be related to the nuclearity of the copper(II) &mgr;-CO(3)(2-) compounds and the superexchange pathway for the different coordination modes of the carbonato bridge are discussed.

White-Light Emission from Layered Halide Perovskites.

Science.gov (United States)

Smith, Matthew D; Karunadasa, Hemamala I

2018-03-20

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

Kinetics of the oxidative hydroxylation of tetraphosphorus in the presence of copper(II) chloride modified by humic (fulvo-) acid

OpenAIRE

Zhaksyntay Kairbekov; Dina Akbayeva; Zh. Eshova

2012-01-01

It was established that in mild conditions (50-70 oC, РО2= 1 atm) white phosphorus effectively is oxidized by oxygen in water-toluene solutions of copper(II) chloride modified by humic (fulvo-) acid to give mainly phosphoric acid. Humic (fulvo-) acid was extracted from brown coal of domestic deposit Kiyakty. For determination of optimum parameters of fulvo-acid extraction the laboratory experiments were carried out using the method of experiment planning. The kinetics, intermediate and final ...

Synergistic effect of halide ions on the corrosion inhibition of aluminium in H{sub 2}SO{sub 4} using 2-acetylphenothiazine

Energy Technology Data Exchange (ETDEWEB)

Ebenso, E.E

2003-03-05

The corrosion inhibition of aluminium in H{sub 2}SO{sub 4} in the presence of 2-acetylphenothiazine (2APTZ) at temperature range of 30-60 deg. C was studied using the weight loss and thermometric techniques. The effect of addition of halides (KCl, KBr, KI) is also reported. The inhibition efficiency (I, %) increased with increase in concentration of 2APTZ. The addition of the halides increased the inhibition efficiency to a considerable extent. The temperature increased the corrosion rate and inhibition efficiency in the range 30-60 deg. C in the absence and presence of the inhibitor and halides. Phenomenon of chemical adsorption is proposed. Flory-Huggins adsorption isotherm equation was obeyed at all the concentrations studied. The decrease in inhibition efficiency (and surface coverage values) was found to be in the order I{sup -}>Br{sup -}>Cl{sup -} which clearly indicates that the radii and the electronegativity of halides play a significant role in the adsorption process. All the data acquired reveal that 2APTZ acts as an inhibitor in the acid environment from the two techniques used. The synergistic effect of 2APTZ and halide ions is discussed.

The Role of Surface Tension in the Crystallization of Metal Halide Perovskites

KAUST Repository

Zhumekenov, Ayan A.; Burlakov, Victor M.; Saidaminov, Makhsud I.; Alofi, Abdulilah; Haque, Mohammed; Turedi, Bekir; Davaasuren, Bambar; Dursun, Ibrahim; Cho, Nam Chul; El-Zohry, Ahmed M.; de Bastiani, Michele; Giugni, Andrea; Torre, Bruno; Di Fabrizio, Enzo M.; Mohammed, Omar F.; Rothenberger, Alexander; Wu, Tao; Goriely, Alain; Bakr, Osman

2017-01-01

The exciting intrinsic properties discovered in single crystals of metal halide perovskites still await their translation into optoelectronic devices. The poor understanding and control of the crystallization process of these materials are current

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

Science.gov (United States)

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.

Monocrystallomimicry in the aerosols of ammonium and cesium halides

International Nuclear Information System (INIS)

Melikhov, I.V.; Kitova, E.N.; Kozlovskaya, EhD.; Kamenskaya, A.N.; Mikheev, N.B.; Kulyukhin, S.A.

1997-01-01

It is experimentally shown that initial CsI and NH 4 Hal nanocrystals combining into mixed aggregates of polyhedral form (pseudo monocrystals) are formed in the process of cocrystallization of ammonium halide and cesium iodide. The origination and growth of the pseudo monocrystals on the account of successive addition of initial crystals is described by the Fokker-Plank equation [ru

Line emissions from sonoluminescence in aqueous solutions of halide salts without noble gases

Energy Technology Data Exchange (ETDEWEB)

Liang, Jinfu, E-mail: liang.shi2007@163.com [The Key Laboratory of Modern Acoustics, Ministry of Education, Institution of Acoustics, Nanjing University, Nanjing 210093 (China); School of Physics and Electronic Science, Guizhou Normal University, Guiyang 550001 (China); Chen, Weizhong, E-mail: wzchen@nju.edu.cn [The Key Laboratory of Modern Acoustics, Ministry of Education, Institution of Acoustics, Nanjing University, Nanjing 210093 (China); Zhou, Chao; Cui, Weicheng; Chen, Zhan [The Key Laboratory of Modern Acoustics, Ministry of Education, Institution of Acoustics, Nanjing University, Nanjing 210093 (China)

2015-02-20

Line emissions of trivalent terbium (Tb{sup 3+}) ion were observed from single-bubble sonoluminescence (SL) in an aqueous solution of terbium chloride (TbCl{sub 3}) that contained no noble gas. In addition, sodium (Na) lines were observed in multi-bubble SL in aqueous solutions of various halide salts that contained no noble gas. These observations show that the halide ions, such as Cl{sup −}, Br{sup −}, and I{sup −}, help for line emissions as the noble gases. The intensity of a line emission depends on both the chemical species produced by cavitation bubbles and the temperature of SL bubble that responds to the driving ultrasound pressure. With the increase of driving pressure, some line emissions attached to the continuous spectrum may become increasingly clear, while other line emissions gradually become indistinct. - Highlights: • Line emissions of Tb(III) ions were observed without the presence of noble gases. • The halide ions help to generate a line emission during sonoluminescence. • The intensity of a line emission mainly depends on the bubble's temperature. • The definition of a line emission is related to the temperature of caviation bubble and the kind of host liquid.

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

Science.gov (United States)

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 (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.

Charge-charge liquid structure factor and the freezing of alkali halides

International Nuclear Information System (INIS)

March, N.H.; Tosi, M.P.

1980-10-01

The peak height of the charge-charge liquid structure factor Ssub(QQ) in molten alkali halides is proposed as a criterion for freezing. Available data on molten alkali chlorides, when extrapolated to the freezing point suggests Ssub(QQ)sup(max) approximately 5. (author)

Process chemistry related to hydrogen isotopes

International Nuclear Information System (INIS)

Iwasaki, Matae; Ogata, Yukio

1991-01-01

Hydrogen isotopes, that is, protium, deuterium and tritium, are all related deeply to energy in engineering region. Deuterium and tritium exist usually as water in extremely thin state. Accordingly, the improvement of the technology for separating these isotopes is a large engineering subject. Further, tritium is radioactive and its half-life period is 12.26 years, therefore, it is desirable to fix it in more stable form besides its confinement in the handling system. As the chemical forms of hydrogen, the molecular hydrogen with highest reactivity, metal hydride, carbon-hydrogen-halogen system compounds, various inorganic hydrides, most stable water and hydroxides are enumerated. The grasping of the behavior from reaction to stable state of these hydrogen compounds and the related materials is the base of process chemistry. The reaction of exchanging isotopes between water and hydrogen on solid catalyzers, the decomposition of ethane halide containing hydrogen, the behavior of water and hydroxides in silicates are reported. The isotope exchange between water and hydrogen is expected to be developed as the process of separating and concentrating hydrogen isotopes. (K.I.) 103 refs

Superconducting nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I)

Energy Technology Data Exchange (ETDEWEB)

Schurz, Christian M.; Shlyk, Larysa; Schleid, Thomas; Niewa, Rainer [Stuttgart Univ. (Germany). Inst. fuer Anorganische Chemie

2011-07-01

Two different polymorphs of the metal nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I) are known to crystallize in layered structures. The two crystal structures differ in the way {sub {infinity}}{sup 2}{l_brace}X[M{sub 2}N{sub 2}]X{r_brace} slabs are stacked along the c-axes. Metal atoms and/or organic molecules can be intercalated into the van-der-Waals gap between these layers. After such an electron-doping via intercalation the prototypic band insulators change into superconductors with moderate high critical temperatures T{sub c} up to 25.5 K. This review gathers information on synthesis routes, structural characteristics and properties of the prototypic nitride halides and the derivatives after electron-doping with a focus on superconductivity. (orig.)

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Transport phenomena in metal-halide lamps : a poly-diagnostic study

NARCIS (Netherlands)

Nimalasuriya, T.

2007-01-01

Worldwide about 20% of all electricity is used for lighting. It is therefore of great interest to develop a lamp that has high e±cacy, good colour rendering and long lifetime. The metal-halide lamp is a gas discharge lamp that meets all these demands. Unfortunately there are still issues with this

Inorganic Lead Halide Perovskite Single Crystals: Phase-Selective Low-Temperature Growth, Carrier Transport Properties, and Self-Powered Photodetection

KAUST Repository

Saidaminov, Makhsud I.

2016-12-06

A rapid, low-temperature, and solution-based route is developed for growing large-sized cesium lead halide perovskite single crystals under ambient conditions. An ultralow minority carrier concentration was measured in CsPbBr3 (≈108 holes per cm3, much lower than in any other lead halide perovskite and crystalline silicon), which enables to realize self-powered photodetectors with a high ON/OFF ratio (105).

Research Update: Physical and electrical characteristics of lead halide perovskites for solar cell applications

Directory of Open Access Journals (Sweden)

Simon A. Bretschneider

2014-04-01

Full Text Available The field of thin-film photovoltaics has been recently enriched by the introduction of lead halide perovskites as absorber materials, which allow low-cost synthesis of solar cells with efficiencies exceeding 16%. The exact impact of the perovskite crystal structure and composition on the optoelectronic properties of the material are not fully understood. Our progress report highlights the knowledge gained about lead halide perovskites with a focus on physical and optoelectronic properties. We discuss the crystal and band structure of perovskite materials currently implemented in solar cells and the impact of the crystal properties on ferroelectricity, ambipolarity, and the properties of excitons.

Surface characteristics, copper release, and toxicity of nano- and micrometer-sized copper and copper(II) oxide particles: a cross-disciplinary study.

OpenAIRE

Midander, Klara; Cronholm, Pontus; Karlsson, Hanna L.; Elihn, Karine; Moller, Lennart; Leygraf, Christofer; Wallinder, Inger Odnevall

2009-01-01

An interdisciplinary and multianalytical research effort is undertaken to assess the toxic aspects of thoroughly characterized nano- and micrometer-sized particles of oxidized metallic copper and copper(II) oxide in contact with cultivated lung cells, as well as copper release in relevant media. All particles, except micrometer-sized Cu, release more copper in serum-containing cell medium (supplemented Dulbecco's minimal essential medium) compared to identical exposures in phosphate-buffered ...

Research Update: Luminescence in lead halide perovskites

Directory of Open Access Journals (Sweden)

Ajay Ram Srimath Kandada

2016-09-01

Full Text Available Efficiency and dynamics of radiative recombination of carriers are crucial figures of merit for optoelectronic materials. Following the recent success of lead halide perovskites in efficient photovoltaic and light emitting technologies, here we review some of the noted literature on the luminescence of this emerging class of materials. After outlining the theoretical formalism that is currently used to explain the carrier recombination dynamics, we review a few significant works which use photoluminescence as a tool to understand and optimize the operation of perovskite based optoelectronic devices.

Determination of HCl and VOC Emission from Thermal Degradation of PVC in the Absence and Presence of Copper, Copper(II Oxide and Copper(II Chloride

Directory of Open Access Journals (Sweden)

Ahamad J. Jafari

2009-01-01

Full Text Available Polyvinyl chloride (PVC has played a key role in the development of the plastic industry over the past 40 years. Thermal degradation of PVC leads to formation of many toxic pollutants such as HCl, aromatic and volatile organic carbon vapors. Thermal degradation of PVC and PVC in the present of copper, cupric oxide and copper(II chloride were investigated in this study using a laboratory scale electrical furnace. HCl and Cl- ion were analyzed by a Dionex ion chromatograph and VOCs compounds were analyzed using GC or GC-MS. The results showed that HCl plus Cl- ion and benzene formed about 99% and 80% respectively in the first step of thermal degradation under air atmosphere. The presence of cupric oxide increases the percentage of short chain hydrocarbons more than 184% and decreases the amount of the major aromatic hydrocarbon and HCl plus Cl- ion to 90% and 65% respectively. The total aromatic hydrocarbon emitted less than when atmosphere was air and difference was statistically significant (Pvalue<0.000

Metal-halide lamp design: atomic and molecular data needed

International Nuclear Information System (INIS)

Lapatovich, Walter P

2009-01-01

Metal-halide lamps are a subset of high intensity discharge (HID) lamps so named because of their high radiance. These lamps are low temperature (∼0.5 eV), weakly ionized plasmas sustained in refractory but light transmissive envelopes by the passage of electric current through atomic and molecular vapors. For commercial applications, the conversion of electric power to light must occur with good efficiency and with sufficient spectral content throughout the visible (380-780 nm) to permit the light so generated to render colors comparable to natural sunlight. This is achieved by adding multiple metals to a basic mercury discharge. Because the vapor pressure of most metals is very much lower than mercury itself, metal-halide salts of the desired metals, having higher vapor pressures, are used to introduce the material into the basic discharge. The metal compounds are usually polyatomic iodides, which vaporize and subsequently dissociate as they diffuse into the bulk plasma. Metals with multiple visible transitions are necessary to achieve high photometric efficiency (efficacy) and good color. Compounds of Sc, Dy, Ho, Tm, Ce, Pr, Yb and Nd are commonly used. The electrons, atoms and radicals are in local thermodynamic equilibrium (LTE), but not with the radiation field. Strong thermal (10 6 K m -1 ) and density gradients are sustained in the discharge. Atomic radiation produced in the high-temperature core transits through colder gas regions where it interacts with cold atoms and un-dissociated molecules before exiting the lamp. Power balance and spectral output of the lamp are directly affected by the strength of atomic transitions. Attempts to simulate the radiative output of functional metal-halide lamps have been successful only in very simple cases. More data (e.g. the atomic transition probabilities of Ce i) are necessary to improve lamp performance, to select appropriate radiators and in scaling the lamp geometry to various wattages for specific applications.

Thermoluminescence response of a mixed ternary alkali halide crystals exposed to gamma rays

International Nuclear Information System (INIS)

Rodriguez M, R.; Perez S, R.; Vazquez P, G.; Riveros, H.; Gonzalez M, P.

2014-08-01

Ionic crystals, mainly alkali halide crystals have been the subject of intense research for a better understanding of the luminescence properties of defects induced by ionizing radiation. The defects in crystals can be produced in appreciable concentration due to elastic stresses, radiation, and addition of impurities. These defects exhibit remarkable thermoluminescence properties. This work is concerned with the Tl properties of a ternary alkali halide crystal after being irradiated with gamma and beta rays. It has been found that the Tl glow peak of the crystal follows a rule of average associated to the Tl Temperatures of the components of the mixture, similarly to the response of europium doped binary mixed crystals KCl x KBr 1-x and KBr x RbBr 1-x . (Author)

Adsorption of lead(II) and copper(II) on activated carbon by complexation with surface functional groups

International Nuclear Information System (INIS)

Pesavento, Maria; Profumo, Antonella; Alberti, Giancarla; Conti, Fabio

2003-01-01

The adsorption of lead(II) and copper(II) on an activated carbon (Filtrasorb 300, Chemviron) was characterized assuming that it takes place by formation of complexes with functional groups, present in the activated carbon. Their concentration and conditional adsorption coefficients were determined for each metal by titration of the carbon in suspension in aqueous phase, at constant acidity, with the metal itself. For each titration point, the concentration of the metal in the solution phase after equilibration was determined, and the data were processed by the Ruzic linearization method, to obtain the concentration of the active sites involved in the sorption, and the conditional constant. The effect of the pH was also examined, in the range 4-6, obtaining that the adsorption increases at increasing pH. The protonation and adsorption constants were determined from the conditional adsorption coefficients obtained at the different acidities. The concentration of the active sites is 0.023 and 0.042 mmol g -1 , and the protonation constants are 1.0x10 6 and 4.6x10 4 M -1 for Pb(II) and Cu(II). The corresponding adsorption constants are respectively 1.4x10 5 and 6.3x10 3 M -1 . All the parameters are affected by a large uncertainty, probably due to the heterogeneity of the active groups in the activated carbon. Even if so, these parameters make it possible a good prediction of the adsorption in a wide range of conditions. Other sorption mechanism can be set up at different conditions, in particular at different pH, as it has been demonstrated in the case of copper(II)

Adsorption of lead(II) and copper(II) on activated carbon by complexation with surface functional groups

Energy Technology Data Exchange (ETDEWEB)

Pesavento, Maria; Profumo, Antonella; Alberti, Giancarla; Conti, Fabio

2003-03-17

The adsorption of lead(II) and copper(II) on an activated carbon (Filtrasorb 300, Chemviron) was characterized assuming that it takes place by formation of complexes with functional groups, present in the activated carbon. Their concentration and conditional adsorption coefficients were determined for each metal by titration of the carbon in suspension in aqueous phase, at constant acidity, with the metal itself. For each titration point, the concentration of the metal in the solution phase after equilibration was determined, and the data were processed by the Ruzic linearization method, to obtain the concentration of the active sites involved in the sorption, and the conditional constant. The effect of the pH was also examined, in the range 4-6, obtaining that the adsorption increases at increasing pH. The protonation and adsorption constants were determined from the conditional adsorption coefficients obtained at the different acidities. The concentration of the active sites is 0.023 and 0.042 mmol g{sup -1}, and the protonation constants are 1.0x10{sup 6} and 4.6x10{sup 4} M{sup -1} for Pb(II) and Cu(II). The corresponding adsorption constants are respectively 1.4x10{sup 5} and 6.3x10{sup 3} M{sup -1}. All the parameters are affected by a large uncertainty, probably due to the heterogeneity of the active groups in the activated carbon. Even if so, these parameters make it possible a good prediction of the adsorption in a wide range of conditions. Other sorption mechanism can be set up at different conditions, in particular at different pH, as it has been demonstrated in the case of copper(II)

Possible configuration of two-knot auto-localized exciton in strainless and deformed alkali halide crystals

International Nuclear Information System (INIS)

Dzhumanov, S.; Tulepbergenov, S.K.; Shunkeev, K.Sh.

2002-01-01

In the paper molecular component of two-knot auto-localized exciton (TALE) occupying centrosymmetric state in alkali halide crystal cubic lattice with local D 2h symmetry is considered. In is suggested that the symmetry lowering of forming small radius auto-localized exciton (ALE) is realizing in order configuration transformation by the scenario: multi-knot continual ALE (with O h symmetry)→six-halide ALE (with O h symmetry)→TALE (with O h symmetry) or by the scenario O h →D 2h . Then for TALE with local D 2h symmetry normal molecular ion shifts are considered as well

Epitaxial Growth of a Methoxy-Functionalized Quaterphenylene on Alkali Halide Surfaces

DEFF Research Database (Denmark)

Balzer, Frank; Sun, Rong; Parisi, Jürgen

2015-01-01

The epitaxial growth of the methoxy functionalized para-quaterphenylene (MOP4) on the (001) faces of the alkali halides NaCl and KCl and on glass is investigated by a combination of lowenergy electron diffraction (LEED), polarized light microscopy (PLM), atomic force microscopy (AFM), and X...

Treatment of model and galvanic waste solutions of copper(II) ions using a lignin/inorganic oxide hybrid as an effective sorbent.

Science.gov (United States)

Ciesielczyk, Filip; Bartczak, Przemysław; Klapiszewski, Łukasz; Jesionowski, Teofil

2017-04-15

A study was made concerning the removal of copper(II) ions from model and galvanic waste solutions using a new sorption material consisting of lignin in combination with an inorganic oxide system. Specific physicochemical properties of the material resulted from combining the activity of the functional groups present in the structure of lignin with the high surface area of the synthesized oxide system (585m 2 /g). Analysis of the porous structure parameters, particle size and morphology, elemental composition and characteristic functional groups confirmed the effective synthesis of the new type of sorbent. A key element of the study was a series of tests of adsorption of copper(II) ions from model solutions. It was determined how the efficiency of the adsorption process was affected by the process time, mass of sorbent, concentration of adsorbate, pH and temperature. Potential regeneration of adsorbent, which provides the possibility of its reusing and recovering the adsorbed copper, was also analyzed. The sorption capacity of the material was measured (83.98mg/g), and the entire process was described using appropriate kinetic models. The results were applied to the design of a further series of adsorption tests, carried out on solutions of real sewage from a galvanizing plant. Copyright © 2017 Elsevier B.V. All rights reserved.

Structural stability, acidity, and halide selectivity of the fluoride riboswitch recognition site

KAUST Repository

Chawla, Mohit

2015-01-14

Using static and dynamics DFT methods we show that the Mg2+/F-/phosphate/water cluster at the center of the fluoride riboswitch is stable by its own and, once assembled, does not rely on any additional factor from the overall RNA fold. Further, we predict that the pKa of the water molecule bridging two Mg cations is around 8.4. We also demonstrate that the halide selectivity of the fluoride riboswitch is determined by the stronger Mg-F bond, which is capable of keeping together the cluster. Replacing F- with Cl- results in a cluster that is unstable under dynamic conditions. Similar conclusions on the structure and energetics of the cluster in the binding pocket of fluoride-inhibited pyrophosphatase suggest that the peculiarity of fluoride is in its ability to establish much stronger metal-halide bonds.

Structural stability, acidity, and halide selectivity of the fluoride riboswitch recognition site

KAUST Repository

Chawla, Mohit; Credendino, Raffaele; Poater, Albert; Oliva, Romina M.; Cavallo, Luigi

2015-01-01

Using static and dynamics DFT methods we show that the Mg2+/F-/phosphate/water cluster at the center of the fluoride riboswitch is stable by its own and, once assembled, does not rely on any additional factor from the overall RNA fold. Further, we predict that the pKa of the water molecule bridging two Mg cations is around 8.4. We also demonstrate that the halide selectivity of the fluoride riboswitch is determined by the stronger Mg-F bond, which is capable of keeping together the cluster. Replacing F- with Cl- results in a cluster that is unstable under dynamic conditions. Similar conclusions on the structure and energetics of the cluster in the binding pocket of fluoride-inhibited pyrophosphatase suggest that the peculiarity of fluoride is in its ability to establish much stronger metal-halide bonds.

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

Science.gov (United States)

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

2018-04-01

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

Tailoring Mixed-Halide, Wide-Gap Perovskites via Multistep Conversion Process

NARCIS (Netherlands)

Bae, D.; Palmstrom, A.; Roelofs, K.; Mei, Bastian Timo; Chorkendorf, I.; Bent, S.F.; Vesborg, P.C.

2016-01-01

Wide-band-gap mixed-halide CH3NH3PbI3–XBrX-based solar cells have been prepared by means of a sequential spin-coating process. The spin-rate for PbI2 as well as its repetitive deposition are important in determining the cross-sectional shape and surface morphology of perovskite, and, consequently,

Homocoupling of benzyl halides catalyzed by POCOP-nickel pincer complexes

KAUST Repository

Chen, Tao

2012-08-01

Two types of POCOP-nickel(II) pincer complexes were prepared by mixing POCOP pincer ligands and NiX 2 in toluene at reflux. The resulting nickel complexes efficiently catalyze the homocoupling reactions of benzyl halides in the presence of zinc. The coupled products were obtained in excellent to quantitative yields. © 2012 Elsevier Ltd. All rights reserved.

Antioxidant, DNA interaction, VEGFR2 kinase, topoisomerase I and in vitro cytotoxic activities of heteroleptic copper(II) complexes of tetrazolo[1,5-a]pyrimidines and diimines

Energy Technology Data Exchange (ETDEWEB)

Haleel, A.; Mahendiran, D. [Post-Graduate and Research Department of Chemistry, The New College (Autonomous), Chennai 600 014 (India); Veena, V.; Sakthivel, N. [Department of Biotechnology, Pondicherry University, Pondicherry 605 014 (India); Rahiman, A. Kalilur, E-mail: akrahmanjkr@gmail.com [Post-Graduate and Research Department of Chemistry, The New College (Autonomous), Chennai 600 014 (India)

2016-11-01

A series of heteroleptic mononuclear copper(II) complexes of the type [Cu(L{sup 1–3})(diimine)]ClO{sub 4} (1–6) containing three tetrazolo[1,5-a]pyrimidine core ligands, ethyl 5-methyl-7-(2-hydroxyphenyl)-4,7-dihydrotetrazolo[1,5-a] pyrimidine-6-carboxylate (HL{sup 1}), ethyl 5-methyl-7-(4-diethylamino-2-hydroxyphenyl)-4,7-dihydrotetrazolo[1,5-a] pyrimidine-6-carboxylate (HL{sup 2}) or ethyl 5-methyl-7-(2-hydroxy-4-nitrophenyl)-4,7-dihydrotetrazolo[1,5-a] pyrimidine-6-carboxylate (HL{sup 3}), and two diimine coligands, 2,2′-bipyridyl (bpy) or 1,10-phenanthroline (phen) have been synthesized and characterized by spectral methods. The geometry of complexes have been determined with the help of electronic absorption and EPR splitting patterns, which suggest four coordinated square planar geometry around copper(II) ion. The lowering of HOMO–LUMO band gap value of complex 4 implies its higher biological activity compared to other complexes. Antioxidant studies revealed that the complexes possess considerable radical scavenging potency against DPPH. The binding studies of the complexes with calf thymus DNA (CT–DNA) revealed groove mode of binding, which was further supported by docking simulation. The complexes 3 and 4 strongly inhibit the topoisomerase I, and also strongly interact with VEGFR2 kinase receptor via π–π, σ–π and hydrogen bonding interaction. Gel electrophoresis experiments demonstrated the ability of the complexes to cleave plasmid DNA in the absence of activators. In vitro cytotoxic activities of the complexes were examined on three cancerous cell lines such as human lung (A549), cervical (HeLa) and colon (HCT-15), and two normal cells such as human embryonic kidney (HEK) and peripheral blood mononuclear cells (PBMCs). The live cell and fluorescent imaging of cancer cells were observed with acridine orange/ethidium bromide staining assay. All encouraging chemical and biological findings indicate that the complex 4 is a suitable candidate

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Ground state depletion – A step towards mid-IR lasing of doped silver halides

Energy Technology Data Exchange (ETDEWEB)

Tsur, Yuval, E-mail: yuvaltsu@post.tau.ac.il [Raymond and Beverly Sackler Faculty of Exact Sciences, Tel-Aviv University, Tel-Aviv 6997801 (Israel); Goldring, Sharone [Applied Physics Division, Soreq NRC, Yavne 81800 (Israel); Galun, Ehud [DDR& D, Ministry of Defense (Israel); Katzir, Abraham [Raymond and Beverly Sackler Faculty of Exact Sciences, Tel-Aviv University, Tel-Aviv 6997801 (Israel)

2016-07-15

We show for the first time ground state absorption saturation in a doped silver halide crystal (AgCl{sub x}Br{sub 1−x}), specifically with cobalt. Spectroscopic studies showed absorption bands in the 1.4–2.5 μm region and emission bands in the 3.8–5.0 μm region, with a 1.5 ms lifetime at low temperatures. Absorption saturation indicates a good low and room temperature lasing feasibility at 4.1 μm. In addition, a comparison of cobalt, nickel and iron as dopants is presented. These doped silver halide crystals can be extruded to form optical fibers, possibly introducing a new family of fiber lasers for the middle infrared.

A mild and efficient procedure for the synthesis of ethers from various alkyl halides

Directory of Open Access Journals (Sweden)

Mosstafa Kazemi

2013-10-01

Full Text Available A simple, mild and practical procedure has been developed for the synthesis of symmetrical and unsymmetrical ethers by using DMSO, TBAI in the presence of K2CO3. We extended the utility of Potassium carbonate as an efficient base for the preparation of ethers. A wide range of alkyl aryl and dialkyl ethers are synthezied from treatment of aliphatic alcohols and phenols with various alkyl halides in the prescence of efficient base Potassium carbonate. Secondary alkyl halides were easily converted to corresponding ethers in releatively good yields . This is a mild, simple and practical procedure for the preparation of ethers in high yields and suitable times under mild condition.

Investigation of sodalites for conditioning halide salts (NaCl and NaI): Comparison of two synthesis routes

Energy Technology Data Exchange (ETDEWEB)

Bardez, Isabelle; Campayo, Lionel; Rigaud, Danielle; Chartier, Myriam; Calvet, Aurelie [CEA, Laboratoire d' Etudes des Materiaux Ceramiques pour le Conditionnement, Site de Marcoule, Batiment 208, B.P. 17171, 30207 Bagnols sur Ceze cedex (France)

2008-07-01

Sodalites with the general formula Na{sub 8}Al{sub 6}Si{sub 6}O{sub 24}X{sub 2} (where X = Cl or I) were investigated for ceramic conditioning of halide salts (NaCl and NaI). Because of the tendency of halides to volatilize at high temperature, two synthesis routes were tested to optimize the halide content in the sodalite phase. The first is based on heating at high temperature of a [nepheline NaAlSiO{sub 4} + salt] mixture prepared by a dry process. The second, performed at low temperature, consists of the reaction in aqueous media between kaolinite (Al{sub 2}Si{sub 2}O{sub 5}(OH){sub 4}), sodium hydroxide (NaOH) and the salt. The present study compares these two syntheses and examines differences between chloro-sodalite and iodo-sodalite based on X-ray diffraction and infrared spectroscopy. The next step will consist in sintering the resulting powder samples to obtain dense ceramics. (authors)

Corrosion inhibition of iron in 0.5 mol L-1 H2SO4 by halide ions

Directory of Open Access Journals (Sweden)

Jeyaprabha C.

2006-01-01

Full Text Available The inhibition effect of halide ions such as iodide, bromide and chloride ions on the corrosion of iron in 0.5 mol L-1 H2SO4 and the adsorption behaviour of these ions on the electrode surface have been studied by polarization and impedance methods. It has been found that the inhibition of nearly 90% has been observed for iodide ions at 2.5 10-3 mol L-1, for bromide ions at 10 10-3 mol L-1 and 80% for chloride ions at 2.5 10-3 mol L-1. The inhibition effect is increased with increase of halide ions concentration in the case of I- and Br- ions, whereas it has decreased in the case of Cl- ion at concentrations higher than 5 10-3 mol L-1. The double layer capacitance values have decreased considerably in the presence of halide ions which indicate that these anions are adsorbed on iron at the corrosion potential.

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

KAUST Repository

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

2014-01-01

The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material.Despite recent advances, however, there are still a number of fundamental aspects of their formation as well

(e,2e) momentum spectroscopic study of the C=C π orbitals of the vinyl halides

International Nuclear Information System (INIS)

Gorunganthu, R.R.; Coplan, M.A.; Leung, K.T.; Tossell, J.A.; Moore, J.H.; Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada; Department of Chemistry, University of Maryland, College Park, Maryland 20742)

1989-01-01

The distribution of electron momentum density has been measured for the outermost occupied orbitals of the vinyl halides and ethylene using the (e,2e) technique. In contrast to the ionization potentials for these π orbitals which decrease monotonically from vinyl fluoride to vinyl iodide, the values of the momenta where the distributions are a maximum, p max , increase from the fluoride through the bromide and then shift back to a lower value for the iodide. This observation can be analyzed in terms of B(r), the Fourier transform of the observed momentum distribution, and ΔB(r), the difference between B(r) functions. The shape of ΔB(r) for the fluoride, chloride, and bromide in comparison to ethylene reflects the effect of the carbon--halogen antibonding interaction in these vinyl halides. On the other hand, in vinyl iodide the antibonding interaction is compensated for by the diffuse iodine 5p character of the molecular orbital. The relation of these observations to chemical properties of the vinyl halides is discussed along with differences between experiment and calculations at low momentum

Thermoluminescence response of a mixed ternary alkali halide crystals exposed to gamma rays

Energy Technology Data Exchange (ETDEWEB)

Rodriguez M, R.; Perez S, R. [Universidad de Sonora, Departamento de Investigacion en Fisica, Apdo. Postal 5-088, 83190 Hermosillo, Sonora (Mexico); Vazquez P, G.; Riveros, H. [UNAM, Instituto de Fisica, Apdo. Postal 20-364, 01000 Mexico D. F. (Mexico); Gonzalez M, P., E-mail: mijangos@cifus.uson.mx [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

2014-08-15

Ionic crystals, mainly alkali halide crystals have been the subject of intense research for a better understanding of the luminescence properties of defects induced by ionizing radiation. The defects in crystals can be produced in appreciable concentration due to elastic stresses, radiation, and addition of impurities. These defects exhibit remarkable thermoluminescence properties. This work is concerned with the Tl properties of a ternary alkali halide crystal after being irradiated with gamma and beta rays. It has been found that the Tl glow peak of the crystal follows a rule of average associated to the Tl Temperatures of the components of the mixture, similarly to the response of europium doped binary mixed crystals KCl{sub x}KBr{sub 1-x} and KBr{sub x}RbBr{sub 1-x}. (Author)

Steric Effects on the Binding of Phosphate and Polyphosphate Anions by Zinc(II) and Copper(II) Dinuclear Complexes of m-Xylyl-bis-cyclen.

Science.gov (United States)

Esteves, Catarina V; Esteban-Gómez, David; Platas-Iglesias, Carlos; Tripier, Raphaël; Delgado, Rita

2018-05-11

The triethylbenzene-bis-cyclen (cyclen = 1,4,7,10-tetraazacyclododecane) compound (tbmce) was designed with an imposed structural rigidity at the m-xylyl spacer to be compared to a less restrained and known parent compound (bmce). The framework of both compounds differs only in the substituents of the m-xylyl spacer. The study was centered in the differences observed in the acid-base reactions of both compounds, their copper(II) and zinc(II) complexation behaviors, as well as in the uptake of phosphate and polyphosphate anions (HPPi 3- , ATP 4- , ADP 3- , AMP 2- , PhPO 4 2- , and HPO 4 2- ). On the one hand, the acid-base reactions showed lower values for the third and fourth protonation constants of tbmce than for bmce, suggesting that the ethyl groups of the spacer in tbmce force the two cyclen units to more conformational restricted positions. On the other hand, the stability constant values for copper(II) and zinc(II) complexes revealed that bmce is a better chelator than tbmce pointing out to additional conformational restraints imposed by the triethylbenzene spacer. The binding studies of phosphates by the dinuclear copper(II) and zinc(II) complexes showed much smaller effective association constants for the dicopper complexes. Single-crystal X-ray and computational (density functional theory) studies suggest that anion binding promotes the formation of tetranuclear entities in which anions are bridging the metal centers. Our studies also revealed the dinuclear zinc(II) complex of bmce as a promising receptor for phosphate anions, with the largest effective association constant of 5.94 log units being observed for the formation of [Zn 2 bmce(HPPi)] + . Accordingly, a colorimetric study via an indicator displacement assay to detect phosphates in aqueous solution found that the [Zn 2 bmce] 4+ complex acts as the best receptor for pyrophosphate displaying a detection limit of 2.5 nM by changes visible to naked eye.

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

DEFF Research Database (Denmark)

Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J.

2014-01-01

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 27000 combinations, and have identified novel mixtures, with significantly improved storage......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...

Thermodynamics of Small Alkali Metal Halide Cluster Ions: Comparison of Classical Molecular Simulations with Experiment and Quantum Chemistry

Czech Academy of Sciences Publication Activity Database

Vlček, L.; Uhlík, F.; Moučka, F.; Nezbeda, Ivo; Chialvo, L.

2015-01-01

Roč. 119, č. 3 (2015), s. 488-500 ISSN 1089-5639 Institutional support: RVO:67985858 Keywords : monte-carlo simulations * molecular-dynamic simulations * classical drude oscillators Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.883, year: 2015

Modulation of electronic and optical properties in mixed halide perovskites CsPbCl3xBr3(1-x) and CsPbBr3xI3(1-x)

Science.gov (United States)

Zhou, Ziqi; Cui, Yu; Deng, Hui-Xiong; Huang, Le; Wei, Zhongming; Li, Jingbo

2017-03-01

The recent discovery of lead halide perovskites with band gaps in the visible presents important potential in the design of high efficient solar cells. CsPbCl3, CsPbBr3 and CsPbI3 are stable compounds within this new family of semiconductors. By performing the first-principles calculation, we explore the structural, electronic and optical properties of CsPbCl3xBr3(1-x) and CsPbBr3xI3(1-x) with various compositions of halide atoms. Structural stability is demonstrated with halide atoms distributing randomly at the halide atomic sites. CsPbCl3xBr3(1-x) and CsPbBr3xI3(1-x) exhibit the modulation of their band gaps by varying the halide composition. Our results also indicate that CsPbCl3xBr3(1-x) and CsPbBr3xI3(1-x) with different halide compositions are suitable to application to solar cells for the general features are well preserved. Good absorption to lights of different wavelengths has been obtained in these mixed halide perovskites.

Copper(II) complexes of alloferon 1 with point mutations (H1A) and (H9A) stability structure and biological activity.

Science.gov (United States)

Matusiak, Agnieszka; Kuczer, Mariola; Czarniewska, Elżbieta; Rosiński, Grzegorz; Kowalik-Jankowska, Teresa

2014-09-01

Mono- and polynuclear copper(II) complexes of the alloferon 1 with point mutations (H1A) A(1)GVSGH(6)GQH(9)GVH(12)G (Allo1A) and (H9A) H(1)GVSGH(6)GQA(9)GVH(12)G (Allo9A) have been studied by potentiometric, UV-visible, CD, EPR spectroscopic and mass spectrometry (MS) methods. To obtain a complete complex speciation different metal-to-ligand molar ratios ranging from 1:1 to 4:1 for Allo1A and to 3:1 for Allo9A were studied. The presence of the His residue in first position of the peptide chain changes the coordination abilities of the Allo9A peptide in comparison to that of the Allo1A. Imidazole-N3 atom of N-terminal His residue of the Allo9A peptide forms stable 6-membered chelate with the terminal amino group. Furthermore, the presence of two additional histidine residues in the Allo9A peptide (H(6),H(12)) leads to the formation of the CuL complex with 4N {NH2,NIm-H(1),NIm-H(6),NIm-H(12)} binding site in wide pH range (5-8). For the Cu(II)-Allo1A system, the results demonstrated that at physiological pH7.4 the predominant complex the CuH-1L consists of the 3N {NH2,N(-),CO,NIm} coordination mode. The inductions of phenoloxidase activity and apoptosis in vivo in Tenebrio molitor cells by the ligands and their copper(II) complexes at pH7.4 were studied. The Allo1A, Allo1K peptides and their copper(II) complexes displayed the lowest hemocytotoxic activity while the most active was the Cu(II)-Allo9A complex formed at pH7.4. The results may suggest that the N-terminal-His(1) and His(6) residues may be more important for their proapoptotic properties in insects than those at positions 9 and 12 in the peptide chain. Copyright © 2014 Elsevier Inc. All rights reserved.

Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides as Lewis Acidic Heterogeneous Catalysts. Providing Some Context for Nanostructured Metal Fluorides.

Science.gov (United States)

Lennon, David; Winfield, John M

2017-01-28

Aspects of the chemistry of selected metal fluorides, which are pertinent to their real or potential use as Lewis acidic, heterogeneous catalysts, are reviewed. Particular attention is paid to β-aluminum trifluoride, aluminum chlorofluoride and aluminas γ and η, whose surfaces become partially fluorinated or chlorinated, through pre-treatment with halogenating reagents or during a catalytic reaction. In these cases, direct comparisons with nanostructured metal fluorides are possible. In the second part of the review, attention is directed to iron(III) and copper(II) metal chlorides, whose Lewis acidity and potential redox function have had important catalytic implications in large-scale chlorohydrocarbons chemistry. Recent work, which highlights the complexity of reactions that can occur in the presence of supported copper(II) chloride as an oxychlorination catalyst, is featured. Although direct comparisons with nanostructured fluorides are not currently possible, the work could be relevant to possible future catalytic developments in nanostructured materials.

The importance of moisture in hybrid lead halide perovskite thin film fabrication

NARCIS (Netherlands)

Eperon, G.E.; Habisreutinger, S.N.; Leijtens, T.; Bruijnaers, B.J.; van Franeker, J.J.; deQuilettes, D.W.; Pathak, S.; Sutton, R.J.; Grancini, G.; Ginger, D.S.; Janssen, R.A.J.; Petrozza, A.; Snaith, H.J.

2015-01-01

Moisture, in the form of ambient humidity, has a significant impact on methylammonium lead halide perovskite films. In particular, due to the hygroscopic nature of the methylammonium component, moisture plays a significant role during film formation. This issue has so far not been well understood

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

Science.gov (United States)

2010-07-01

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

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

Science.gov (United States)

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.

Protonation of octadecylamine Langmuir monolayer by adsorption of halide counterions

Science.gov (United States)

Sung, Woongmo; Avazbaeva, Zaure; Lee, Jonggwan; Kim, Doseok

Langmuir monolayer consisting of octadecylamine (C18H37NH2, ODA) was investigated by heterodyne vibrational sum-frequency generation (HD-VSFG) spectroscopy in conjunction with surface pressure-area (π- A) isotherm, and the result was compared with that from cationic-lipid (DPTAP) Langmuir monolayer. In case of ODA monolayer on pure water, both SF intensity of water OH band and the surface pressure were significantly smaller than those of the DPTAP monolayer implying that only small portion of the amine groups (-NH3+ is protonated in the monolayer. In the presence of sodium halides (NaCl and NaI) in the subphase water, it was found that the sign of Imχ (2) of water OH band remained the same as that of the ODA monolayer on pure water, but there was a substantial increase in the SF amplitude. From this, we propose that surface excess of the halide counterions (Cl- and I-) makes the solution condition near the ODA monolayer/water interface more acidic so that ODA molecules in the monolayer are more positively charged, which works to align the water dipoles at the interface.

Multitarget trehalose-carnosine conjugates inhibit Aβ aggregation, tune copper(II) activity and decrease acrolein toxicity.

Science.gov (United States)

Grasso, Giuseppa Ida; Bellia, Francesco; Arena, Giuseppe; Satriano, Cristina; Vecchio, Graziella; Rizzarelli, Enrico

2017-07-28

Increasing evidence is accumulating, showing that neurodegenerative disorders are somehow associated with the toxicity of amyloid aggregates, metal ion dyshomeostasis as well as with products generated by oxidative stress. Within the biological oxidation products, acrolein does have a prominent role. A promising strategy to deal with the above neurogenerative disorders is to use multi-functions bio-molecules. Herein, we show how a class of bio-conjugates takes advantage of the antiaggregating, antioxidant and antiglycating properties of trehalose and carnosine. Their ability to sequester acrolein and to inhibit both self- and metal-induced aggregation is here reported. The copper(II) coordination properties of a new trehalose-carnosine conjugate and the relative antioxidant effects have also been investigated. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Complexes cobalt(II, zinc(II and copper(II with some newly synthesized benzimidazole derivatives and their antibacterial activity

Directory of Open Access Journals (Sweden)

S. O. PODUNAVAC-KUZMANOVIC

1999-05-01

Full Text Available The preparation and properties of some complexes of cobalt(II, zinc(II and copper(II with several newly synthesized benzimidazole derivatives (L are reported. The complexes, of the general formula [MCl2L2] (M=Co(II, Zn(II and [CuCl2L(H2O], have a tetrahedral structure. The complexes were characterized by elemental analysis, molar conductivity, magnetic susceptibility measurements, IR and absorption electronic spectra. The antibacterial activitiy of the benzimidazoles and their complexes was evaluated against Erwinia carotovora subsp. carotovora and Erwinia amylovora. The complexes were found to be more toxic than the ligands.

A Nanostructured Lipid System as a Strategy to Improve the in Vitro Antibacterial Activity of Copper(II Complexes

Directory of Open Access Journals (Sweden)

Patricia B. da Silva

2015-12-01

Full Text Available The aim of this study was to construct a nanostructured lipid system as a strategy to improve the in vitro antibacterial activity of copper(II complexes. New compounds with the general formulae [CuX2(INH2]·nH2O (X = Cl− and n = 1 (1; X = NCS− and n = 5 (2; X = NCO− and n = 4 (3; INH = isoniazid, a drug widely used to treat tuberculosis derived from the reaction between the copper(II chloride and isoniazid in the presence or absence of pseudohalide ions (NCS− or NCO− were synthesized and characterized by infrared spectrometry, electronic absorption spectroscopy, electron paramagnetic resonance (EPR spectroscopy, elemental analysis, melting points and complexometry with 2,2′,2′′,2′′′-(Ethane-1,2-diyldinitrilotetraacetic acid (EDTA. The characterization techniques allowed us to confirm the formation of the copper(II complexes. The Cu(II complexes were loaded into microemulsion (MEs composed of 10% phase oil (cholesterol, 10% surfactant [soy oleate and Brij® 58 (1:2] and 80% aqueous phase (phosphate buffer pH = 7.4 prepared by sonication. The Cu(II complex-loaded MEs displayed sizes ranging from 158.0 ± 1.060 to 212.6 ± 1.539 nm, whereas the polydispersity index (PDI ranged from 0.218 ± 0.007 to 0.284 ± 0.034. The antibacterial activity of the free compounds and those that were loaded into the MEs against Staphylococcus aureus ATCC® 25923 and Escherichia coli ATCC® 25922, as evaluated by a microdilution technique, and the cytotoxicity index (IC50 against the Vero cell line (ATCC® CCL-81TM were used to calculate the selectivity index (SI. Among the free compounds, only compound 2 (MIC 500 μg/mL showed activity for S. aureus. After loading the compounds into the MEs, the antibacterial activity of compounds 1, 2 and 3 was significantly increased against E. coli (MIC’s 125, 125 and 500 μg/mL, respectively and S. aureus (MICs 250, 500 and 125 μg/mL, respectively. The loaded compounds were less toxic against the Vero

Copper(II) and palladium(II) complexes with tridentate NSO donor Schiff base ligand: Synthesis, characterization and structures

Science.gov (United States)

Kumar, Sujit Baran; Solanki, Ankita; Kundu, Suman

2017-09-01

Mononuclear copper(II) complex [CuL2] and palladium(II) complexes [Pd(X)L] where X = benzoate(bz) or salicylate(sal) and HL = 2-(methylthio)phenylimino)methyl)phenol, a Schiff base ligand with NSO coordination sites have been synthesized and characterized by microanalyses, IR, UV-Visible spectra, conductivity measurement and magnetic studies. Crystal structures of all the complexes have been solved by single crystal X-ray diffraction studies and showed that there are two molecules in a unit cell in the [CuL2] complex - one molecule has square planar geometry whereas second molecule has distorted square pyramidal geometry and palladium(II) complexes have distorted square planar geometry.

Combinatorial screening of halide perovskite thin films and solar cells by mask-defined IR laser molecular beam epitaxy

OpenAIRE

Kawashima, Kazuhiro; Okamoto, Yuji; Annayev, Orazmuhammet; Toyokura, Nobuo; Takahashi, Ryota; Lippmaa, Mikk; Itaka, Kenji; Suzuki, Yoshikazu; Matsuki, Nobuyuki; Koinuma, Hideomi

2017-01-01

Abstract As an extension of combinatorial molecular layer epitaxy via ablation of perovskite oxides by a pulsed excimer laser, we have developed a laser molecular beam epitaxy (MBE) system for parallel integration of nano-scaled thin films of organic?inorganic hybrid materials. A pulsed infrared (IR) semiconductor laser was adopted for thermal evaporation of organic halide (A-site: CH3NH3I) and inorganic halide (B-site: PbI2) powder targets to deposit repeated A/B bilayer films where the thic...

Analogy between temperature dependent radiation effects in alkali halide crystals and crystalline ammonia

International Nuclear Information System (INIS)

Blum, A.

1977-01-01

Pikaev, Ershov, and Makarov recently reported the characteristic shape of Arrhenius-type dependence for F-centers slow part (millisecond) decay in alkali halide crystals irradiated at different temperatures. The decay rate is constant when the temperature is below the limiting value (T/sub lim/) and exhibits constant activation energy (E/sub A/) at temperatures above T/sub lim/ up to the melting point. A similar dependence has been observed for crystalline ammonia radiolysis yields (H 2 and N 2 ) in the temperature range from 77 to 195 0 K (ammonia melting point) with a limiting value of 105 0 K for N 2 and 119 0 K for H 2 . The coincidence between the alkali halide and ammonia data does not seem to be formal and there are indications showing a closer analogy between these two cases

Intrinsic Defect Physics in Indium-based Lead-free Halide Double Perovskites.

Science.gov (United States)

Xu, Jian; Liu, Jian-Bo; Liu, Bai-Xin; Huang, Bing

2017-09-21

Lead-free halide double perovskites (HDPs) are expected to be promising photovoltaic (PV) materials beyond organic-inorganic halide perovskite, which is hindered by its structural instability and toxicity. The defect- and stability-related properties of HDPs are critical for the use of HDPs as important PV absorbers, yet their reliability is still unclear. Taking Cs 2 AgInBr 6 as a representative, we have systemically investigated the defect properties of HDPs by theoretical calculations. First, we have determined the stable chemical potential regions to grow stoichiometric Cs 2 AgInBr 6 without structural decomposition. Second, we reveal that Ag-rich and Br-poor are the ideal chemical potential conditions to grow n-type Cs 2 AgInBr 6 with shallow defect levels. Third, we find the conductivity of Cs 2 AgInBr 6 can change from good n-type, to poorer n-type, to intrinsic semiconducting depending on the growth conditions. Our studies provided important guidance for experiments to fabricate Pb-free perovskite-based solar cell devices with superior PV performances.

Sodium-Metal-Halide Battery Energy Storage for DoD Installations

Science.gov (United States)

2017-10-24

electrical equipment for AC interface PDE Pacific Data Electric V&F Voltage and Frequency, power quality measurements VA Volt-Amp, units for apparent...Metal-Halide technology could operate at extreme ambient temperatures, but the early prototypes did struggle with managing sand ingress.  The...peak power Not tested 3. PV smoothing Measure improvement in power quality Power meter measurements Power quality improvements 15-min

Copper(II) cyanido-bridged bimetallic nitroprusside-based complexes: Syntheses, X-ray structures, magnetic properties, 57Fe Moessbauer spectroscopy and thermal studies

International Nuclear Information System (INIS)

Travnicek, Zdenek; Herchel, Radovan; Mikulik, Jiri; Zboril, Radek

2010-01-01

Three heterobimetallic cyanido-bridged copper(II) nitroprusside-based complexes of the compositions [Cu(tet)Fe(CN) 5 NO].H 2 O (1), where tet=N,N'-bis(3-aminopropyl)ethylenediamine, [Cu(hto)Fe(CN) 5 NO].2H 2 O (2), where hto=1,3,6,9,11,14-hexaazatricyclo[12.2.1.1 6,9 ]octadecane and [Cu(nme) 2 Fe(CN) 5 NO].H 2 O (3), where nme=N-methylethylenediamine, were synthesized and characterized by elemental analyses, 57 Fe Moessbauer and FTIR spectroscopies, thermal analysis, magnetic measurements and single-crystal X-ray analysis. The products of thermal degradation processes of 2 and 3 were studied by XRD, 57 Fe Moessbauer spectroscopy, SEM and EDS, and they were identified as mixtures of CuFe 2 O 4 and CuO. - Three heterobimetallic cyano-bridged copper(II) nitroprusside-based complexes of the general compositions of [Cu(L)Fe(CN) 5 NO].xH 2 O, where L=N,N'-bis(3-aminopropyl)ethylenediamine (complex 1), 1,3,6,9,11,14-hexaazatricyclo[12.2.1.1 6,9 ]-octadecane (complex 2) and N-methylethylenediamine (complex 3), were synthesized, and fully structurally and magnetically characterized. SEM, EDS, XRD and 57 Fe Moessbauer experiments were used for characterization of thermal decomposition products of complexes 2 and 3.

Rapid Microwave-Assisted Copper-Catalyzed Nitration of Aromatic Halides with Nitrite Salts

Energy Technology Data Exchange (ETDEWEB)

Paik, Seung Uk; Jung, Myoung Geun [Keimyung University, Daegu (Korea, Republic of)

2012-02-15

A rapid and efficient copper-catalyzed nitration of aryl halides has been established under microwave irradiation. The catalytic systems were found to be the most effective with 4-substituted aryl iodides leading to nearly complete conversions. Nitration of aromatic compounds is one of the important industrial processes as underlying intermediates in the manufacture of a wide range of chemicals such as dyes, pharmaceuticals, agrochemicals and explosives. General methods for the nitration of aromatic compounds utilize strongly acidic conditions employing nitric acid or a mixture of nitric and sulfuric acids, sometimes leading to problems with poor regioselectivity, overnitration, oxidized byproducts and excess acid waste in many cases of functionalized aromatic compounds. Several other nitrating agents or methods avoiding harsh reaction conditions have been explored using metal nitrates, nitrite salts, and ionic liquid-mediated or microwave-assisted nitrations. Recently, copper or palladium compounds have been successfully used as efficient catalysts for the arylation of amines with aryl halides under mild conditions.

Efficient Photon Recycling and Radiation Trapping in Cesium Lead Halide Perovskite Waveguides

KAUST Repository

Dursun, Ibrahim

2018-05-26

Cesium lead halide perovskite materials have attracted considerable attention for potential applications in lasers, light emitting diodes and photodetectors. Here, we provide the experimental and theoretical evidence for photon recycling in CsPbBr3 perovskite microwires. Using two-photon excitation, we recorded photoluminescence (PL) lifetimes and emission spectra as a function of the lateral distance between PL excitation and collection positions along the microwire, with separations exceeding 100 µm. At longer separations, the PL spectrum develops a red-shifted emission peak accompanied by an appearance of well-resolved rise times in the PL kinetics. We developed quantitative modeling that accounts for bimolecular recombination and photon recycling within the microwire waveguide and is sufficient to account for the observed decay modifications. It relies on a high radiative efficiency in CsPbBr3 perovskite microwires and provides crucial information about the potential impact of photon recycling and waveguide trapping on optoelectronic properties of cesium lead halide perovskite materials.

Rapid Microwave-Assisted Copper-Catalyzed Nitration of Aromatic Halides with Nitrite Salts

International Nuclear Information System (INIS)

Paik, Seung Uk; Jung, Myoung Geun

2012-01-01

A rapid and efficient copper-catalyzed nitration of aryl halides has been established under microwave irradiation. The catalytic systems were found to be the most effective with 4-substituted aryl iodides leading to nearly complete conversions. Nitration of aromatic compounds is one of the important industrial processes as underlying intermediates in the manufacture of a wide range of chemicals such as dyes, pharmaceuticals, agrochemicals and explosives. General methods for the nitration of aromatic compounds utilize strongly acidic conditions employing nitric acid or a mixture of nitric and sulfuric acids, sometimes leading to problems with poor regioselectivity, overnitration, oxidized byproducts and excess acid waste in many cases of functionalized aromatic compounds. Several other nitrating agents or methods avoiding harsh reaction conditions have been explored using metal nitrates, nitrite salts, and ionic liquid-mediated or microwave-assisted nitrations. Recently, copper or palladium compounds have been successfully used as efficient catalysts for the arylation of amines with aryl halides under mild conditions

Radiation processes in organic halides (Cl, Br, I) studied by ESR spectroscopy

International Nuclear Information System (INIS)

Symons, M.C.R.

1980-01-01

Electron-loss from alkyl halides (Cl, Br, I) gives Rhal. + which may dimerise to give (Rhal-halR) + σ* radicals with characteristic ESR spectra, or may lose H + to give α-halo radicals (R 2 Chal) also with well characterised ESR spectra. Electron-capture gives dissociation, but there may be weak residual charge-transfer interaction between R. and hal - which gives rise to well defined hyperfine coupling from the halide nuclei. Loss of β-hydrogen gives β-halo radicals, R 2 C-CH 2 hal (Cl,Br) whose conformation, established by ESR spectroscopy, is such that the halogen atom lies out of the radical plane so that overlap between the half-filled 2p(π) orbital and the C-hal (σ) orbital is maximised. Electron addition to α-halocarboxylates and related compounds probably gives β-halo radical anions, (R 2 C[hal]CO 2 H) - with a similar preferred conformation. Alternative structures are considered for these species. (author)

Energetics and dynamics in organic–inorganic halide perovskite photovoltaics and light emitters

International Nuclear Information System (INIS)

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

2015-01-01

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

Relationship between thermoluminescence and X-ray induced luminescence in alkali halides

International Nuclear Information System (INIS)

Aguilar, M.; Lopez, F.J.; Jaque, F.

1978-01-01

The wavelength spectra of thermoluminescence and X-ray induced luminescence in pure and divalent cation doped alkali halides, in the temperature range LNT-RT have been studied. The more important conclusion is that the wavelength spectra in both cases are very similar. This allows a new point of view to be presented on thermoluminescence mechanisms. (author)

Special features of the formation of high-conductivity phases of halides of alkali metals at superhigh pressures

International Nuclear Information System (INIS)

Babushkin, A.N.; Babushkina, G.V.

1999-01-01

The halides of alkali metals are the simplest crystals with the ionic nature of chemical bonds and are used widely as modelling materials in high-pressure physics. As a result of previous theoretical and experimental (optical, structural, electro-physical and shock-waves) investigations it was shown that these materials may be characterised by the overlapping of the valency and conduction bands and by the formation of groups of free charge carriers at pressures of the megabaric level. However, the authors know of no data on the direct investigations of the electrophysical properties of the halides of alkali metals at such high static pressures. The end of this investigation was to examine the temperature dependences of the electrical conductivity and thermal EMF of halides of alkali metals AX (A = Na, K, Rb, Cs, X = Cl, Br, I) in a wide temperature range at pressures from 10 to 50 GPa in order to reveal the general leisure since governing the change of their electronic structures, in particular, the transition to the state with the activation-type or metallic conductivity

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Energy Technology Data Exchange (ETDEWEB)

Shmyreva, Anna A. [Center for Magnetic Resonance, St. Petersburg State University, St. Petersburg 198504 (Russian Federation); Safdari, Majid; Furó, István [Department of Chemistry, KTH Royal Institute of Technology, SE-10044 Stockholm (Sweden); Dvinskikh, Sergey V., E-mail: sergeid@kth.se [Department of Chemistry, KTH Royal Institute of Technology, SE-10044 Stockholm (Sweden); Laboratory of Biomolecular NMR, St. Petersburg State University, St. Petersburg 199034 (Russian Federation)

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 enhancement 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.

Luminescent decay and spectra of impurity-activated alkali halides under high pressure

International Nuclear Information System (INIS)

Klick, D.I.

1977-01-01

The effect of high pressure on the luminescence of alkali halides doped with the transition-metal ions Cu + and Ag + and the heavy-metal ions In + and Tl + was investigated to 140 kbar. Measurement of spectra allowed the prediction of kinetic properties, and the predictions agree with lifetime data

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

2010-07-01

... Halogen HAP Emissions or HAP Metals Emissions From Process Vents 3 Table 3 to Subpart FFFF of Part 63... 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...

Quantitative positron annihilation studies in citrates, halides and oxyhalides chemisorbed on γ-alumina catalyst

International Nuclear Information System (INIS)

Luo, X.H.; Jean, Y.C.; Cheng, K.L.

1987-01-01

A quantitative study of the γ-alumina catalyst chemisorbed by nitrates, halides, and oxyhalides has been conducted with the positron annihilation spectroscopy (PAS). Catalysts containing Fe, Co, or Ni have been extensively used in chemical industry and petroleum refining. The positron or Ps annihilation can provide a profile information about the bulk, near surface, and void. It is an in-situ surface technique. The PAS technique has shown its capability to determine the nitrate or chloride in γ-alumina as low as 0.02% in solids. It is interesting to note that the PAS may offer the oxidation state information in solids. This is not surprising because the positron annihilation is sensitive to the electron density variation in environments. Positron annihilation models for halides and oxyhalides are proposed

Linear chrono-amperometry using re-dissolution: application to halides

International Nuclear Information System (INIS)

Perchard, J.-P.; Buvet, M.; Molina, R.

1966-06-01

The possibility of applying linear chrono-amperometry to analysis was studied using a falling-drop mercury electrode. Measurements of the cations were carried out by direct reduction or by prior formation of an amalgam, which is then oxidized. Using the first technique, the minimum concentration that can be attained is about 10 -6 M and the reproducibility of the results is of the order of 2%. With the second method the sensitivity is much improved: in the concentration range of 10 -7 to 10 -8 M, the scatter of the results is less than 10% if the agitation and temperature conditions are kept constant. The halides are determined by re-dissolving the mercurous halide deposit formed by electrolysis. From the analytical point of view, the sensitivity is limited in the domain where the phenomena can be interpreted and used. In the case of the chloride ion the lower limit of this zone is close to 10 -5 M; it is 10 -6 M for the bromide and less than 10 -7 M for the iodide. For lower concentrations, simple laws that might be applied in analysis are no longer valid. However, the splitting of the peak observed during the reduction of the mercurous iodide deposit was interpreted as showing that the mono-molecular Hg 2 I 2 layer formed on the drop has particular electrochemical properties. (authors) [fr

Formation of a dinuclear copper(II) complex through the cleavage of CN bond of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole

Energy Technology Data Exchange (ETDEWEB)

Shardin, Rosidah; Pui, Law Kung; Yamin, Bohari M. [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, UKM 43600 Bangi, Selangor (Malaysia); Kassim, Mohammad B. [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, UKM 43600 Bangi, Selangor, Malaysia and Fuel Cell Institute, Universiti Kebangsaan Malaysia, UKM 43600 Bangi, Selangor (Malaysia)

2014-09-03

A simple mononuclear octahedral copper(II) complex was attempted from the reaction of three moles of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole and one mole of copper(II) perchlorate hexahydrate in methanol. However, the product of the reaction was confirmed to be a dinuclear copper(II) complex with μ-(3-(pyridin-2-yl)-pyrazolato) and 3-(pyridin-2-yl)-1H-pyrazole ligands attached to each of the Cu(II) centre atom. The copper(II) ion assisted the cleavage of the C{sub benzoyl}N bond afforded a 3-(pyridin-2-yl)-1H-pyrazole molecule. Deprotonation of the 3-(pyridin-2-yl)-1H-pyrazole gave a 3-(pyridin-2-yl)-pyrazolato, which subsequently reacted with the Cu(II) ion to give the (3-(pyridin-2-yl)-pyrazolato)(3-(pyridin-2-yl)-1H-pyrazole)Cu(II) product moiety. The structure of the dinuclear complex was confirmed by x-ray crystallography. The complex crystallized in a monoclinic crystal system with P2(1)/n space group and cell dimensions of a = 12.2029(8) Å, b = 11.4010(7) Å, c = 14.4052(9) Å and β = 102.414(2)°. The compound was further characterized by mass spectrometry, CHN elemental analysis, infrared and UV-visible spectroscopy and the results concurred with the x-ray structure. The presence of d-d transition at 671 nm (ε = 116 dm{sup 3} mol{sup −1} cm{sup −1}) supports the presence of Cu(II) centres.

Ferromagnetic interaction in an asymmetric end-to-end azido double-bridged copper(II) dinuclear complex: a combined structure, magnetic, polarized neutron diffraction and theoretical study.

Science.gov (United States)

Aronica, Christophe; Jeanneau, Erwann; El Moll, Hani; Luneau, Dominique; Gillon, Béatrice; Goujon, Antoine; Cousson, Alain; Carvajal, Maria Angels; Robert, Vincent

2007-01-01

A new end-to-end azido double-bridged copper(II) complex [Cu(2)L(2)(N(3))2] (1) was synthesized and characterized (L=1,1,1-trifluoro-7-(dimethylamino)-4-methyl-5-aza-3-hepten-2-onato). Despite the rather long Cu-Cu distance (5.105(1) A), the magnetic interaction is ferromagnetic with J= +16 cm(-1) (H=-JS(1)S(2)), a value that has been confirmed by DFT and high-level correlated ab initio calculations. The spin distribution was studied by using the results from polarized neutron diffraction. This is the first such study on an end-to-end system. The experimental spin density was found to be localized mainly on the copper(II) ions, with a small degree of delocalization on the ligand (L) and terminal azido nitrogens. There was zero delocalization on the central nitrogen, in agreement with DFT calculations. Such a picture corresponds to an important contribution of the d(x2-y2) orbital and a small population of the d(z2) orbital, in agreement with our calculations. Based on a correlated wavefunction analysis, the ferromagnetic behavior results from a dominant double spin polarization contribution and vanishingly small ionic forms.

Synthesis of mononuclear copper(II) complexes of N3O2 and N4O2 donors containing Schiff base ligands: Theoretical and biological observations

Science.gov (United States)

Mancha Madha, K.; Gurumoorthy, P.; Arul Antony, S.; Ramalakshmi, N.

2017-09-01

A new series of six mononuclear copper(II) complexes were synthesized from N3O2 and N4O2 donors containing Schiff base ligands, and characterized by various spectral methods. The geometry of the complexes was determined using UV-Vis, EPR and DFT calculations. The complexes of N3O2 donors (1-3) adopted square pyramidal geometry and the remaining complexes of N4O2 donors (4-6) show distorted octahedral geometry around copper(II) nuclei. Redox properties of the complexes show a one-electron irreversible reduction process in the cathodic potential (Epc) region from -0.74 to -0.98 V. The complexes show potent antioxidant activity against DPPH radicals. Molecular docking studies of complexes showed σ-π interaction, hydrogen bonding, electrostatic and van der Waals interactions with VEGFR2 kinase receptor. In vitro cytotoxicity of the complexes was tested against human breast cancer (MDA-MB-231) cell lines and one normal human dermal fibroblasts (NHDF) cell line through MTT assay. The morphological assessment data obtained by Hoechst 33258 and AO/EB staining revealed that the complexes induce apoptosis pathway of cell death.

Radiophotoluminescence of alkali-halide crystals stimulated by Bessel laser beam

CERN Document Server

Lyakh, V V; Kochubey, D I; Gyunsburg, K E; Zvezdova, N P; Kochubey, D I; Sedova, Y G; Koronkevich, V P; Poleschuk, A G; Sedukhin, A G

2000-01-01

A new approach to realization of optimal high-resolution reading of deep X-ray images in X-ray-sensitive materials on the base of alkali-halide crystals modified with admixtures has been suggested and investigated experimentally. A possibility to use diffraction axicons with ring aperture for forming micron bright light beams (spatially truncated Bessel beams) which can efficiently de-excite radiophotoluminescence centers lying at large depth in crystals is also presented.

Unusual saccharin-N,O (carbonyl) coordination in mixed-ligand copper(II) complexes: Synthesis, X-ray crystallography and biological activity

Science.gov (United States)

Mokhtaruddin, Nur Shuhada Mohd; Yusof, Enis Nadia Md; Ravoof, Thahira B. S. A.; Tiekink, Edward R. T.; Veerakumarasivam, Abhi; Tahir, Mohamed Ibrahim Mohamed

2017-07-01

Three tridentate Schiff bases containing N and S donor atoms were synthesized via the condensation reaction between S-2-methylbenzyldithiocarbazate with 2-acetyl-4-methylpyridine (S2APH); 4-methyl-3-thiosemicarbazide with 2-acetylpyridine (MT2APH) and 4-ethyl-3-thiosemicarbazide with 2-acetylpyridine (ET2APH). Three new, binuclear and mixed-ligand copper(II) complexes with the general formula, [Cu(sac)(L)]2 (sac = saccharinate anion; L = anion of the Schiff base) were then synthesized, and subsequently characterized by IR and UV/Vis spectroscopy as well as by molar conductivity and magnetic susceptibility measurements. The Schiff bases were also spectroscopically characterized using NMR and MS to further confirm their structures. The spectroscopic data indicated that the Schiff bases behaved as a tridentate NNS donor ligands coordinating via the pyridyl-nitrogen, azomethine-nitrogen and thiolate-sulphur atoms. Magnetic data indicated a square pyramidal environment for the complexes and the conductivity values showed that the complexes were essentially non-electrolytes in DMSO. The X-ray crystallographic analysis of one complex, [Cu(sac)(S2AP)]2 showed that the Cu(II) atom was coordinated to the thiolate-S, azomethine-N and pyridyl-N donors of the S2AP Schiff base and to the saccharinate-N from one anion, as well as to the carbonyl-O atom from a symmetry related saccharinate anion yielding a centrosymmetric binuclear complex with a penta-coordinate, square pyramidal geometry. All the copper(II) saccharinate complexes were found to display strong cytotoxic activity against the MCF-7 and MDA-MB-231 human breast cancer cell lines.

F-center and self-trapped exciton formation in strongly excited alkali halide crystals

International Nuclear Information System (INIS)

Kravchenko, V.A.; Yakovlev, V.Yu.

1988-01-01

Method of luminescent and absorption spectroscopy with time resolution was used to study the effect of density of electron pulse excitation (t p =10 -8 s, P=(10 5 -10 8 ) WXcm -2 ) on efficiency of η ε two-halide autolocalized exciton (TALE) and F-centers (η F ) formation in CsI, CsBr, KBr, KI alkali halide crystals. It was established that for all studied systems the elevation of P power of electron beam (EB) from 10 5 up to 5X10 7 WXcm -2 resulted to sufficient decrease of production efficiency and yield of TALE luminescence. In the case when F-centers of colour are induced predominantly by pulsed irradiation in crystals, F-center yield is independent of P. If F-centers and TALE are produced in comparable amounts (CsBr crystals, T=80 K), η ε decrease with P growth is accompanied by η F growth

A Simple Halide-to-Anion Exchange Method for Heteroaromatic Salts and Ionic Liquids

Directory of Open Access Journals (Sweden)

Neus Mesquida

2012-04-01

Full Text Available A broad and simple method permitted halide ions in quaternary heteroaromatic and ammonium salts to be exchanged for a variety of anions using an anion exchange resin (A− form in non-aqueous media. The anion loading of the AER (OH− form was examined using two different anion sources, acids or ammonium salts, and changing the polarity of the solvents. The AER (A− form method in organic solvents was then applied to several quaternary heteroaromatic salts and ILs, and the anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Relying on the hydrophobicity of the targeted ion pair for the counteranion swap, organic solvents with variable polarity were used, such as CH3OH, CH3CN and the dipolar nonhydroxylic solvent mixture CH3CN:CH2Cl2 (3:7 and the anion exchange was equally successful with both lipophilic cations and anions.

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

Science.gov (United States)

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.

A new approach for crystallization of copper(ii) oxide hollow nanostructures with superior catalytic and magnetic response

Science.gov (United States)

Singh, Inderjeet; Landfester, Katharina; Chandra, Amreesh; Muñoz-Espí, Rafael

2015-11-01

We report the synthesis of copper(ii) oxide hollow nanostructures at ambient pressure and close to room temperature by applying the soft templating effect provided by the confinement of droplets in miniemulsion systems. Particle growth can be explained by considering a mechanism that involves both diffusion and reaction control. The catalytic reduction of p-nitrophenol in aqueous media is used as a model reaction to prove the catalytic activity of the materials: the synthesized hollow structures show nearly 100 times higher rate constants than solid CuO microspheres. The kinetic behavior and the order of the reduction reaction change due to the increase of the surface area of the hollow structures. The synthesis also leads to modification of physical properties such as magnetism.We report the synthesis of copper(ii) oxide hollow nanostructures at ambient pressure and close to room temperature by applying the soft templating effect provided by the confinement of droplets in miniemulsion systems. Particle growth can be explained by considering a mechanism that involves both diffusion and reaction control. The catalytic reduction of p-nitrophenol in aqueous media is used as a model reaction to prove the catalytic activity of the materials: the synthesized hollow structures show nearly 100 times higher rate constants than solid CuO microspheres. The kinetic behavior and the order of the reduction reaction change due to the increase of the surface area of the hollow structures. The synthesis also leads to modification of physical properties such as magnetism. Electronic supplementary information (ESI) available: Associated structural and morphological analysis, XPS characterization, BET surface area, catalytic measurements, recycle tests of the catalyst, and magnetic characterizations. See DOI: 10.1039/c5nr05579b

Nature of the superionic transition in Ag+ and Cu+ halides

International Nuclear Information System (INIS)

Keen, D.A.; Hull, S.; Barnes, A.C.; Berastegui, P.; Crichton, W.A.; Madden, P.A.; Tucker, M.G.; Wilson, M.

2003-01-01

Silver and copper halides generally display an abrupt (first-order) transition to the superionic state. However, powder diffraction studies and molecular dynamics (MD) simulations of AgI under hydrostatic pressure both indicate that a continuous superionic transition occurs on heating. The gradual onset of the highly conducting state is accompanied by an increasing fraction of dynamic Frenkel defects, a peak in the specific heat and anomalous behavior of the lattice expansion. Similar methods have been employed to investigate the proposed continuous superionic transition between the two ambient pressure face centered cubic phases of CuI. This is difficult to examine experimentally, because the hexagonal β phase exists over a narrow temperature range between the γ (cation ordered) and α (cation disordered) phases. MD simulations performed with the simulation box constrained to remain cubic at all temperatures show that, although limited Cu + Frenkel disorder occurs within γ-CuI, CuI undergoes an abrupt superionic transition at 670 K to the superionic α phase. This is supported by powder neutron diffraction studies of CuI lightly doped with Cs + to prevent stabilization of the β phase. The implications of these results on the phase transitions of other copper and silver halide superionic conductors are discussed

Dehalogenation of aromatic halides by polyaniline/zero-valent iron composite nanofiber: Kinetics and mechanisms

CSIR Research Space (South Africa)

Giri, S

2016-03-01

Full Text Available Dehalogenation of aryl halides was demonstrated using polyaniline/zero valent iron composite nanofiber (termed as PANI/Fe0) as a cheap, efficient and environmentally friendly heterogeneous catalyst. The catalyst was prepared via rapid mixing...

Kinetics of halide release of haloalkane dehalogenase : Evidence for a slow conformational change

NARCIS (Netherlands)

Schanstra, JP; Janssen, DB; Schanstra, Joost P.

1996-01-01

Haloalkane dehalogenase converts haloalkanes to their corresponding alcohols and halides, The reaction mechanism involves the formation of a covalent alkyl-enzyme complex which is hydrolyzed by water. The active site is a hydrophobic cavity buried between the main domain and the cap domain of the

2-D images of the metal-halide lamp obtained by experiment and model

NARCIS (Netherlands)

Flikweert, A.J.; Beks, M.L.; Nimalasuriya, T.; Kroesen, G.M.W.; Mullen, van der J.J.A.M.; Stoffels, W.W.

2008-01-01

The metal-halide lamp shows color segregation caused by diffusion and convection. Two-dimensional imaging of the arc discharge under varying gravity conditions aids in the understanding of the flow phenomena. In this paper, we show results obtained by experiments and by numerical simulations in

Behaviour of alkali halides as materials for optical components of high power lasers

International Nuclear Information System (INIS)

Apostol, D.I.; Mihailescu, N.I.; Ghiordanescu, V.; Nistor, C.L.; Nistor, V.S.; Teodorescu, V.; Voda, M.

1978-01-01

The physical phenomena taking place in alkali halides when a CO 2 laser radiation is passing through have been reviewed. A special emphasis has been put on the specific qualities which such materials should have for being used as components for high power lasers. (author)

Copper(II) oxide solubility behavior in aqueous sodium phosphate solutions at elevated temperatures

International Nuclear Information System (INIS)

Ziemniak, S.E.; Jones, M.E.; Combs, K.E.S.

1990-02-01

A platinum-lined, flowing autoclave facility is used to investigate the solubility behavior of copper(II) oxide (CuO) in aqueous sodium phosphate solutions at temperatures between 292 and 535 K. Copper solubilities are observed to increase continuously with temperature and phosphate concentration. The measured solubility is examined via a Cu(II) ion hydrolysis/complexing model and thermodynamic functions for the hydrolysis/complexing reactions are obtained from a least- squares analysis of the data. Altogether, thermochemical properties are established for five anionic complexes: Cu(OH) 3 - , Cu(OH) 4 = , Cu(OH) 2 (HPO 4 ) = , Cu(OH) 3 (H 2 PO 4 ) = , and Cu(OH) 2 (PO 4 ) ≡ . Precise thermochemical parameters are also derived for the Cu(OH) + hydroxocomplex based on CuO solubility behavior previously observed in pure water (*) at elevated temperatures. The relative ease of Cu(II) ion hydrolysis is such that Cu(OH) 3 - species become the preferred hydroxocomplex for pH ≥ 9.4. 20 refs., 8 figs., 6 tabs

INTERRELATION OF ACIDITY-BASICITY, SOLUBILITY AND ABILITY TO INTERACTION OF HALIDES OF MX AND M'X2 (M - Li ÷ Cs, M' - Be ÷ Ba, X - Cl ÷ I TYPES

Directory of Open Access Journals (Sweden)

V. F. Zinchenko

2015-11-01

Full Text Available The size-charge factor of basicity for definition of the acid-base properties of alkaline both alkaline-earth metals and Be halides is offered. The certain interrelation of the specified factor, and also the magnitudes connected with energy of a crystal lattice (temperature of boiling and enthalpy of evaporation of salt with its solubility in water, and also with enthalpy of hydration is established. It is shown that the minimum solubility possess alkaline metals halides (KCl for chlorides, RbBr for Rubidium halides and CsI for alkaline metals halides as a whole at which value of the factor of basicity is equal to 0.83, i.e. it is slightly less than 1. Among alkaline-earth metals halides the lowest solubility has BaCl2 with the highest value of the factor of basicity (0.4. An absolute value of enthalpy of hydration for salts crystal-hydrates possesses tens kJ/mol H2O and increases with reduction of the factor of basicity at transition from metals chlorides to iodides, and also at cationic substitution by easier analogue. Qualitative correlation between a difference of basicity of binary halides and their ability to interaction with formation of complex compounds of various degree of durability is established. At an average difference of basicities 0.4 in halide systems are formed incongruently melting, and at 0.6-0.8 and more – congruently melting compounds. Forecasting of solubility of complex halide of CsSrCl3 composition on the basis of its value of equalized basicity is carried out.

Quaternary oxide halides of group 15 with zinc and cadmium; Quaternaere Oxidhalogenide der Gruppe 15 mit Zink und Cadmium

Energy Technology Data Exchange (ETDEWEB)

Rueck, Nadia

2014-07-30

The present thesis ''Quaternary oxide halides of group 15 with zinc and cadmium'' deals with the chemical class of oxide halides, which contain d-block element cations and pnicogens. Over the past few years compounds containing pnicogene cations are intensively investigated. The reason for this is the free electron pair of the Pn{sup 3+} cation, which is responsible for some interesting properties. Free electron pairs do not only impact the spatial structure of molecules but also the properties of materials. The object of this work was the synthesis and characterization of compounds containing Pn{sup 3+} cations with free electron pairs. Due to the structure-determining effect of these free electron pairs and in combination with halides it is possible to synthesize compounds with low-dimensional structures like chains and layers. In these compounds the structure is separated into halophilic and chalcophilic sub-structures, which are held together only by weak Van der Waals forces.

Hot working alkali halides for laser window applications

International Nuclear Information System (INIS)

Koepke, B.G.; Anderson, R.H.; Stokes, R.J.

1975-01-01

The techniques used to hot work alkali halide crystals into laser window blanks are reviewed. From the point of view of high power laser window applications one of the materials with a high figure of merit is KCl. Thus the materials examined are KCl and alloys of KCl-KBr containing 5 mole percent KBr. The fabrication techniques include conventional and constrained press forging, isostatic press forging and hot rolling. Optical properties are paramount to the ultimate usefulness of these materials. Results on the optical properties of the hot worked material are included together with mechanical properties and microstructural data

Synthesis of halide- and solvent free metal borohydrides

DEFF Research Database (Denmark)

Grinderslev, Jakob; Møller, Kasper Trans; Richter, Bo

have challenges due to their high desorption kinetics and limited reversibility at moderate conditions.[2],[3],[4] In this work, we present a new approach to synthesize halide- and solvent free metal borohydrides starting from the respective metal hydride. The synthetic strategy ensures that no metal...... to the metal. Hence, the powdered M(BH4)3∙DMS is heated to 140 °C for 4 hours to obtain pure M(BH4)3. The rare-earth metal borohydrides have been investigated by infrared spectroscopy and thermal analysis (TGA-DSC-MS). Furthermore, the structural trends are investigated by synchrotron radiation powder X...

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

Science.gov (United States)

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.

Monitoring of heavy/toxic metals and halides in surface/ground water (abstract)

International Nuclear Information System (INIS)

Viqar-un-Nisa; Ahmed, R.; Husain, M.

1999-01-01

Water is essential for maintaining physical and social life. Human and animal consumption is perhaps the most evident essential use of water. Water quality and quantity have become critical issues, affecting all life. The importance of water in our lives, combined with the threats, make water resources use a global problem. Among the different pollutants toxic metals, metalloids and halides have special significance. Industrial effluents and municipal wastewater are normally drained into water streams, rivers and other reservoirs thus polluting these significantly. Quality of our water resources especially is an issue, which continues to arouse the attention of concerned scientists, legislators and the general public. Among various pollutant chemicals, the heavy metals and metalloids are present at trace levels in various compartments of the environment. Some metals become toxic even at trace levels because of the important features that distinguishes metals from other pollutants is that they are not biodegradable. The halides like Cl, Br, and I from different sources can enter easily into water systems and then they make their way directly into the human body. The intake of toxic as wells as essential elements through water and other food items like vegetables, milk wheat flour etc. is significant. The abundance or deficiency of these meals as well as halides results in abnormal metabolic functions. Due to excessive demand for trace analysis in water and other materials a variety of techniques and instrumentation has been developed. Determination of heavy metals ions is of the highest interest in environmental analysis. Among the food materials water is most important because of their large consumption by man. Also toxic metals in water may be in dissolved ionic form, which directly go into human metabolism and start their toxic action. Presence of even small amounts of toxic metals in drinking water can produce serious health hazards. (author)

Thermochromic halide perovskite solar cells.

Science.gov (United States)

Lin, Jia; Lai, Minliang; Dou, Letian; Kley, Christopher S; Chen, Hong; Peng, Fei; Sun, Junliang; Lu, Dylan; Hawks, Steven A; Xie, Chenlu; Cui, Fan; Alivisatos, A Paul; Limmer, David T; Yang, Peidong

2018-03-01

Smart photovoltaic windows represent a promising green technology featuring tunable transparency and electrical power generation under external stimuli to control the light transmission and manage the solar energy. Here, we demonstrate a thermochromic solar cell for smart photovoltaic window applications utilizing the structural phase transitions in inorganic halide perovskite caesium lead iodide/bromide. The solar cells undergo thermally-driven, moisture-mediated reversible transitions between a transparent non-perovskite phase (81.7% visible transparency) with low power output and a deeply coloured perovskite phase (35.4% visible transparency) with high power output. The inorganic perovskites exhibit tunable colours and transparencies, a peak device efficiency above 7%, and a phase transition temperature as low as 105 °C. We demonstrate excellent device stability over repeated phase transition cycles without colour fade or performance degradation. The photovoltaic windows showing both photoactivity and thermochromic features represent key stepping-stones for integration with buildings, automobiles, information displays, and potentially many other technologies.

Thermochromic halide perovskite solar cells

Science.gov (United States)

Lin, Jia; Lai, Minliang; Dou, Letian; Kley, Christopher S.; Chen, Hong; Peng, Fei; Sun, Junliang; Lu, Dylan; Hawks, Steven A.; Xie, Chenlu; Cui, Fan; Alivisatos, A. Paul; Limmer, David T.; Yang, Peidong

2018-03-01

Smart photovoltaic windows represent a promising green technology featuring tunable transparency and electrical power generation under external stimuli to control the light transmission and manage the solar energy. Here, we demonstrate a thermochromic solar cell for smart photovoltaic window applications utilizing the structural phase transitions in inorganic halide perovskite caesium lead iodide/bromide. The solar cells undergo thermally-driven, moisture-mediated reversible transitions between a transparent non-perovskite phase (81.7% visible transparency) with low power output and a deeply coloured perovskite phase (35.4% visible transparency) with high power output. The inorganic perovskites exhibit tunable colours and transparencies, a peak device efficiency above 7%, and a phase transition temperature as low as 105 °C. We demonstrate excellent device stability over repeated phase transition cycles without colour fade or performance degradation. The photovoltaic windows showing both photoactivity and thermochromic features represent key stepping-stones for integration with buildings, automobiles, information displays, and potentially many other technologies.

Surface and zeta-potentials of silver halide single crystals: pH-dependence in comparison to particle systems

International Nuclear Information System (INIS)

Selmani, Atiða; Kallay, Nikola; Preočanin, Tajana; Lützenkirchen, Johannes

2014-01-01

We have carried out surface and zeta-potential measurements on AgCl and AgBr single crystals. As for particle systems we find that, surprisingly and previously unnoted, the zeta-potential exhibits pH-dependence, while the surface potential does not. A possible interpretation of these observations is the involvement of water ions in the interfacial equilibria and in particular, stronger affinity of the hydroxide ion compared to the proton. The pH-dependence of the zeta-potential can be suppressed at sufficiently high silver concentrations, which agrees with previous measurements in particle systems where no pH-dependence was found at high halide ion concentrations. The results suggest a subtle interplay between the surface potential determining the halide and silver ion concentrations, and the water ions. Whenever the charge due to the halide and silver ions is sufficiently high, the influence of the proton/hydroxide ion on the zeta-potential vanishes. This might be related to the water structuring at the relevant interfaces which should be strongly affected by the surface potential. Another interesting observation is accentuation of the assumed water ion effect on the zeta-potential at the flat single crystal surfaces compared to the corresponding silver halide colloids. Previous generic MD simulations have indeed predicted that hydroxide ion adsorption is accentuated on flat/rigid surfaces. A thermodynamic model for AgI single crystals was developed to describe the combined effects of iodide, silver and water ions, based on two independently previously published models for AgI (that only consider constituent and background electrolyte ions) and inert surfaces (that only consider water and background electrolyte ions). The combined model correctly predicts all the experimentally observed trends. (paper)

A comparative study of semi-empirical interionic potentials for alkali halides - II

International Nuclear Information System (INIS)

Khwaja, F.A.; Naqvi, S.H.

1985-08-01

A comprehensive study of some semi-empirical interionic potentials is carried out through the calculation of the cohesive energy, relative stability and pressure induced solid-solid phase transformations in alkali halides. The theoretical values of these properties of the alkali halides are obtained using a new set of van der Waals coefficients and zero-point energy in the expression for interionic potential. From the comparison of the present calculations with some previous sophisticated ab-initio quantum-mechanical calculations and other semi-empirical approaches, it is concluded that the present calculations in the simplest central pairwise interaction description with the new values of the van der Waals coefficients and zero-point energy are in better agreement with the experimental data than the previous calculations. It is also concluded that in some cases the better choice of the interionic potential alone in the simplest semi-empirical picture of interaction gives an agreement of the theoretical predictions with the experimental data much superior to the ab-initio quantum mechanical approaches. (author)

Macromolecules containing bipyridine and terpyridine metal complexes: towards metallo-supramolecular polymers

NARCIS (Netherlands)

Schubert, U.S.; Eschbaumer, C.

2002-01-01

The ability of a broad range of N-heterocycles to act as very effective and stable complexation agents for several transition metal ions, such as cobalt(II), copper(II), nickel(II), and ruthenium(II), has long been known in analytical chemistry. This behavior was later utilized in supramolecular

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

Science.gov (United States)

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.

Amination of Aryl Halides and Esters Using Intensified Continuous Flow Processing

Directory of Open Access Journals (Sweden)

Thomas M. Kohl

2015-09-01

Full Text Available Significant process intensification of the amination reactions of aryl halides and esters has been demonstrated using continuous flow processing. Using this technology traditionally difficult amination reactions have been performed safely at elevated temperatures. These reactions were successfully conducted on laboratory scale coil reactor modules with 1 mm internal diameter (ID and on a preparatory scale tubular reactor with 6 mm ID containing static mixers.

Antimalarial, antimicrobial, cytotoxic, DNA interaction and SOD like activities of tetrahedral copper(II) complexes

Science.gov (United States)

Mehta, Jugal V.; Gajera, Sanjay B.; Patel, Mohan N.

2015-02-01

The mononuclear copper(II) complexes with P, O-donor ligand and different fluoroquinolones have been synthesized and characterized by elemental analysis, electronic spectra, TGA, EPR, FT-IR and LC-MS spectroscopy. An antimicrobial efficiency of the complexes has been tested against five different microorganisms in terms of minimum inhibitory concentration (MIC) and displays very good antimicrobial activity. The binding strength and binding mode of the complexes with Herring Sperm DNA (HS DNA) have been investigated by absorption titration and viscosity measurement studies. The studies suggest the classical intercalative mode of DNA binding. Gel electrophoresis assay determines the ability of the complexes to cleave the supercoiled form of pUC19 DNA. Synthesized complexes have been tested for their SOD mimic activity using nonenzymatic NBT/NADH/PMS system and found to have good antioxidant activity. All the complexes show good cytotoxic and in vitro antimalarial activities.

REPLACEMENT OF TRYPTOPHAN RESIDUES IN HALOALKANE DEHALOGENASE REDUCES HALIDE BINDING AND CATALYTIC ACTIVITY

NARCIS (Netherlands)

KENNES, C; PRIES, F; KROOSHOF, GH; BOKMA, E; Kingma, Jacob; JANSSEN, DB

1995-01-01

Haloalkane dehalogenase catalyzes the hydrolytic cleavage of carbon-halogen bonds in short-chain haloalkanes. Two tryptophan residues of the enzyme (Trp125 and Trp175) form a halide-binding site in the active-site cavity, and were proposed to play a role in catalysis. The function of these residues

Kinetics of cesium lead halide perovskite nanoparticle growth; focusing and de-focusing of size distribution

Science.gov (United States)

Koolyk, Miriam; Amgar, Daniel; Aharon, Sigalit; Etgar, Lioz

2016-03-01

In this work we study the kinetics of cesium lead halide perovskite nanoparticle (NP) growth; the focusing and de-focusing of the NP size distribution. Cesium lead halide perovskite NPs are considered to be attractive materials for optoelectronic applications. Understanding the kinetics of the formation of these all-inorganic perovskite NPs is critical for reproducibly and reliably generating large amounts of uniformly sized NPs. Here we investigate different growth durations for CsPbI3 and CsPbBr3 NPs, tracking their growth by high-resolution transmission electron microscopy and size distribution analysis. As a result, we are able to provide a detailed model for the kinetics of their growth. It was observed that the CsPbI3 NPs exhibit focusing of the size distribution in the first 20 seconds of growth, followed by de-focusing over longer growth durations, while the CsPbBr3 NPs show de-focusing of the size distribution starting from the beginning of the growth. The monomer concentration is depleted faster in the case of CsPbBr3 than in the case of CsPbI3, due to faster diffusion of the monomers, which increases the critical radius and results in de-focusing of the population. Accordingly, focusing is not observed within 40 seconds of growth in the case of CsPbBr3. This study provides important knowledge on how to achieve a narrow size distribution of cesium lead halide perovskite NPs when generating large amounts of these promising, highly luminescent NPs.In this work we study the kinetics of cesium lead halide perovskite nanoparticle (NP) growth; the focusing and de-focusing of the NP size distribution. Cesium lead halide perovskite NPs are considered to be attractive materials for optoelectronic applications. Understanding the kinetics of the formation of these all-inorganic perovskite NPs is critical for reproducibly and reliably generating large amounts of uniformly sized NPs. Here we investigate different growth durations for CsPbI3 and CsPbBr3 NPs, tracking

Temperature dependent halogen activation by N2O5 reactions on halide-doped ice surfaces

Directory of Open Access Journals (Sweden)

J. A. Thornton

2012-06-01

Full Text Available We examined the reaction of N2O5 on frozen halide salt solutions as a function of temperature and composition using a coated wall flow tube technique coupled to a chemical ionization mass spectrometer (CIMS. The molar yield of photo-labile halogen compounds was near unity for almost all conditions studied, with the observed reaction products being nitryl chloride (ClNO2 and/or molecular bromine (Br2. The relative yield of ClNO2 and Br2 depended on the ratio of bromide to chloride ions in the solutions used to form the ice. At a bromide to chloride ion molar ratio greater than 1/30 in the starting solution, Br2 was the dominant product otherwise ClNO2 was primarily produced on these near pH-neutral brines. We demonstrate that the competition between chlorine and bromine activation is a function of the ice/brine temperature presumably due to the preferential precipitation of NaCl hydrates from the brine below 250 K. Our results provide new experimental confirmation that the chemical environment of the brine layer changes with temperature and that these changes can directly affect multiphase chemistry. These findings have implications for modeling air-snow-ice interactions in polar regions and likely in polluted mid-latitude regions during winter as well.

Phase space investigation of the lithium amide halides

Energy Technology Data Exchange (ETDEWEB)

Davies, Rosalind A. [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Hydrogen and Fuel Cell Group, School of Chemical Engineering, University of Birmingham, Edgbaston B15 2TT (United Kingdom); Hewett, David R.; Korkiakoski, Emma [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Thompson, Stephen P. [Diamond Light Source, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0QX (United Kingdom); Anderson, Paul A., E-mail: p.a.anderson@bham.ac.uk [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom)

2015-10-05

Highlights: • The lower limits of halide incorporation in lithium amide have been investigated. • The only amide iodide stoichiometry observed was Li{sub 3}(NH{sub 2}){sub 2}I. • Solid solutions were observed in both the amide chloride and amide bromide systems. • A 46% reduction in chloride content resulted in a new phase: Li{sub 7}(NH{sub 2}){sub 6}Cl. • New low-chloride phase maintained improved H{sub 2} desorption properties of Li{sub 4}(NH{sub 2}){sub 3}Cl. - Abstract: An investigation has been carried out into the lower limits of halide incorporation in lithium amide (LiNH{sub 2}). It was found that the lithium amide iodide Li{sub 3}(NH{sub 2}){sub 2}I was unable to accommodate any variation in stoichiometry. In contrast, some variation in stoichiometry was accommodated in Li{sub 7}(NH{sub 2}){sub 6}Br, as shown by a decrease in unit cell volume when the bromide content was reduced. The amide chloride Li{sub 4}(NH{sub 2}){sub 3}Cl was found to adopt either a rhombohedral or a cubic structure depending on the reaction conditions. Reduction in chloride content generally resulted in a mixture of phases, but a new rhombohedral phase with the stoichiometry Li{sub 7}(NH{sub 2}){sub 6}Cl was observed. In comparison to LiNH{sub 2}, this new low-chloride phase exhibited similar improved hydrogen desorption properties as Li{sub 4}(NH{sub 2}){sub 3}Cl but with a much reduced weight penalty through addition of chloride. Attempts to dope lithium amide with fluoride ions have so far proved unsuccessful.

Can Ferroelectric Polarization Explain the High Performance of Hybrid Halide Perovskite Solar Cells?

NARCIS (Netherlands)

Sherkar, Tejas; Koster, L. Jan Anton

The power conversion efficiency of photovoltaic cells based on the use of hybrid halide perovskites, CH3NH3PbX3 (X = Cl, Br, I), now exceeds 20%. Recently, it was suggested that this high performance originates from the presence of ferroelectricity in the perovskite, which is hypothesized to lower

Spectral and Dynamical Properties of Single Excitons, Biexcitons, and Trions in Cesium-Lead-Halide Perovskite Quantum Dots.

Science.gov (United States)

Makarov, Nikolay S; Guo, Shaojun; Isaienko, Oleksandr; Liu, Wenyong; Robel, István; Klimov, Victor I

2016-04-13

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

Facile synthesis of gold coated copper(II) hydroxide pine-needle-like micro/nanostructures for surface-enhanced Raman scattering

Science.gov (United States)

Long, Kailin; Du, Deyang; Luo, Xiaoguang; Zhao, Weiwei; Wu, Zhangting; Si, Lifang; Qiu, Teng

2014-08-01

This work reports a facile method to fabricate gold coated copper(II) hydroxide pine-needle-like micro/nanostructures for surface-enhanced Raman scattering (SERS) application. The effects of reaction parameters on the shape, size and surface morphology of the products are systematically investigated. The as-prepared 3D hierarchical structures have the advantage of a large surface area available for the formation of hot spots and the adsorption of target analytes, thus dramatically improving the Raman signals. The finite difference time domain calculations indicate that the pine-needle-like model pattern may demonstrate a high quality SERS property owing to the high density and abundant hot spot characteristic in closely spaced needle-like arms.

Organometallic halide perovskite single crystals having low deffect density and methods of preparation thereof

KAUST Repository

Bakr, Osman; Shi, Dong

2016-01-01

The present disclosure presents a method of making a single crystal organometallic halide perovskites, with the formula: AMX3, wherein A is an organic cation, M is selected from the group consisting of: Pb, Sn, Cu, Ni, Co, Fe, Mn, Pd, Cd, Ge, and Eu

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

Science.gov (United States)

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.

NEW THIO S2- ADDUCTS WITH ANTIMONY (III AND V HALIDE: SYNTHESIS AND INFRARED STUDY

Directory of Open Access Journals (Sweden)

HASSAN ALLOUCH

2013-12-01

Full Text Available Five new S2- adducts with SbIII and SbV halides have been synthesized and studied by infrared. Discrete structures have been suggested, the environment around the antimony being tetrahedral, trigonal bipyramidal or octahedral.

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

Science.gov (United States)

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.

Energy distributions of atoms sputtered from alkali halides by 540 eV electrons, Ch.1

International Nuclear Information System (INIS)

Overeijnder, H.; Szymonski, M.; Haring, A.; Vries, A.E. de

1978-01-01

The emission of halogen and alkali atoms, occurring under bombardment of alkali halides with electrons has been investigated. The electron energy was 540 eV and the temperature of the target was varied between room temperature and 400 0 C. The energy distribution of the emitted neutral particles was measured with a time of flight method. It was found that either diffusing interstitial halogen atoms or moving holes dominate the sputtering process above 200 0 C. Below 150 0 C alkali halides with lattice parameters s/d >= 0.33 show emission of non-thermal halogen atoms. s is the interionic space between two halogen ions in a direction and d is the diameter of a halogen atom. In general the energy distribution of the alkali and halogen atoms is thermal above 200 0 C, but not Maxwellian. (Auth.)

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

DEFF Research Database (Denmark)

Pandey, Mohnish; Jacobsen, Karsten Wedel; Thygesen, Kristian Sommer

2016-01-01

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 (C4H9NH3)2MX2Y2, 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....

Inorganic hole conductor-based lead halide perovskite solar cells with 12.4% conversion efficiency

KAUST Repository

Qin, Peng

2014-05-12

Organo-lead halide perovskites have attracted much attention for solar cell applications due to their unique optical and electrical properties. With either low-temperature solution processing or vacuum evaporation, the overall conversion efficiencies of perovskite solar cells with organic hole-transporting material were quickly improved to over 15% during the last 2 years. However, the organic hole-transporting materials used are normally quite expensive due to complicated synthetic procedure or high-purity requirement. Here, we demonstrate the application of an effective and cheap inorganic p-type hole-transporting material, copper thiocyanate, on lead halide perovskite-based devices. With low-temperature solution-process deposition method, a power conversion efficiency of 12.4% was achieved under full sun illumination. This work represents a well-defined cell configuration with optimized perovskite morphology by two times of lead iodide deposition, and opens the door for integration of a class of abundant and inexpensive material for photovoltaic application. © 2014 Macmillan Publishers Limited.

Excitonic and electron-hole mechanisms of the creation of Frenkel defect in alkali halides

International Nuclear Information System (INIS)

Lushchik, A.; Kirm, M.; Lushchik, Ch.; Vasil'chenko, E.

2000-01-01

Excitonic and electron-hole (e-h) mechanisms of stable F centre creation by VUV radiation in alkali halide crystals are discussed. In KCl at 4.2 K, the efficiency of stable F-H pair creation is especially high at the direct optical formation of triplet excitons with n=1. At 200-400 K, the creation processes of stable F centres in KCl are especially efficient at the formation of one-halide exciton in the Urbach tail of an exciton absorption. In KCl and KBr, the decay of a cation exciton (∼20 eV) causes the formation of two e-h pairs, while in NaCl a cation exciton (33.5 eV) decays into two e-h and an anion exciton. An elastic uniaxial stress of a crystal excited by VUV radiation decreases the mean free path of excitons before their self-trapping (KI) and increases the mean free path of hot holes before self-trapping (NaCl)

Inorganic hole conductor-based lead halide perovskite solar cells with 12.4% conversion efficiency

KAUST Repository

Qin, Peng; Tanaka, Soichiro; Ito, Seigo; Tetreault, Nicolas; Manabe, Kyohei; Nishino, Hitoshi; Nazeeruddin, Mohammad Khaja; Grä tzel, Michael

2014-01-01

Organo-lead halide perovskites have attracted much attention for solar cell applications due to their unique optical and electrical properties. With either low-temperature solution processing or vacuum evaporation, the overall conversion efficiencies of perovskite solar cells with organic hole-transporting material were quickly improved to over 15% during the last 2 years. However, the organic hole-transporting materials used are normally quite expensive due to complicated synthetic procedure or high-purity requirement. Here, we demonstrate the application of an effective and cheap inorganic p-type hole-transporting material, copper thiocyanate, on lead halide perovskite-based devices. With low-temperature solution-process deposition method, a power conversion efficiency of 12.4% was achieved under full sun illumination. This work represents a well-defined cell configuration with optimized perovskite morphology by two times of lead iodide deposition, and opens the door for integration of a class of abundant and inexpensive material for photovoltaic application. © 2014 Macmillan Publishers Limited.

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

Science.gov (United States)

Jurgensen, Charles Willard

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

Nonlinear optical and G-Quadruplex DNA stabilization properties of novel mixed ligand copper(II) complexes and coordination polymers: Synthesis, structural characterization and computational studies

Science.gov (United States)

Rajasekhar, Bathula; Bodavarapu, Navya; Sridevi, M.; Thamizhselvi, G.; RizhaNazar, K.; Padmanaban, R.; Swu, Toka

2018-03-01

The present study reports the synthesis and evaluation of nonlinear optical property and G-Quadruplex DNA Stabilization of five novel copper(II) mixed ligand complexes. They were synthesized from copper(II) salt, 2,5- and 2,3- pyridinedicarboxylic acid, diethylenetriamine and amide based ligand (AL). The crystal structure of these complexes were determined through X-ray diffraction and supported by ESI-MAS, NMR, UV-Vis and FT-IR spectroscopic methods. Their nonlinear optical property was studied using Gaussian09 computer program. For structural optimization and nonlinear optical property, density functional theory (DFT) based B3LYP method was used with LANL2DZ basis set for metal ion and 6-31G∗ for C,H,N,O and Cl atoms. The present work reveals that pre-polarized Complex-2 showed higher β value (29.59 × 10-30e.s.u) as compared to that of neutral complex-1 (β = 0.276 × 10-30e.s.u.) which may be due to greater advantage of polarizability. Complex-2 is expected to be a potential material for optoelectronic and photonic technologies. Docking studies using AutodockVina revealed that complex-2 has higher binding energy for both G-Quadruplex DNA (-8.7 kcal/mol) and duplex DNA (-10.1 kcal/mol). It was also observed that structure plays an important role in binding efficiency.

Molecular dispersion energy parameters for alkali and halide ions in aqueous solution

International Nuclear Information System (INIS)

Reiser, S.; Deublein, S.; Hasse, H.; Vrabec, J.

2014-01-01

Thermodynamic properties of aqueous solutions containing alkali and halide ions are determined by molecular simulation. The following ions are studied: Li + , Na + , K + , Rb + , Cs + , F − , Cl − , Br − , and I − . The employed ion force fields consist of one Lennard-Jones (LJ) site and one concentric point charge with a magnitude of ±1 e. The SPC/E model is used for water. The LJ size parameter of the ion models is taken from Deublein et al. [J. Chem. Phys. 136, 084501 (2012)], while the LJ energy parameter is determined in the present study based on experimental self-diffusion coefficient data of the alkali cations and the halide anions in aqueous solutions as well as the position of the first maximum of the radial distribution function of water around the ions. On the basis of these force field parameters, the electric conductivity, the hydration dynamics of water molecules around the ions, and the enthalpy of hydration is predicted. Considering a wide range of salinity, this study is conducted at temperatures of 293.15 and 298.15 K and a pressure of 1 bar

Structural and Chemical Analysis of Gadolinium Halides Encapsulated within WS 2 Nanotubes

KAUST Repository

Anumol, E A

2016-05-18

The hollow cavities of nanotubes could serve as templates for the growth of size- and shape-confined functional nanostructures, giving rise to novel materials and properties. In this work, considering their potential application as MRI contrast agents, gadolinium halides are encapsulated within the hollow cavities of inorganic nanotubes of WS2 by capillary filling to obtain GdX3@WS2 nanotubes (where X = Cl, Br or I and @ means encapsulated in). Aberration corrected scanning/transmission electron microscopy (S/TEM) and spectroscopy is employed to understand the morphology and composition of the GdI3@WS2 nanotubes. The three dimensional morphology is studied with STEM tomography but understanding the compositional information is a non-trivial matter due to the presence of multiple high atomic number elements. Therefore, energy dispersive X-ray spectroscopy (EDS) tomography was employed revealing the three dimensional chemical composition. Molecular dynamics simulations of the filling procedure shed light into the mechanics behind the formation of the confined gadolinium halide crystals. The quasi-1D system employed here serves as an example of a TEM-based chemical nanotomography method that could be extended to other materials, including beam-sensitive soft materials.

Structural and Chemical Analysis of Gadolinium Halides Encapsulated within WS 2 Nanotubes

KAUST Repository

Anumol, E A; Enyashin, Andrey; Batra, Nitin M; Da Costa, Pedro M. F. J.; Francis, Leonard Deepak

2016-01-01

The hollow cavities of nanotubes could serve as templates for the growth of size- and shape-confined functional nanostructures, giving rise to novel materials and properties. In this work, considering their potential application as MRI contrast agents, gadolinium halides are encapsulated within the hollow cavities of inorganic nanotubes of WS2 by capillary filling to obtain GdX3@WS2 nanotubes (where X = Cl, Br or I and @ means encapsulated in). Aberration corrected scanning/transmission electron microscopy (S/TEM) and spectroscopy is employed to understand the morphology and composition of the GdI3@WS2 nanotubes. The three dimensional morphology is studied with STEM tomography but understanding the compositional information is a non-trivial matter due to the presence of multiple high atomic number elements. Therefore, energy dispersive X-ray spectroscopy (EDS) tomography was employed revealing the three dimensional chemical composition. Molecular dynamics simulations of the filling procedure shed light into the mechanics behind the formation of the confined gadolinium halide crystals. The quasi-1D system employed here serves as an example of a TEM-based chemical nanotomography method that could be extended to other materials, including beam-sensitive soft materials.

The Study of Reducing Krypton-85 Activity in Metal Halide Lamp%降低金卤灯内氪-85活度的研究

Institute of Scientific and Technical Information of China (English)

叶碧君

2012-01-01

通过测试及分析不同氪-85活度填充气体的同规格金卤灯的各项性能参数,研究了在确保金卤灯各项性能的前提下,降低金卤灯中氪-85活度的可行性及金卤灯中氪-85存在的必要性,可以为今后确定金卤灯中需添加的最低氪-85活度提供参考。%By analyzing the parameters of metal halide lamps which are filled with gas with different activity of krypton-85, the paper studies the feasibility of reducing krypton-85 activity in metal halide lamp while ensuring the lamp performance, and proves the necessity of its existence of krypton-85 in metal halide lamp. it can provide us a reference to determine the minimum krypton-85 activity to he added in metal halide lamps.

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 −}?

Energy Technology Data Exchange (ETDEWEB)

Réal, Florent, E-mail: florent.real@univ-lille1.fr; Severo Pereira Gomes, André; Guerrero Martínez, Yansel Omar; Vallet, Valérie [Université de Lille, CNRS, UMR 8523–PhLAM–Physique des Lasers Atomes et Molécules, F-59000 Lille (France); Ayed, Tahra; Galland, Nicolas [CEISAM UMR CNRS 6230, Université de Nantes, 2 Rue de la Houssinière, BP 92208 F-44322 Nantes Cedex 3 (France); Masella, Michel [Laboratoire de Biologie Structurale et Radiobiologie, Service de Bioénergétique, Biologie Structurale et Mécanismes, Institut de Biologie et de Technologies de Saclay, CEA Saclay, F-91191 Gif sur Yvette Cedex (France)

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, 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.

Inhibition performance of a gemini surfactant and its co-adsorption effect with halides on mild steel in 0.25 M H{sub 2}SO{sub 4} solution

Energy Technology Data Exchange (ETDEWEB)

Wang Xiumei [State Key Laboratory for Corrosion and Protection, Institute of Metal Research Chinese Academy of Sciences, Shenyang 110016 (China); School of Materials Science and Engineering, Shenyang Jianzhu University, Shenyang 110168 (China); Yang Huaiyu, E-mail: hyyang@imr.ac.cn [State Key Laboratory for Corrosion and Protection, Institute of Metal Research Chinese Academy of Sciences, Shenyang 110016 (China); Wang Fuhui [State Key Laboratory for Corrosion and Protection, Institute of Metal Research Chinese Academy of Sciences, Shenyang 110016 (China)

2012-02-15

Highlights: Black-Right-Pointing-Pointer 1,4-Bis (1-chlorobenzyl-benzimidazolyl)-butane has good inhibition effect for mild steel in H{sub 2}SO{sub 4}. Black-Right-Pointing-Pointer The compound acts as a mixed-type inhibitor and obeys Langmuir adsorption isotherm. Black-Right-Pointing-Pointer Halide ions can improve the inhibition property of compound via the co-adsorption effect. Black-Right-Pointing-Pointer The adsorbed halides play an important intermediate bridge role in co-adsorption process. Black-Right-Pointing-Pointer The obtained results can supply the bases for the future using of cationic inhibitor. - Abstract: The inhibition performance of a cationic gemini-surfactant (CBB) and its co-adsorption behavior with halides on mild steel in 0.25 M H{sub 2}SO{sub 4} solution was studied by weight loss and electrochemical techniques. Results showed that the compound could effectively inhibit the mild steel corrosion and acted as a mixed-type inhibitor by suppressing simultaneously anodic and cathodic reactions. Addition of the halides improve the inhibition efficiency of CBB and the synergistic effect increase in the order of I{sup -} > Br{sup -} > Cl{sup -}, revealing that halides radii and their electronegativity may play significant roles in co-adsorption with the cationic inhibitor.

Evaluation of field test equipment for halide and DOP testing

International Nuclear Information System (INIS)

Schreiber, K.L.; Kovach, J.L.

1975-01-01

The Nucon Testing Services Department, field testing at power reactor sites, has performed tests using R-11, R-12, and R-112 in conjunction with gas chromatographs and direct reading halide detectors. The field operational experience with these detector systems, thus sensitivity, precision, and manner of field calibration, are presented. Laboratory experiments regarding 3 H-tagged methyl iodide for in place leak testing of adsorber systems indicate a low hazard, high reliability process for leak testing in facilities where atmospheric cross contamination occurs. (U.S.)

Tetranuclear copper(II) complexes bridged by alpha-D-glucose-1-phosphate and incorporation of sugar acids through the Cu4 core structural changes.

Science.gov (United States)

Kato, Merii; Sah, Ajay Kumar; Tanase, Tomoaki; Mikuriya, Masahiro

2006-08-21

Tetranuclear copper(II) complexes containing alpha-D-glucose-1-phosphate (alpha-D-Glc-1P), [Cu4(mu-OH){mu-(alpha-D-Glc-1P)}2(bpy)4(H2O)2]X3 [X = NO3 (1a), Cl (1b), Br (1c)], and [Cu4(mu-OH){mu-(alpha-D-Glc-1P)}2(phen)4(H2O)2](NO3)3 (2) were prepared by reacting the copper(II) salt with Na2[alpha-D-Glc-1P] in the presence of diimine ancillary ligands, and the structure of 2 was characterized by X-ray crystallography to comprise four {Cu(phen)}2+ fragments connected by the two sugar phosphate dianions in 1,3-O,O' and 1,1-O mu4-bridging fashion as well as a mu-hydroxo anion. The crystal structure of 2 involves two chemically independent complex cations in which the C2 enantiomeric structure for the trapezoidal tetracopper(II) framework is switched according to the orientation of the alpha-D-glucopyranosyl moieties. Temperature-dependent magnetic susceptibility data of 1a indicated that antiferromagnetic spin coupling is operative between the two metal ions joined by the hydroxo bridge (J = -52 cm(-1)) while antiferromagnetic interaction through the Cu-O-Cu sugar phosphate bridges is weak (J = -13 cm(-1)). Complex 1a readily reacted with carboxylic acids to afford the tetranuclear copper(II) complexes, [Cu4{mu-(alpha-D-Glc-1P)}2(mu-CA)2(bpy)4](NO3)2 [CA = CH3COO (3), o-C6H4(COO)(COOH) (4)]. Reactions with m-phenylenediacetic acid [m-C6H4(CH2COOH)2] also gave the discrete tetracopper(II) cationic complex [Cu4{mu-(alpha-D-Glc-1P)}2(mu-m-C6H4(CH2COO)(CH2COOH))2(bpy)4](NO3)2 (5a) as well as the cluster polymer formulated as {[Cu4{mu-(alpha-D-Glc-1P)}2(mu-m-C6H4(CH2COO)2)(bpy)4](NO3)2}n (5b). The tetracopper structure of 1a is converted into a symmetrical rectangular core in complexes 3, 4, and 5b, where the hydroxo bridge is dissociated and, instead, two carboxylate anions bridge another pair of Cu(II) ions in a 1,1-O monodentate fashion. The similar reactions were applied to incorporate sugar acids onto the tetranuclear copper(II) centers. Reactions of 1a with delta

Conceptual design of an angular multiplexed rare-gas-halide laser-fusion driver. Final technical report, 1 August 1979-31 May 1980

International Nuclear Information System (INIS)

Parks, J.H.

1980-11-01

A conceptual definition for angular multiplexed rare gas halide drivers was formulated and several design examples analyzed. Angular multiplexed rare gas-halide lasers, in particular the KrF* laser, can be designed to meet ICF requirements. These lasers are scalable, emit at short wavelengths (KrF* 250 nm), and through the use of optical angular multiplexing, produce the required high energy (approx. 1 to 5 MJ) in a short pulse (approx. 10 nsec) with projected overall efficiency in the range of 5 to 7%

Solution and solid-state studies on the halide binding affinity of perfluorophenyl-armed uranyl-salophen receptors enhanced by anion-π interactions

Energy Technology Data Exchange (ETDEWEB)

Leoni, Luca; Mele, Andrea; Giannicchi, Ilaria; Mihan, Francesco Yafteh; Dalla Cort, Antonella [Dipartimento di Chimica and IMC-CNR, Universita di Roma La Sapienza (Italy); Puttreddy, Rakesh; Jurcek, Ondrej; Rissanen, Kari [University of Jyvaeskylae, Department of Chemistry, Nanoscience Center (Finland)

2016-12-23

The enhancement of the binding between halide anions and a Lewis acidic uranyl-salophen receptor has been achieved by the introduction of pendant electron-deficient arene units into the receptor skeleton. The association and the occurrence of the elusive anion-π interaction with halide anions (as tetrabutylammonium salts) have been demonstrated in solution and in the solid state, providing unambiguous evidence on the interplay of the concerted interactions responsible for the anion binding. (copyright 2016 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Synthesis, physico-chemical characterization and biological activity of copper(ii and nickel(ii complexes with l-benzoyl-2-methylbenzimidazole derivatives

Directory of Open Access Journals (Sweden)

Podunavac-Kuzmanović Sanja O.

2002-01-01

Full Text Available Chlorides of copper(II and nickel(ll react with 1-benzoyl-2-methylbenzimidazole or 1-(4-chlorobenzoyl-2-methylbenzimidazole to give complexes of the type [M(LnCln(H20∙Cln (M = Cu or Ni; L = (1-benzoyl-2-methylbenzimidazole or 1-(4-chlorobenzoyl-2-methylbenzimidazole; n=O, 1 or 2. The complexes were synthesized and characterized by elemental analysis, molar conductivity magnetic susceptibility measurements and IR spectra. These studies suggest that all the complexes possess an octahedral stereochemistry. The antibacterial activity of (1-benzoyl-2-methylbenzimidazole or 1-(4-chlorobenzoyl-2-methylbenzimidazole and their complexes was evaluated against Escherichia coli and Bacillus sp.

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

Energy Technology Data Exchange (ETDEWEB)

Jaffe, Adam; Lin, Yu [Photon; Mao, Wendy L. [Photon; Karunadasa, Hemamala I.

2017-03-10

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 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. 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.

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

Science.gov (United States)

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.

USSR Report, Chemistry

Science.gov (United States)

1987-02-10

acid anhydride with esters of phosphorous acid , which demonstrated that, in reactions of dialkyl phosphites with the anhydride, the... PHOSPHOROUS ACID ESTERS WITH HEPTAFLUOROBUTYRIC ACID ANHYDRIDE. PART 3. DONOR-ACCEPTOR INTERACTIONS Leningrad: ZHURNAL OBSHCHEY KHIMII in Russian Vol 56, No...Reaction of Thioesters and Amidothioesters of Phosphorous Acid With Poly Halogenated Methane Derivatives and Alkyl Halides (0. G. Sinyashin, Sh.

Kinetics of the oxidative hydroxylation of tetraphosphorus in the presence of copper(II chloride modified by humic (fulvo- acid

Directory of Open Access Journals (Sweden)

Zhaksyntay Kairbekov

2012-12-01

Full Text Available It was established that in mild conditions (50-70 oC, РО2= 1 atm white phosphorus effectively is oxidized by oxygen in water-toluene solutions of copper(II chloride modified by humic (fulvo- acid to give mainly phosphoric acid. Humic (fulvo- acid was extracted from brown coal of domestic deposit Kiyakty. For determination of optimum parameters of fulvo-acid extraction the laboratory experiments were carried out using the method of experiment planning. The kinetics, intermediate and final products, optimum conditions of new catalytic reaction of P4 oxidation by oxygen in water medium were defined by kinetics, volumometry, redox-potentiometry, 31Р{1Н} NMR spectroscopy and  titration. 

An air-stable copper reagent for nucleophilic trifluoromethylthiolation of aryl halides

KAUST Repository

Weng, Zhiqiang

2012-12-12

A series of copper(I) trifluoromethyl thiolate complexes have been synthesized from the reaction of CuF2 with Me3SiCF 3 and S8 (see scheme; Cu red, F green, N blue, S yellow). These air-stable complexes serve as reagents for the efficient conversion of a wide range of aryl halides into the corresponding aryl trifluoromethyl thioethers in excellent yields. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An air-stable copper reagent for nucleophilic trifluoromethylthiolation of aryl halides

KAUST Repository

Weng, Zhiqiang; He, Weiming; Chen, Chaohuang; Lee, Richmond; Tan, Davin; Lai, Zhiping; Kong, Dedao; Yuan, Yaofeng; Huang, Kuo-Wei

2012-01-01

A series of copper(I) trifluoromethyl thiolate complexes have been synthesized from the reaction of CuF2 with Me3SiCF 3 and S8 (see scheme; Cu red, F green, N blue, S yellow). These air-stable complexes serve as reagents for the efficient conversion of a wide range of aryl halides into the corresponding aryl trifluoromethyl thioethers in excellent yields. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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.

Oligo-m-phenyleneoxalamide copper(II) mesocates as electro-switchable ferromagnetic metal-organic wires.

Science.gov (United States)

Pardo, Emilio; Ferrando-Soria, Jesús; Dul, Marie-Claire; Lescouëzec, Rodrigue; Journaux, Yves; Ruiz-García, Rafael; Cano, Joan; Julve, Miguel; Lloret, Francesc; Cañadillas-Delgado, Laura; Pasán, Jorge; Ruiz-Pérez, Catalina

2010-11-15

Double-stranded copper(II) string complexes of varying nuclearity, from di- to tetranuclear species, have been prepared by the Cu(II)-mediated self-assembly of a novel family of linear homo- and heteropolytopic ligands that contain two outer oxamato and either zero (1 b), one (2 b), or two (3 b) inner oxamidato donor groups separated by rigid 2-methyl-1,3-phenylene spacers. The X-ray crystal structures of these Cu(II) (n) complexes (n=2 (1 d), 3 (2 d), and 4 (3 d)) show a linear array of metal atoms with an overall twisted coordination geometry for both the outer CuN(2)O(2) and inner CuN(4) chromophores. Two such nonplanar all-syn bridging ligands 1 b-3 b in an anti arrangement clamp around the metal centers with alternating M and P helical chiralities to afford an overall double meso-helicate-type architecture for 1 d-3 d. Variable-temperature (2.0-300 K) magnetic susceptibility and variable-field (0-5.0 T) magnetization measurements for 1 d-3 d show the occurrence of S=nS(Cu) (n=2-4) high-spin ground states that arise from the moderate ferromagnetic coupling between the unpaired electrons of the linearly disposed Cu(II) ions (S(Cu)=1/2) through the two anti m-phenylenediamidate-type bridges (J values in the range of +15.0 to 16.8 cm(-1)). Density functional theory (DFT) calculations for 1 d-3 d evidence a sign alternation of the spin density in the meta-substituted phenylene spacers in agreement with a spin polarization exchange mechanism along the linear metal array with overall intermetallic distances between terminal metal centers in the range of 0.7-2.2 nm. Cyclic voltammetry (CV) and rotating-disk electrode (RDE) electrochemical measurements for 1 d-3 d show several reversible or quasireversible one- or two-electron steps that involve the consecutive metal-centered oxidation of the inner and outer Cu(II) ions (S(Cu)=1/2) to diamagnetic Cu(III) ones (S(Cu)=0) at relatively low formal potentials (E values in the range of

Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

CERN Document Server

Park, Y T; Kim, M S; Kwon, J H

2002-01-01

Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed.

Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

Energy Technology Data Exchange (ETDEWEB)

Park, Yong Tae; Song, Myong Geun; Kim, Moon Sub; Kwon, Jeong Hee [Kyungpook National Univ., Daegu (Korea, Republic of)

2002-09-01

Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed.

Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

International Nuclear Information System (INIS)

Park, Yong Tae; Song, Myong Geun; Kim, Moon Sub; Kwon, Jeong Hee

2002-01-01

Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed

Electron-stimulated desorption of lithium ions from lithium halide thin films

International Nuclear Information System (INIS)

Markowski, Leszek

2007-01-01

Electron-stimulated desorption of positive lithium ions from thin layers of lithium halides deposited onto Si(1 1 1) are investigated by the time-of-flight technique. The determined values of isotope effect of the lithium ( 6 Li + / 7 Li + ) are 1.60 ± 0.04, 1.466 ± 0.007, 1.282 ± 0.004, 1.36 ± 0.01 and 1.33 ± 0.01 for LiH, LiF, LiCl, LiBr and LiI, respectively. The observed most probable kinetic energies of 7 Li + are 1.0, 1.9, 1.1, 0.9 and 0.9 eV for LiH, LiF, LiCl, LiBr and LiI, respectively, and seem to be independent of the halide component mass. The values of lithium ion emission yield, lithium kinetic energy and lithium isotope effect suggest that the lattice relaxation is only important in the lithium ion desorption process from the LiH system. In view of possible mechanisms and processes involved into lithium ion desorption the obtained results indicate that for LiH, LiCl, LiBr and LiI the ions desorb in a rather classical way. However, for LiF, ion desorption has a more quantum character and the modified wave packet squeezing model has to be taken into account

Scandium Terminal Imido Chemistry.

Science.gov (United States)

Lu, Erli; Chu, Jiaxiang; Chen, Yaofeng

2018-02-20

of two p-d π bonds between the scandium ion and the nitrogen atom of the imido ligand and showed that the dianionic [NR] 2- imido ligand acts as a 2σ,4π electron donor. Subsequent studies of the scandium terminal imides revealed highly versatile and intriguing reactivity of the Sc═N bond. This included cycloaddition toward various unsaturated bonds, C-H/Si-H/B-H bond activations and catalytic hydrosilylation, dehydrofluorination of fluoro-substituted benzenes/alkanes, CO 2 and H 2 activations, activation of elemental selenium, coordination with other transition metal halides, etc. Since our initial success in 2010, and with contributions from us and across the community, this young, vibrant research field has rapidly flourished into one of the most active frontiers of rare-earth metal chemistry. The prospect of extending Ln═N chemistry to other rare-earth metals and/or different metal oxidation states, as well as exploiting their stoichiometric and catalytic reactivities, continues to attract research effort. Herein we present an account of our investigations into scandium terminal imido chemistry as a timely summary, in the hope that our studies will be of interest to this readership.

Photoluminescence properties of Er-doped Ge–In(Ga)–S glasses modified by caesium halides

Czech Academy of Sciences Publication Activity Database

Ivanova, Z.G.; Zavadil, Jiří; Kostka, P.; Djouama, T.; Reinfelde, M.

2017-01-01

Roč. 254, č. 6 (2017), č. článku 1600662. ISSN 0370-1972 Institutional support: RVO:67985882 Keywords : caesium halides * chalcohalide glasses * erbium doping * transmission spectroscopy * photoluminiscence Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass OBOR OECD: Ceramics Impact factor: 1.674, year: 2016

Photoluminescence properties of Er-doped Ge–In(Ga)–S glasses modified by caesium halides

Czech Academy of Sciences Publication Activity Database

Ivanova, Z.G.; Zavadil, Jiří; Kostka, Petr; Djouama, T.; Reinfelde, M.

2017-01-01

Roč. 254, č. 6 (2017), č. článku 1600662. ISSN 0370-1972 Institutional support: RVO:67985891 Keywords : caesium halides * chalcohalide glasses * erbium doping * transmission spectroscopy * photoluminiscence Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass OBOR OECD: Ceramics Impact factor: 1.674, year: 2016

Synthesis, thermogravimetric, spectroscopic and theoretical characterization of copper(II) complex with 4-chloro-2-nitrobenzenosulfonamide

Science.gov (United States)

Camí, G.; Chacón Villalba, E.; Di Santi, Y.; Colinas, P.; Estiu, G.; Soria, D. B.

2011-05-01

4-Chloro-2-nitrobenzenesulfonamide (ClNbsa) was purified and characterized. A new copper(II) complex, [Cu(ClNbsa) 2(NH 3) 2], has been prepared using the sulfonamide as ligand. The thermal behavior of both, the ligand and the Cu(II) complex, was investigated by thermogravimetric analyses (TG) and differential thermal analysis (DT), and the electronic characteristics analyzed by UV-VIS, FTIR, Raman and 1H NMR spectroscopies. The experimental IR, Raman and UV-VIS spectra have been assigned on the basis of DFT calculations at the B3LYP level of theory using the standard (6-31 + G ∗∗) basis set. The geometries have been fully optimized in vacuum and in modeled dimethylsulfoxide (DMSO) solvent, using for the latter a continuum solvation model that reproduced the experimental conditions of the UV-VIS spectroscopy. The theoretical results converged to stable conformations for the free sulfonamide and for the complex, suggesting for the latter a distorted square planar geometry in both environments.

Effect of chromone-substituted benzothiazolium halides on photosynthetic processes

International Nuclear Information System (INIS)

Kralova, K.; Sersen, F.; Gasparova, R.; Lacova, M.

1998-01-01

The effects of 3-R 2 -2[2-(6-R 1 -chromone-3-yl)ethenyl]benzothiazolium halides (CBH) on photosynthetic electron transport in spinach chloroplasts and in the legal suspension of Chlorella vulgaris were investigated. Using EPR spectroscopy it was confirmed that these compounds containing in their molecules two heterocyclic skeletons, namely benzothiazole and chromone, interact with the intermediate D + , corresponding to the tyrosine radical Tyr D situated in D 2 protein on the donor side of photosystem 2. Consequently, higher concentrations of CBH inhibited oxygen evolution rate in Chlorella vulgaris and the inhibitory effectiveness depended on the lipophilicity of the of the compound. (authors)

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

Science.gov (United States)

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.

Comparative study of energy-efficiency and conservation systems for ceramic metal-halide discharge lamps

International Nuclear Information System (INIS)

Hermoso Orzáez, Manuel Jesús; Andrés Díaz, José Ramón de

2013-01-01

Interest in energy savings in urban lighting is gaining traction and has become a priority for municipal administrations. LED (light-emitting diode) technology appears to be the clear future lighting choice. However, this technology is still rapidly developing and has not been sufficiently tested. As an intermediate step, alternative proposals for energy-saving equipment for traditional discharge lamps are desirable so that the current technologies can coexist with the new LED counterparts for the short and medium term. This article provides a comparative study between two efficiency and energy-saving systems for discharge lamps with metal-halide and ceramic technologies, i.e., a lighting flow dimmer-stabilizer and a double-level electronic ballast. - Highlights: ► It has been demonstrated the possibility of regulating ceramic metal-halide lamps with lighting flow dimmer-stabilizer. ► Electronic ballasts can save approximately double quantity of energy than lighting flow dimmer-stabilizers. ► The use of lighting flow dimmer-stabilizer is more profitable than electronic ballasts due to costs and reliability

Progress on Perovskite Materials and Solar Cells with Mixed Cations and Halide Anions.

Science.gov (United States)

Ono, Luis K; Juarez-Perez, Emilio J; Qi, Yabing

2017-09-13

Organic-inorganic halide perovskite materials (e.g., MAPbI 3 , FAPbI 3 , etc.; where MA = CH 3 NH 3 + , FA = CH(NH 2 ) 2 + ) have been studied intensively for photovoltaic applications. Major concerns for the commercialization of perovskite photovoltaic technology to take off include lead toxicity, long-term stability, hysteresis, and optimal bandgap. Therefore, there is still need for further exploration of alternative candidates. Elemental composition engineering of MAPbI 3 and FAPbI 3 has been proposed to address the above concerns. Among the best six certified power conversion efficiencies reported by National Renewable Energy Laboratory on perovskite-based solar cells, five are based on mixed perovskites (e.g., MAPbI 1-x Br x , FA 0.85 MA 0.15 PbI 2.55 Br 0.45 , Cs 0.1 FA 0.75 MA 0.15 PbI 2.49 Br 0.51 ). In this paper, we review the recent progress on the synthesis and fundamental aspects of mixed cation and halide perovskites correlating with device performance, long-term stability, and hysteresis. In the outlook, we outline the future research directions based on the reported results as well as related topics that warrant further investigation.

Interplay between organic cations and inorganic framework and incommensurability in hybrid lead-halide perovskite CH3NH3PbBr3

Science.gov (United States)

Guo, Yinsheng; Yaffe, Omer; Paley, Daniel W.; Beecher, Alexander N.; Hull, Trevor D.; Szpak, Guilherme; Owen, Jonathan S.; Brus, Louis E.; Pimenta, Marcos A.

2017-09-01

Organic-inorganic coupling in the hybrid lead-halide perovskite is a central issue in rationalizing the outstanding photovoltaic performance of these emerging materials. Here, we compare and contrast the evolution of the structure and dynamics of hybrid CH3NH3PbBr3 and inorganic CsPbBr3 lead-halide perovskites with temperature, using Raman spectroscopy and single-crystal x-ray diffraction. Results reveal a stark contrast between their order-disorder transitions, which are abrupt for the hybrid whereas smooth for the inorganic perovskite. X-ray diffraction observes an intermediate incommensurate phase between the ordered and the disordered phases in CH3NH3PbBr3 . Low-frequency Raman scattering captures the appearance of a sharp soft mode in the incommensurate phase, ascribed to the theoretically predicted amplitudon mode. Our work highlights the interaction between the structural dynamics of organic cation CH3NH3+ and the lead-halide framework, and unravels the competition between tendencies for the organic and inorganic moieties to minimize energy in the incommensurate phase of the hybrid perovskite structure.

Synthesis, molecular docking and DNA binding studies of phthalimide-based copper(II) complex: In vitro antibacterial, hemolytic and antioxidant assessment

Science.gov (United States)

Arif, Rizwan; Nayab, Pattan Sirajuddin; Ansari, Istikhar A.; Shahid, M.; Irfan, Mohammad; Alam, Shadab; Abid, Mohammad; Rahisuddin

2018-05-01

In the present research work, we prepared N-substituted phthalimide, 2-(-(2-(2-(2-(1,3-dioxoisoindoline-2-yl-ethylamino)ethylamino)ethyl)isoindoline-1,3-dione (DEEI) and its copper(II) complex. The ligand (DEEI) and its Cu(II) complex were structurally identified using absorption, FTIR, NMR, electron spin resonance, X-ray diffraction spectral studies, thermogravimetric and elemental analyses. The electronic spectrum and magnetic moment value proposed that Cu(II) complex has square planar geometry. The DNA interaction ability of the ligand (DEEI) and Cu(II) complex was studied by means of absorption and fluorescence spectrophotometer, viscosity measurements, cyclic voltammetery, and circular dichroism methods. The extent of DNA binding (Kb) with Calf thymus (Ct-DNA) follows the order of Cu(II) complex (1.11 × 106 M-1) > DEEI (1.0 × 105 M-1), indicating that Cu(II) complex interact with Ct-DNA through groove binding mode and more sturdily than ligand (DEEI). Interestingly, in silico predictions were corroborated with in vitro DNA binding studies. The antibacterial evaluation of these compounds was screened against a panel of bacterial strains Pseudomonas aeruginosa (MTCC 2453), Salmonella enterica (MTCC 3224), Streptococcus pneumoniae (MTCC 655), Enterococcus faecalis (MTCC 439), Klebsiella pneumonia and Escherichia coli (ATCC 25922). The results showed that the copper(II) complex has significant antibacterial potential (IC50 = 0.0019 μg/mL) against Salmonella enteric comparable with ligand (DEEI) and standard drug ciprofloxacin. Growth curve study of Cu(II) complex against only three bacterial strains S. enterica, E. faecalis and S. pneumoniae showed its bactericidal nature. Cu(II) complex showed less than 2% hemolysis on human RBCs indicating its non toxic nature. The results of antioxidant assay demonstrated that scavenging activity of Cu(II) complex is higher as compared to ligand and ascorbic acid as standard.

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

Science.gov (United States)

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.

Photocleavage of DNA by copper(II) complexes

Indian Academy of Sciences (India)

Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560 012 e-mail: ... induced DNA cleavage activity is summarized in this article. ... per(II) complexes play important roles in DNA cleavage reactions.

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

Science.gov (United States)

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.

Copper(II) catalysis in cyanide conversion into ethyl carbamate in spirits and relevant reactions.

Science.gov (United States)

Aresta, M; Boscolo, M; Franco, D W

2001-06-01

The role of copper(II) species in the oxidation of inorganic cyanide to cyanate and in the conversion of cyanate or urea into ethyl carbamate was investigated. The oxidation process has been shown to be independent from the dissolved oxygen. Elemental analysis and infrared spectroscopy have shown the formation of a mixed copper carbonate/hydroxide in the process of oxidation of cyanide to cyanate in water/ethanol. The complexation to Cu(II) of cyanate formed upon cyanide oxidation makes the former more susceptible to nucleophilic attack from ethanol, with conversion into ethyl carbamate. Comparatively, urea has a minor role with respect to cyanide in the formation of ethyl carbamate. Therefore, the urea present in some samples of Brazilian sugar cane spirit (cachaça) has been shown to have almost no influence on the ethyl carbamate content of cachaças, which comes essentially from cyanide. Fe(II,III) affords results similar to those found with Cu(II). Some suggestions are presented to avoid ethyl carbamate formation in spirits during distillation.

UV and X radiation effects on the stability of calcium halide phosphate phosphors. 2

International Nuclear Information System (INIS)

Tews, W.; Getter, R.; Kleemann, M.

1983-01-01

Sb(V) and Sb(III) concentrations in calcium halide phosphate phosphors have been investigated as a function of time of irradiation with near UV and X radiation. It was found that the reduction of both Sb(V) and Sb(III) to elemental Sb results in intensity losses. The reductions follow consecutive first-order kinetics and first-order kinetics, respectively

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

Science.gov (United States)

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.

Interaction between metals and nucleic acids. Part 3. Synthesis and structural studies of copper(II) complexes with Schiff base ligands derived from barbituric acid

Energy Technology Data Exchange (ETDEWEB)

Sasaki, I.; Gaudemer, A.; Chiaroni, A.; Riche, C.

1986-02-17

Schiff bases have been prepared from 5-formylbarbituric acid and 5-formyl-1,3-dimethyl-barbituric acid and various di- or tri-amines. The structure of the corresponding copper(II) complexes have been established by elemental analysis and spectroscopic methods. The molecular structure of one of the complexes, Cu(DiMeBardpt), was determined by X-ray diffraction. Electrochemical study shows that these complexes are reduced at slightly more negative potentials than the corresponding complexes obtained from uracil, which suggests that these new ligands are better electron-donors.

Radiation chemistry of aqueous trichloroethene

International Nuclear Information System (INIS)

Cooper, R.

1998-01-01

Full text: Halogenated hydrocarbons have played a key role in Industrial processes for many years. The problems of disposal of used solvents and chloroderivatives is now a problem facing chemical companies, industrial and domestic users. A range of treatments have been suggested and tried from high efficiency incineration to photo-catalytic hydrolysis. Radiation chemistry offers a route to dissolution and dehalogenation of halocarbons in general by virtue of free radical reactions and in particular the dissociative electron capture process resulting from the generation of solvated electrons. RCl + e - aq → R + Cl - aq . The fate of the free radical, R, is crucial to the subsequent degradation of the halocarbon. It will probably contain more organic chlorine, or other halogens, which ideally should be degradable to inert inorganic halide. In this study pulse radiolysis studies have been conducted on aqueous solutions of trichloroethene (TCE) which is a commonly used industrial cleaning solvent. The production of free radicals has been monitored by fast time resolution absorption spectroscopy using a pulse radiolysis facility at the Australian Radiation Laboratory Yallambie Victoria. Fee radical species have been detected in pulse electron irradiated solutions of TCE at various pH's and in the presence of Oxygen and Nitrous oxide. The nature of these radical species will be discussed. The production of inorganic chlorine is being monitored by a spectrophotometric technique based upon a mercuric thiocyanate/ ferric ion complexation which can detect free chloride ion concentrations down to ppm levels

Synthesis and properties of complexes of copper(II), nickel(II), cobalt(II) and uranyl ions with 3-(p-tolylsulphonamido)rhodamine

International Nuclear Information System (INIS)

El-Bindary, A.A.; El-Sonbati, A.Z.

2000-01-01

Metal complexes of copper(II), nickel(II), cobalt(II) and uranyl ions with 3-(p-tolylsulphonamido)rhodamine (HL) have been prepared and characterized by chemical and thermal analyses, molar conductivity , magnetic susceptibility measurements, and infrared, electronic and EPR spectra. The visible and EPR spectra indicated that the Cu(II) complex has a tetragonal geometry. From EPR spectrum of the Cu(II) complex,various parameters were calculated. The crystal field parameters of Ni(II) complex were calculated and were found to agree fairly well with the values reported for known square pyramidal complexes. The infrared spectral studies showed a monobasic bidentate behaviour with the oxygen and nitrogen donor system. Thermal stabilities of the complexes are also reported. (author)

Stability constants of glutarate complexes of copper(II), zinc(II), cobalt(II) and uranyl(II) by paper electrophoresis

International Nuclear Information System (INIS)

Singh, R.K.P.; Yadava, J.R.; Yadava, K.L.

1981-01-01

Stability constants of Copper(II), Zinc(II), Cobalt(II) and Uranyl(II) glutarates have been determined by paper electrophoresis. Glutaric acid (0.005 mol dmsup(-3)) was added to the background electrolyte : 0.1 mol dmsup(-3) HClO 4 . The proportions of (CH 2 ) 3 COOH COO - and (CH 2 ) 3 C 2 O 4 2- were varied by changing the pH of the electrolyte. These anions yielded the complexes Cu(CH 2 ) 3 C 2 O 4 , [Zn(CH 2 ) 3 COOH COO] + [Co(CH 2 ) 3 COOH COO] + and UO 2 (CH 2 ) 3 C 2 O 4 whose stability constants are found to be 10sup(3.9), 10sup(2.9), 10sup(2.7) and 10sup(13.5) respectively. (author)

All-Inorganic Colloidal Quantum Dot Photovoltaics Employing Solution-Phase Halide Passivation

KAUST Repository

Ning, Zhijun

2012-09-12

A new solution-phase halide passivation strategy to improve the electronic properties of colloidal quantum dot films is reported. We prove experimentally that the approach leads to an order-of-magnitude increase in mobility and a notable reduction in trap state density. We build solar cells having the highest efficiency (6.6%) reported using all-inorganic colloidal quantum dots. The improved photocurrent results from increased efficiency of collection of infrared-generated photocarriers. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An heterogeneous nucleation model for the irradiation coloring of alkali halides

International Nuclear Information System (INIS)

Aguilar, M.; Jaque, F.; Agullo-Lopez, F.

1980-01-01

An heterogeneous nucleation model for the radiation-induced coloring of alkali halides is presented. The model assumes a primary mechanism producing F and H pairs, followed by secondary thermally activated reactions including F-H recombination as well interstitial capture. The existence of a very unstable interstitial aggregate is explicitely considered. The model is able to account for the three-stages structure of the F-coloring curve and the inhibition in the occurrence of the late-stage by lowering dose-rate or by impurity doping

All-Inorganic Colloidal Quantum Dot Photovoltaics Employing Solution-Phase Halide Passivation

KAUST Repository

Ning, Zhijun; Ren, Yuan; Hoogland, Sjoerd; Voznyy, Oleksandr; Levina, Larissa; Stadler, Philipp; Lan, Xinzheng; Zhitomirsky, David; Sargent, Edward H.

2012-01-01

A new solution-phase halide passivation strategy to improve the electronic properties of colloidal quantum dot films is reported. We prove experimentally that the approach leads to an order-of-magnitude increase in mobility and a notable reduction in trap state density. We build solar cells having the highest efficiency (6.6%) reported using all-inorganic colloidal quantum dots. The improved photocurrent results from increased efficiency of collection of infrared-generated photocarriers. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Genesis, challenges and opportunities for colloidal lead halide perovskite nanocrystals

Science.gov (United States)

Akkerman, Quinten A.; Rainò, Gabriele; Kovalenko, Maksym V.; Manna, Liberato

2018-05-01

Lead halide perovskites (LHPs) in the form of nanometre-sized colloidal crystals, or nanocrystals (NCs), have attracted the attention of diverse materials scientists due to their unique optical versatility, high photoluminescence quantum yields and facile synthesis. LHP NCs have a `soft' and predominantly ionic lattice, and their optical and electronic properties are highly tolerant to structural defects and surface states. Therefore, they cannot be approached with the same experimental mindset and theoretical framework as conventional semiconductor NCs. In this Review, we discuss LHP NCs historical and current research pursuits, challenges in applications, and the related present and future mitigation strategies explored.

Status quo of ceramic material for metal halide discharge lamps

International Nuclear Information System (INIS)

Kappen, Theo G M M

2005-01-01

Polycrystalline alumina is an excellent ceramic material for use as the envelope for metal halide discharge lamps. Although this material was introduced in the mid-1960s, and is thus already known for several decades, recent years have seen considerable effort aimed at further development of these ceramic envelope materials. Developments are not only in the field of ceramic shaping technologies, but are also concentrated on the material properties of the ceramic material itself. Optical, mechanical as well as the chemical properties of the ceramic envelope are strongly controlled by the shape as well as the microstructure of the ceramics used

Structure and energetics of trivalent metal halides

International Nuclear Information System (INIS)

Hutchinson, F.

1999-01-01

Metal trihalide (MX 3 ) systems represent a stern challenge in terms of constructing transferable potential models. Starting from a previously published set of potentials, 'extended' ionic models are developed which, at the outset, include only anion polarization. Deficiencies in these models, particularly for smaller (highly polarizing) cations, axe shown to be significant. For example, crystal structures different to those observed experimentally axe adopted. The potentials axe improved upon by reference to ab initio information available for alkali halides with the 'constraint' that the parameters transfer systematically in a physically transparent manner, for example, in terms of ion radii. The possible influence of anion compression ('breathing') and the relative abundance of anion-anion interactions are considered. Simulation techniques axe developed to allow for the effective simulation of any system symmetry and for the study of transitions between different crystals (constant stress). The developed models are fully tested for a large range of metal trichloride (MCl 3 ) systems. Particular attention is paid to the comparison with recent neutron and X-ray diffraction data on the liquid state. Polarization effects axe shown to be vital in reproducing strong experimental features. The excellent agreement between simulation and experiment allows for differences in experimental procedures to be highlighted. The transferability is further tested by modelling mixtures of the lanthanides with alkali halides with potentials unchanged from the pure systems. The complex evolution of the melt structure is highlighted as the concentration of MCl 3 increases. The effectiveness of the models is tested by reference to dynamical properties. Particular attention is paid to the comparison with Raman scattering data available for a wide range of systems and mixture concentrations. The simulated spectra are generated both by a simple molecular picture of the underlying

Variable Charge and Electrical Double Layer of Mineral-Water Interfaces: Silver Halides versus Metal (Hydr)Oxides

NARCIS (Netherlands)

Hiemstra, T.

2012-01-01

Classically, silver (Ag) halides have been used to understand thermodynamic principles of the charging process and the corresponding development of the electrical double layer (EDL). A mechanistic approach to the processes on the molecular level has not yet been carried out using advanced surface

Transformation of Sintered CsPbBr3 Nanocrystals to Cubic CsPbI3 and Gradient CsPbBrxI3-x through Halide Exchange.

Science.gov (United States)

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

2016-07-13

All-inorganic cesium lead halide (CsPbX3, X = Br(-), I(-)) perovskites could potentially provide comparable photovoltaic performance with enhanced stability compared to organic-inorganic lead halide species. However, small-bandgap cubic CsPbI3 has been difficult to study due to challenges forming CsPbI3 in the cubic phase. Here, a low-temperature procedure to form cubic CsPbI3 has been developed through a halide exchange reaction using films of sintered CsPbBr3 nanocrystals. The reaction was found to be strongly dependent upon temperature, featuring an Arrhenius relationship. Additionally, film thickness played a significant role in determining internal film structure at intermediate reaction times. Thin films (50 nm) showed only a small distribution of CsPbBrxI3-x species, while thicker films (350 nm) exhibited much broader distributions. Furthermore, internal film structure was ordered, featuring a compositional gradient within film. Transient absorption spectroscopy showed the influence of halide exchange on the excited state of the material. In thicker films, charge carriers were rapidly transferred to iodide-rich regions near the film surface within the first several picoseconds after excitation. This ultrafast vectorial charge-transfer process illustrates the potential of utilizing compositional gradients to direct charge flow in perovskite-based photovoltaics.

Energy transfer and infrared-to-visible upconversion luminescence of Er3+/Yb3+-codoped halide modified tellurite glasses

International Nuclear Information System (INIS)

Zhang, Q.Y.; Feng, Z.M.; Yang, Z.M.; Jiang, Z.H.

2006-01-01

We report on the energy transfer and frequency upconversion spectroscopic properties of Er 3+ -doped and Er 3+ /Yb 3+ -codoped TeO 2 -ZnO-Na 2 O-PbCl 2 halide modified tellurite glasses upon excitation with 808 and 978 nm laser diode. Three intense emissions centered at around 529, 546 and 657 nm, alongwith a very weak blue emission at 410 nm have clearly been observed for the Er 3+ /Yb 3+ -codoped halide modified tellurite glasses upon excitation at 978 nm and the involved mechanisms are explained. The quadratic dependence of fluorescence on excitation laser power confirms the fact that the two-photon contribute to the infrared to green-red upconversion emissions. And the blue upconversion at 410 nm involved a sequential three-photon absorption process

Synthesis of E-Alkyl Alkenes from Terminal Alkynes via Ni-Catalyzed Cross-Coupling of Alkyl Halides with B-Alkenyl-9-borabicyclo[3.3.1]nonanes.

Science.gov (United States)

Di Franco, Thomas; Epenoy, Alexandre; Hu, Xile

2015-10-02

The first Ni-catalyzed Suzuki-Miyaura coupling of alkyl halides with alkenyl-(9-BBN) reagents is reported. Both primary and secondary alkyl halides including alkyl chlorides can be coupled. The coupling method can be combined with hydroboration of terminal alkynes, allowing the expedited synthesis of functionalized alkyl alkenes from readily available alkynes with complete (E)-selectivity in one pot. The method was applied to the total synthesis of (±)-Recifeiolide, a natural macrolide.

Absorption lineshape of FA centers in alkali halides

International Nuclear Information System (INIS)

Baldacchini, G.; Giovenale, E.; De Matteis, F.; Scacco, A.; Somma, F.; Grassano, U.M.

1988-01-01

The line shape of the absorption bands of F A centers in alkali halides have been studied for the first time. The new method used for this investigation is based on the determination of the overlap between the F A1 and F A2 bands from luminescence measurements. The experimental results have been compared with calculated values deduced from the theoretical F A bands of different shapes. For both F A (I) centers in KCl:Na + and F A (II) centers in KCl:Li + and RbCl:Li + the absorption lineshape at low temperature is much closer to a sum of two Lorentzian curves than that of two Gaussian or Poissonian bands. This results shows an unexpected difference with the F centers, whose absorption lineshape is known to be Poissonian at the same temperatures

M-center growth in alkali halides: computer simulation

International Nuclear Information System (INIS)

Aguilar, M.; Jaque, F.; Agullo-Lopez, F.

1983-01-01

The heterogeneous interstitial nucleation model previously proposed to explain F-center growth curves in irradiated alkali halides has been extended to account for M-center kinetics. The interstitials produced during the primary irradiation event are assumed to be trapped at impurities and interstitial clusters or recombine with F and M centers. For M-center formation two cases have been considered: (a) diffusion and aggregation of F centers, and (b) statistical generation and pairing of F centers. Process (b) is the only one consistent with the quadratic relationship between M and F center concentrations. However, to account for the F/M ratios experimentally observed as well as for the role of dose-rate, a modified statistical model involving random creation and association of F + -F pairs has been shown to be adequate. (author)

Water-Induced Dimensionality Reduction in Metal-Halide Perovskites

KAUST Repository

Turedi, Bekir

2018-03-30

Metal-halide perovskite materials are highly attractive materials for optoelectronic applications. However, the instability of perovskite materials caused by moisture and heat-induced degradation impairs future prospects of using these materials. Here we employ water to directly transform films of the three-dimensional (3D) perovskite CsPbBr3 to stable two-dimensional (2D) perovskite-related CsPb2Br5. A sequential dissolution-recrystallization process governs this water induced transformation under PbBr2 rich condition. We find that these post-synthesized 2D perovskite-related material films exhibit excellent stability against humidity and high photoluminescence quantum yield. We believe that our results provide a new synthetic method to generate stable 2D perovskite-related materials that could be applicable for light emitting device applications.

Pressure-Induced Structural Evolution and Band Gap Shifts of Organometal Halide Perovskite-Based Methylammonium Lead Chloride.

Science.gov (United States)

Wang, Lingrui; Wang, Kai; Xiao, Guanjun; Zeng, Qiaoshi; Zou, Bo

2016-12-15

Organometal halide perovskites are promising materials for optoelectronic devices. Further development of these devices requires a deep understanding of their fundamental structure-property relationships. The effect of pressure on the structural evolution and band gap shifts of methylammonium lead chloride (MAPbCl 3 ) was investigated systematically. Synchrotron X-ray diffraction and Raman experiments provided structural information on the shrinkage, tilting distortion, and amorphization of the primitive cubic unit cell. In situ high pressure optical absorption and photoluminescence spectra manifested that the band gap of MAPbCl 3 could be fine-tuned to the ultraviolet region by pressure. The optical changes are correlated with pressure-induced structural evolution of MAPbCl 3 , as evidenced by band gap shifts. Comparisons between Pb-hybrid perovskites and inorganic octahedra provided insights on the effects of halogens on pressure-induced transition sequences of these compounds. Our results improve the understanding of the structural and optical properties of organometal halide perovskites.

XAFS Study of the Ferro- and Antiferromagnetic Binuclear Copper(II) Complexes of Azomethine Based Tridentate Ligands

International Nuclear Information System (INIS)

Vlasenko, Valery G.; Vasilchenko, Igor S.; Shestakova, Tatiana E.; Uraev, Ali I.; Burlov, Anatolii S.; Garnovskii, Alexander D.; Pirog, Irina V.

2007-01-01

Binuclear copper complexes are known to be models for metalloenzymes containing copper active sites, and some of them are of considerable interest due to their magnetic and charge transfer properties. The reactions of the complex formation of bibasic tridentate heterocyclic imines with copper acetate leads to two types of chelates with mono deprotonated ligands and with totally deprotonated ligands. Cu K-edge EXAFS has been applied to determine the local structure around the metal center in copper(II) azomethine complexes with five tridentate ligands: 1-(salycilideneimino)- or 1-(2-tosylaminobenzilideneimino)-2-amino(oxo, thio)benzimidazoles. It has been found that some of the chelates studied are bridged binuclear copper complexes, and others are mononuclear complexes. The copper-copper interatomic distances in the bridged binuclear copper complexes were found to be 2.85-3.01 A. Variable temperature magnetic susceptibility data indicate the presence of both ferromagnetic and antiferromagnetic interactions within the dimer, the former is dominating at low temperatures and the latter at high temperatures

CuI-Catalyzed: One-Pot Synthesis of Diaryl Disulfides from Aryl Halides and Carbon Disulfide

Directory of Open Access Journals (Sweden)

Mohammad Soleiman-Beigi

2013-01-01

Full Text Available A new application of carbon disulfide in the presence of KF/Al2O3 is reported for the synthesis of organic symmetrical diaryl disulfides. These products were synthesized by one-pot reaction of aryl halides with the in situ generated trithiocarbonate ion in the presence of copper under air atmosphere.

Touching is believing: interrogating halide perovskite solar cells at the nanoscale via scanning probe microscopy

Science.gov (United States)

Li, Jiangyu; Huang, Boyuan; Nasr Esfahani, Ehsan; Wei, Linlin; Yao, Jianjun; Zhao, Jinjin; Chen, Wei

2017-10-01

Halide perovskite solar cells based on CH3NH3PbI3 and related materials have emerged as the most exciting development in the next generation photovoltaic technologies, yet the microscopic phenomena involving photo-carriers, ionic defects, spontaneous polarization, and molecular vibration and rotation interacting with numerous grains, grain boundaries, and interfaces are still inadequately understood. In fact, there is still need for an effective method to interrogate the local photovoltaic properties of halide perovskite solar cells that can be directly traced to their microstructures on one hand and linked to their device performance on the other hand. In this perspective, we propose that scanning probe microscopy (SPM) techniques have great potential to realize such promises at the nanoscale, and highlight some of the recent progresses and challenges along this line of investigation toward local probing of photocurrent, work function, ionic activities, polarization switching, and chemical degradation. We also emphasize the importance of multi-modality imaging, in-operando scanning, big data analysis, and multidisciplinary collaboration for further studies toward fully understanding of these complex systems.

An objective protocol for comparing the noise performance of silver halide film and digital sensor

Science.gov (United States)

Cao, Frédéric; Guichard, Frédéric; Hornung, Hervé; Tessière, Régis

2012-01-01

Digital sensors have obviously invaded the photography mass market. However, some photographers with very high expectancy still use silver halide film. Are they only nostalgic reluctant to technology or is there more than meets the eye? The answer is not so easy if we remark that, at the end of the golden age, films were actually scanned before development. Nowadays film users have adopted digital technology and scan their film to take advantage from digital processing afterwards. Therefore, it is legitimate to evaluate silver halide film "with a digital eye", with the assumption that processing can be applied as for a digital camera. The article will describe in details the operations we need to consider the film as a RAW digital sensor. In particular, we have to account for the film characteristic curve, the autocorrelation of the noise (related to film grain) and the sampling of the digital sensor (related to Bayer filter array). We also describe the protocol that was set, from shooting to scanning. We then present and interpret the results of sensor response, signal to noise ratio and dynamic range.

Hydrolysis in the organic phase during the extraction of alkali metal halides and water by copper bis(2-ethylhexyl)phosphate

International Nuclear Information System (INIS)

Golovanov, V.I.; Kuznetsov, S.M.

2001-01-01

Experimental data on extraction of halides, among which are LiCl and CsCl, and water by copper di-(2-ethylhexyl)phosphate solutions in respect to hydrolysis mechanism of reaction are generalized. Copper di-(2-ethylhexyl)phosphate manifests properties of ionogen colloidal surfactant in water. Extraction of halides by copper di-(2-ethylhexyl)phosphate was shown to be visualized by the process of capsule formation in MHal molecules, as well as in hydrolyzed MOH and HHal forms of electrolyte by Cu 4 (D2EHF) 8 · hH 2 O clathrate-like micellar associates. The model of hydrolysis mechanism is not different from proposed earlier model of electrolyte extraction with their partial dissociation in organic phase [ru

Effects of Halide Ions on the Carbamidocyclophane Biosynthesis in Nostoc sp. CAVN2

Science.gov (United States)

Preisitsch, Michael; Heiden, Stefan E.; Beerbaum, Monika; Niedermeyer, Timo H. J.; Schneefeld, Marie; Herrmann, Jennifer; Kumpfmüller, Jana; Thürmer, Andrea; Neidhardt, Inga; Wiesner, Christoph; Daniel, Rolf; Müller, Rolf; Bange, Franz-Christoph; Schmieder, Peter; Schweder, Thomas; Mundt, Sabine

2016-01-01

In this study, the influence of halide ions on [7.7]paracyclophane biosynthesis in the cyanobacterium Nostoc sp. CAVN2 was investigated. In contrast to KI and KF, supplementation of the culture medium with KCl or KBr resulted not only in an increase of growth but also in an up-regulation of carbamidocyclophane production. LC-MS analysis indicated the presence of chlorinated, brominated, but also non-halogenated derivatives. In addition to 22 known cylindrocyclophanes and carbamidocyclophanes, 27 putative congeners have been detected. Nine compounds, carbamidocyclophanes M−U, were isolated, and their structural elucidation by 1D and 2D NMR experiments in combination with HRMS and ECD analysis revealed that they are brominated analogues of chlorinated carbamidocyclophanes. Quantification of the carbamidocyclophanes showed that chloride is the preferably utilized halide, but incorporation is reduced in the presence of bromide. Evaluation of the antibacterial activity of 30 [7.7]paracyclophanes and related derivatives against selected pathogenic Gram-positive and Gram-negative bacteria exhibited remarkable effects especially against methicillin- and vancomycin-resistant staphylococci and Mycobacterium tuberculosis. For deeper insights into the mechanisms of biosynthesis, the carbamidocyclophane biosynthetic gene cluster in Nostoc sp. CAVN2 was studied. The gene putatively coding for the carbamoyltransferase has been identified. Based on bioinformatic analyses, a possible biosynthetic assembly is discussed. PMID:26805858