Reduction of RuVI≡N to RuIII-NH3 by Cysteine in Aqueous Solution.

Science.gov (United States)

Wang, Qian; Man, Wai-Lun; Lam, William W Y; Yiu, Shek-Man; Tse, Man-Kit; Lau, Tai-Chu

2018-05-21

The reduction of metal nitride to ammonia is a key step in biological and chemical nitrogen fixation. We report herein the facile reduction of a ruthenium(VI) nitrido complex [(L)Ru VI (N)(OH 2 )] + (1, L = N, N'-bis(salicylidene)- o-cyclohexyldiamine dianion) to [(L)Ru III (NH 3 )(OH 2 )] + by l-cysteine (Cys), an ubiquitous biological reductant, in aqueous solution. At pH 1.0-5.3, the reaction has the following stoichiometry: [(L)Ru VI (N)(OH 2 )] + + 3HSCH 2 CH(NH 3 )CO 2 → [(L)Ru III (NH 3 )(OH 2 )] + + 1.5(SCH 2 CH(NH 3 )CO 2 ) 2 . Kinetic studies show that at pH 1 the reaction consists of two phases, while at pH 5 there are three distinct phases. For all phases the rate law is rate = k 2 [1][Cys]. Studies on the effects of acidity indicate that both HSCH 2 CH(NH 3 + )CO 2 - and - SCH 2 CH(NH 3 + )CO 2 - are kinetically active species. At pH 1, the reaction is proposed to go through [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a), [(L)Ru III (NH 2 SCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (3), and [(L)Ru IV (NH 2 )(OH 2 )] + (4) intermediates. On the other hand, at pH around 5, the proposed intermediates are [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 )(OH 2 )] + (2b) and [(L)Ru IV (NH 2 )(OH 2 )] + (4). The intermediate ruthenium(IV) sulfilamido species, [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a) and the final ruthenium(III) ammine species, [(L)Ru III (NH 3 )(MeOH)] + (5) (where H 2 O was replaced by MeOH) have been isolated and characterized by various spectroscopic methods.

Formation of nitrogen complexes when [Ru(NH3)5H2O]2+ ion reaction with diazo-acetic ester and aromatic salts of diazonium

International Nuclear Information System (INIS)

Shur, V.B.; Tikhonova, I.A.; Vol'pin, M.E.

1978-01-01

A possibility of formation of nitrogen complexes during transition metal compound interaction with aliphatic and aromatic diazo compounds is studied. It is shown that at the interaction of [Ru(NH 3 ) 5 H 2 O] 2+ with diazo-acetic ester in water (pH7) at 20 deg, quick splitting of the CN-bond in the ester molecule takes place with the formation of [Ru(NH 3 ) 5 N 2 ] 2+ and [(NH 3 ) 5 RuN 2 Ru(NH 3 ) 5 ] 4+ (NRRN) nitrogen complexes. The sum yield of complexes comprises 86% taking into acount diazo-acetic ester. Aromatic salts of diazonium, n-O 3 SC 6 H 4 N 2 and p-quinone diazide react with the [Ru(NH 3 ) 5 H 2 O] 2+ excess forming NRRN (the yield equals 40-53%). The reaction mechanism is discussed

Charge carrier localised in zero-dimensional (CH3NH3)3Bi2I9 clusters.

Science.gov (United States)

Ni, Chengsheng; Hedley, Gordon; Payne, Julia; Svrcek, Vladimir; McDonald, Calum; Jagadamma, Lethy Krishnan; Edwards, Paul; Martin, Robert; Jain, Gunisha; Carolan, Darragh; Mariotti, Davide; Maguire, Paul; Samuel, Ifor; Irvine, John

2017-08-01

A metal-organic hybrid perovskite (CH 3 NH 3 PbI 3 ) with three-dimensional framework of metal-halide octahedra has been reported as a low-cost, solution-processable absorber for a thin-film solar cell with a power-conversion efficiency over 20%. Low-dimensional layered perovskites with metal halide slabs separated by the insulating organic layers are reported to show higher stability, but the efficiencies of the solar cells are limited by the confinement of excitons. In order to explore the confinement and transport of excitons in zero-dimensional metal-organic hybrid materials, a highly orientated film of (CH 3 NH 3 ) 3 Bi 2 I 9 with nanometre-sized core clusters of Bi 2 I 9 3- surrounded by insulating CH 3 NH 3 + was prepared via solution processing. The (CH 3 NH 3 ) 3 Bi 2 I 9 film shows highly anisotropic photoluminescence emission and excitation due to the large proportion of localised excitons coupled with delocalised excitons from intercluster energy transfer. The abrupt increase in photoluminescence quantum yield at excitation energy above twice band gap could indicate a quantum cutting due to the low dimensionality.Understanding the confinement and transport of excitons in low dimensional systems will aid the development of next generation photovoltaics. Via photophysical studies Ni et al. observe 'quantum cutting' in 0D metal-organic hybrid materials based on methylammonium bismuth halide (CH 3 NH 3 )3Bi 2 I 9 .

Structural determinants of NH3 and NH4+ transport by mouse Rhbg, a renal Rh glycoprotein.

Science.gov (United States)

Abdulnour-Nakhoul, Solange; Le, Trang; Rabon, Edd; Hamm, L Lee; Nakhoul, Nazih L

2016-12-01

Renal Rhbg is localized to the basolateral membrane of intercalated cells and is involved in NH 3 /NH 4 + transport. The structure of Rhbg is not yet resolved; however, a high-resolution crystal structure of AmtB, a bacterial homolog of Rh, has been determined. We aligned the sequence of Rhbg to that of AmtB and identified important sites of Rhbg that may affect transport. Our analysis positioned three conserved amino acids, histidine 183 (H183), histidine 342 (H342), and tryptophan 230 (W230), within the hydrophobic pore where they presumably serve to control NH 3 transport. A fourth residue, phenylalanine 128 (F128) was positioned at the upper vestibule, presumably contributing to recruitment of NH 4 + We generated three mutations each of H183, H342, W230, and F128 and expressed them in frog oocytes. Immunolabeling showed that W230 and F128 mutants were localized to the cell membrane, whereas H183 and H342 staining was diffuse and mostly intracellular. To determine function, we compared measurements of NH 3 /NH 4 + and methyl amine (MA)/methyl ammonium (MA + )-induced currents, intracellular pH, and surface pH (pHs) among oocytes expressing the mutants, Rhbg, or injected with H 2 O. In H183 and W230 mutants, NH 4 + -induced current and intracellular acidification were inhibited compared with that of Rhbg, and MA-induced intracellular alkalinization was completely absent. Expression of H183A or W230A mutants inhibited NH 3 /NH 4 + - and MA/MA + -induced decrease in pHs to the level observed in H 2 O-injected oocytes. Mutations of F128 did not significantly affect transport of NH 3 or NH 4 + These data demonstrated that mutating H183 or W230 caused loss of function but not F128. H183 and H342 may affect membrane expression of the transporter.

Photostriction of CH3NH3PbBr3 Perovskite Crystals

KAUST Repository

Wei, Tzu-Chiao

2017-07-17

Organic-inorganic hybrid perovskite materials exhibit a variety of physical properties. Pronounced coupling between phonon, organic cations, and the inorganic framework suggest that these materials exhibit strong light-matter interactions. The photoinduced strain of CH3 NH3 PbBr3 is investigated using high-resolution and contactless in situ Raman spectroscopy. Under illumination, the material exhibits large blue shifts in its Raman spectra that indicate significant structural deformations (i.e., photostriction). From these shifts, the photostrictive coefficient of CH3 NH3 PbBr3 is calculated as 2.08 × 10-8 m2 W-1 at room temperature under visible light illumination. The significant photostriction of CH3 NH3 PbBr3 is attributed to a combination of the photovoltaic effect and translational symmetry loss of the molecular configuration via strong translation-rotation coupling. Unlike CH3 NH3 PbI3 , it is noted that the photostriction of CH3 NH3 PbBr3 is extremely stable, demonstrating no signs of optical decay for at least 30 d. These results suggest the potential of CH3 NH3 PbBr3 for applications in next-generation optical micro-electromechanical devices.

Effects of N Fertilizer Sources and Tillage Practices on NH3 Volatilization, Grain Yield, and N Use Efficiency of Rice Fields in Central China

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Tianqi Liu

2018-03-01

Full Text Available Tillage practices and nitrogen (N sources are important factors affecting rice production. Few studies, however, have examined the interactions between tillage practices and N fertilizer sources on NH3 volatilization, nitrogen use efficiency (NUE, and rice grain yield. This study aimed to investigate the effects of N fertilizer sources (no N fertilizer, inorganic N fertilizer, organic N fertilizer alone, organic N fertilizer plus inorganic N fertilizer, and slow-release N fertilizer plus inorganic N fertilizer and tillage practices (no-tillage [NT] and conventional intensive tillage [CT] on NH3 flux, grain yield, and NUE in the rice field of central China. N sources significantly affected NH3 volatilization, as the cumulative volatilization from the treatments of inorganic N fertilizer, organic N fertilizer, organic N fertilizer plus inorganic N fertilizer, slow-release N fertilizer plus inorganic N fertilizer was 4.19, 2.13, 3.42, and 2.23 folds in 2013, and 2.49, 1.68, 2.08, and 1.85 folds in 2014 compared with that under no N fertilizer treatment, respectively. The organic N fertilizer treatment had the lowest grain yield and NUE among all N fertilizer treatments, while slow-release N fertilizer plus inorganic N fertilizer treatment led to relatively higher grain yield and the greatest N use efficiency. Moreover, NT only markedly increased NH3 volatilization from basal fertilizer by 10–14% in average compared with CT, but had no obvious effects on total volatilization during the whole seasons. Tillage practices had no significant effects on grain yield and NUE. Our study suggested that the combination of slow-release N fertilizer plus inorganic N fertilizer and NT might be a sustainable method for mitigating greenhouse gas and NH3 emissions and improving grain yield and NUE in paddy fields of central China.

Effects of N Fertilizer Sources and Tillage Practices on NH3 Volatilization, Grain Yield, and N Use Efficiency of Rice Fields in Central China.

Science.gov (United States)

Liu, Tianqi; Huang, Jinfeng; Chai, Kaibin; Cao, Cougui; Li, Chengfang

2018-01-01

Tillage practices and nitrogen (N) sources are important factors affecting rice production. Few studies, however, have examined the interactions between tillage practices and N fertilizer sources on NH 3 volatilization, nitrogen use efficiency (NUE), and rice grain yield. This study aimed to investigate the effects of N fertilizer sources (no N fertilizer, inorganic N fertilizer, organic N fertilizer alone, organic N fertilizer plus inorganic N fertilizer, and slow-release N fertilizer plus inorganic N fertilizer) and tillage practices (no-tillage [NT] and conventional intensive tillage [CT]) on NH 3 flux, grain yield, and NUE in the rice field of central China. N sources significantly affected NH 3 volatilization, as the cumulative volatilization from the treatments of inorganic N fertilizer, organic N fertilizer, organic N fertilizer plus inorganic N fertilizer, slow-release N fertilizer plus inorganic N fertilizer was 4.19, 2.13, 3.42, and 2.23 folds in 2013, and 2.49, 1.68, 2.08, and 1.85 folds in 2014 compared with that under no N fertilizer treatment, respectively. The organic N fertilizer treatment had the lowest grain yield and NUE among all N fertilizer treatments, while slow-release N fertilizer plus inorganic N fertilizer treatment led to relatively higher grain yield and the greatest N use efficiency. Moreover, NT only markedly increased NH 3 volatilization from basal fertilizer by 10-14% in average compared with CT, but had no obvious effects on total volatilization during the whole seasons. Tillage practices had no significant effects on grain yield and NUE. Our study suggested that the combination of slow-release N fertilizer plus inorganic N fertilizer and NT might be a sustainable method for mitigating greenhouse gas and NH 3 emissions and improving grain yield and NUE in paddy fields of central China.

The reaction of TcCl3(Me2PhP)3 with dithio ligands. Synthesis, characterization and X-ray crystal structures of [TcCl2(Me2PhP)2(Me2dtp)]and [Tc(Me2PhP)(Etxan)3](Me2PhP=dimethylphenylphosphine, Me2dtp-=O,O'-dimethyldithiophosphate, Etxan-=ethylxanthate)

International Nuclear Information System (INIS)

Lorenz, B.; Schmidt, K.; Hiller, W.; Abram, U.; Huebener, R.

1993-01-01

Trichlorotris (dimethylphenylphosphine)technetium(III); [TcCl 3 (Me 2 PhP) 3 ], reacts with dithio ligands to form chelate complexes of different compositions and coordinations geometries. The reaction with ethylxanthate (Etxan - ) yields the diamagnetic seven-coordinate [Tc(Me 2 PhP)(Etxan) 3 ], which crystallizes monoclinic in the space group P2 2 /c with Z = 4 (a = 18.44(5), b = 9.2(1), c = 15.36(6) A, β = 104.3(2) ). The final R value is 0.029. The metal has a pentagonal-bipyramidal environment. With ammonium dimethyldithiophosphate, (NH 4 )Me 2 dtp, [TcCl 3 (Me 2 PhP) 3 ] forms the paramagnetic [TcCl 2 (Me 2 PhP) 2 (Me 2 dtp) in which the technetium atom has a distorted octahedral coordination sphere. The compound crystallizes orthorhombic, space group Pbcn, with Z = 4 (a = 16.20(1), b = 10.445(1), c 14.878(1)). The final R value is 0.031. The chloro ligands are in trans arrangement. (orig.)

Investigation on thermal evaporated CH3NH3PbI3 thin films

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Youzhen Li

2015-09-01

Full Text Available CH3NH3I, PbI2 and CH3NH3PbI3 films were fabricated by evaporation and characterized with X-ray Photoelectron Spectroscopy (XPS and X-ray diffraction (XRD. The XPS results indicate that the PbI2 and CH3NH3PbI3 films are more uniform and stable than the CH3NH3I film. The atomic ratio of the CH3NH3I, PbI2 and CH3NH3PbI3 films are C:N:I=1.00:1.01:0.70, Pb:I= 1.00:1.91 and C: N: Pb: I = 1.29:1.07:1.00:2.94, respectively. The atomic ratio of CH3NH3PbI3 is very close to that of the ideal perovskite. Small angle x-ray diffraction results demonstrate that the as evaporated CH3NH3PbI3 film is crystalline. The valence band maximum (VBM and work function (WF of the CH3NH3PbI3 film are about 0.85eV and 4.86eV, respectively.

Irradiated NH3 and ND3 - two new target materials for polarized targets

International Nuclear Information System (INIS)

Meyer, W.

1982-11-01

A study of dynamic nuclear polarization (DNP) in NH 3 and ND 3 was made at the Bonn 2.5 GeV electron synchrotron. The paramagnetic radicals in the polycristalline ammonia beads were created by irradiation in the high intensity 20 MeV electron beam (> 10 14 electrons/sec) of the injection linac. During irradiation the ammonia beads, produced by dropping into liquid nitrogen, were cooled in liquid argon at approx.= 90 K. DNP measurements were performed at 1 K, 0.5 K and 0.2 K in a 2.5 T magnetic field. Samples of NH 3 , prepared in this way, yielded a maximum proton polarization of 66% at a temperature of 0.5 K with a short polarization build-up time of 9 minutes. ND 3 could be polarized at a temperature of 0.2 K up to 31%. The radiation resistance of the polarization of NH 3 is better than that of butanol. (orig.)

Effective identification of (NH4)2CO3 and NH4HCO3 concentrations in NaHCO3 regeneration process from desulfurized waste.

Science.gov (United States)

Govindan, Muthuraman; Karunakaran, Kannan; Nallasamy, Palanisami; Moon, Il Shik

2015-01-01

This work describes the quantitative analysis of (NH4)2CO3 and NH4HCO3 using a simple solution phase titration method. Back titration results at various (NH4)2CO3-NH4HCO3 ratios demonstrated that 6:4 ratio caused a 3% error in their differentiation, but very high errors were found at other ratios. A similar trend was observed for the double indicator method, especially when strong acid HCl was used as a titrant, where still less errors (2.5%) at a middle ratio of (NH4)2CO3-NH4HCO3 was found. Remaining ratios with low (NH4)2CO3 (2:8, 4:6) show high +ve error (found concentration is less) and high (NH4)2CO3 (7:3, 8:2, and 9:1) show high -ve error (found concentration is higher) and vice versa for NH4HCO3. In replacement titration using Na2SO4, at both higher end ratios of (NH4)2CO3-NH4HCO3 (2:8 and 9:1), both -ve and +ve errors were minimized to 75% by partial equilibrium arrest between (NH4)2CO3 and NH2COONH4, instead of more than 100% observed in back titration and only double indicator methods. In the presence of (NH4)2SO4 both -ve and +ve error% are completely reduced to 3±1 at ratios 2:8, 4:6, and 6:4 of (NH4)2CO3-NH4HCO3, which demonstrates that the equilibrium transformation between NH2COONH4 and (NH4)2CO3 is completely controlled. The titration conducted at lower temperature (5 °C) in the presence of (NH4)2SO4 at higher ratios of (NH4)2CO3-NH4HCO3 (7:3, 8:2,and 9:1) shows complete minimization of both -ve and +ve errors to 2±1%, which explains the complete arresting of equilibrium transformation. Finally, the developed method shows 2±1% error in differentiation of CO3(2-) and HCO3(-) in the regeneration process of NaHCO3 from crude desulfurized sample. The developed method is more promising to differentiate CO3(2-) and HCO3(-) in industrial applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Near room temperature approaches for the preparation of air-stable and crystalline CH{sub 3}NH{sub 3}PbI{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Gujarathi, Yogini D.; Haram, Santosh K., E-mail: haram@chem.unipune.ac.in

2016-04-15

This work demonstrates an exotic role of CH{sub 2}Cl{sub 2} in a formation of stable phase of highly crystalline CH{sub 3}NH{sub 3}PbI{sub 3} perovskite, on a bulk scale. In the first method, a partially-reacted product obtained after co-grinding of precursors viz. CH{sub 3}NH{sub 3}I and PbI{sub 2}was sonicated in CH{sub 2}Cl{sub 2} to form pure phase of CH{sub 3}NH{sub 3}PbI{sub 3}. In second method, the precursors in γ-Butyrolactone were treated with CH{sub 2}Cl{sub 2} to form crystalline and phase-pure CH{sub 3}NH{sub 3}PbI{sub 3}. X-ray Diffraction analysis confirmed the formation of stable and highly crystalline tetragonal phase of CH{sub 3}NH{sub 3}PbI{sub 3} perovskite having space group I4cm. Well-defined rhombo-hexagonal dodecahedron crystals were seen in SEM and TEM images. Exceptional air stability of CH{sub 3}NH{sub 3}PbI{sub 3} so forms are attributed to adsorption of CH{sub 2}Cl{sub 2}. Optical band gaps obtained from the diffused reflectance spectra (Kubelka–Munk analysis), matched very well with the one estimated from Cyclic Voltammetry (CV). Valence band and conduction band edge positions estimated from the CV analysis are in good agreement with the one reported from UV photoelectron spectroscopy. Both the samples gave steady state fluorescence at ca. 750 nm with quantum yields in the range 15–35.5%. - Highlights: • A role of CH{sub 2}Cl{sub 2} is brought out in formation of stable CH{sub 3}NH{sub 3}PbI{sub 3} perovskite. • Cyclic voltammetry has been used to estimate the band edge positions. • Excellent fluorescence quantum yield, underlines the minimal structural defects.

Photostriction of CH3NH3PbBr3 Perovskite Crystals

KAUST Repository

Wei, Tzu-Chiao; Wang, Hsin-Ping; Li, Ting-You; Lin, Chun-Ho; Hsieh, Ying-Hui; Chu, Ying-Hao; He, Jr-Hau

2017-01-01

.e., photostriction). From these shifts, the photostrictive coefficient of CH3 NH3 PbBr3 is calculated as 2.08 × 10-8 m2 W-1 at room temperature under visible light illumination. The significant photostriction of CH3 NH3 PbBr3 is attributed to a combination

Thin-Film Transformation of NH4 PbI3 to CH3 NH3 PbI3 Perovskite: A Methylamine-Induced Conversion-Healing Process.

Science.gov (United States)

Zong, Yingxia; Zhou, Yuanyuan; Ju, Minggang; Garces, Hector F; Krause, Amanda R; Ji, Fuxiang; Cui, Guanglei; Zeng, Xiao Cheng; Padture, Nitin P; Pang, Shuping

2016-11-14

Methylamine-induced thin-film transformation at room-temperature is discovered, where a porous, rough, polycrystalline NH 4 PbI 3 non-perovskite thin film converts stepwise into a dense, ultrasmooth, textured CH 3 NH 3 PbI 3 perovskite thin film. Owing to the beneficial phase/structural development of the thin film, its photovoltaic properties undergo dramatic enhancement during this NH 4 PbI 3 -to-CH 3 NH 3 PbI 3 transformation process. The chemical origins of this transformation are studied at various length scales. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Brightly Luminescent and Color-Tunable Colloidal CH3NH3PbX3 (X = Br, I, Cl) Quantum Dots: Potential Alternatives for Display Technology.

Science.gov (United States)

Zhang, Feng; Zhong, Haizheng; Chen, Cheng; Wu, Xian-gang; Hu, Xiangmin; Huang, Hailong; Han, Junbo; Zou, Bingsuo; Dong, Yuping

2015-04-28

Organometal halide perovskites are inexpensive materials with desirable characteristics of color-tunable and narrow-band emissions for lighting and display technology, but they suffer from low photoluminescence quantum yields at low excitation fluencies. Here we developed a ligand-assisted reprecipitation strategy to fabricate brightly luminescent and color-tunable colloidal CH3NH3PbX3 (X = Br, I, Cl) quantum dots with absolute quantum yield up to 70% at room temperature and low excitation fluencies. To illustrate the photoluminescence enhancements in these quantum dots, we conducted comprehensive composition and surface characterizations and determined the time- and temperature-dependent photoluminescence spectra. Comparisons between small-sized CH3NH3PbBr3 quantum dots (average diameter 3.3 nm) and corresponding micrometer-sized bulk particles (2-8 μm) suggest that the intense increased photoluminescence quantum yield originates from the increase of exciton binding energy due to size reduction as well as proper chemical passivations of the Br-rich surface. We further demonstrated wide-color gamut white-light-emitting diodes using green emissive CH3NH3PbBr3 quantum dots and red emissive K2SiF6:Mn(4+) as color converters, providing enhanced color quality for display technology. Moreover, colloidal CH3NH3PbX3 quantum dots are expected to exhibit interesting nanoscale excitonic properties and also have other potential applications in lasers, electroluminescence devices, and optical sensors.

Interfacial electronic structures revealed at the rubrene/CH3NH3PbI3 interface.

Science.gov (United States)

Ji, Gengwu; Zheng, Guanhaojie; Zhao, Bin; Song, Fei; Zhang, Xiaonan; Shen, Kongchao; Yang, Yingguo; Xiong, Yimin; Gao, Xingyu; Cao, Liang; Qi, Dong-Chen

2017-03-01

The electronic structures of rubrene films deposited on CH 3 NH 3 PbI 3 perovskite have been investigated using in situ ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). It was found that rubrene molecules interacted weakly with the perovskite substrate. Due to charge redistribution at their interface, a downward 'band bending'-like energy shift of ∼0.3 eV and an upward band bending of ∼0.1 eV were identified at the upper rubrene side and the CH 3 NH 3 PbI 3 substrate side, respectively. After the energy level alignment was established at the rubrene/CH 3 NH 3 PbI 3 interface, its highest occupied molecular orbital (HOMO)-valence band maximum (VBM) offset was found to be as low as ∼0.1 eV favoring the hole extraction with its lowest unoccupied molecular orbital (LUMO)-conduction band minimum (CBM) offset as large as ∼1.4 eV effectively blocking the undesired electron transfer from perovskite to rubrene. As a demonstration, simple inverted planar solar cell devices incorporating rubrene and rubrene/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole transport layers (HTLs) were fabricated in this work and yielded a champion power conversion efficiency of 8.76% and 13.52%, respectively. Thus, the present work suggests that a rubrene thin film could serve as a promising hole transport layer for efficient perovskite-based solar cells.

A new NH 3 orbital of the NH 3/Ni(110) surface observed by metastable quenching spectroscopy

Science.gov (United States)

Lee, Lihwa; Arias, Jose; Hanrahan, Ciaran; Martin, Richard M.; Metiu, Horia

1986-01-01

By using metastable quenching spectroscopy we have found a new NH 3 filled orbital (in the language of one electron theory) for NH 3/Ni(110), located at the Fermi level of the surface. The orbital is not observed when NH 3 is adsorbed on Ni(110), but it is detected for NH 3 adsorbed on polycrystalline Al.

NMR Spectroscopic Characterization of Methylcobalt(III) Compounds with Classical Ligands. Crystal Structures of [Co(NH(3))(5)(CH(3))]S(2)O(6), trans-[Co(en)(2)(NH(3))(CH(3))]S(2)O(6) (en = 1,2-Ethanediamine), and [Co(NH(3))(6)]-mer,trans-[Co(NO(2))(3)(NH(

DEFF Research Database (Denmark)

Kofod, Pauli; Harris, Pernille; Larsen, Sine

1997-01-01

magnetic resonance spectroscopy and by absorption spectroscopy. Single-crystal X-ray structure determinations at 122.0(5) K were performed on [Co(NH(3))(5)(CH(3))]S(2)O(6) (1), trans-[Co(en)(2)(NH(3))(CH(3))]S(2)O(6) (2), and [Co(NH(3))(6)]-mer,trans-[Co(NO(2))(3)(NH(3))(2)(CH(3))](2)-trans-[Co(NO(2...

Photoelectric characteristics of CH3NH3PbI3/p-Si heterojunction

Science.gov (United States)

Yamei, Wu; Ruixia, Yang; Hanmin, Tian; Shuai, Chen

2016-05-01

Organic-inorganic hybrid perovskite CH3NH3PbI3 film is prepared on p-type silicon substrate using the one-step solution method to form a CH3NH3PbI3/p-Si heterojunction. The film morphology and structure are characterized by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The photoelectric properties of the CH3NH3PbI3/p-Si heterojunction are studied by testing the current-voltage (I-V) with and without illumination and capacitance-voltage (C-V) characteristics. It turns out from the I-V curve without illumination that the CH3NH3PbI3/p-Si heterojunction has a rectifier feature with the rectification ratio over 70 at the bias of ±5 V. Also, there appears a photoelectric conversion phenomenon on this heterojunction with a short circuit current (Isc) of 0.16 μA and an open circuit voltage (Voc) of about 10 mV The high frequency C-V characteristic of the Ag/CH3NH3PbI3/p-Si heterojunction turns out to be similar to that of the metal-insulator-semiconductor (MIS) structure, and a parallel translation of the C-V curve along the forward voltage axis is found. This parallel translation means the existence of defects at the CH3NH3PbI3/p-Si interface and positive fixed charges in the CH3NH3PbI3 layer. The defects at the interface of the CH3NH3PbI3/p-Si heterojunction result in the dramatic decline of the Voc. Besides, the C-V test of CH3NH3PbI3 film shows a non-linear dielectric property and the dielectric value is about 4.64 as calculated. Project supported by the Hebei Province Natural Science Foundation of China (No. F2014202184) and the Tianjin Natural Science Foundation of China (No. 15JCZDJC37800).

Effect of interactions between carbon dioxide enrichment and NH4+/NO3- ratio on pH of culturing nutrient solution,growth and vigor of tomato root system

Institute of Scientific and Technical Information of China (English)

Juan LI; Jianmin ZHOU

2008-01-01

A growth chamber experiment was conducted to investigate the influence of NH4+/NO3- ratio and elevated CO2 concentration on the pH in nutrient solution,growth and root vigor system of tomato seedling roots,which attempts to understand whether the elevated CO2 concentration can alleviate the harmful effects of higher NH4+-N concentration in nutrient solutions on the tomato root system.Tomato (Lycopersicon esculenturn Mill.var.Hezuo 906) was grown in pots with nutrient solutions varying in NH4+/NO3- ratio (0:1,1:3,1:1,3:1and 1:0) and the growth chambers were supplied with with the growth process and CO2 concentration increased.At both CO2 levels,pH increased when 100% NO3--N was supplied and decreased in other treatments.The pH decrease in the nutrient solution was directly correlated to the NH4+-N proportion.The pH value was more reduced in 100% NH4+-N nutrient solution than increased in the 100% NO3--N nutrient solution.CO2 enrichment increased the dry weight of shoots and roots,root vigor system,total absorbing area and active absorbing area of tomato seedlings.All the measurement indexes above were increased in the elevated CO2 concentration treatment with the NO3- proportion increase in the nutrient solutions.Thus,under the elevated CO2 concentration,the dry weights of shoots and roots,root vigor system,total root absorbing area and active absorbing area were found to be inversely correlated to NH4+/NO3- ratio,leading to about 65.8%,78.0%,18.9%,12.9% and 18.9% increase,respectively,compared with that under the ambient CO2 concentration.Our results indicated that tomato seedling roots may benefit mostly from CO2 enrichment when 100% NO3--N nutrient solutions was supplied,but the CO2 concentration elevation did not alleviate the harmful effects when 100% NHa+-N was supplied.

Crystal structure of [UO2(NH35]NO3·NH3

Directory of Open Access Journals (Sweden)

Patrick Woidy

2016-12-01

Full Text Available Pentaammine dioxide uranium(V nitrate ammonia (1/1, [UO2(NH35]NO3·NH3, was obtained in the form of yellow crystals from the reaction of caesium uranyl nitrate, Cs[UO2(NO33], and uranium tetrafluoride, UF4, in dry liquid ammonia. The [UO2]+ cation is coordinated by five ammine ligands. The resulting [UO2(NH35] coordination polyhedron is best described as a pentagonal bipyramid with the O atoms forming the apices. In the crystal, numerous N—H...N and N—H...O hydrogen bonds are present between the cation, anion and solvent molecules, leading to a three-dimensional network.

A liquid-based eutectic system: LiBH4·NH 3-nNH3BH3 with high dehydrogenation capacity at moderate temperature

KAUST Repository

Tan, Yingbin; Guo, Yanhui; Li, Shaofeng; Sun, Weiwei; Zhu, Yihan; Li, Qi; Yu, Xuebin

2011-01-01

A novel eutectic hydrogen storage system, LiBH4·NH 3-nNH3BH3, which exists in a liquid state at room temperature, was synthesized through a simple mixing of LiBH 4·NH3 and NH3BH3 (AB). In the temperature range of 90-110 °C, the eutectic system

Nitrogen-Utilization by Plant-Species from Acid Heathland Soils .2. Growth and Shoot/Root Partitioning of No3- Assimilation at Constant Low Ph and Varying No3-/Nh4+ Ratio

NARCIS (Netherlands)

Troelstra, S.R.; Wagenaar, R.; Smant, W.

1995-01-01

The growth of four heathland species, two grasses (D. flexuosa, M. caerulea) and two dwarf shrubs (C. vulgaris, E. tetralix), was tested in solution culture at pH 4.0 with 2 mol m(-3) N, varying the NO3-/NH4+ ratio up to 40% nitrate. In addition, measurements of NRA, plant chemical composition, and

UV photoprocessing of NH3 ice: photon-induced desorption mechanisms

Science.gov (United States)

Martín-Doménech, R.; Cruz-Díaz, G. A.; Muñoz Caro, G. M.

2018-01-01

Ice mantles detected on the surface of dust grains towards the coldest regions of the interstellar medium can be photoprocessed by the secondary ultraviolet (UV) field present in dense cloud interiors. In this work, we present UV-irradiation experiments under astrophysically relevant conditions of pure NH3 ice samples in an ultra-high vacuum chamber where solid samples were deposited on to a substrate at 8 K. The ice analogues were subsequently photoprocessed with a microwave-discharged hydrogen-flow lamp. The induced radiation and photochemistry led to the production of H2, N2 and N2H4. In addition, photodesorption to the gas phase of the original ice component, NH3, and two of the three detected photoproducts, H2 and N2, was observed thanks to a quadrupole mass spectrometer (QMS). Calibration of the QMS allowed quantification of the photodesorption yields, leading to Ypd (NH3) = 2.1^{+2.1}_{-1.0} × 10-3 molecules/{incident photon}, which remained constant during the whole experiments, while photodesorption of H2 and N2 increased with fluence, pointing towards an indirect photodesorption mechanism involving energy transfer for these species. Photodesorption yield of N2 molecules after a fluence equivalent to that experienced by ice mantles in space was similar to that of the NH3 molecules (Ypd (N2) = 1.7^{+1.7}_{-0.9} × 10-3 molecules/{incident photon}).

Polymeric cobalt(ii) thiolato complexes - syntheses, structures and properties of [Co(SMes)2] and [Co(SPh)2NH3].

Science.gov (United States)

Eichhöfer, Andreas; Buth, Gernot

2016-11-01

Reactions of [Co(N(SiMe 3 ) 2 ) 2 thf] with 2.1 equiv. of MesSH (Mes = C 6 H 2 -2,4,6-(CH 3 ) 3 ) yield dark brown crystals of the one dimensional chain compound [Co(SMes) 2 ]. In contrast reactions of [Co(N(SiMe 3 ) 2 ) 2 thf] with 2.1 equiv. of PhSH result in the formation of a dark brown almost X-ray amorphous powder of 'Co(SPh) 2 '. Addition of aliquots of CH 3 OH to the latter reaction resulted in the almost quantitative formation of crystalline ammonia thiolato complexes either [Co(SPh) 2 (NH 3 ) 2 ] or [Co(SPh) 2 NH 3 ]. Single crystal XRD reveals that [Co(SPh) 2 NH 3 ] forms one-dimensional chains in the crystal via μ 2 -SPh bridges whereas [Co(SPh) 2 (NH 3 ) 2 ] consists at a first glance of isolated distorted tetrahedral units. Magnetic measurements suggest strong antiferromagnetic coupling for the two chain compounds [Co(SMes) 2 ] (J = -38.6 cm -1 ) and [Co(SPh) 2 NH 3 ] (J = -27.1 cm -1 ). Interestingly, also the temperature dependence of the susceptibility of tetrahedral [Co(SPh) 2 (NH 3 ) 2 ] shows an antiferromagnetic transition at around 6 K. UV-Vis-NIR spectra display d-d bands in the NIR region between 500 and 2250 nm. Thermal gravimetric analysis of [Co(SPh) 2 (NH 3 ) 2 ] and [Co(SPh) 2 NH 3 ] reveals two well separated cleavage processes for NH 3 and SPh 2 upon heating accompanied by the stepwise formation of 'Co(SPh) 2 ' and cobalt sulfide.

A liquid-based eutectic system: LiBH4·NH 3-nNH3BH3 with high dehydrogenation capacity at moderate temperature

KAUST Repository

Tan, Yingbin

2011-01-01

A novel eutectic hydrogen storage system, LiBH4·NH 3-nNH3BH3, which exists in a liquid state at room temperature, was synthesized through a simple mixing of LiBH 4·NH3 and NH3BH3 (AB). In the temperature range of 90-110 °C, the eutectic system showed significantly improved dehydrogenation properties compared to the neat AB and LiBH 4·NH3 alone. For example, in the case of the LiBH4·NH3/AB with a mole ratio of 1:3, over 8 wt.% hydrogen could be released at 90 °C within 4 h, while only 5 wt.% hydrogen released from the neat AB at the same conditions. Through a series of experiments it has been demonstrated that the hydrogen release of the new system is resulted from an interaction of AB and the NH3 group in the LiBH4·NH3, in which LiBH4 works as a carrier of ammonia and plays a crucial role in promoting the interaction between the NH3 group and AB. The enhanced dehydrogenation of LiBH 4·NH3/AB may result from the polar liquid state reaction environments and the initially promoted formation of the diammoniate of diborane, which will facilitate the B-H⋯H-N interaction between LiBH4·NH3 and AB. Kinetics analysis revealed that the rate-controlling steps of the dehydrogenation process are three-dimensional diffusion of hydrogen at temperatures ranging from 90 to 110 °C. This journal is © The Royal Society of Chemistry.

Wide range tuning of the size and emission color of CH3NH3PbBr3 quantum dots by surface ligands

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Xin Fang

2017-08-01

Full Text Available Organic-inorganic halide perovskite CH3NH3PbX3 (X= I, Br, Cl quantum dots (QDs possess the characters of easy solution-process, high luminescence yield, and unique size-dependent optical properties. In this work, we have improved the nonaqueous emulsion method to synthesize halide perovskite CH3NH3PbBr3 QDs with tunable sizes. Their sizes have been tailored from 5.29 to 2.81 nm in diameter simply by varying the additive amount of surfactant, n-octylamine from 5 to 120 μL. Correspondingly, the photoluminescence (PL peaks shift markedly from 520 nm to very deep blue, 436 nm due to quantum confinement effect. The PL quantum yields exceed 90% except for the smallest QDs. These high-quality QDs have potential to build high-performance optoelectronic devices.

Optical monitoring of CH3NH3PbI3 thin films upon atmospheric exposure

International Nuclear Information System (INIS)

Ghimire, Kiran; Zhao, Dewei; Cimaroli, Alex; Ke, Weijun; Yan, Yanfa; Podraza, Nikolas J

2016-01-01

CH 3 NH 3 PbI 3 perovskite films of interest for photovoltaic (PV) devices have been prepared by (i) vapor deposition and (ii) solution processing. Complex dielectric function ( ε   =   ε 1   +  i ε 2 ) spectra and structural parameters of the films have been extracted using near infrared to ultraviolet spectroscopic ellipsometry. In situ real time spectroscopic ellipsometry (RTSE) over a 48 h period has been performed on vapor deposited CH 3 NH 3 PbI 3 after the deposition in normal atmospheric laboratory ambient conditions. Analysis of RTSE data for vapor deposited CH 3 NH 3 PbI 3 film prepared under un-optimized conditions identifies phase segregated PbI 2 and CH 3 NH 3 I at the substrate/film interface and unreacted PbI 2 and CH 3 NH 3 I on the film surface. This analysis also provides the time dependence of the effective thicknesses of perovskite film, unreacted components, and phase segregated layers to track CH 3 NH 3 PbI 3 decomposition. (paper)

Photovoltaic properties of Cu-doped CH3NH3PbI3 with perovskite structure

Science.gov (United States)

Shirahata, Yasuhiro; Oku, Takeo

2017-01-01

Photovoltaic properties of copper (Cu)-doped perovskite (CH3NH3PbCuxI3+x) photovoltaic devices with different Cu content were investigated. The CH3NH3PbCuxI3+x films were polycrystalline with a tetragonal system, and their lattice constants and crystallite size varied with Cu doping. Compared to conversion efficiencies of non-doped CH3NH3PbI3 photovoltaic device, those of CH3NH3PbCuxI3+x photovoltaic devises increased. The improvement of photovoltaic properties was attributed to partial substitution of Cu at the Pb sites.

CH3NH3Pb1-xMgxI3 perovskites as environmentally friendly photovoltaic materials

Science.gov (United States)

Zhang, Y. D.; Feng, J.

2018-01-01

In an effort to reduce the toxicity of Pb in perovskite solar cells, the band structures, electron and hole effective masses, and electronic and optical properties of the novel perovskites CH3NH3Pb1-xMgxI3 were predicted using density functional theory with the scalar relativistic generalized gradient approximation. The calculation results indicated that the introduction of the Mg component caused the band gaps of the CH3NH3Pb1-xMgxI3 compounds to exceed that of CH3NH3PbI3. The calculated absorption coefficients of the CH3NH3PbI3 and CH3NH3Pb1-xMgxI3 perovskites revealed that substituting 12.5 mol % of the Pb in CH3NH3PbI3 with Mg had little effect on the absorption ability. Surprisingly, it was also found that CH3NH3Pb0.75Mg0.25I3 retained up to 83% of the absorption performance relative to CH3NH3PbI3. This indicates that the amount of toxic Pb used in perovskite solar cells could be reduced by a quarter while retaining over 80% of the light-absorbing ability. In general, these novel CH3NH3Pb1-xMgxI3 (x ≤ 0.25) perovskites represent promising candidates for environmentally friendly light-harvesting materials for use in solar cells.

CH3NH3PbI3 based solar cell: Modified by antisolvent treatment

Science.gov (United States)

Nandi, Pronoy; Giri, Chandan; Bansode, Umesh; Topwal, D.

2017-05-01

Solar cells based on new class of organic inorganic hybrid perovskite CH3NH3PbI3 were prepared by Ethyl acetate (EA); antisolvent treatment for the first time. This treatment results in new morphology for CH3NH3PbI3 thin film. FESEM image shows microrod type structures of CH3NH3PbI3 after EA antisolvent treatment. Energy band diagram was constructed using photoluminescence and photoemission studies. A better power conversion efficiency was achieved in EA treated film compare to without EA treated film.

Real-time observation of formation and relaxation dynamics of NH4 in (CH3OH)m(NH3)n clusters.

Science.gov (United States)

Yamada, Yuji; Nishino, Yoko; Fujihara, Akimasa; Ishikawa, Haruki; Fuke, Kiyokazu

2009-03-26

The formation and relaxation dynamics of NH4(CH3OH)m(NH3)n clusters produced by photolysis of ammonia-methanol mixed clusters has been observed by a time-resolved pump-probe method with femtosecond pulse lasers. From the detailed analysis of the time evolutions of the protonated cluster ions, NH4(+)(CH3OH)m(NH3)n, the kinetic model has been constructed, which consists of sequential three-step reaction: ultrafast hydrogen-atom transfer producing the radical pair (NH4-NH2)*, the relaxation process of radical-pair clusters, and dissociation of the solvated NH4 clusters. The initial hydrogen transfer hardly occurs between ammonia and methanol, implying the unfavorable formation of radical pair, (CH3OH2-NH2)*. The remarkable dependence of the time constants in each step on the number and composition of solvents has been explained by the following factors: hydrogen delocalization within the clusters, the internal conversion of the excited-state radical pair, and the stabilization of NH4 by solvation. The dependence of the time profiles on the probe wavelength is attributed to the different ionization efficiency of the NH4(CH3OH)m(NH3)n clusters.

Low Temperature Catalyst for NH3 Removal

Science.gov (United States)

Monje, Oscar; Melendez, Orlando

2013-01-01

Air revitalization technologies maintain a safe atmosphere inside spacecraft by the removal of C02, ammonia (NH3), and trace contaminants. NH3 onboard the International Space Station (ISS) is produced by crew metabolism, payloads, or during an accidental release of thermal control refrigerant. Currently, the ISS relies on removing NH3 via humidity condensate and the crew wears hooded respirators during emergencies. A different approach to cabin NH3 removal is to use selective catalytic oxidation (SCO), which builds on thermal catalytic oxidation concepts that could be incorporated into the existing TCCS process equipment architecture on ISS. A low temperature platinum-based catalyst (LTP-Catalyst) developed at KSC was used for converting NH3 to H20 and N2 gas by SCO. The challenge of implementing SCO is to reduce formation of undesirable byproducts like NOx (N20 and NO). Gas mixture analysis was conducted using FTIR spectrometry in the Regenerable VOC Control System (RVCS) Testbed. The RVCS was modified by adding a 66 L semi-sealed chamber, and a custom NH3 generator. The effect of temperature on NH3 removal using the LTP-Catalyst was examined. A suitable temperature was found where NH3 removal did not produce toxic NO, (NO, N02) and N20 formation was reduced.

Synthesis of 15N-enriched urea (CO(15NH22 from 15NH3, CO, and S in a discontinuous process

Directory of Open Access Journals (Sweden)

C. R. Sant Ana Filho

2012-12-01

Full Text Available CO(15NH22 enriched with the stable isotope 15N was synthesized based on a reaction involving CO, 15NH3, and S in the presence of CH3OH. The method differs from the industrial method; a stainless steel reactor internally lined with polytetrafluoroethylene (PTFE was used in a discontinuous process under low pressure and temperature. The yield of the synthesis was evaluated as a function of the parameters: the amount of reagents, reaction time, addition of H2S, liquid solution and reaction temperature. The results showed that under optimum conditions (1.36, 4.01, and 4.48 g of 15NH3, CO, and S, respectively, 40 ml CH3OH, 40 mg H2S, 100 ºC and 120 min of reaction 1.82 g (yield 76.5% of the compound was obtained per batch. The synthesized CO(15NH22 contained 46.2% N, 0.55% biuret, melting point of 132.55 ºC and did not exhibit isotopic fractionation. The production cost of CO(15NH22 with 90.0 at. % 15N was US$ 238.60 per gram.

On the growth of CH3NH3PbI3-xClx single crystal and characterization

Science.gov (United States)

Su, J.; Wang, W. F.; Lei, Y.; Zhang, L.; Xu, L. H.; Wang, D.; Lu, D.; Bai, Y.

2018-05-01

In this paper, CH3NH3PbI3-xClx crystal was grown by solution cooling method with CH3NH3I and PbCl2 as raw materials. Lead compounds and CH3NH3PbI3-xClx crystal with size about 6 mm × 4 mm × 2 mm were obtained. The chemical reactions with different CH3NH3I/PbCl2 ratios were analyzed. XPS shows the content of chlorine in CH3NH3PbI3-xClx is about 0.91%. PXRD, FT-IR, Raman and absorbance spectra were used to study the structure and optical properties of CH3NH3PbI3-xClx by comparing with CH3NH3PbI3 crystal. The CH3NH3PbI3-xClx crystal grown is of tetragonal structure with the lattice constants a = b = 8.8165 Å, c = 12.7920 Å and the bandgap value of 1.57 eV.

Generation of nanopores during desorption of NH3 from Mg(NH3)6Cl2

DEFF Research Database (Denmark)

Hummelshøj, Jens Strabo; Sørensen, Rasmus Zink; Kostova, M.Y.

2006-01-01

It is shown that nanopores are formed during desorption of NH3 from Mg(NH3)6Cl2, which has been proposed as a hydrogen storage material. The system of nanopores facilitates the transport of desorbed ammonia away from the interior of large volumes of compacted storage material. DFT calculations sh...

The energy level alignment at the CH_3NH_3PbI_3/pentacene interface

International Nuclear Information System (INIS)

Ji, Gengwu; Zhao, Bin; Song, Fei; Zheng, Guanhaojie; Zhang, Xiaonan; Shen, Kongchao; Yang, Yingguo; Chen, Shi; Gao, Xingyu

2017-01-01

Highlights: • The Energy Level Alignment at the CH_3NH_3PbI_3/Pentacene Interface was resolved experimentally. • The downward band bending and the dipole found at the pentacene side would favorably drive holes away from the interface into pentacene. • A ∼0.7 eV offset between pentacene HOMO and CH_3NH_3PbI_3 VBM would be in favor of hole transfer whereas a ∼1.35 eV offset between pentacene LUMO and CH_3NH_3PbI_3 CBM should efficiently block the unwanted electron transfer from perovskite to pentacene. • Pentacene could be a viable hole transfer material candidate on perovskite to be explored in perovskite devices. - Abstract: Pentacene thin film on CH_3NH_3PbI_3 was studied by in-situ X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy to determine their interfacial energy level alignment. A 0.2 eV downward band bending together with a 0.1 eV interfacial dipole was found at the pentacene side, whereas there was no band bending found at the CH_3NH_3PbI_3 side. The offset between CH_3NH_3PbI_3 Valance Band Maximum (VBM) and pentacene Highest Occupied Molecular Orbital (HOMO) and that between CH_3NH_3PbI_3 Conduction Band Minimum (CBM) and pentacene Lowest Unoccupied Molecular Orbital (LUMO) was determined to be 0.7 and 1.35 eV, respectively. The band alignment at this interface is favor of efficient hole transfer, which suggests pentacene as a viable HTL candidate to be explored in perovskite solar cells.

CH3NH3Pb1−xMgxI3 perovskites as environmentally friendly photovoltaic materials

Directory of Open Access Journals (Sweden)

Y. D. Zhang

2018-01-01

Full Text Available In an effort to reduce the toxicity of Pb in perovskite solar cells, the band structures, electron and hole effective masses, and electronic and optical properties of the novel perovskites CH3NH3Pb1−xMgxI3 were predicted using density functional theory with the scalar relativistic generalized gradient approximation. The calculation results indicated that the introduction of the Mg component caused the band gaps of the CH3NH3Pb1−xMgxI3 compounds to exceed that of CH3NH3PbI3. The calculated absorption coefficients of the CH3NH3PbI3 and CH3NH3Pb1−xMgxI3 perovskites revealed that substituting 12.5 mol % of the Pb in CH3NH3PbI3 with Mg had little effect on the absorption ability. Surprisingly, it was also found that CH3NH3Pb0.75Mg0.25I3 retained up to 83% of the absorption performance relative to CH3NH3PbI3. This indicates that the amount of toxic Pb used in perovskite solar cells could be reduced by a quarter while retaining over 80% of the light-absorbing ability. In general, these novel CH3NH3Pb1−xMgxI3 (x ≤ 0.25 perovskites represent promising candidates for environmentally friendly light-harvesting materials for use in solar cells.

Mesoscopic CH 3 NH 3 PbI 3 /TiO 2 Heterojunction Solar Cells

KAUST Repository

Etgar, Lioz

2012-10-24

We report for the first time on a hole conductor-free mesoscopic methylammonium lead iodide (CH 3NH 3PbI 3) perovskite/TiO 2 heterojunction solar cell, produced by deposition of perovskite nanoparticles from a solution of CH 3NH 3I and PbI 2 in γ-butyrolactone on a 400 nm thick film of TiO 2 (anatase) nanosheets exposing (001) facets. A gold film was evaporated on top of the CH 3NH 3PbI 3 as a back contact. Importantly, the CH 3NH 3PbI 3 nanoparticles assume here simultaneously the roles of both light harvester and hole conductor, rendering superfluous the use of an additional hole transporting material. The simple mesoscopic CH 3NH 3PbI 3/TiO 2 heterojunction solar cell shows impressive photovoltaic performance, with short-circuit photocurrent J sc= 16.1 mA/cm 2, open-circuit photovoltage V oc = 0.631 V, and a fill factor FF = 0.57, corresponding to a light to electric power conversion efficiency (PCE) of 5.5% under standard AM 1.5 solar light of 1000 W/m 2 intensity. At a lower light intensity of 100W/m 2, a PCE of 7.3% was measured. The advent of such simple solution-processed mesoscopic heterojunction solar cells paves the way to realize low-cost, high-efficiency solar cells. © 2012 American Chemical Society.

Different transport behaviors of NH4 (+) and NH3 in transmembrane cyclic peptide nanotubes.

Science.gov (United States)

Zhang, Mingming; Fan, Jianfen; Xu, Jian; Weng, Peipei; Lin, Huifang

2016-10-01

Two water-filled transmembrane cyclic peptide nanotubes (CPNTs) of 8×cyclo-(WL)n=4,5/POPE were chosen to investigate the dependences of the transport properties of the positive NH4 (+) and neutral NH3 on the channel radius. Molecular dynamic simulations revealed that molecular charge, size, ability to form H-bonds and channel radius all significantly influence the behaviors of NH4 (+) and NH3 in a CPNT. Higher electrostatic interactions, more H-bonds, and water-bridges were found in the NH4 (+) system, resulting in NH4 (+) meeting higher energy barriers, while NH3 can enter, exit and permeate the channels effortlessly. This work sheds a first light on the differences between the mechanisms of NH4 (+) and NH3 moving in a CPNT at an atomic level. Graphical Abstract Snapshot of the simulation system of NH4 (+)_octa-CPNT with an NH4 (+) initially positioned at one mouth of the tube, PMF profiles for single NH4 (+) ion and NH3 molecule moving through water-filled transmembrane CPNTs of 8×cyclo-(WL)n=4,5/POPE and sketch graphs of the possible H-bond forms of NH3 and NH4 (+) with the neighboring water.

In vitro growth of Brassocattleya orchid hybrid in different concentrations of KNO3, NH4NO3 and benzylaminopurine Cultivo in vitro de Brassocattleya (Orchidaceae em diferentes concentrações de KNO3, NH4NO3 e benzilaminopurina

Directory of Open Access Journals (Sweden)

Jean C Cardoso

2011-09-01

Full Text Available One of the most important applications of plant tissue culture is mass propagation of ornamental plants. This experiment evaluated the effect of different concentrations of NH4NO3 and KNO3 and BAP on the in vitro growth of orchid hybrid Brassocattleya 'Pastoral'. Seedlings of this orchid hybrid were used as explants and cultivated in medium with mineral salts and vitamins from the MS medium (Murashige & Skoog, 1962, with the macronutrients P, Ca and Mg reduced by half, and with an addition of 25 g L-1 of sucrose, 0.1 g L-1 of myo-inositol and 1.5 g L-1 of activated charcoal. Agar-agar was added (6.5 g L-1 and the pH was adjusted to 5.8. As treatments, four concentrations of the NH4NO3 and KNO3 (2x; 1x; ½ and ¼ MS medium and three concentrations of BAP (0.0; 0.5 and 1.0 mg L-1 were assayed. The multiplication, growth in height, fresh and dry weight and sugar level in dry weight of sprouts were evaluated. There occurred a higher growth in height with 0.25x NH4NO3 and KNO3 salts concentrations of MS medium and higher rate of multiplication with combination of NH4NO3 and KNO3 reduced by half of the MS medium concentration and 1.0 mg L-1 BAP.Entre as maiores aplicações da cultura de tecidos de plantas está a propagação massal de mudas de plantas ornamentais. O objetivo deste trabalho foi avaliar o cultivo in vitro de um híbrido de orquídea Brassocattleya em diferentes concentrações de NH4NO3, KNO3 e BAP. Foram utilizadas sementes do híbrido de orquídea Brassocattleya 'Pastoral' e as plantas foram cultivadas em meio MS com redução pela metade das fontes de P, Mg e Ca e adição de 25 g L-1 de sacarose, 100 mg L-1 de mio-inositol, 1,5 g L-1 de carvão ativo e 6,5 g L-1 de ágar-ágar, sendo o pH ajustado para 5,8. Como tratamentos foram usados quatro concentrações dos sais NH4NO3 e KNO3 (2x; 1x; ½ e ¼ do meio MS e três concentrações de BAP (0,0; 0,5 e 1,0 mg L-1. Avaliou-se a multiplicação, o crescimento em altura, massa fresca

Degradation mechanism of CH3NH3PbI3 perovskite materials upon exposure to humid air

International Nuclear Information System (INIS)

Shirayama, Masaki; Kato, Masato; Fujiseki, Takemasa; Hara, Shota; Kadowaki, Hideyuki; Murata, Daisuke; Fujiwara, Hiroyuki; Miyadera, Tetsuhiko; Sugita, Takeshi; Chikamatsu, Masayuki

2016-01-01

Low stability of organic-inorganic perovskite (CH 3 NH 3 PbI 3 ) solar cells in humid air environments is a serious drawback which could limit practical application of this material severely. In this study, from real-time spectroscopic ellipsometry characterization, the degradation mechanism of ultra-smooth CH 3 NH 3 PbI 3 layers prepared by a laser evaporation technique is studied. We present evidence that the CH 3 NH 3 PbI 3 degradation in humid air proceeds by two competing reactions of (i) the PbI 2 formation by the desorption of CH 3 NH 3 I species and (ii) the generation of a CH 3 NH 3 PbI 3 hydrate phase by H 2 O incorporation. In particular, rapid phase change occurs in the near-surface region and the CH 3 NH 3 PbI 3 layer thickness reduces rapidly in the initial 1 h air exposure even at a low relative humidity of 40%. After the prolonged air exposure, the CH 3 NH 3 PbI 3 layer is converted completely to hexagonal platelet PbI 2 /hydrate crystals that have a distinct atomic-scale multilayer structure with a period of 0.65 ± 0.05 nm. We find that conventional x-ray diffraction and optical characterization in the visible region, used commonly in earlier works, are quite insensitive to the surface phase change. Based on results obtained in this work, we discuss the degradation mechanism of CH 3 NH 3 PbI 3 in humid air.

Probing interfacial electronic properties of graphene/CH3NH3PbI3 heterojunctions: A theoretical study

Science.gov (United States)

Hu, Jisong; Ji, Gepeng; Ma, Xinguo; He, Hua; Huang, Chuyun

2018-05-01

Interfacial interactions and electronic properties of graphene/CH3NH3PbI3 heterojunctions were investigated by first-principles calculations incorporating semiempirical dispersion-correction scheme to describe van der Waals interactions. Two lattice match configurations between graphene and CH3NH3PbI3(0 0 1) slab were constructed in parallel contact and both of them were verified to form remarkable van der Waals heterojunctions with similar work functions. Our calculated energy band structures show that the Dirac-cone of graphene and the direct band gap of CH3NH3PbI3 are still preserved in the heterojunctions, thus graphene can be a promising candidate either as a capping or supporting layer for encapsulating CH3NH3PbI3 layer. It is identified that the Schottky barrier of graphene/CH3NH3PbI3 heterojunctions can be controlled by the interlayer distance and affected by the stacking pattern of graphene and CH3NH3PbI3. The 3D charge density differences present the build-in internal electric field from graphene to CH3NH3PbI3 after interface equilibrium and thus, a low n-type Schottky barrier is needed for high efficient charge transferring in the interface. The possible mechanism of the band edge modulations in the heterojunctions and corresponding photoinduced charge transfer processes are also described.

NH (X 3 summation -, v=1--3) formation and vibrational relaxation in electron-irradiated Ar/N2/H2 mixtures

International Nuclear Information System (INIS)

Dodd, J.A.; Lipson, S.J.; Flanagan, D.J.; Blumberg, W.A.M.; Person, J.C.; Green, B.D.

1991-01-01

Measurements of the dynamics of NH(X 3 summation - , v =1--3), created in electron-irradiated N 2 /H 2 and Ar/N 2 /H 2 mixtures, have been performed. Time-resolved Fourier spectroscopy was used to observe NH(v→v--1) vibrational fundamental band emission. Time-dependent populations were then determined by spectral fitting. Subsequent kinetic fitting of these populations using a single-quantum relaxation model and a power-law dependence of k v on v yielded the following NH(v =1--3) relaxation rate constants (units of 10 -14 cm 3 s -1 ): k v=1 (N 2 )=1.2±0.5, k v=2 (N 2 )=3.8±1.5, k v=3 (N 2 )=7.5±2.5; k v=1 (Ar)=0.2±0.1, k v=2 (Ar)=0.5±0.2, k v=3 (Ar)=0.8±0.3; k v=1 (H 2 )≤50, k v=2 (H 2 )≤100, k v=3 (H 2 )≤150. In addition, the N 2 /H 2 data provided a measurement of the nascent excited vibrational state distribution resulting from the reaction N( 2 D)+H 2 →NH(X,v)+H. The ratio NH(1):NH(2):NH(3) was found to be 1.0:0.97:0.81 (±0.28 in each value). Comparison of the observed nascent distribution with that of a statistical model suggests that the ratio NH(0):NH(1)=0.47. Using this derived distribution, we find the average product level left-angle v right-angle =1.6, and the fraction of the available product energy in vibration left-angle f v right-angle =0.44

Communication: Equivalence between symmetric and antisymmetric stretching modes of NH3 in promoting H + NH3 → H2 + NH2 reaction

Science.gov (United States)

Song, Hongwei; Yang, Minghui; Guo, Hua

2016-10-01

Vibrational excitations of reactants sometimes promote reactions more effectively than the same amount of translational energy. Such mode specificity provides insights into the transition-state modulation of reactivity and might be used to control chemical reactions. We report here a state-of-the-art full-dimensional quantum dynamical study of the hydrogen abstraction reaction H + NH3 → H2 + NH2 on an accurate ab initio based global potential energy surface. This reaction serves as an ideal candidate to study the relative efficacies of symmetric and degenerate antisymmetric stretching modes. Strong mode specificity, particularly for the NH3 stretching modes, is demonstrated. It is further shown that nearly identical efficacies of the symmetric and antisymmetric stretching modes of NH3 in promoting the reaction can be understood in terms of local-mode stretching vibrations of the reactant molecule.

Fabrication of CH3NH3PbI3/PVP Composite Fibers via Electrospinning and Deposition

Science.gov (United States)

Chao, Li-Min; Tai, Ting-Yu; Chen, Yueh-Ying; Lin, Pei-Ying; Fu, Yaw-Shyan

2015-01-01

In our study, one-dimensional PbI2/polyvinylpyrrolidone (PVP) composition fibers have been prepared by using PbI2 and PVP as precursors dissolved in N,N-dimethylformamide via a electrospinning process. Dipping the fibers into CH3NH3I solution changed its color, indicating the formation of CH3NH3PbI3, to obtain CH3NH3PbI3/PVP composite fibers. The structure, morphology and composition of the all as-prepared fibers were characterized by using X-ray diffraction and scanning electron microscopy. PMID:28793517

Fabrication of CH3NH3PbI3/PVP Composite Fibers via Electrospinning and Deposition

Directory of Open Access Journals (Sweden)

Li-Min Chao

2015-08-01

Full Text Available In our study, one-dimensional PbI2/polyvinylpyrrolidone (PVP composition fibers have been prepared by using PbI2 and PVP as precursors dissolved in N,N-dimethylformamide via a electrospinning process. Dipping the fibers into CH3NH3I solution changed its color, indicating the formation of CH3NH3PbI3, to obtain CH3NH3PbI3/PVP composite fibers. The structure, morphology and composition of the all as-prepared fibers were characterized by using X-ray diffraction and scanning electron microscopy.

Crystal Structure Formation of CH3NH3PbI3-xClx Perovskite

Directory of Open Access Journals (Sweden)

Shiqiang Luo

2016-02-01

Full Text Available Inorganic-organic hydride perovskites bring the hope for fabricating low-cost and large-scale solar cells. At the beginning of the research, two open questions were raised: the hysteresis effect and the role of chloride. The presence of chloride significantly improves the crystallization and charge transfer property of the perovskite. However, though the long held debate over of the existence of chloride in the perovskite seems to have now come to a conclusion, no prior work has been carried out focusing on the role of chloride on the electronic performance and the crystallization of the perovskite. Furthermore, current reports on the crystal structure of the perovskite are rather confusing. This article analyzes the role of chloride in CH3NH3PbI3-xClx on the crystal orientation and provides a new explanation about the (110-oriented growth of CH3NH3PbI3 and CH3NH3PbI3-xClx.

Order-disorder phase transition in the peroxidovanadium complex NH4[VO(O2)2(NH3)].

Science.gov (United States)

Schwendt, Peter; Gyepes, Róbert; Chrappová, Jana; Němec, Ivan; Vaněk, Přemysl

2018-07-05

Complex NH 4 [VO(O 2 ) 2 (NH 3 )] (1) undergoes an order-disorder phase transition at T c ~258K. This transition is accompanied by change in the space group of the orthorhombic lattice and also by significant structural rearrangements of the constituent molecules, which are pertinent mostly to their NH 4 + ions and their ammonia ligands. The low-temperature solid state IR and Raman spectra of 1 were corroborated by solid-state computations that employed Gaussian functions as the basis set. Results of these computations yielded excellent agreement with experimental data. On the curves of temperature dependence of vibrational modes, the phase transition is expressed by an abrupt change of the slope above T c . Copyright © 2018 Elsevier B.V. All rights reserved.

Shape-Evolution Control of hybrid perovskite CH3NH3PbI3 crystals via solvothermal synthesis

Science.gov (United States)

Zhang, Baohua; Guo, Fuqiang; Yang, Lianhong; Jia, Xiuling; Liu, Bin; Xie, Zili; Chen, Dunjun; Lu, Hai; Zhang, Rong; Zheng, Youdou

2017-02-01

We systematically synthesized CH3NH3PbI3 crystals using solvothermal process, and the reaction conditions such as concentration of the precursor, temperature, time, and lead source have been comprehensively investigated to obtain shape-controlled CH3NH3PbI3 crystals. The results showed that the CH3NH3PbI3 crystals exhibit tetragonal phase and the crystals change from nanoparticles to hopper-faced cuboids. Photoluminescence spectra of the crystals obtained with different lead sources show a blue shift due to the presence of defects in the crystals, and the peak intensity is very sensitive to the lead sources. Moreover, impurities (undesirable byproducts and excess components like HI or CH3NH2) presented during crystal growth can result in hopper growth.

Transparent CH{sub 3}NH{sub 3}SnCl{sub 3}/Al-ZnO p-n heterojunction diode

Energy Technology Data Exchange (ETDEWEB)

Kumar, Sunil, E-mail: skbgudha@gmail.com; Ansari, Mohd Zubair; Khare, Neeraj [Department of Physics, Indian Institute of Technology, Hauz Khas, New Delhi, Delhi-110016 (India)

2016-05-23

A p-type Organic inorganic tin chloride (CH{sub 3}NH{sub 3}SnCl{sub 3}) perovskite thin film has been synthesized by solution method. An n-type 1% Al doped ZnO (AZO) film has been deposited on FTO substrate by ultrasonic assisted chemical vapor deposition technique. A transparent CH{sub 3}NH{sub 3}SnCl{sub 3}/AZO p-n heterojunction diode has been fabricated by spin coating technique. CH{sub 3}NH{sub 3}SnCl{sub 3}/AZO p-n heterojunction shows 75% transparency in the visible region. I-V characteristic of CH{sub 3}NH{sub 3}SnCl{sub 3}/AZO p-n heterojunction shows rectifying behavior of the diode. The diode parameters calculated as ideality factor η=2.754 and barrier height Φ= 0.76 eV. The result demonstrates the potentiality of CH{sub 3}NH{sub 3}SnCl{sub 3}/AZO p-n heterojunction for transparent electronics.

MARVEL analysis of the measured high-resolution spectra of 14NH3

International Nuclear Information System (INIS)

Al Derzi, Afaf R.; Furtenbacher, Tibor; Tennyson, Jonathan; Yurchenko, Sergei N.; Császár, Attila G.

2015-01-01

Accurate, experimental rotational–vibrational energy levels and line positions, with associated labels and uncertainties, are reported for the ground electronic state of the symmetric-top 14 NH 3 molecule. All levels and lines are based on critically reviewed and validated high-resolution experimental spectra taken from 56 literature sources. The transition data are in the 0.7–17 000 cm −1 region, with a large gap between 7000 and 15 000 cm −1 . The MARVEL (Measured Active Rotational–Vibrational Energy Levels) algorithm is used to determine the energy levels. Out of the 29 450 measured transitions 10 041 and 18 947 belong to ortho- and para- 14 NH 3 , respectively. A careful analysis of the related experimental spectroscopic network (SN) allows 28 530 of the measured transitions to be validated, 18 178 of these are unique, while 462 transitions belong to floating components. Despite the large number of spectroscopic measurements published over the last 80 years, the transitions determine only 30 vibrational band origins of 14 NH 3 , 8 for ortho- and 22 for para- 14 NH 3 . The highest J value, where J stands for the rotational quantum number, for which an energy level is validated is 31. The number of experimental-quality ortho- and para- 14 NH 3 rovibrational energy levels is 1724 and 3237, respectively. The MARVEL energy levels are checked against ones in the BYTe first-principles database, determined previously. The lists of validated lines and levels for 14 NH 3 are deposited in the Supporting Information to this paper. Combination of the MARVEL energy levels with first-principles absorption intensities yields a huge number of experimental-quality rovibrational lines, which should prove to be useful for the understanding of future complex high-resolution spectroscopy on 14 NH 3 ; these lines are also deposited in the Supporting Information to this paper

MARVEL analysis of the measured high-resolution spectra of 14NH3

Science.gov (United States)

Al Derzi, Afaf R.; Furtenbacher, Tibor; Tennyson, Jonathan; Yurchenko, Sergei N.; Császár, Attila G.

2015-08-01

Accurate, experimental rotational-vibrational energy levels and line positions, with associated labels and uncertainties, are reported for the ground electronic state of the symmetric-top 14NH3 molecule. All levels and lines are based on critically reviewed and validated high-resolution experimental spectra taken from 56 literature sources. The transition data are in the 0.7-17 000 cm-1 region, with a large gap between 7000 and 15 000 cm-1. The MARVEL (Measured Active Rotational-Vibrational Energy Levels) algorithm is used to determine the energy levels. Out of the 29 450 measured transitions 10 041 and 18 947 belong to ortho- and para-14NH3, respectively. A careful analysis of the related experimental spectroscopic network (SN) allows 28 530 of the measured transitions to be validated, 18 178 of these are unique, while 462 transitions belong to floating components. Despite the large number of spectroscopic measurements published over the last 80 years, the transitions determine only 30 vibrational band origins of 14NH3, 8 for ortho- and 22 for para-14NH3. The highest J value, where J stands for the rotational quantum number, for which an energy level is validated is 31. The number of experimental-quality ortho- and para-14NH3 rovibrational energy levels is 1724 and 3237, respectively. The MARVEL energy levels are checked against ones in the BYTe first-principles database, determined previously. The lists of validated lines and levels for 14NH3 are deposited in the Supporting Information to this paper. Combination of the MARVEL energy levels with first-principles absorption intensities yields a huge number of experimental-quality rovibrational lines, which should prove to be useful for the understanding of future complex high-resolution spectroscopy on 14NH3; these lines are also deposited in the Supporting Information to this paper.

Optoelectronic and Photovoltaic Properties of the Air-Stable Organohalide Semiconductor (CH 3 NH 3 ) 3 Bi 2 I 9

KAUST Repository

Abulikemu, Mutalifu

2016-07-14

Lead halide perovskite materials have shown excellent optoelectronic as well as photovoltaic properties. However, the presence of lead and the chemical instability relegate lead halide perovskites to research applications only. Here, we investigate an emerging lead-free and air stable compound (CH3NH3)3Bi2I9 as a non-toxic potential alternative to lead halide perovskites. We have synthesized thin films, powders and millimeter-scale single crystals of (CH3NH3)3Bi2I9 and investigated their structural and optoelectronic properties. We demonstrate that the degree of crystallinity strongly affects the optoelectronic properties of the material, resulting in significantly different band gaps in polycrystalline thin films and single crystals. Surface photovoltage spectroscopy reveals outstanding photocharge generation in the visible (<700 nm), while transient absorption spectroscopy and space charge limited current measurements point to a long exciton lifetime and a high carrier mobility, respectively, similar to lead halide perovskites, pointing to the remarkable potential of this semiconductor. Photovoltaic devices fabricated using this material yield low power conversion efficiency (PCE) to date, but the PCE is expected to rise with improvements in thin film processing and device engineering.

General working principles of CH3NH3PbX3 perovskite solar cells.

Science.gov (United States)

Gonzalez-Pedro, Victoria; Juarez-Perez, Emilio J; Arsyad, Waode-Sukmawati; Barea, Eva M; Fabregat-Santiago, Francisco; Mora-Sero, Ivan; Bisquert, Juan

2014-02-12

Organometal halide perovskite-based solar cells have recently realized large conversion efficiency over 15% showing great promise for a new large scale cost-competitive photovoltaic technology. Using impedance spectroscopy measurements we are able to separate the physical parameters of carrier transport and recombination in working devices of the two principal morphologies and compositions of perovskite solar cells, viz. compact thin films of CH3NH3PbI(3-x)Clx and CH3NH3PbI3 infiltrated on nanostructured TiO2. The results show nearly identical spectral characteristics indicating a unique photovoltaic operating mechanism that provides long diffusion lengths (1 μm). Carrier conductivity in both devices is closely matched, so that the most significant differences in performance are attributed to recombination rates. These results highlight the central role of the CH3NH3PbX3 semiconductor absorber in carrier collection and provide a new tool for improved optimization of perovskite solar cells. We report for the first time a measurement of the diffusion length in a nanostructured perovskite solar cell.

Study of the structural phase transitions of (CH 3NH 3) 3Sb 2Cl 9 (MACA) and (CH 3NH 3) 3Bi 2Cl 9 (MACB) by infrared spectroscopy

Science.gov (United States)

Bator, G.; Jakubas, R.; Malarski, Z.

1991-06-01

Infrared spectra of polycrystalline (CH 3NH 3) 3Sb 2Cl 9 and (CH 3NH 3) 3Bi 2Cl 9 have been studied in the temperature range 90-300 K. A systematic temperature dependence study of the internal modes has been carried out. We discuss the effects of the dynamic state of methylammonium (MA) cations on their vibrational spectra. The results show that the dynamics of MA cations in both compounds is similar in higher (about 300 K) and lower temperature (in the vicinity of 100 K) regions. Substantial differences are revealed in the intermediate temperature interval. The results are in good agreement with earlier dielectric, calorimetric and 1H NMR studies.

Comparative genomic and physiological analysis of nutrient response to NH4+, NH4+:NO3- and NO3- in barley seedlings.

Science.gov (United States)

Lopes, Marta S; Araus, José L

2008-09-01

Long-term differences in photosynthesis, respiration and growth of plants receiving distinct nitrogen (N) sources imply that N metabolism generates signals that regulate metabolism and development. The molecular basis of these signals remains unclear. Here we studied the gene expression profiles of barley (Hordeum vulgare L. cv. Graphic) seedlings fertilized either with ammonium (NH4+), with ammonium and nitrate (NH4+:NO3-), or with nitrate (NO3-) only. Our transcriptome analysis after 48 h of growth in these N sources showed major changes in the expression of genes involved in N metabolism (nitrate reductase), signalling (protein kinases and protein phosphatases), photosynthesis (chlorophyll a/b-binding protein and a PsbQ domain), where increases in NO3- as compared with NH4+ were observed. Moreover, NH4+ assimilation induced genes participating in C and sugars metabolism (phosphoglycerate kinase, glucosyltranferase and galactokinase), respiration (cytochrome c oxidase), protein fate (heat shock proteins) and development (MTN3-like protein). These changes in gene expression could well explain the long-term growth depression observed in NH4+ plants. Even if a few genes participating in protein fate (proteases) and development (OsNAC5) were upregulated in NH4+ as compared with NH4+:NO3-, the general pattern of expression was quite similar between these two N sources. Taken together, these results indicated that other downstream mechanisms should be involved in the synergetic long-term response of NH4+:NO3-.

Dissociation of NH3 and NH2D by high power CO2 laser radiation

International Nuclear Information System (INIS)

Jacobs, R.R.

1976-08-01

Multiquantum dissociation of polyatomics using intense CO 2 lasers resulting in isotopic enrichment has been demonstrated for several molecules. In this presentation, the possibility of selective dissociation of NH 3 and NH 2 D by high power laser radiation at 10 μm will be considered. Relevant work performed at the Lawrence Livermore Laboratory and elsewhere will be summarized. In this review, attention will be given to four distinct mechanisms that can play varying degrees of importance in such investigations. Discussion will deal with the usefulness of two-resonant-frequency molecular excitation, the role of buffer gases, and the need to monitor the yields into the ground and excited electronic states of the dissociated fragments

Role of NH3 and NH4+ transporters in renal acid-base transport.

Science.gov (United States)

Weiner, I David; Verlander, Jill W

2011-01-01

Renal ammonia excretion is the predominant component of renal net acid excretion. The majority of ammonia excretion is produced in the kidney and then undergoes regulated transport in a number of renal epithelial segments. Recent findings have substantially altered our understanding of renal ammonia transport. In particular, the classic model of passive, diffusive NH3 movement coupled with NH4+ "trapping" is being replaced by a model in which specific proteins mediate regulated transport of NH3 and NH4+ across plasma membranes. In the proximal tubule, the apical Na+/H+ exchanger, NHE-3, is a major mechanism of preferential NH4+ secretion. In the thick ascending limb of Henle's loop, the apical Na+-K+-2Cl- cotransporter, NKCC2, is a major contributor to ammonia reabsorption and the basolateral Na+/H+ exchanger, NHE-4, appears to be important for basolateral NH4+ exit. The collecting duct is a major site for renal ammonia secretion, involving parallel H+ secretion and NH3 secretion. The Rhesus glycoproteins, Rh B Glycoprotein (Rhbg) and Rh C Glycoprotein (Rhcg), are recently recognized ammonia transporters in the distal tubule and collecting duct. Rhcg is present in both the apical and basolateral plasma membrane, is expressed in parallel with renal ammonia excretion, and mediates a critical role in renal ammonia excretion and collecting duct ammonia transport. Rhbg is expressed specifically in the basolateral plasma membrane, and its role in renal acid-base homeostasis is controversial. In the inner medullary collecting duct (IMCD), basolateral Na+-K+-ATPase enables active basolateral NH4+ uptake. In addition to these proteins, several other proteins also contribute to renal NH3/NH4+ transport. The role and mechanisms of these proteins are discussed in depth in this review.

Deuterium isotope effects on the dipole moment and polarizability of HCl and NH3

International Nuclear Information System (INIS)

Scher, C.; Ravid, B.; Halevi, E.A.

1982-01-01

A previously described adaptation of the conventional Debye procedure for the direct determination of small dipole moment and polarizability differences between two polar gases is applied to the isotopic pairs DCl-HCl and ND 3 -NH 3 . The dipole moment difference obtained for the first isotopic pair, by using the Debye-Van Vleck equation for electric susceptibility, μ(DCl) - μ(HCl) = 0.005 5 +/- 0.0002 D, is consistent with published spectroscopically determined values of μ 00 (DCl) and μ 00 (HCl), while that obtained by using the classical Debye equation is not. For the second pair, use of the Debye-Van Vleck equation, along with a correction for thermal population of vibrationally excited levels, is shown to be essential and yields μ(ND) 3 - μ(NH 3 ) = +0.013 5 +/- 0.001 D and α(ND 3 ) - α(NH 3 ) = -(2.2 +/- 1.7) x 10 -26 cm 3

Rate-based modelling of combined SO2 removal and NH3 recycling integrated with an aqueous NH3-based CO2 capture process

International Nuclear Information System (INIS)

Li, Kangkang; Yu, Hai; Qi, Guojie; Feron, Paul; Tade, Moses; Yu, Jingwen; Wang, Shujuan

2015-01-01

Highlights: • A rigorous, rate-based model for an NH 3 –CO 2 –SO 2 –H 2 O system was developed. • Model predictions are in good agreement with pilot plant results. • >99.9% of SO 2 was captured and >99.9% of slipped ammonia was reused. • The process is highly adaptable to the variations of SO 2 /NH 3 level, temperatures. - Abstract: To reduce the costs of controlling emissions from coal-fired power stations, we propose an advanced and effective process of combined SO 2 removal and NH 3 recycling, which can be integrated with the aqueous NH 3 -based CO 2 capture process to simultaneously achieve SO 2 and CO 2 removal, NH 3 recycling and flue gas cooling in one process. A rigorous, rate-based model for an NH 3 –CO 2 –SO 2 –H 2 O system was developed and used to simulate the proposed process. The model was thermodynamically and kinetically validated by experimental results from the open literature and pilot-plant trials, respectively. Under typical flue gas conditions, the proposed process has SO 2 removal and NH 3 reuse efficiencies of >99.9%. The process is strongly adaptable to different scenarios such as high SO 2 levels in flue gas, high NH 3 levels from the CO 2 absorber and high flue gas temperatures, and has a low energy requirement. Because the process simplifies flue gas desulphurisation and resolves the problems of NH 3 loss and SO 2 removal, it could significantly reduce the cost of CO 2 and SO 2 capture by aqueous NH 3

The energy level alignment at the CH{sub 3}NH{sub 3}PbI{sub 3}/pentacene interface

Energy Technology Data Exchange (ETDEWEB)

Ji, Gengwu [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204 (China); University of Chinese Academy of Science, Beijing 100049 (China); Zhao, Bin; Song, Fei [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204 (China); Zheng, Guanhaojie; Zhang, Xiaonan [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204 (China); University of Chinese Academy of Science, Beijing 100049 (China); Shen, Kongchao [Department of Physics, Zhejiang University, Hangzhou 310027 (China); Yang, Yingguo [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204 (China); Chen, Shi, E-mail: ChenShi@ntu.edu.sg [Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371 (Singapore); Gao, Xingyu, E-mail: gaoxingyu@sinap.ac.cn [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204 (China)

2017-01-30

Highlights: • The Energy Level Alignment at the CH{sub 3}NH{sub 3}PbI{sub 3}/Pentacene Interface was resolved experimentally. • The downward band bending and the dipole found at the pentacene side would favorably drive holes away from the interface into pentacene. • A ∼0.7 eV offset between pentacene HOMO and CH{sub 3}NH{sub 3}PbI{sub 3} VBM would be in favor of hole transfer whereas a ∼1.35 eV offset between pentacene LUMO and CH{sub 3}NH{sub 3}PbI{sub 3} CBM should efficiently block the unwanted electron transfer from perovskite to pentacene. • Pentacene could be a viable hole transfer material candidate on perovskite to be explored in perovskite devices. - Abstract: Pentacene thin film on CH{sub 3}NH{sub 3}PbI{sub 3} was studied by in-situ X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy to determine their interfacial energy level alignment. A 0.2 eV downward band bending together with a 0.1 eV interfacial dipole was found at the pentacene side, whereas there was no band bending found at the CH{sub 3}NH{sub 3}PbI{sub 3} side. The offset between CH{sub 3}NH{sub 3}PbI{sub 3} Valance Band Maximum (VBM) and pentacene Highest Occupied Molecular Orbital (HOMO) and that between CH{sub 3}NH{sub 3}PbI{sub 3} Conduction Band Minimum (CBM) and pentacene Lowest Unoccupied Molecular Orbital (LUMO) was determined to be 0.7 and 1.35 eV, respectively. The band alignment at this interface is favor of efficient hole transfer, which suggests pentacene as a viable HTL candidate to be explored in perovskite solar cells.

Synthesis and properties of ternary (K, NH4, H3O)-jarosites precipitated from Acidithiobacillus ferrooxidans cultures in simulated bioleaching solutions

International Nuclear Information System (INIS)

Sandy Jones, F.; Bigham, Jerry M.; Gramp, Jonathan P.; Tuovinen, Olli H.

2014-01-01

The purpose of this study was to synthesize a series of solid solution jarosites by biological oxidation of ferrous iron at pH 2.2–4.4 and ambient temperature in media containing mixtures of K + (0, 1, 4, 6, 12, 31 mM) and NH 4 + (6.1, 80, 160, 320 mM). The starting material was a liquid medium for Acidithiobacillus ferrooxidans comprised of 120 mM FeSO 4 solution and mineral salts at pH 2.2. Following inoculation with A. ferrooxidans, the cultures were incubated in shake flasks at 22 °C. As bacteria oxidized ferrous iron, ferric iron hydrolyzed and precipitated as jarosite-group minerals (AFe 3 (SO 4 ) 2 (OH) 6 ) and/or schwertmannite (idealized formula Fe 8 O 8 (OH) 6 (SO 4 )·nH 2 O). The precipitates were characterized by X-ray diffraction (XRD), elemental analysis, and Munsell color. Schwertmannite was the dominant mineral product at low combinations of K + (≤ 4 mM) and NH 4 + (≤ 80 mM) in the media. At higher single or combined concentrations, yellowish jarosite phases were produced, and Munsell hue provided a sensitive means of detecting minor schwertmannite in the oxidation products. Although the hydrated ionic radii of K + and NH 4 + are similar, K + greatly facilitated the formation of a jarosite phase compared to NH 4 + . Unit cell and cell volume calculations from refinements of the powder XRD patterns indicated that the jarosite phases produced were mostly ternary (K, NH 4 , H 3 O)-solid solutions that were also deficient in structural Fe, especially at low NH 4 contents. Thus, ferric iron precipitation from the simulated bioleaching systems yielded solid solutions of jarosite with chemical compositions that were dependent on the relative concentrations of K + and NH 4 + in the synthesis media. No phase separations involving discrete, end-member K-jarosite or NH 4 -jarosite were detected in the un-aged precipitates. - Highlights: • Fe(III) precipitates formed in A. ferrooxidans culture solutions were characterized. • The monovalent cation

Electrochemical and SEM studies of tetra-ammine platinum (II) (Pt(NH3)4)(OH)2 solution

International Nuclear Information System (INIS)

Wan Jeffrey Basirun

2002-01-01

Electrochemical studies include cyclic voltammetry with microelectrodes were done on a solution of tetra-ammine platinum (II) (Pt(NH 3 ) 4 )(OH) 2 at pH 13 and showed that the electrochemical reduction of this compound was no different from the tetra-ammine platinum (II) (Pt(NH 3 ) 4 )(HPO 4 ) at pH 10.4. The solution was instable to high temperatures and results have shown that electroplating can be done at a limited temperature range for longer periods of time or at higher temperatures for short periods of time. Scanning electron microscopy was done on some of the constant current electrodeposited samples at high temperatures and result obtained was satisfactory. (Authors)

Evolution of Chemical Composition, Morphology, and Photovoltaic Efficiency of CH 3 NH 3 PbI 3 Perovskite under Ambient Conditions

KAUST Repository

Huang, Weixin; Manser, Joseph S.; Kamat, Prashant V.; Ptasinska, Sylwia

2016-01-01

© 2015 American Chemical Society. The surface composition and morphology of CH3NH3PbI3 perovskite films stored for several days under ambient conditions were investigated by X-ray photoelectron spectroscopy, scanning electron microscopy, and X-ray diffraction techniques. Chemical analysis revealed the loss of CH3NH3 + and I- species from CH3NH3PbI3 and its subsequent decomposition into lead carbonate, lead hydroxide, and lead oxide. After long-term storage under ambient conditions, morphological analysis revealed the transformation of randomly distributed defects and cracks, initially present in the densely packed crystalline structure, into relatively small grains. In contrast to PbI2 powder, CH3NH3PbI3 exhibited a different degradation trend under ambient conditions. Therefore, we propose a plausible CH3NH3PbI3 decomposition pathway that explains the changes in the chemical composition of CH3NH3PbI3 under ambient conditions. In addition, films stored under such conditions were incorporated into photovoltaic cells, and their performances were examined. The chemical changes in the decomposed films were found to cause a significant decrease in the photovoltaic efficiency of CH3NH3PbI3.

Evolution of Chemical Composition, Morphology, and Photovoltaic Efficiency of CH 3 NH 3 PbI 3 Perovskite under Ambient Conditions

KAUST Repository

Huang, Weixin

2016-01-12

© 2015 American Chemical Society. The surface composition and morphology of CH3NH3PbI3 perovskite films stored for several days under ambient conditions were investigated by X-ray photoelectron spectroscopy, scanning electron microscopy, and X-ray diffraction techniques. Chemical analysis revealed the loss of CH3NH3 + and I- species from CH3NH3PbI3 and its subsequent decomposition into lead carbonate, lead hydroxide, and lead oxide. After long-term storage under ambient conditions, morphological analysis revealed the transformation of randomly distributed defects and cracks, initially present in the densely packed crystalline structure, into relatively small grains. In contrast to PbI2 powder, CH3NH3PbI3 exhibited a different degradation trend under ambient conditions. Therefore, we propose a plausible CH3NH3PbI3 decomposition pathway that explains the changes in the chemical composition of CH3NH3PbI3 under ambient conditions. In addition, films stored under such conditions were incorporated into photovoltaic cells, and their performances were examined. The chemical changes in the decomposed films were found to cause a significant decrease in the photovoltaic efficiency of CH3NH3PbI3.

Photovoltaic performance and the energy landscape of CH3NH3PbI3.

Science.gov (United States)

Zhou, Yecheng; Huang, Fuzhi; Cheng, Yi-Bing; Gray-Weale, Angus

2015-09-21

Photovoltaic cells with absorbing layers of certain perovskites have power conversion efficiencies up to 20%. Among these materials, CH3NH3PbI3 is widely used. Here we use density-functional theory to calculate the energies and rotational energy barriers of a methylammonium ion in the α or β phase of CH3NH3PbI3 with differently oriented neighbouring methylammonium ions. Our results suggest the methylammonium ions in CH3NH3PbI3 prefer to rotate collectively, and to be parallel to their neighbours. Changes in polarization on rotation of methylammonium ions are two to three times larger than those on relaxation of the lead ion from the centre of its coordination shell. The preferences for parallel configuration and concerted rotation, with the polarisation changes, are consistent with ferroelectricity in the material, and indicate that this polarisation is governed by methylammonium orientational correlations. We show that the field due to this polarisation is strong enough to screen the field hindering charge transport, and find this screening field in agreement with experiment. We examine two possible mechanisms for the effect of methylammonium ion rotation on photovoltaic performance. One is that rearrangement of methylammoniums promotes the creation and transport of charge carriers. Some effective masses change greatly, but changes in band structure with methylammonium rotation are not large enough to explain current-voltage hysteresis behaviour. The second possible mechanism is that polarization screens the hindering electric field, which arises from charge accumulation in the transport layers. Polarization changes on methylammonium rotation favour this second mechanism, suggesting that collective reorientation of methylammonium ions in the bulk crystal are in significant part responsible for the hysteresis and power conversion characteristics of CH3NH3PbI3 photovoltaic cells.

The electronic and optical properties of CH3NH3MoI3 perovskite

Science.gov (United States)

Kansara, Shivam; Sonvane, Yogesh; Gupta, Sanjeev K.

2018-05-01

In this work, a first-principles theoretical study of hybrid perovskite CH3NH3MoI3 is performed using PBE exchange-correlation approximations in density functional theory. The results of electronic band structure are 0.90 eV (M-point: Direct) and 0.60 eV (R-X point: Indirect), respectively. We have also calculated the dielectric properties such as real, imaginary, extension coefficient (K) and reflectivity (R) properties of hybrid perovskite CH3NH3MoI3. The low-bandgap molecules are used to absorb near-IR range and typically having a bandgap smaller than 1.6 eV. This is particularly attractive in organic photovoltaics (OPV), photodetectors (PDs), and ambipolar field-effect transistors (FETs).

Surface modification of pitch-based spherical activated carbon by CVD of NH3 to improve its adsorption to uric acid

International Nuclear Information System (INIS)

Liu Chaojun; Liang Xiaoyi; Liu Xiaojun; Wang Qin; Zhan Liang; Zhang Rui; Qiao Wenming; Ling Licheng

2008-01-01

Surface chemistry of pitch-based spherical activated carbon (PSAC) was modified by chemical vapor deposition of NH 3 (NH 3 -CVD) to improve the adsorption properties of uric acid. The texture and surface chemistry of PSAC were studied by N 2 adsorption, pH PZC (point of zero charge), acid-base titration and X-ray photoelectron spectroscopy (XPS). NH 3 -CVD has a limited effect on carbon textural characteristics but it significantly changed the surface chemical properties, resulting in positive effects on uric acid adsorption. After modification by NH 3 -CVD, large numbers of nitrogen-containing groups (especially valley-N and center-N) are introduced on the surface of PSAC, which is responsible for the increase of pH PZC , surface basicity and uric acid adsorption capacity. Pseudo-second-order kinetic model can be used to describe the dynamic adsorption of uric acid on PSAC, and the thermodynamic parameters show that the adsorption of uric acid on PSAC is spontaneous, endothermic and irreversible process in nature

Surface modification of pitch-based spherical activated carbon by CVD of NH 3 to improve its adsorption to uric acid

Science.gov (United States)

Liu, Chaojun; Liang, Xiaoyi; Liu, Xiaojun; Wang, Qin; Zhan, Liang; Zhang, Rui; Qiao, Wenming; Ling, Licheng

2008-08-01

Surface chemistry of pitch-based spherical activated carbon (PSAC) was modified by chemical vapor deposition of NH 3 (NH 3-CVD) to improve the adsorption properties of uric acid. The texture and surface chemistry of PSAC were studied by N 2 adsorption, pH PZC (point of zero charge), acid-base titration and X-ray photoelectron spectroscopy (XPS). NH 3-CVD has a limited effect on carbon textural characteristics but it significantly changed the surface chemical properties, resulting in positive effects on uric acid adsorption. After modification by NH 3-CVD, large numbers of nitrogen-containing groups (especially valley-N and center-N) are introduced on the surface of PSAC, which is responsible for the increase of pH PZC, surface basicity and uric acid adsorption capacity. Pseudo-second-order kinetic model can be used to describe the dynamic adsorption of uric acid on PSAC, and the thermodynamic parameters show that the adsorption of uric acid on PSAC is spontaneous, endothermic and irreversible process in nature.

Optical constants of CH3NH3PbBr3 perovskite thin films measured by spectroscopic ellipsometry

KAUST Repository

Alias, Mohd Sharizal

2016-07-14

The lack of optical constants information for hybrid perovskite of CH3NH3PbBr3 in thin films form can delay the progress of efficient LED or laser demonstration. Here, we report on the optical constants (complex refractive index and dielectric function) of CH3NH3PbBr3 perovskite thin films using spectroscopic ellipsometry. Due to the existence of voids, the refractive index of the thin films is around 8% less than the single crystals counterpart. The energy bandgap is around 2.309 eV as obtained from photoluminescence and spectrophotometry spectra, and calculated from the SE analysis. The precise measurement of optical constants will be useful in designing optical devices using CH3NH3PbBr3 thin films.

[UO2(NH3)5]Br2·NH3: synthesis, crystal structure, and speciation in liquid ammonia solution by first-principles molecular dynamics simulations.

Science.gov (United States)

Woidy, Patrick; Bühl, Michael; Kraus, Florian

2015-04-28

Pentaammine dioxido uranium(VI) dibromide ammonia (1/1), [UO2(NH3)5]Br2·NH3, was synthesized in the form of yellow crystals by the reaction of uranyl bromide, UO2Br2, with dry liquid ammonia. The compound crystallizes orthorhombic in space group Cmcm and is isotypic to [UO2(NH3)5]Cl2·NH3 with a = 13.2499(2), b = 10.5536(1), c = 8.9126(1) Å, V = 1246.29(3) Å(3) and Z = 4 at 123 K. The UO2(2+) cation is coordinated by five ammine ligands and the coordination polyhedron can be best described as pentagonal bipyramid. Car-Parrinello molecular dynamics simulations are reported for [UO2(NH3)5](2+) in the gas phase and in liquid NH3 solution (using the BLYP density functional). According to free-energy simulations, solvation by ammonia has only a small effect on the uranyl-NH3 bond strength.

Meteorite impacts on ancient oceans opened up multiple NH3 production pathways.

Science.gov (United States)

Shimamura, Kohei; Shimojo, Fuyuki; Nakano, Aiichiro; Tanaka, Shigenori

2017-05-10

A recent series of shock experiments by Nakazawa et al. starting in 2005 (e.g. [Nakazawa et al., Earth Planet. Sci. Lett., 2005, 235, 356]) suggested that meteorite impacts on ancient oceans would have yielded a considerable amount of NH 3 to the early Earth from atmospheric N 2 and oceanic H 2 O through reduction by meteoritic iron. To clarify the mechanisms, we imitated the impact events by performing multi-scale shock technique-based ab initio molecular dynamics in the framework of density functional theory in combination with multi-scale shock technique (MSST) simulations. Our previous simulations with impact energies close to that of the experiments revealed picosecond-order rapid NH 3 production during shock compression [Shimamura et al., Sci. Rep., 2016, 6, 38952]. It was also shown that the reduction of N 2 took place with an associative mechanism as seen in the catalysis of nitrogenase enzymes. In this study, we performed an MSST-AIMD simulation to investigate the production by meteorite impacts with higher energies, which are closer to the expected values on the early Earth. It was found that the amount of NH 3 produced further increased. We also found that the increased NH 3 production is due to the emergence of multiple reaction mechanisms at increased impact energies. We elucidated that the reduction of N 2 was not only attributed to the associative mechanism but also to a dissociative mechanism as seen in the Haber-Bosch process and to a mechanism through a hydrazinium ion. The emergence of these multiple production mechanisms capable of providing a large amount of NH 3 would support the suggestions from recent experiments much more strongly than was previously believed, i.e., shock-induced NH 3 production played a key role in the origin of life on Earth.

Rapid ammonia gas transport accounts for futile transmembrane cycling under NH3/NH4+ toxicity in plant roots.

Science.gov (United States)

Coskun, Devrim; Britto, Dev T; Li, Mingyuan; Becker, Alexander; Kronzucker, Herbert J

2013-12-01

Futile transmembrane NH3/NH4(+) cycling in plant root cells, characterized by extremely rapid fluxes and high efflux to influx ratios, has been successfully linked to NH3/NH4(+) toxicity. Surprisingly, the fundamental question of which species of the conjugate pair (NH3 or NH4(+)) participates in such fluxes is unresolved. Using flux analyses with the short-lived radioisotope (13)N and electrophysiological, respiratory, and histochemical measurements, we show that futile cycling in roots of barley (Hordeum vulgare) seedlings is predominately of the gaseous NH3 species, rather than the NH4(+) ion. Influx of (13)NH3/(13)NH4(+), which exceeded 200 µmol g(-1) h(-1), was not commensurate with membrane depolarization or increases in root respiration, suggesting electroneutral NH3 transport. Influx followed Michaelis-Menten kinetics for NH3 (but not NH4(+)), as a function of external concentration (Km = 152 µm, Vmax = 205 µmol g(-1) h(-1)). Efflux of (13)NH3/(13)NH4(+) responded with a nearly identical Km. Pharmacological characterization of influx and efflux suggests mediation by aquaporins. Our study fundamentally revises the futile-cycling model by demonstrating that NH3 is the major permeating species across both plasmalemma and tonoplast of root cells under toxicity conditions.

The Luminescence of CH3 NH3 PbBr3 Perovskite Nanoparticles Crests the Summit and Their Photostability under Wet Conditions is Enhanced.

Science.gov (United States)

Gonzalez-Carrero, Soranyel; Francés-Soriano, Laura; González-Béjar, María; Agouram, Saïd; Galian, Raquel E; Pérez-Prieto, Julia

2016-10-01

CH 3 NH 3 PbBr 3 perovskite nanoparticles (P AD ) are prepared with a photoluminescence quantum yield of ≈100% in air atmosphere by using the quasi-spherical shaped 2-adamantylammonium bromide (ADBr) as the only capping ligand. The photostability under wet conditions of this kind of nanoparticles is enhanced by using cucurbit[7]uril-adamantylammonium (AD@CB) host-guest complexes as the capping ligand. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparative study of wheat utilization of NH4 and NO3 as sources of N-fertilizer using N15 technique

International Nuclear Information System (INIS)

Khalifa, Kh.

1993-05-01

Two field experiments were conducted separately on wheat (Cultivar ACSAD-65) in 1987/1988 at the Research Station of Arabic Center for the Studies of Arid Zones and Dry Lands (ACSAD) in Deir-Ezzor, Using N 15 methodology to compare the efficient utilization of N 15 -NO 3 and N 15 -N H 4 radicals as sources of nitrogen applied in three different levels (50, 100 and 200 Kg N/ha and two placement methods (Top-dressed and Side-dressed). The results indicate that Ndff % in the from of N 15 -NH 4 was higher than N 15 -NO 3 in both placements, at different growth stages, consequently, when using N-NH 4 form, N-uptake was higher than N-NO 3 form; the efficiency of N-NH 4 was higher than N-NO 3 in most cases regardless of the method of placement; the rate of applied nitrogen in both forms (N-NH 4 and N-NO 3 ) had higher effect on yield more than the placements; side-dressed placement had higher effect on the efficiency of the utilization of N-NO 3 and N-NH 4 as well as on crop yield than the Top-dressed; using N-NO 3 , A-values in the three growth stages of crop at the nitrogen levels used, were higher than using N-NH 4 in both placements; and finally using N-NO 3 in the second and third stages of crop growth, the yield was higher than using N-NH 4 and almost similar in the first stages. (author). 9 refs., 26 tabs

[Ag(NH3)2]Ag(OsO3N)2: a new nitridoosmate(VIII)

International Nuclear Information System (INIS)

Wickleder, M.S.; Pley, Martin

2004-01-01

Dark brown single crystals of [Ag(NH 3 ) 2 ]Ag(OsO 3 N) 2 were obtained from the reaction of Ag 2 CO 3 , OsO 4 , and NH 3 in aqueous solution. The crystal structure was solved in the monoclinic space group C2/m, with the following unit-cell dimensions: a=1962.5(3), b=633.1(1), c=812.6(1) pm, β=96.71(1) deg. The final reliability factor was R=0.0256 for 1034 reflections with I>2σ(I). Linear [Ag(NH 3 ) 2 ] + ions are present oriented perpendicular to the [010] direction, leading to short Ag + -Ag + distances of 316 pm. A second type of Ag + ions in the crystal structure present coordination number '6+1' and are surrounded by oxygen and nitrogen atoms of the nitridoosmate groups. Within the first of the two crystallographically distinguishable anions one can clearly differentiate between oxygen and nitrogen atoms while the second one exhibits a N/O disorder over two positions. The infrared spectrum of [Ag(NH 3 ) 2 ]Ag(OsO 3 N) 2 shows the typical absorptions which can be attributed to the complex anions and the NH 3 ligands

Observation of lower defect density in CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} solar cells by admittance spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Jiang, Minlin; Lan, Fei; Tao, Quan; Li, Guangyong, E-mail: gaod@pitt.edu, E-mail: gul6@pitt.edu [Department of Electrical and Computer Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15260 (United States); Zhao, Bingxin [Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15260 (United States); Key Laboratory of Advanced Functional Materials, College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124 (China); Wu, Jiamin; Gao, Di, E-mail: gaod@pitt.edu, E-mail: gul6@pitt.edu [Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15260 (United States)

2016-06-13

The introduction of Cl into CH{sub 3}NH{sub 3}PbI{sub 3} precursors is reported to enhance the performance of CH{sub 3}NH{sub 3}PbI{sub 3} solar cell, which is attributed to the significantly increased diffusion lengths of carriers in CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} solar cell. It has been assumed but never experimentally approved that the defect density in CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} solar cell should be reduced according to the higher carrier lifetime observed from photoluminescence (PL) measurement. We have fabricated CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} solar cell by adding a small amount of Cl source into CH{sub 3}NH{sub 3}PbI{sub 3} precursor. The performance of CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} solar cell is significantly improved from 15.39% to 18.60%. Results from scanning electron microscopy and X-ray diffraction indicate that the morphologies and crystal structures of CH{sub 3}NH{sub 3}PbI{sub 3} and CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} thin films remain unchanged. Open circuit voltage decay and admittance spectroscopy characterization jointly approve that Cl plays an extremely important role in suppressing the formation of defects in perovskite solar cells.

Degradation mechanism of CH{sub 3}NH{sub 3}PbI{sub 3} perovskite materials upon exposure to humid air

Energy Technology Data Exchange (ETDEWEB)

Shirayama, Masaki; Kato, Masato; Fujiseki, Takemasa; Hara, Shota; Kadowaki, Hideyuki; Murata, Daisuke; Fujiwara, Hiroyuki, E-mail: fujiwara@gifu-u.ac.jp [Department of Electrical, Electronic and Computer Engineering, Gifu University, 1-1 Yanagido, Gifu 501-1193 (Japan); Miyadera, Tetsuhiko; Sugita, Takeshi; Chikamatsu, Masayuki [Research Center for Photovoltaics, National Institute of Advanced Industrial Science and Technology (AIST), Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8568 (Japan)

2016-03-21

Low stability of organic-inorganic perovskite (CH{sub 3}NH{sub 3}PbI{sub 3}) solar cells in humid air environments is a serious drawback which could limit practical application of this material severely. In this study, from real-time spectroscopic ellipsometry characterization, the degradation mechanism of ultra-smooth CH{sub 3}NH{sub 3}PbI{sub 3} layers prepared by a laser evaporation technique is studied. We present evidence that the CH{sub 3}NH{sub 3}PbI{sub 3} degradation in humid air proceeds by two competing reactions of (i) the PbI{sub 2} formation by the desorption of CH{sub 3}NH{sub 3}I species and (ii) the generation of a CH{sub 3}NH{sub 3}PbI{sub 3} hydrate phase by H{sub 2}O incorporation. In particular, rapid phase change occurs in the near-surface region and the CH{sub 3}NH{sub 3}PbI{sub 3} layer thickness reduces rapidly in the initial 1 h air exposure even at a low relative humidity of 40%. After the prolonged air exposure, the CH{sub 3}NH{sub 3}PbI{sub 3} layer is converted completely to hexagonal platelet PbI{sub 2}/hydrate crystals that have a distinct atomic-scale multilayer structure with a period of 0.65 ± 0.05 nm. We find that conventional x-ray diffraction and optical characterization in the visible region, used commonly in earlier works, are quite insensitive to the surface phase change. Based on results obtained in this work, we discuss the degradation mechanism of CH{sub 3}NH{sub 3}PbI{sub 3} in humid air.

Preparation of silver chloride nanoparticles by a mechanical treatment of the system NH4Cl−AgNO3−NH4NO3

Directory of Open Access Journals (Sweden)

Farit Urakaev

2014-08-01

Full Text Available Silver chloride nanoparticles dispersed within ammonium nitrate matrix have been prepared though displacement mechanochemical reaction NH4Cl + AgNO3 + z NH4NO3 = (z+1 NH4 NO3 + AgCl at various z coefficients z1 = 7.22 and z2 = 3.64. The intermediate compound of NH4Ag(NO32 were recorded after mechanochemical processing of studied system. By using simultaneous TG and DSC measurements possibilities to prepare silver chloride in its free form have been discussed by using thermal treatment.

Emulsion Synthesis of Size-Tunable CH3NH3PbBr3 Quantum Dots: An Alternative Route toward Efficient Light-Emitting Diodes.

Science.gov (United States)

Huang, Hailong; Zhao, Fangchao; Liu, Lige; Zhang, Feng; Wu, Xian-gang; Shi, Lijie; Zou, Bingsuo; Pei, Qibing; Zhong, Haizheng

2015-12-30

We report a facile nonaqueous emulsion synthesis of colloidal halide perovskite quantum dots by controlled addition of a demulsifier into an emulsion of precursors. The size of resulting CH3NH3PbBr3 quantum dots can be tuned from 2 to 8 nm by varying the amount of demulsifier. Moreover, this emulsion synthesis also allows the purification of these quantum dots by precipitation from the colloidal solution and obtains solid-state powder which can be redissolved for thin film coating and device fabrication. The photoluminescence quantum yields of the quantum dots is generally in the range of 80-92%, and can be well-preserved after purification (∼80%). Green light-emitting diodes fabricated comprising a spin-cast layer of the colloidal CH3NH3PbBr3 quantum dots exhibited maximum current efficiency of 4.5 cd/A, power efficiency of 3.5 lm/W, and external quantum efficiency of 1.1%. This provides an alternative route toward high efficient solution-processed perovskite-based light-emitting diodes. In addition, the emulsion synthesis is versatile and can be extended for the fabrication of inorganic halide perovskite colloidal CsPbBr3 nanocrystals.

Two-center three-electron bonding in ClNH{sub 3} revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH{sub 3} → ClNH{sub 2} + H reaction

Energy Technology Data Exchange (ETDEWEB)

Moradi, Christopher P.; Douberly, Gary E., E-mail: douberly@uga.edu [Department of Chemistry, University of Georgia, Athens, Georgia 30602-2556 (United States); Xie, Changjian; Guo, Hua [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States); Kaufmann, Matin [Department of Physical Chemistry II, Ruhr-University Bochum, D-44801 Bochum (Germany)

2016-04-28

Pyrolytic dissociation of Cl{sub 2} is employed to dope helium droplets with single Cl atoms. Sequential addition of NH{sub 3} to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH{sub 3} → ClNH{sub 2} + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C{sub 3v} symmetric top. Frequency shifts from NH{sub 3} and dipole moment measurements are consistent with a ClNH{sub 3} complex containing a relatively strong two-center three-electron (2c–3e) bond. The nature of the 2c–3e bonding in ClNH{sub 3} is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. Computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH{sub 3}Cl and Cl–HNH{sub 2}, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH{sub 3} → HCl + NH{sub 2}.

MINERAL NITROGEN SOURCES (N-NO3- AND N-NH4+ ON GROWTH OF GRÁPIA (Apuleia leiocarpa (Vog. Macbride SEEDLINGS

Directory of Open Access Journals (Sweden)

Fernando Teixeira Nicoloso

2010-08-01

Full Text Available Grápia (Apuleia leiocarpa (Vog. Macbride is an important native forest species that has been in extinction process. The aim of this study was to evaluate the effect of mineral nitrogen source on growth of grápia seedlings. Five variations in the concentration of N-NO3- and N-NH4+ (5:0, 4:1, 2,5:2,5, 1:4, and 0:5 mM of N were tested in an entirely random statistical design with 16 replicates. The experimental unity consisted of a vessel containing 3,0 kg of a Paleudalf soil and two plants, under glasshouse conditions. From 60 to 150 days after fertilization (DAF, the plant growth and soil pH were monthly analyzed from four replicates randomly taken. Independently of the nitrogen source used, the soil pH decreased, and on 150 DAF the smallest pH variation was 0.33 and the largest one was 0.47 pH units, respectively, on treatments with 5 N-NO3-:0 N-NH4+ and 0 N-NO3-:5 N-NH4+ ratios. The presence of N-NH4+, from 1 to 5 mM, induced necrosis in old leaves and their ulterior abscission. To 150 DAF, in the presence of 5 mM N-NH4+, the plant survival was reduced to 31%. The effect of nitrogen sources on plant growth appeared to be depended on plant age and/or of their transformations in the soil. To 120 DAF, the presence of N-NH4+ from 2,5 to 5 mM reduced the number of stalk nodes, plant height, stem diameter, dry weight of leaves, of stem, of roots, and of the whole plant. However, to 150 DAF, because of the regain on the growth rate, these differences were not observed, with exception of the root/shoot dry weight ratio that was reduced on the exclusive presence of N-NH4+. The suitable N-NO3-:N-NH4+ ratio in the fertilization to grow grápia seedlings, can not exceed, respectively, 4:1.

The sensitivity of particle pH to NH3: Can high NH3 cause London Fog conditions?

Science.gov (United States)

Weber, R. J.; Guo, H.; Nenes, A.

2017-12-01

High ammonia emissions from agriculture or other sources have been suggested to elevate ambient particle pH levels to near neutral acidity (pH=7), a condition that promotes rapid SO2 oxidation by NO2 to form aerosol sulfate concentration consistent with "London fog" levels. This mechanism has been used to explain pollution haze events in China. Predicted pH for locations in the US and Europe show fine particles are highly acidic with pH typically less than 2. The results are consistent with measured ammonia and nitric acid gas-particle partitioning, validating predicted pH levels. Using these data sets from representative sites around the world we conduct a thermodynamic analysis of aerosol pH and its sensitivity to ammonia levels. We find that particle pH, regardless of ammonia levels, is always acidic even for the unusually high ammonia levels found in highly polluted Asian cities, Beijing (pH=4.5) and Xi'an (pH=5), locations where sulfate production from NOx is proposed. These results indicate that sulfur dioxide oxidation through a NO2-mediated pathway is not likely in China, nor any other region of the world (e.g., US, Mediterranean) since the fine aerosol is consistently acidic. The mildly acidic conditions would, however, permit rapid oxidation of sulfur dioxide through transition metal chemistry. The limited alkalinity from the carbonate buffer in dust and seasalt can provide the only likely set of conditions where NO2-mediated oxidation of SO2 outcompetes with other well-established pathways.

Herschel/HIFI deepens the circumstellar NH3 enigma

NARCIS (Netherlands)

Menten, K. M.; Wyrowski, F.; Alcolea, J.; De Beck, E.; Decin, L.; Marston, A. P.; Bujarrabal, V.; Cernicharo, J.; Dominik, C.; Justtanont, K.; de Koter, A.; Melnick, G.; Neufeld, D. A.; Olofsson, H.; Planesas, P.; Schmidt, M.; Schoier, F. L.; Szczerba, R.; Teyssier, D.; Waters, L. B. F. M.; Edwards, K.; Olberg, M.; Phillips, T. G.; Morris, P.; Salez, M.; Caux, E.

2010-01-01

Context. Circumstellar envelopes (CSEs) of a variety of evolved stars have been found to contain ammonia (NH3) in amounts that exceed predictions from conventional chemical models by many orders of magnitude. Aims. The observations reported here were performed in order to better constrain the NH3

Rietveld refinement of the crystal structure of perovskite solar cells using CH3NH3PbI3 and other compounds

Science.gov (United States)

Ando, Yuji; Ohishi, Yuya; Suzuki, Kohei; Suzuki, Atsushi; Oku, Takeo

2018-01-01

The crystal structures of perovskite thin films including CH3NH3PbI3, CH3NH3Pb1-xSbxI3, and CH3NH3PbI3-yCly in the solar cell configuration were studied by using Rietveld refinement. For the CH3NH3PbI3 and CH3NH3Pb1-xSbxI3 samples, satisfactory agreement with the measured profiles was obtained with a weighted profile R-factor (Rwp) of as low as 3%. It was shown that the site occupancy of methylammonium (MA) was decreased in the antimonized cell due to the compensation effect of an increased positive charge brought about by replacing Pb2+ with Sb3+. Photovoltaic measurements showed that the power conversion efficiency was enhanced by adding a small amount of Sb to the CH3NH3PbI3 cell, but it was monotonically decreased as the mole fraction of Sb exceeded 0.03. This variation of the conversion efficiency was considered as a result of suppressed crystallization of PbI2 and carrier recombination via MA vacancies in the antimonized cells. In the case of CH3NH3PbI2.88Cl0.12 sample, the agreement with the measured profile with an Rwp of as high as 7% suggested the co-existence of cubic and tetragonal phases in the chlorinated cell.

Effects of CsBr addition on the performance of CH3NH3PbI3-xClx-based solar cells

Science.gov (United States)

Ueoka, Naoki; Oku, Takeo; Ohishi, Yuya; Tanaka, Hiroki; Suzuki, Atsushi; Sakamoto, Hiroki; Yamada, Masahiro; Minami, Satoshi; Tsukada, Shinichiro

2018-01-01

Perovskite-type photovoltaic devices were prepared by a spin-coating method using a precursor solution of CH3NH3I and lead(II) chloride in N,N-dimethylformamide. Effects of cesium bromide (CsBr) addition on the photovoltaic properties and microstructures of the perovskite phase were investigated. The fill factor was increased by adding the CsBr to the CH3NH3PbI3-xClx precursor solution, which resulted in increase of the conversion efficiency. The crystallinity of the CH3NH3PbI3-xClx perovskite phase was also improved by adding the CsBr to the H3NH3PbI3-xClx precursor solution.

Synthesis and structural characterization of two cobalt phosphites: 1-D (H3NC6H4NH3)Co(HPO3)2 and 2-D (NH4)2Co2(HPo3)3

International Nuclear Information System (INIS)

Cheng, C.-C.; Chang, W.-K.; Chiang, R.-K.; Wang, S.-L.

2010-01-01

Two new cobalt phosphites, (H 3 NC 6 H 4 NH 3 )Co(HPO 3 ) 2 (1) and (NH 4 ) 2 Co 2 (HPO 3 ) 3 (2), have been synthesized and characterized by single-crystal X-ray diffraction. All the cobalt atoms of 1 are in tetrahedral CoO 4 coordination. The structure of 1 comprises twisted square chains of four-rings, which contain alternating vertex-shared CoO 4 tetrahedra and HPO 3 groups. These chains are interlinked with trans-1,4-diaminocyclohexane cations by hydrogen bonds. The 2-D structure of 2 comprises anionic complex sheets with ammonium cations present between them. An anionic complex sheet contains three-deck phosphite units, which are interconnected by Co 2 O 9 to form complex layers. Magnetic susceptibility measurements of 1 and 2 showed that they have a weak antiferromagnetic interaction. - Graphical abstract: The 2-D structure of (NH 4 ) 2 Co 2 (HPO 3 ) 3 comprises anionic complex sheets with ammonium cations present between them. An anionic complex sheet contains three-deck phosphite units, which are interconnected by dimmeric Co 2 O 9 to form complex layers.

Enhanced photovoltaic performance of CH3NH3PbBrXI3-X-based perovskite solar cells via anti-solvent extraction

Science.gov (United States)

Jiang, Zhaoyi; Zhang, Weijia; Lu, Chaoqun; Ma, Denghao; Liu, Haixu; Yu, Wei; Zhang, Yu; Ma, Qiang; Zhang, Yulong

2018-06-01

In this paper, the two-step sequential deposition method was used to prepare the CH3NH3PbBrXI3-X films by introducing CH3NH3Br in the precursors. The surface morphology of the PbI2 films was controlled by anti-solvent extraction (ASE) to improve the microstructure and photo-physical properties of the perovskite films. It was noteworthy that, compared to the compact PbI2 films, the porous PbI2 films facilitated the growth of crystals and bromine incorporation in films, and the prepared perovskite films exhibited enlarged grain size, increased light absorption, enhanced Br incorporation and prolonged carrier lifetime, which resulted in excellent photo-electrical properties of the CH3NH3PbBrXI3-X films. With porous PbI2 templates, the inverted planar perovskite solar cells based on films with appropriate Br incorporation (CH3NH3Br/CH3NH3I mole ratio = 3/7) showed a photovoltaic conversion efficiency (PCE) of 14.9%, and the stability of the devices in air was elevated. Consequently, the high-quality CH3NH3PbBrXI3-X films can be obtained with porous PbI2 templates for improving the performance of the perovskite solar cells.

Effects of acute NH3 air pollution on N-sensitive and N-tolerant lichen species.

Science.gov (United States)

Paoli, Luca; Maslaňáková, Ivana; Grassi, Alice; Bačkor, Martin; Loppi, Stefano

2015-12-01

Lichens are sensitive to the presence of ammonia (NH3) in the environment. However, in order to use them as reliable indicators in biomonitoring studies, it is necessary to establish unequivocally the occurrence of certain symptoms following the exposure to NH3 in the environment. In this paper, we simulated an episode of acute air pollution due to the release of NH3. The biological effects of acute air pollution by atmospheric NH3 have been investigated using N-sensitive (Flavoparmelia caperata) and N-tolerant (Xanthoria parietina) species. Lichen samples were exposed to ecologically relevant NH3 concentrations for 8 weeks, simulating three areas of impact: a control area (2 μg/m(3)), an area of intermediate impact (2-35 μg/m(3)) and an area of high impact (10-315 μg/m(3)), with a peak of pollution reached between the fourth and fifth week. Ammonia affected both the photobiont and the mycobiont in F. caperata, while in X. parietina only the photosynthetic performance of the photobiont was altered after exposure to the highest concentration. In the photobiont of F. caperata we recorded chlorophyll degradation as indicated by OD435/415 ratio, decrease of the photosynthetic performance (as reflected by the maximum quantum yield of primary photochemistry FV/FM and the performance index PIABS); in the mycobiont, ergosterol reduction, membrane lipid peroxidation (as reflected by the increase of thiobarbituric acid reactive substances), alteration (decrease) of the secondary metabolite usnic acid. No effects were detected on caperatic acid and dehydrogenase activity. In X. parietina, the only signal determined by NH3 was the alteration of FV/FM and the performance index PIABS. The results suggest that physiological parameters in N-sensitive lichens well reflect the effects of NH3 exposure and can be applied as early indicators in monitoring studies. Copyright © 2015 Elsevier Inc. All rights reserved.

Surface-exchange of NOx and NH3 above a winter wheat field in the Yangtze Delta, China

Institute of Scientific and Technical Information of China (English)

FANG Shuan-gxi; ZHANG Yi; MU Yu-jing

2006-01-01

A four-dynamic-chamber system was constructed to measure NOx and NH3 surface-exchange between a typical wheat field and the fluxes of NO2 and NH3 were negatively correlated with their ambient concentrations during the investigated period. The compensation point of NO2 between the wheat field and the atmosphere was 11.9 μg/m3. The emissions of NO-N and NH3-N from the urea applied to the wheat field were 2.3% and 0.2%, respectively, which indicated that the main pathway of N loss from the investigated winter wheat field was NO. Application of a mixture of urea and lignin increased the emissions of NO, but also greatly increased the yield of the winter wheat.

Crystallographic Investigations into Properties of Acentric Hybrid Perovskite Single Crystals NH(CH3)3SnX3(X = Cl, Br)

KAUST Repository

Dang, Yangyang

2016-10-11

The hybrid perovskites with special optoelectronic properties have attracted more attention to the scientific and industrial applications. However, because of the toxicity and instability of lead complexes, there is interest in finding a nontoxic substitute for the lead in the halides perovskites and solving the ambiguous crystal structures and phase transition of NH(CH3)3SnX3 (X = Cl, Br). Here, we report the bulk crystal growths and different crystal morphologies of orthorhombic hybrid perovskites NH(CH3)3SnX3 (X = Cl, Br) in an ambient atmosphere by bottom-seeded solution growth (BSSG) method. More importantly, detailed structural determination and refinements, phase transition, band gap, band structure calculations, nonlinear optical (NLO) properties, XPS, thermal properties, and stability of NH(CH3)3SnX3 (X = Cl, Br) single crystals are demonstrated. NH(CH3)3SnCl3 single crystal undergoes reversible structural transformation from orthorhombic space group Cmc21 (no. 36) to monoclinic space group Cc (no. 9) and NH(CH3)3SnBr3 belongs to the orthorhombic space group Pna21 (no. 33) by DSC, single-crystal X-ray diffraction and temperature-dependent SHG measurements, which clarify the former results. These results should pave the way for further studies of these materials in optoelectronics.

Meteorite Impact-Induced Rapid NH3 Production on Early Earth: Ab Initio Molecular Dynamics Simulation

Science.gov (United States)

Shimamura, Kohei; Shimojo, Fuyuki; Nakano, Aiichiro; Tanaka, Shigenori

2016-12-01

NH3 is an essential molecule as a nitrogen source for prebiotic amino acid syntheses such as the Strecker reaction. Previous shock experiments demonstrated that meteorite impacts on ancient oceans would have provided a considerable amount of NH3 from atmospheric N2 and oceanic H2O through reduction by meteoritic iron. However, specific production mechanisms remain unclear, and impact velocities employed in the experiments were substantially lower than typical impact velocities of meteorites on the early Earth. Here, to investigate the issues from the atomistic viewpoint, we performed multi-scale shock technique-based ab initio molecular dynamics simulations. The results revealed a rapid production of NH3 within several picoseconds after the shock, indicating that shocks with greater impact velocities would provide further increase in the yield of NH3. Meanwhile, the picosecond-order production makes one expect that the important nitrogen source precursors of amino acids were obtained immediately after the impact. It was also observed that the reduction of N2 proceeded according to an associative mechanism, rather than a dissociative mechanism as in the Haber-Bosch process.

Field-effect transistors with high mobility and small hysteresis of transfer characteristics based on CH3NH3PbBr3 films

Science.gov (United States)

Aleshin, A. N.; Shcherbakov, I. P.; Trapeznikova, I. N.; Petrov, V. N.

2017-12-01

Field-effect transistor (FET) structures based on soluble organometallic perovskites, CH3NH3PbBr3, were obtained and their electrical properties were studied. FETs made of CH3NH3PbBr3 films possess current- voltage characteristics (IVs) typical for ambipolar FETs with saturation regime. The transfer characteristics of FETs based on CH3NH3PbBr3 have an insignificant hysteresis and slightly depend on voltage at the source-drain. Mobilities of charge carriers (holes) calculated from IVs of FETs based on CH3NH3PbBr3 at 300 K in saturation and weak field regimes were 5 and 2 cm2/V s, respectively, whereas electron mobility is 3 cm2/V s, which exceeds the mobility value 1 cm2/V s obtained earlier for FETs based on CH3NH3PbI3.

New Type of 2D Perovskites with Alternating Cations in the Interlayer Space, (C(NH ₂ ) ₃ )(CH ₃ NH ₃ ) _n Pb _n I _3n+1 : Structure, Properties, and Photovoltaic Performance

Energy Technology Data Exchange (ETDEWEB)

Soe, Chan Myae Myae; Stoumpos, Constantinos C.; Kepenekian, Mikaël; Traoré, Boubacar; Tsai, Hsinhan; Nie, Wanyi; Wang, Binghao; Katan, Claudine; Seshadri, Ram; Mohite, Aditya D.; Even, Jacky; Marks, Tobin J.; Kanatzidis, Mercouri G. (UCSB); (NWU); (LANL); (CNRS-UMR)

2017-11-01

We present the new homologous series (C(NH2)3)(CH3NH3)nPbnI3n+1 (n = 1, 2, 3) of layered 2D perovskites. Structural characterization by single-crystal X-ray diffraction reveals that these compounds adopt an unprecedented structure type, which is stabilized by the alternating ordering of the guanidinium and methylammonium cations in the interlayer space (ACI). Compared to the more common Ruddlesden–Popper (RP) 2D perovskites, the ACI perovskites have a different stacking motif and adopt a higher crystal symmetry. The higher symmetry of the ACI perovskites is expressed in their physical properties, which show a characteristic decrease of the bandgap with respect to their RP perovskite counterparts with the same perovskite layer thickness (n). The compounds show a monotonic decrease in the optical gap as n increases: Eg = 2.27 eV for n = 1 to Eg = 1.99 eV for n = 2 and Eg = 1.73 eV for n = 3, which show slightly narrower gaps compared to the corresponding RP perovskites. First-principles theoretical electronic structure calculations confirm the experimental optical gap trends suggesting that the ACI perovskites are direct bandgap semiconductors with wide valence and conduction bandwidths. To assess the potential of the ACI perovskites toward solar cell applications, we studied the (C(NH2)3)(CH3NH3)3Pb3I10 (n = 3) compound. Compact thin films from the (C(NH2)3)(CH3NH3)3Pb3I10 compound with excellent surface coverage can be obtained from the antisolvent dripping method. Planar photovoltaic devices from optimized ACI perovskite films yield a power-conversion-efficiency of 7.26% with a high open-circuit voltage of ~1 V and a striking fill factor of ~80%.

Room temperature three-photon pumped CH3NH3PbBr3 perovskite microlasers

Science.gov (United States)

Gao, Yisheng; Wang, Shuai; Huang, Can; Yi, Ningbo; Wang, Kaiyang; Xiao, Shumin; Song, Qinghai

2017-03-01

Hybrid lead halide perovskites have made great strides in next-generation light-harvesting and light emitting devices. Recently, they have also shown great potentials in nonlinear optical materials. Two-photon absorption and two-photon light emission have been thoroughly studied in past two years. However, the three-photon processes are rarely explored, especially for the laser emissions. Here we synthesized high quality CH3NH3PbBr3 perovskite microstructures with solution processed precipitation method and studied their optical properties. When the microstructures are pumped with intense 1240 nm lasers, we have observed clear optical limit effect and the band-to-band photoluminescence at 540 nm. By increasing the pumping density, whispering-gallery-mode based microlasers have been achieved from CH3NH3PbBr3 perovskite microplate and microrod for the first time. This work demonstrates the potentials of hybrid lead halide perovskites in nonlinear photonic devices.

Electron paramagnetic resonance of gamma irradiated (CH3)3NHClO4 and CH3NH3ClO4 single crystals

International Nuclear Information System (INIS)

Yavuz, Metin; Koeksal, Fevzi

1999-01-01

Gamma irradiation damage centers in (CH 3 ) 3 NHClO 4 and CH 3 NH 3 ClO 4 single crystals have been investigated at room temperature by the electron paramagnetic resonance (EPR) technique. It has been found that γ-irradiation produces the (CH 3 ) 3 N + radical in the first, and NH + 3 and ClO 3 radicals in the second compound. The EPR parameters of the observed radicals have been determined and discussed

Formation of simple nitrogen hydrides NH and NH2 at cryogenic temperatures through N + NH3→ NH + NH2 reaction: dark cloud chemistry of nitrogen.

Science.gov (United States)

Nourry, Sendres; Krim, Lahouari

2016-07-21

Although NH3 molecules interacting with ground state nitrogen atoms N((4)S) seem not to be a very reactive system without providing additional energy to initiate the chemical process, we show through this study that, in the solid phase, at very low temperature, NH3 + N((4)S) reaction leads to the formation of the amidogen radical NH2. Such a dissociation reaction previously thought to occur exclusively through UV photon or energetic particle irradiation is in this work readily occurring just by stimulating the mobility of N((4)S)-atoms in the 3-10 K temperature range in the solid sample. The N((4)S)-N((4)S) recombination may be the source of metastable molecular nitrogen N2(A), a reactive species which might trigger the NH3 dissociation or react with ground state nitrogen atoms N((4)S) to form excited nitrogen atoms N((4)P/(2)D) through energy transfer processes. Based on our obtained results, it is possible to propose reaction pathways to explain the NH2 radical formation which is the first step in the activation of stable species such as NH3, a chemical induction process that, in addition to playing an important role in the origin of molecular complexity in interstellar space, is known to require external energy supplies to occur in the gas phase.

Synthesis, Resistivity, and Thermal Properties of the Cubic Perovskite NH 2CH=NH 2SnI 3and Related Systems

Science.gov (United States)

Mitzi, D. B.; Liang, K.

1997-12-01

Combining concentrated hydriodic acid solutions of tin(II) iodide and formamidine acetate in an inert atmosphere results in the precipitation of a new conducting organic-inorganic compound, NH 2CH=NH 2SnI 3, which at room temperature adopts a cubic perovskite structure. The lattice constant for NH 2CH=NH 2SnI 3is found to be a=6.316(1) Å, which is approximately 1.2% larger than that for the isostructural compound CH 3NH 3SnI 3. The electrical resistivity of a pressed pellet of the new compound exhibits semimetallic temperature dependence from 10 to 300 K, with evidence of a structural transition at approximately 75 K. NH 2CH=NH 2SnI 3begins to slowly decompose in an inert atmosphere at temperatures as low as 200°C, with bulk decomposition/melting occurring above 300°C. The properties of the formamidinium-based perovskite are compared with those of the related cubic (at room temperature) perovskite CH 3NH 3SnI 3and the mixed-cation system (CH 3NH 3) 1- x(NH 2CH=NH 2) xSnI 3.

LPG and NH3 sensing characteristics of DC electrochemically deposited Co3O4 films

Science.gov (United States)

Shelke, P. N.; Khollam, Y. B.; Gunjal, S. D.; Koinkar, P. M.; Jadkar, S. R.; Mohite, K. C.

2015-03-01

Present communication reports the LPG and NH3 sensing properties of Co3O4 films prepared on throughly cleaned stainless steel (SS) and copper (CU) substrates by using DC electrochemical deposition method followed by air annealing at 350°C/2 h. The resultant films are characterized by using X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy (SEM). The LPG and NH3 gas sensing properties of these films are measured at room temperature (RT) by using static gas sensing system at different concentrations of test gas ranging from 25 ppm to 350 ppm. The XRD and Raman spectroscopy studies clearly indicated the formation of pure cubic spinel Co3O4 in all films. The LPG and NH3 gas sensing properties of films showed (i) the increase in sensitivity factor (S.F.) with gas concentrations and (ii) more sensibility to LPG as compared to NH3 gas. In case of NH3 gas (conc. 150 ppm) and LPG gas (conc. 60 ppm) sensing, the maximum S.F. = 270 and 258 are found for the films deposited on CU substrates, respectively. For all films, the response time (3-5 min.) is found to be much higher than the recovery time (30-50 sec). For all films, the response and recovery time are found to be higher for LPG as compared to NH3 gas. Further, repeatability-reproducibility in gas sensing properties is clearly noted by analysis of data for number of cycles recorded for all films from different set of depositions.

Effects of atmospheric ammonia (NH3) on terrestrial vegetation: a review

International Nuclear Information System (INIS)

Krupa, S.V.

2003-01-01

A review of atmospheric ammonia (NH 3 ) and ammonium (NH 4 + ) deposition and their effects on plants. - At the global scale, among all N (nitrogen) species in the atmosphere and their deposition on to terrestrial vegetation and other receptors, NH 3 (ammonia) is considered to be the foremost. The major sources for atmospheric NH 3 are agricultural activities and animal feedlot operations, followed by biomass burning (including forest fires) and to a lesser extent fossil fuel combustion. Close to its sources, acute exposures to NH 3 can result in visible foliar injury on vegetation. NH 3 is deposited rapidly within the first 4-5 km from its source. However, NH 3 is also converted in the atmosphere to fine particle NH 4 + (ammonium) aerosols that are a regional scale problem. Much of our current knowledge of the effects of NH 3 on higher plants is predominantly derived from studies conducted in Europe. Adverse effects on vegetation occur when the rate of foliar uptake of NH 3 is greater than the rate and capacity for in vivo detoxification by the plants. Most to least sensitive plant species to NH 3 are native vegetation > forests > agricultural crops. There are also a number of studies on N deposition and lichens, mosses and green algae. Direct cause and effect relationships in most of those cases (exceptions being those locations very close to point sources) are confounded by other environmental factors, particularly changes in the ambient SO 2 (sulfur dioxide) concentrations. In addition to direct foliar injury, adverse effects of NH 3 on higher plants include alterations in: growth and productivity, tissue content of nutrients and toxic elements, drought and frost tolerance, responses to insect pests and disease causing microorganisms (pathogens), development of beneficial root symbiotic or mycorrhizal associations and inter species competition or biodiversity. In all these cases, the joint effects of NH 3 with other air pollutants such as all-pervasive O 3 or

X-ray and NQR studies of bromoindate(III) complexes. [C2H5NH3]4InBr7, [C(NH2)3]3InBr6, and [H3NCH2C(CH3)2CH2NH3]InBr5

International Nuclear Information System (INIS)

Iwakiri, Takeharu; Ishihara, Hideta; Terao, Hiromitsu; Lork, Enno; Gesing, Thorsten M.

2017-01-01

The crystal structures of [C 2 H 5 NH 3 ] 4 InBr 7 (1), [C(NH 2 ) 3 ] 3 InBr 6 (2), and [H 3 NCH 2 C(CH 3 ) 2 CH 2 NH 3 ]InBr 5 (3) were determined at 100(2) K: monoclinic, P2 1 /n, a=1061.94(3), b=1186.40(4), c=2007.88(7) pm, β= 104.575(1) , Z=4 for 1; monoclinic, C2/c, a=3128.81(12), b=878.42(3), c=2816.50(10) pm, β=92.1320(10) , Z=16 for 2; orthorhombic, P2 1 2 1 2 1 , a=1250.33(5), b=1391.46(6), c=2503.22(9) pm, Z=4 for 3. The structure of 1 contains an isolated octahedral [InBr 6 ] 3- ion and a Br - ion. The structure of 2 contains three different isolated octahedral [InBr 6 ] 3- ions. The structure of 3 has a corner-shared double-octahedral [In 2 Br 11 ] 5- ion and an isolated tetrahedral [InBr 4 ] - ion. The 81 Br nuclear quadrupole resonance (NQR) lines of the terminal Br atoms of the compounds are widely spread in frequency, and some of them show unusual positive temperature dependence. These observations manifest the N-H..Br-In hydrogen bond networks developed between the cations and anions to stabilize the crystal structures. The 81 Br NQR and differential thermal analysis (DTA) measurements have revealed the occurrence of unique phase transitions in 1 and 3. When the bond angles were estimated from the electric field gradient (EFG) directions calculated by the molecular orbital (MO) methods, accurate values were obtained for [InBr 6 ] 3- of 1 and for [In 2 Br 11 ] 5- and [InBr 4 ] - of 3, except for several exceptions in those for the latter two ions. On the other hand, the calculations of 81 Br NQR frequencies have produced up to 1.4 times higher values than the observed ones.

Biochar produced from oak sawdust by Lanthanum (La)-involved pyrolysis for adsorption of ammonium (NH4(+)), nitrate (NO3(-)), and phosphate (PO4(3-)).

Science.gov (United States)

Wang, Zhanghong; Guo, Haiyan; Shen, Fei; Yang, Gang; Zhang, Yanzong; Zeng, Yongmei; Wang, Lilin; Xiao, Hong; Deng, Shihuai

2015-01-01

A series of biochars were prepared by pyrolyzing oak sawdust with/without LaCl3 involvement at temperature of 300-600 °C, and approximate and ultimate analyses were carried out to check their basic characteristics. Meanwhile, the releases of readily soluble NH4(+), NO3(-) and PO4(3-) from biochars and the adsorption of NH4(+), NO3(-) and PO4(3-) by biochars were investigated. Results indicated that the involvement of LaCl3 in pyrolysis could advance the temperature of maximum mass loss by 10 °C compared with oak sawdust (CK), and potentially promoted biochar yield. Overall, the releases of readily soluble NH4(+), NO3(-) and PO4(3-) from biochars were negatively related to pyrolysis temperature, and the releases were greatly weakened by La-biochars. Additionally, the adsorption to NH4(+) can be promoted by the biochars produced at low temperature. On the contrary, the NO3(-) adsorption can be improved by increasing pyrolysis temperature. The highest PO4(3-) adsorption was achieved by the biochars produced at 500 °C. According to the results of adsorption isotherms, the maximum adsorption capacity of NH4(+), NO3(-) and PO4(3-) can be significantly promoted by 1.9, 11.2, and 4.5 folds using La-biochars. Based on the observations of FT-IR, SEM-EDS, and surface functional groups, the improvement of NH4(+) adsorption was potentially associated with the existing acidic function groups (phenolic-OH and carboxyl C=O). The increased basic functional groups on La-biochars were beneficial to improve NO3(-) and PO4(3-) adsorption. Besides, PO4(3-) adsorption was also potentially related to the formed La2O3. Copyright © 2014 Elsevier Ltd. All rights reserved.

Synthesis, characterization, and application of Zn(NH 3)(CO3) for selective adsorptive separation of CO2

Science.gov (United States)

Khazeni, Naasser

This study explores the potential of Zn(NH3)(CO3) for selective CO2 separation. It develops a novel, highly controllable, single-pot synthesis approach based on urea hydrolysis and solvothermal aging to increase the feasibility of synthesizing Zn(NH3)(CO3), determines the structure of Zn(NH3)(CO3) in detail through single crystal X-ray diffraction and powder X-ray diffraction analyses, and performs adsorption analyses for the compound using CO2, N 2, H2, O2, and CH4 as adsorptives. Through adsorptive characterization, a systematic adsorbent selection screening is performed to assess the potential application of Zn(NH3)(CO 3) for adsorptive separation of CO2 from an upstream gas mixture of power generation, hydrogen production, and natural gas industries. Structural analysis shows Zn(NH3)(CO3) to have an inorganic helical framework that consists of a small helix of (ZnOCO) 2 and a large helix of (ZnOCO)4 with two ammines (NH 3) pendant from every other zinc. In terms of adsorption capacity and CO2 selectivity, Zn(NH3)(CO3) adsorbed 0.550 mmole/g CO2 at 293 K and 4500 mmHg, but only 0.047 mmole/g N 2, 0.084 mmole/g H2, 0.207 mmole/g 02, and 0.060 mmole/g CH4 at the same temperature and pressure. This behavior demonstrates considerable equilibrium selectivities - 36, 31, 63, and 11 - for separating CO2 from CH4, CO2 from H 2, CO2 from N2, and CO2 from 02, respectively. During adsorption, the pendant ammines act as the gates of check-valves: applied pressure opens the gates for adsorption; and during desorption, the gates are closed, trapping the adsorbates, until a reduction of pressure to near-atmospheric levels. Therefore, Zn(NH3)(CO3) exhibits low-pressure H3 or H4 hysteresis, indicating that the Zn(NH3)(CO3) framework can achieve gas storage at near-atmospheric pressures. Additionally, the compound proves structurally stable, with an adsorption decrease of 0.8% after 20 adsorption/desorption cycles - a factor that, considered with the other characteristics of Zn(NH

Crystal structure of (NH4)2[Fe(II) 5(HPO3)6], a new open-framework phosphite.

Science.gov (United States)

Berrocal, Teresa; Mesa, Jose Luis; Larrea, Edurne; Arrieta, Juan Manuel

2014-11-01

Di-ammonium hexa-phosphito-penta-ferrate(II), (NH4)2[Fe5(HPO3)6], was synthesized under mild hydro-thermal conditions and autogeneous pressure, yielding twinned crystals. The crystal structure exhibits an [Fe(II) 5(HPO3)6](2-) open framework with NH4 (+) groups as counter-cations. The anionic skeleton is based on (001) sheets of [FeO6] octa-hedra (one with point-group symmetry 3.. and one with .2.) linked along [001] through [HPO3](2-) oxoanions. Each sheet is constructed from 12-membered rings of edge-sharing [FeO6] octa-hedra, giving rise to channels with a radius of ca 3.1 Å in which the disordered NH4 (+) cations are located. The IR spectrum shows vibrational bands typical for phosphite and ammonium groups.

Synthesis and properties of ternary (K, NH{sub 4}, H{sub 3}O)-jarosites precipitated from Acidithiobacillus ferrooxidans cultures in simulated bioleaching solutions

Energy Technology Data Exchange (ETDEWEB)

Sandy Jones, F.; Bigham, Jerry M. [School of Environment and Natural Resources, Ohio State University, 2021 Coffey Road, Columbus, OH 43210 (United States); Gramp, Jonathan P. [Department of Microbiology, Ohio State University, 484 West 12th Avenue, Columbus, OH 43210 (United States); Tuovinen, Olli H., E-mail: tuovinen.1@osu.edu [Department of Microbiology, Ohio State University, 484 West 12th Avenue, Columbus, OH 43210 (United States)

2014-11-01

The purpose of this study was to synthesize a series of solid solution jarosites by biological oxidation of ferrous iron at pH 2.2–4.4 and ambient temperature in media containing mixtures of K{sup +} (0, 1, 4, 6, 12, 31 mM) and NH{sub 4}{sup +} (6.1, 80, 160, 320 mM). The starting material was a liquid medium for Acidithiobacillus ferrooxidans comprised of 120 mM FeSO{sub 4} solution and mineral salts at pH 2.2. Following inoculation with A. ferrooxidans, the cultures were incubated in shake flasks at 22 °C. As bacteria oxidized ferrous iron, ferric iron hydrolyzed and precipitated as jarosite-group minerals (AFe{sub 3}(SO{sub 4}){sub 2}(OH){sub 6}) and/or schwertmannite (idealized formula Fe{sub 8}O{sub 8}(OH){sub 6}(SO{sub 4})·nH{sub 2}O). The precipitates were characterized by X-ray diffraction (XRD), elemental analysis, and Munsell color. Schwertmannite was the dominant mineral product at low combinations of K{sup +} (≤ 4 mM) and NH{sub 4}{sup +} (≤ 80 mM) in the media. At higher single or combined concentrations, yellowish jarosite phases were produced, and Munsell hue provided a sensitive means of detecting minor schwertmannite in the oxidation products. Although the hydrated ionic radii of K{sup +} and NH{sub 4}{sup +} are similar, K{sup +} greatly facilitated the formation of a jarosite phase compared to NH{sub 4}{sup +}. Unit cell and cell volume calculations from refinements of the powder XRD patterns indicated that the jarosite phases produced were mostly ternary (K, NH{sub 4}, H{sub 3}O)-solid solutions that were also deficient in structural Fe, especially at low NH{sub 4} contents. Thus, ferric iron precipitation from the simulated bioleaching systems yielded solid solutions of jarosite with chemical compositions that were dependent on the relative concentrations of K{sup +} and NH{sub 4}{sup +} in the synthesis media. No phase separations involving discrete, end-member K-jarosite or NH{sub 4}-jarosite were detected in the un-aged precipitates

Interfacial Charge-Carrier Trapping in CH3NH3PbI3-Based Heterolayered Structures Revealed by Time-Resolved Photoluminescence Spectroscopy.

Science.gov (United States)

Yamada, Yasuhiro; Yamada, Takumi; Shimazaki, Ai; Wakamiya, Atsushi; Kanemitsu, Yoshihiko

2016-06-02

The fast-decaying component of photoluminescence (PL) under very weak pulse photoexcitation is dominated by the rapid relaxation of the photoexcited carriers into a small number of carrier-trapping defect states. Here, we report the subnanosecond decay of the PL under excitation weaker than 1 nJ/cm(2) both in CH3NH3PbI3-based heterostructures and bare thin films. The trap-site density at the interface was evaluated on the basis of the fluence-dependent PL decay profiles. It was found that high-density defects determining the PL decay dynamics are formed near the interface between CH3NH3PbI3 and the hole-transporting Spiro-OMeTAD but not at the CH3NH3PbI3/TiO2 interface and the interior regions of CH3NH3PbI3 films. This finding can aid the fabrication of high-quality heterointerfaces, which are required improving the photoconversion efficiency of perovskite-based solar cells.

Effects of atmospheric ammonia (NH3) on terrestrial vegetation: a review.

Science.gov (United States)

Krupa, S V

2003-01-01

At the global scale, among all N (nitrogen) species in the atmosphere and their deposition on to terrestrial vegetation and other receptors, NH3 (ammonia) is considered to be the foremost. The major sources for atmospheric NH3 are agricultural activities and animal feedlot operations, followed by biomass burning (including forest fires) and to a lesser extent fossil fuel combustion. Close to its sources, acute exposures to NH3 can result in visible foliar injury on vegetation. NH3 is deposited rapidly within the first 4-5 km from its source. However, NH3 is also converted in the atmosphere to fine particle NH4+ (ammonium) aerosols that are a regional scale problem. Much of our current knowledge of the effects of NH3 on higher plants is predominantly derived from studies conducted in Europe. Adverse effects on vegetation occur when the rate of foliar uptake of NH3 is greater than the rate and capacity for in vivo detoxification by the plants. Most to least sensitive plant species to NH3 are native vegetation > forests > agricultural crops. There are also a number of studies on N deposition and lichens, mosses and green algae. Direct cause and effect relationships in most of those cases (exceptions being those locations very close to point sources) are confounded by other environmental factors, particularly changes in the ambient SO2 (sulfur dioxide) concentrations. In addition to direct foliar injury, adverse effects of NH3 on higher plants include alterations in: growth and productivity, tissue content of nutrients and toxic elements, drought and frost tolerance, responses to insect pests and disease causing microorganisms (pathogens), development of beneficial root symbiotic or mycorrhizal associations and inter species competition or biodiversity. In all these cases, the joint effects of NH3 with other air pollutants such as all-pervasive O3 or increasing CO2 concentrations are poorly understood. While NH3 uptake in higher plants occurs through the shoots, NH4

CH3NH3PbI3 grain growth and interfacial properties in meso-structured perovskite solar cells fabricated by two-step deposition

Science.gov (United States)

Yao, Zhibo; Wang, Wenli; Shen, Heping; Zhang, Ye; Luo, Qiang; Yin, Xuewen; Dai, Xuezeng; Li, Jianbao; Lin, Hong

2017-12-01

Although the two-step deposition (TSD) method is widely adopted for the high performance perovskite solar cells (PSCs), the CH3NH3PbI3 perovskite crystal growth mechanism during the TSD process and the photo-generated charge recombination dynamics in the mesoporous-TiO2 (mp-TiO2)/CH3NH3PbI3/hole transporting material (HTM) system remains unexploited. Herein, we modified the concentration of PbI2 (C(PbI2)) solution to control the perovskite crystal properties, and observed an abnormal CH3NH3PbI3 grain growth phenomenon atop mesoporous TiO2 film. To illustrate this abnormal grain growth mechanism, we propose that a grain ripening process is taking place during the transformation from PbI2 to CH3NH3PbI3, and discuss the PbI2 nuclei morphology, perovskite grain growing stage, as well as Pb:I atomic ratio difference among CH3NH3PbI3 grains with different morphology. These C(PbI2)-dependent perovskite morphologies resulted in varied charge carrier transfer properties throughout the mp-TiO2/CH3NH3PbI3/HTM hybrid, as illustrated by photoluminescence measurement. Furthermore, the effect of CH3NH3PbI3 morphology on light absorption and interfacial properties is investigated and correlated with the photovoltaic performance of PSCs.

Rapid Ammonia Gas Transport Accounts for Futile Transmembrane Cycling under NH3/NH4+ Toxicity in Plant Roots1[C][W

Science.gov (United States)

Coskun, Devrim; Britto, Dev T.; Li, Mingyuan; Becker, Alexander; Kronzucker, Herbert J.

2013-01-01

Futile transmembrane NH3/NH4+ cycling in plant root cells, characterized by extremely rapid fluxes and high efflux to influx ratios, has been successfully linked to NH3/NH4+ toxicity. Surprisingly, the fundamental question of which species of the conjugate pair (NH3 or NH4+) participates in such fluxes is unresolved. Using flux analyses with the short-lived radioisotope 13N and electrophysiological, respiratory, and histochemical measurements, we show that futile cycling in roots of barley (Hordeum vulgare) seedlings is predominately of the gaseous NH3 species, rather than the NH4+ ion. Influx of 13NH3/13NH4+, which exceeded 200 µmol g–1 h–1, was not commensurate with membrane depolarization or increases in root respiration, suggesting electroneutral NH3 transport. Influx followed Michaelis-Menten kinetics for NH3 (but not NH4+), as a function of external concentration (Km = 152 µm, Vmax = 205 µmol g–1 h–1). Efflux of 13NH3/13NH4+ responded with a nearly identical Km. Pharmacological characterization of influx and efflux suggests mediation by aquaporins. Our study fundamentally revises the futile-cycling model by demonstrating that NH3 is the major permeating species across both plasmalemma and tonoplast of root cells under toxicity conditions. PMID:24134887

13N-NH3 PET in the diagnosis of astrocytomas: preliminary result

International Nuclear Information System (INIS)

Zhang Xiangsong; He Zuoxiang; Tang Anwu

2004-01-01

Objective: To evaluate the feasibility of diagnosing the astrocytoma with 13N-NH3 PET imaging. Methods 13N-NH3 and 18F-fluorodeoxyglucose (FDG) PET imaging were performed in seven cases of astrocytomas including 3 anteoperative astrocytomas, 2 recurrent astrocytomas, 2 brain injury or necrosis after the operation and radiotherapy. The radioactivity ratios of the tumor and normal white matter (T/WM) were calculated. Results: The tumor lesions in 3 anteoperative astrocytomas and 2 recurrent astrocytomas all uptake 13N-NH3. The average T/WM on 13N-NH3 images was 1.82±0.21, and T/WM on 13N-NH3 and 18F-FDG images were 1.98 and 0.97 for one case with grade 1 astrocytoma. 13N-NH3 and 18F-FDG PET imaging both showed decreased uptake in 2 brain injury or necrosis after the operation and radiotherapy of astrocytomas. Conclusions: 13N-NH3 was uptaken in astrocytomas. 13N-NH3 can be useful in the diagnosis of astrocytoma, and potentially improve diagnostic accuracy of astrocytoma, especially in low-grade astrocytoma. (authors)

13N-NH3 PET in the diagnosis of astrocytomas: preliminary result

International Nuclear Information System (INIS)

Zhang Xiangsong; He Zuoxiang; Tang Anwu

2004-01-01

Objective: To evaluate the feasibility of diagnosing the astrocytoma with 13N-NH3 PET imaging. Methods: 13N-NH3 and 18F-fluorodeoxyglucose (FDG) PET imaging were performed in seven cases of astrocytomas including 3 anteoperative astrocytomas, 2 recurrent astrocytomas, 2 brain injury or necrosis after the operation and radiotherapy. The radioactivity ratios of the tumor and normal white matter (T/WM) were calculated. Results: The tumor lesions in 3 anteoperative astrocytomas and 2 recurrent astrocytomas all uptake 13N-NH3 .The average T/WM on 13N-NH3 images was 1.82±0.21, and T/WM on 13N-NH3 and 18F-FDG images were 1.98 and 0.97 for one case with grade 1 astrocytoma. 13N-NH3 and 18F-FDG PET imaging both showed decreased uptake in 2 brain injury or necrosis after the operation and radiotherapy of astrocytomas. Conclusions: 13N-NH3 was uptaken in astrocytomas. 13N-NH3 can be useful in the diagnosis of astrocytoma, and potentially improve diagnostic accuracy of astrocytoma, especially in low-grade astrocytoma. (authors)

Imaging a multidimensional multichannel potential energy surface: Photodetachment of H(-)(NH3) and NH4 (.).

Science.gov (United States)

Hu, Qichi; Song, Hongwei; Johnson, Christopher J; Li, Jun; Guo, Hua; Continetti, Robert E

2016-06-28

Probes of the Born-Oppenheimer potential energy surfaces governing polyatomic molecules often rely on spectroscopy for the bound regions or collision experiments in the continuum. A combined spectroscopic and half-collision approach to image nuclear dynamics in a multidimensional and multichannel system is reported here. The Rydberg radical NH4 and the double Rydberg anion NH4 (-) represent a polyatomic system for benchmarking electronic structure and nine-dimensional quantum dynamics calculations. Photodetachment of the H(-)(NH3) ion-dipole complex and the NH4 (-) DRA probes different regions on the neutral NH4 PES. Photoelectron energy and angular distributions at photon energies of 1.17, 1.60, and 2.33 eV compare well with quantum dynamics. Photoelectron-photofragment coincidence experiments indicate dissociation of the nascent NH4 Rydberg radical occurs to H + NH3 with a peak kinetic energy of 0.13 eV, showing the ground state of NH4 to be unstable, decaying by tunneling-induced dissociation on a time scale beyond the present scope of multidimensional quantum dynamics.

Room temperature solution processed low dimensional CH3NH3PbI3 NIR detector

Science.gov (United States)

Besra, N.; Paul, T.; Sarkar, P. K.; Thakur, S.; Sarkar, S.; Das, A.; Chanda, K.; Sardar, K.; Chattopadhyay, K. K.

2018-05-01

Metal halide perovskites have recently drawn immense research interests among the worldwide scientific community due to their excellent light harvesting capabilities and above all, cost effectiveness. These new class of materials have already been used as efficient optoelectronic devices e.g. solar cells, photo detectors, etc. Here in this work, room temperature NIR (near infra red) response of organic-inorganic lead halide perovskite CH3NH3PbI3 (Methylammonium lead tri iodide) nanorods has been studied. A very simple solution process technique has been adopted to synthesize CH3NH3PbI3 nanostructures at room temperature. The NIR exposure upon the sample resulted in a considerable hike in its dark current with very good responsivity (0.37 mA/W). Along with that, a good on-off ratio (41.8) was also obtained when the sample was treated under a pulsed NIR exposure with operating voltage of 2 V. The specific detectivity of the device came in the order of 1010 Jone.

Evidence of amino acid precursors: C-N bond coupling in simulated interstellar CO2/NH3 ices

Science.gov (United States)

Esmaili, Sasan

2015-08-01

Low energy secondary electrons are abundantly produced in astrophysical or planetary ices by the numerous ionizing radiation fields typically encountered in space environments and may thus play a role in the radiation processing of such ices [1]. One approach to determine their chemical effect is to irradiate nanometer thick molecular solids of simple molecular constituents, with energy selected electron beams and to monitor changes in film chemistry with the surface analytical techniques [2].Of particular interest is the formation of HCN, which is a signature of dense gases in interstellar clouds, and is ubiquitous in the ISM. Moreover, the chemistry of HCN radiolysis products such as CN- may be essential to understand of the formation of amino acids [3] and purine DNA bases. Here we present new results on the irradiation of multilayer films of CO2 and NH3 with 70 eV electrons, leading to CN bond formations. The electron stimulated desorption (ESD) yields of cations and anions are recorded as a function of electron fluence. The prompt desorption of cationic reaction/scattering products [4], is observed at low fluence (~4x1013 electrons/cm2). Detected ions include C2+, C2O2+, C2O+, CO3+, C2O3+ or CO4+ from pure CO2, and N+, NH+, NH2+, NH3+, NH4+, N2+, N2H+ from pure NH3, and NO+, NOH+ from CO2/NH3 mixtures. Most saliently, increasing signals of negative ion products desorbing during prolonged irradiation of CO2/NH3 films included C2-, C2H-, C2H2-, as well as CN-, HCN- and H2CN-. The identification of particular product ions was accomplished by using 13CO2 and 15NH3 isotopes. The chemistry induced by electrons in pure films of CO2 and NH3 and mixtures with composition ratios (3:1), (1:1), and (1:3), was also studied by X-ray photoelectron spectroscopy (XPS). Irradiation of CO2/NH3 mixed films at 22 K produces species containing the following bonds/functional groups identified by XPS: C=O, O-H, C-C, C-O, C=N and N=O. (This work has been funded by NSERC).

Atmospheric NH3 as plant nutrient: A case study with Brassica oleracea

International Nuclear Information System (INIS)

Castro, Ana; Stulen, Ineke; De Kok, Luit J.

2008-01-01

Nutrient-sufficient and nitrate- or sulfate-deprived plants of Brassica oleracea L. were exposed to 4 μl l -1 NH 3 (2.8 mg m -3 ), and effects on biomass production and allocation, N-compounds and root morphology investigated. Nitrate-deprived plants were able to transfer to atmospheric NH 3 as nitrogen source, but biomass allocation in favor of the root was not changed by exposure to NH 3 . NH 3 reduced the difference in total root length between nitrate-sufficient and nitrate-deprived plants, and increased the specific root length in the latter. The internal N status, therefore, might be involved in controlling root length in B. oleracea. Root surface area, volume and diameter were unaffected by both nitrate deprivation and NH 3 exposure. In sulfate-deprived plants an inhibitory effect of NH 3 on root morphological parameters was observed. These plants, therefore, might be more susceptible to atmospheric NH 3 than nitrate-deprived plants. The relevance of the present data under field conditions is discussed. - Atmospheric NH 3 can serve as sole N source for Brassica oleracea, but does not change root biomass allocation in nitrate-deprived plants

Biochar application mode influences nitrogen leaching and NH3 volatilization losses in a rice paddy soil irrigated with N-rich wastewater.

Science.gov (United States)

Sun, Haijun; Min, Ju; Zhang, Hailin; Feng, Yanfang; Lu, Kouping; Shi, Weiming; Yu, Min; Li, Xuewen

2017-07-11

Impacts of biochar application mode on nitrogen (N) leaching, ammonia (NH 3 ) volatilization, rice grain yield and N use efficiency (NUE) are not well understood. Therefore, a field experiment was conducted to evaluate those impacts in a rice paddy soil received 225 kg N ha -1 from either urea or N-rich wastewater. One treatment received 10 t ha -1 biochar with the basal fertilization, and the other received same total amount of biochar but split applied with the three split N applications with same ratio as N fertilizer split ratio (40%, 30% and 30%). Results showed that N leaching loads were 4.20-6.22 kg ha -1 . Biochar one-time application reduced N leaching by 23.1%, and biochar split application further reduced N leaching by 32.4%. Total NH 3 volatilization loss was 15.5-24.5 kg ha -1 . Biochar one-time application did not influence the NH 3 volatilization, but biochar split application stimulated the cumulative NH 3 volatilization by 57.7%. Both biochar treatments had no influence on NUE and rice grain yield. In conclusion, biochar application mode indeed influences the N leaching and NH 3 volatilization in rice paddy soils, and biochar one-time application should be recommended for reducing N leaching without increasing NH 3 volatilization.

mer-Triammine trifluorido vanadium(III), mer-[VF{sub 3}(NH{sub 3}){sub 3}]. Synthesis and crystal structure

Energy Technology Data Exchange (ETDEWEB)

Woidy, Patrick [Technische Univ. Muenchen, Garching (Germany). Zentrale Technisch-Wissenschaftliche Betriebseinheit Radiochemie Muenchen RCM; Kraus, Florian [Marburg Univ. (Germany). Anorganische und Fluorchemie

2015-07-01

Vanadium trifluoride reacts with dry liquid ammonia under the formation of lilac plate-shaped crystals of mer-triammine trifluorido vanadium(III) (1), mer-[VF{sub 3}(NH{sub 3}){sub 3}]. Single-crystal X-ray analysis was carried out at low temperature to elucidate the structure. The compound crystallizes in the monoclinic space group P2{sup 1}/c with a = 5.7284(4), b = 9.2033(5), c = 10.5271(6) Aa, beta = 91.795(6)°, and V = 554.72(6) Aa{sup 3} at 123 K with Z = 4. The discrete [VF{sub 3}(NH{sub 3}){sub 3}] molecules are interconnected by hydrogen bonds.

Moessbauer study of 57Fe isolated in NH3 and NH3/Xe matrices

International Nuclear Information System (INIS)

Saitovitch, E.M.B.; Litterst, F.J.; Micklitz, H.

1981-01-01

Moessbauer studies on 57 Fe isolated in solid ammonia and ammonia/xenon mixtures were perfomed at 4.2 K and 77 K. They show clearly that atomic iron reacts only with one ammonia molecule forming FeNH 3 which is stable in an ammonia matrix up to 77 K. In addition a compound is formed which is attributed to an iron (II) hexammine. (Author) [pt

Room temperature atomic layer deposited Al2O3 on CH3NH3PbI3 characterized by synchrotron-based X-ray photoelectron spectroscopy

Science.gov (United States)

Kot, Małgorzata; Das, Chittaranjan; Henkel, Karsten; Wojciechowski, Konrad; Snaith, Henry J.; Schmeisser, Dieter

2017-11-01

An ultrathin Al2O3 film deposited on methylammonium lead triiodide (CH3NH3PbI3) perovskite has the capability to suppress the carrier recombination process and improve the perovskite solar cells efficiency and stability. However, annealing at temperatures higher than 85 °C degrades the CH3NH3PbI3 perovskite film. The X-ray photoelectron spectroscopy study performed in this work indicates that it is possible to grow Al2O3 by atomic layer deposition on the perovskite at room temperature, however, besides pure Al2O3 some OH groups are found and the creation of lead and iodine oxides at the Al2O3/CH3NH3PbI3 interface takes place.

Urban NH3 levels and sources in six major Spanish cities.

Science.gov (United States)

Reche, Cristina; Viana, Mar; Karanasiou, Angeliki; Cusack, Michael; Alastuey, Andrés; Artiñano, Begoña; Revuelta, M Aranzazu; López-Mahía, Purificación; Blanco-Heras, Gustavo; Rodríguez, Sergio; Sánchez de la Campa, Ana M; Fernández-Camacho, Rocío; González-Castanedo, Yolanda; Mantilla, Enrique; Tang, Y Sim; Querol, Xavier

2015-01-01

A detailed spatial and temporal assessment of urban NH3 levels and potential emission sources was made with passive samplers in six major Spanish cities (Barcelona, Madrid, A Coruña, Huelva, Santa Cruz de Tenerife and Valencia). Measurements were conducted during two different periods (winter-autumn and spring-summer) in each city. Barcelona showed the clearest spatial pattern, with the highest concentrations in the old city centre, an area characterised by a high population density and a dense urban architecture. The variability in NH3 concentrations did not follow a common seasonal pattern across the different cities. The relationship of urban NH3 with SO2 and NOX allowed concluding on the causes responsible for the variations in NH3 levels between measurement periods observed in Barcelona, Huelva and Madrid. However, the factors governing the variations in A Coruña, Valencia and Santa Cruz de Tenerife are still not fully understood. This study identified a broad variability in NH3 concentrations at the city-scale, and it confirms that NH3 sources in Spanish urban environments are vehicular traffic, biological sources (e.g. garbage containers), wastewater treatment plants, solid waste treatment plants and industry. The importance of NH3 monitoring in urban environments relies on its role as a precursor of secondary inorganic species and therefore PMX. Further research should be addressed in order to establish criteria to develop and implement mitigation strategies for cities, and to include urban NH3 sources in the emission inventories. Copyright © 2014 Elsevier Ltd. All rights reserved.

Improvement of photovoltaic performance of the inverted planar perovskite solar cells by using CH3NH3PbI3-xBrx films with solvent annealing

Science.gov (United States)

Wang, Shan; Zhang, Weijia; Ma, Denghao; Jiang, Zhaoyi; Fan, Zhiqiang; Ma, Qiang; Xi, Yilian

2018-01-01

In this paper, the CH3NH3PbI3-xBrx films with various Br-doping contents were successfully prepared by solution processed deposition and followed by annealing process. This method simultaneously modified the morphology and composition of the CH3NH3PbI3 film. The effects of annealing treatment of CH3NH3PbI3-xBrx films under N2 and DMSO conditions on the microstructure of films and photoelectric properties of the solar cells were systematically investigated. The relationship of the component ratio of RBr/I= CH3NH3PbI3-xBrx/CH3NH3PbI3 in the resulting perovskite versus CH3NH3Br concentration also was explored. The results revealed that the CH3NH3PbI3-xBrx films annealed under DMSO exhibited increased grain sizes, enhanced crystallinity, enlarged bandgap and reduced defect density compared with that of the N2 annealing. It also was found that the RBr/I linearly increased in the resulting perovskite with the increased of CH3NH3Br concentration in the methylammonium halide mixture solutions. Furthermore, the photovoltaic performances of devices fabricated using DMSO precursor solvent were worse than that of DMF under N2 annealing atmosphere. When CH3NH3Br concentration was 7.5 mg ml-1, the planar perovskite solar cell based on CH3NH3PbI3-xBrx annealed under DMSO showed the best efficiency of 13.7%.

Effects of CuBr addition to CH3NH3PbI3(Cl) perovskite photovoltaic devices

Science.gov (United States)

Oku, Takeo; Ohishi, Yuya; Tanaka, Hiroki

2018-01-01

Effects of CuBr addition to perovskite CH3NH3PbI3(Cl) precursor solutions on photovoltaic properties were investigated. The CH3NH3Pb(Cu)I3(Cl,Br)-based photovoltaic devices were fabricated by a spin-coating technique, and the microstructures of the devices were investigated by X-ray diffraction, optical microscopy and scanning electron microscopy. Current density-voltage characteristics were improved by a small amount of CuBr addition, which resulted in improvement of the conversion efficiencies of the devices. The structure analysis showed decrease of unit cell volume and increase of Cu/Br composition by the CuBr addition, which would indicate the Cu/Br substitution at the Pb/I sites in the perovskite crystal, respectively.

Na+/H+ and Na+/NH4+ exchange activities of zebrafish NHE3b expressed in Xenopus oocytes

Science.gov (United States)

Ito, Yusuke; Kato, Akira; Hirata, Taku; Hirose, Shigehisa

2014-01-01

Zebrafish Na+/H+ exchanger 3b (zNHE3b) is highly expressed in the apical membrane of ionocytes where Na+ is absorbed from ion-poor fresh water against a concentration gradient. Much in vivo data indicated that zNHE3b is involved in Na+ absorption but not leakage. However, zNHE3b-mediated Na+ absorption has not been thermodynamically explained, and zNHE3b activity has not been measured. To address this issue, we overexpressed zNHE3b in Xenopus oocytes and characterized its activity by electrophysiology. Exposure of zNHE3b oocytes to Na+-free media resulted in significant decrease in intracellular pH (pHi) and intracellular Na+ activity (aNai). aNai increased significantly when the cytoplasm was acidified by media containing CO2-HCO3− or butyrate. Activity of zNHE3b was inhibited by amiloride or 5-ethylisopropyl amiloride (EIPA). Although the activity was accompanied by a large hyperpolarization of ∼50 mV, voltage-clamp experiments showed that Na+/H+ exchange activity of zNHE3b is electroneutral. Exposure of zNHE3b oocytes to medium containing NH3/NH4+ resulted in significant decreases in pHi and aNai and significant increase in intracellular NH4+ activity, indicating that zNHE3b mediates the Na+/NH4+ exchange. In low-Na+ (0.5 mM) media, zNHE3b oocytes maintained aNai of 1.3 mM, and Na+-influx was observed when pHi was decreased by media containing CO2-HCO3− or butyrate. These results provide thermodynamic evidence that zNHE3b mediates Na+ absorption from ion-poor fresh water by its Na+/H+ and Na+/NH4+ exchange activities. PMID:24401990

Improvement of CH3NH3PbI3 thin film using the additive 1,8-diiodooctane for planar heterojunction perovskite cells

Science.gov (United States)

Abdulrahman, Solh; Wang, Chunhua; Cao, Chenghao; Zhang, Chujun; Yang, Junliang; Jiang, Li

2017-10-01

The thin-film quality is critical for obtaining high-performance perovskite solar cells (PSCs). The additive 1,8-diiodooctane (DIO) was used to control the morphology and structure of CH3NH3PbI3 perovskite thin films, and planar heterojunction (PHJ) PSCs with an architecture of ITO/PEDOT: PSS/CH3NH3PbI3/PCBM/Al was fabricated. It was found that the DIO played an important role on CH3NH3PbI3 thin-film quality and the performance of PHJ-PSCs. With the optimal volume ratio of 2%, the compact and uniform high-quality CH3NH3PbI3 thin films with enhanced crystallinity and less roughness were achieved, resulting in the great improvement of power conversion efficiency (PCE) from about 4.5% to over 9.0%. The research results indicate that the additive DIO is a simple and effective method to produce high-quality perovskite thin film and accordingly develop high-performance PHJ-PSCs.

Interactions of nickel(II) with histones. Stability and solution structure of complexes with CH3CO-Cys-Ala-Ile-His-NH2, a putative metal binding sequence of histone H3.

Science.gov (United States)

Bal, W; Lukszo, J; Jezowska-Bojczuk, M; Kasprzak, K S

1995-01-01

Nickel(II) compounds are established human carcinogens, but the molecular mechanisms underlying their activity are only partially known. One mechanism may include mediation by nickel of promutagenic oxidative DNA damage that depends on Ni(II) binding to chromatin. To characterize such binding at the histone moiety of chromatin, we synthesized the peptide CH3CO-Cys-Ala-Ile-His-NH2 (L), a model of the evolutionarily conserved motif in histone H3 with expected affinity for transition metals, and evaluated its reactivity toward Ni(II). Combined spectroscopic (UV/vis, CD, NMR) and potentiometric measurements showed that, at physiological pH, mixtures of Ni(II) and L yielded unusual macrochelate complexes, NiL and NiL2, in which the metal cation was bound through Cys and His side chains in a square-planar arrangement. Above pH 9, a NiH-3L complex was formed, structurally analogous to typical square-planar nickel complexes. These complexes are expected to catalyze oxidation reactions, and therefore, coordination of Ni(II) by the L motif in core histone H3 may be a key event in oxidative DNA base damage observed in the process of Ni(II)-induced carcinogenesis.

Investigation of Structural and Electronic Properties of CH3NH3PbI3 Stabilized by Varying Concentrations of Poly(Methyl Methacrylate (PMMA

Directory of Open Access Journals (Sweden)

Celline Awino

2017-08-01

Full Text Available Studies have shown that perovskites have a high potential of outdoing silicon based solar cells in terms of solar energy conversion, but their rate of degradation is also high. This study reports on improvement on the stability of CH3NH3PbI3 by passivating it with polymethylmethacrylate (PMMA. Structural and electronic properties of CH3NH3PbI3 stabilized by polymethylmethacrylate (PMMA were investigated by varying concentrations of PMMA in the polymer solutions. Stability tests were performed over a period of time using modulated surface photovoltage (SPV spectroscopy, X-ray diffraction (XRD, and photoluminescence (PL measurements. The XRD patterns confirm the tetragonal structure of the deposited CH3NH3PbI3 for every concentration of PMMA. Furthermore, CH3NH3PbI3 coated with 40 mg/mL of PMMA did not show any impurity phase even after storage in air for 43 days. The Tauc gap (ETauc determined on the basis of the in-phase SPV spectra was found in the range from 1.585 to 1.62 eV for the samples stored during initial days, but shifted towards lower energies as the storage time increased. This can be proposed to be due to different chemical reactions between CH3NH3PbI3/PMMA interfaces and air. PL intensity increased with increasing concentration of PMMA except for the perovskite coated with 40 mg/mL of PMMA. PL quenching in the perovskite coated with 40 mg/mL of PMMA can be interpreted as fast electron transfer towards the substrate in the sample. This study shows that, with an optimum concentration of PMMA coating on CH3NH3PbI3, the lifetime and hence stability on electrical and structural behavior of CH3NH3PbI3 is improved.

Dendrimer ligands-capped CH3NH3PbBr3 perovskite nanocrystals with delayed halide exchange and record stability against both moisture and water

Science.gov (United States)

Xu, Yiren; Xu, Shuhong; Shao, Haibao; Jiang, Han; Cui, Yiping; Wang, Chunlei

2018-06-01

CH3NH3PbBr3 perovskite nanocrystals (NCs) suffer from poor stability because of their high sensitivity to environmental moisture and water. To solve this problem, previous works mainly focus on embedding perovskite NCs into water-resistant matrix to form large composites (size of microns or larger). As an alternative solution without serious changing of NC size, enhancing the stability of perovskite NCs themselves by ligand engineering is rarely reported. In this work, we used hyperbranched polyamidoamine (PAMAM) dendrimers with two different generations (G0 and G4) to synthesize CH3NH3PbBr3 perovskite NCs with high photoluminescence (PL) quantum yields (QY) above 70% and a new record stability. A novel dendrimers generation-dependent stability of perovskite NCs was observed. The water-resistance time is 18 h (27 h) for perovskite NCs capped by G0 (G4) generation of PAMAM, which is 7 times (11 times) longer than that of traditional oleic acid-capped NCs. Similar PAMAM generation-related stability is also observed in moisture-resistance tests. The stability time against moisture is 500 h (800 h) for G0 (G4) generation of PAMAM-capped perovskite NCs, which is a new record stability time against moisture for CH3NH3PbBr3 perovskite NCs. In addition, our results also indicate that PAMAM ligands outside perovskite NCs can dramatically slow down the speed of halide exchange. Even for the mixture of perovskite NCs with two different halide composition, the original luminescence properties of PAMAM-capped perovskite NCs can retain after mixing. In view of slow halide exchange speed, excellent water and moisture stability, PAMAM dendrimers-capped perovskite NCs and their mixture are available as color conversion single layer in fabrication of light-emitting diodes (LED).

Dendrimer ligands-capped CH3NH3PbBr3 perovskite nanocrystals with delayed halide exchange and record stability against both moisture and water.

Science.gov (United States)

Xu, Yiren; Xu, Shuhong; Shao, Haibao; Jiang, Han; Cui, Yiping; Wang, Chunlei

2018-06-08

CH 3 NH 3 PbBr 3 perovskite nanocrystals (NCs) suffer from poor stability because of their high sensitivity to environmental moisture and water. To solve this problem, previous works mainly focus on embedding perovskite NCs into water-resistant matrix to form large composites (size of microns or larger). As an alternative solution without serious changing of NC size, enhancing the stability of perovskite NCs themselves by ligand engineering is rarely reported. In this work, we used hyperbranched polyamidoamine (PAMAM) dendrimers with two different generations (G0 and G4) to synthesize CH 3 NH 3 PbBr 3 perovskite NCs with high photoluminescence (PL) quantum yields (QY) above 70% and a new record stability. A novel dendrimers generation-dependent stability of perovskite NCs was observed. The water-resistance time is 18 h (27 h) for perovskite NCs capped by G0 (G4) generation of PAMAM, which is 7 times (11 times) longer than that of traditional oleic acid-capped NCs. Similar PAMAM generation-related stability is also observed in moisture-resistance tests. The stability time against moisture is 500 h (800 h) for G0 (G4) generation of PAMAM-capped perovskite NCs, which is a new record stability time against moisture for CH 3 NH 3 PbBr 3 perovskite NCs. In addition, our results also indicate that PAMAM ligands outside perovskite NCs can dramatically slow down the speed of halide exchange. Even for the mixture of perovskite NCs with two different halide composition, the original luminescence properties of PAMAM-capped perovskite NCs can retain after mixing. In view of slow halide exchange speed, excellent water and moisture stability, PAMAM dendrimers-capped perovskite NCs and their mixture are available as color conversion single layer in fabrication of light-emitting diodes (LED).

Homogeneous Emission Line Broadening in the Organo Lead Halide Perovskite CH3NH3PbI3-xClx.

Science.gov (United States)

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

2014-04-17

The organic-inorganic hybrid perovskites methylammonium lead iodide (CH3NH3PbI3) and the partially chlorine-substituted mixed halide CH3NH3PbI3-xClx emit strong and broad photoluminescence (PL) around their band gap energy of ∼1.6 eV. However, the nature of the radiative decay channels behind the observed emission and, in particular, the spectral broadening mechanisms are still unclear. Here we investigate these processes for high-quality vapor-deposited films of CH3NH3PbI3-xClx using time- and excitation-energy dependent photoluminescence spectroscopy. We show that the PL spectrum is homogenously broadened with a line width of 103 meV most likely as a consequence of phonon coupling effects. Further analysis reveals that defects or trap states play a minor role in radiative decay channels. In terms of possible lasing applications, the emission spectrum of the perovskite is sufficiently broad to have potential for amplification of light pulses below 100 fs pulse duration.

Mixed adenine/guanine quartets with three trans-a2 Pt(II) (a=NH(3) or MeNH(2)) cross-links: linkage and rotational isomerism, base pairing, and loss of NH(3).

Science.gov (United States)

Albertí, Francisca M; Rodríguez-Santiago, Luis; Sodupe, Mariona; Mirats, Andrea; Kaitsiotou, Helena; Sanz Miguel, Pablo J; Lippert, Bernhard

2014-03-17

Of the numerous ways in which two adenine and two guanines (N9 positions blocked in each) can be cross-linked by three linear metal moieties such as trans-a2 Pt(II) (with a=NH3 or MeNH2 ) to produce open metalated purine quartets with exclusive metal coordination through N1 and N7 sites, one linkage isomer was studied in detail. The isomer trans,trans,trans-[{Pt(NH3 )2 (N7-9-EtA-N1)2 }{Pt(MeNH2 )2 (N7-9-MeGH)}2 ][(ClO4 )6 ]⋅3H2 O (1) (with 9-EtA=9-ethyladenine and 9-MeGH=9-methylguanine) was crystallized from water and found to adopt a flat Z-shape in the solid state as far as the trinuclear cation is concerned. In the presence of excess 9-MeGH, a meander-like construct, trans,trans,trans-[{Pt(NH3 )2 (N7-9-EtA-N1)2 }{Pt(MeNH2 )2 (N7-9-MeGH)2 }][(ClO4 )6 ]⋅[(9-MeGH)2 ]⋅7 H2 O (2) is formed, in which the two extra 9-MeGH nucleobases are hydrogen bonded to the two terminal platinated guanine ligands of 1. Compound 1, and likewise the analogous complex 1 a (with NH3 ligands only), undergo loss of an ammonia ligand and formation of NH4 (+) when dissolved in [D6 ]DMSO. From the analogy between the behavior of 1 and 1 a it is concluded that a NH3 ligand from the central Pt atom is lost. Addition of 1-methylcytosine (1-MeC) to such a DMSO solution reveals coordination of 1-MeC to the central Pt. In an analogous manner, 9-MeGH can coordinate to the central Pt in [D6 ]DMSO. It is proposed that the proton responsible for formation of NH4 (+) is from one of the exocyclic amino groups of the two adenine bases, and furthermore, that this process is accompanied by a conformational change of the cation from Z-form to U-form. DFT calculations confirm the proposed mechanism and shed light on possible pathways of this process. Calculations show that rotational isomerism is not kinetically hindered and that it would preferably occur previous to the displacement of NH3 by DMSO. This displacement is the most energetically costly step, but it is compensated by the proton

First principles investigation of half-metallicity and spin gapless semiconductor in CH3NH3Cr x Pb1- x I3 mixed perovskites

Science.gov (United States)

Huang, H. M.; Zhu, Z. W.; Zhang, C. K.; He, Z. D.; Luo, S. J.

2018-04-01

The structural, electronic and magnetic properties of organic-inorganic hybrid mixed perovskites CH3NH3Cr x Pb1- x I3 ( x = 0.25, 0.50, 0.75, 1.00) in cubic, tetragonal and orthorhombic phases have been investigated by first-principles calculation. The results indicate that the tetragonal CH3NH3Cr0.75Pb0.25I3 is a spin gapless semiconductor with Curie temperature of 663 K estimated using mean field approximation. All other CH3NH3Cr x Pb1- x I3 mixed perovskites are half-metallic ferromagnets together with 100% spin polarization, and their total magnetic moment are 4.00, 8.00, 12.00 and 16.00 µB per unit cell for x = 0.25, 0.50, 0.75 and 1.00, respectively. The effect of , and orientation of organic cation CH3NH3 + on the electronic properties of CH3NH3Cr0.50Pb0.50I3 was investigated. The results show that the CH3NH3 + in different orientations have a slight effect on the lattice constants, the energy gap in minority-spin states, half-metallic gap, local magnetic moment, and Curie temperature.

Towards validation of ammonia (NH3) measurements from the IASI satellite

Science.gov (United States)

Van Damme, M.; Clarisse, L.; Dammers, E.; Liu, X.; Nowak, J. B.; Clerbaux, C.; Flechard, C. R.; Galy-Lacaux, C.; Xu, W.; Neuman, J. A.; Tang, Y. S.; Sutton, M. A.; Erisman, J. W.; Coheur, P. F.

2015-03-01

Limited availability of ammonia (NH3) observations is currently a barrier for effective monitoring of the nitrogen cycle. It prevents a full understanding of the atmospheric processes in which this trace gas is involved and therefore impedes determining its related budgets. Since the end of 2007, the Infrared Atmospheric Sounding Interferometer (IASI) satellite has been observing NH3 from space at a high spatio-temporal resolution. This valuable data set, already used by models, still needs validation. We present here a first attempt to validate IASI-NH3 measurements using existing independent ground-based and airborne data sets. The yearly distributions reveal similar patterns between ground-based and space-borne observations and highlight the scarcity of local NH3 measurements as well as their spatial heterogeneity and lack of representativity. By comparison with monthly resolved data sets in Europe, China and Africa, we show that IASI-NH3 observations are in fair agreement, but they are characterized by a smaller variation in concentrations. The use of hourly and airborne data sets to compare with IASI individual observations allows investigations of the impact of averaging as well as the representativity of independent observations for the satellite footprint. The importance of considering the latter and the added value of densely located airborne measurements at various altitudes to validate IASI-NH3 columns are discussed. Perspectives and guidelines for future validation work on NH3 satellite observations are presented.

THE KINETICS OF NH(4)+ AND NO3(-) UPTAKE BY DOUGLAS-FIR FROM SINGLE N-SOLUTIONS AND FROM SOLUTIONS CONTAINING BOTH NH(4)+ AND NO3(-)

NARCIS (Netherlands)

KAMMINGAVANWIJK, C; PRINS, HBA

The kinetics of NH4+ and NO3- uptake in young Douglas fir trees (Pseudotsuga menziesii [Mirb.] Franco) were studied in solutions, containing either one or both N species. Using solutions containing a single N species, the V(max) of NH4+ uptake was higher than that of NO3- uptake. The K(m) of NH4+

Appropriate NH4+: NO3- ratio improves low light tolerance of mini Chinese cabbage seedlings.

Science.gov (United States)

Hu, Linli; Liao, Weibiao; Dawuda, Mohammed Mujitaba; Yu, Jihua; Lv, Jian

2017-01-23

In northwest of China, mini Chinese cabbage (Brassica pekinensis) is highly valued by consumers, and is widely cultivated during winter in solar-greenhouses where low light (LL) fluence (between 85 and 150 μmol m -2 s -1 in day) is a major abiotic stress factor limiting plant growth and crop productivity. The mechanisms with which various NH 4 + : NO 3 - ratios affected growth and photosynthesis of mini Chinese cabbage under normal (200 μmol m -2 s -1 ) and low (100 μmol m -2 s -1 ) light conditions was investigated. The four solutions with different ratios of NH 4 + : NO 3 - applied were 0:100, 10:90, 15:85 and 25:75 with the set up in a glasshouse in hydroponic culture. The most appropriate NH 4 + : NO 3 - ratio that improved the tolerance of mini Chinese cabbage seedlings to LL was found in our current study. Under low light, the application of NH 4 + : NO 3 - (10:90) significantly stimulated growth compared to only NO 3 - by increasing leaf area, canopy spread, biomass accumulation, and net photosynthetic rate. The increase in net photosynthetic rate was associated with an increase in: 1) maximum and effective quantum yield of PSII; 2) activities of Calvin cycle enzymes; and 3) levels of mRNA relative expression of several genes involved in Calvin cycle. In addition, glucose, fructose, sucrose, starch and total carbohydrate, which are the products of CO 2 assimilation, accumulated most in the cabbage leaves that were supplied with NH 4 + : NO 3 - (10:90) under LL condition. Low light reduced the carbohydrate: nitrogen (C: N) ratio while the application of NH 4 + : NO 3 - (10:90) alleviated the negative effect of LL on C: N ratio mainly by increasing total carbohydrate contents. The application of NH 4 + :NO 3 - (10:90) increased rbcL, rbcS, FBA, FBPase and TK expression and/or activities, enhanced photosynthesis, carbohydrate accumulation and improved the tolerance of mini Chinese cabbage seedlings to LL. The results of this study would provide

Thermodynamic modeling of NH_3-CO_2-SO_2-K_2SO_4-H_2O system for combined CO_2 and SO_2 capture using aqueous NH_3

International Nuclear Information System (INIS)

Qi, Guojie; Wang, Shujuan

2017-01-01

Highlights: • A new application of aqueous NH_3 based combined CO_2 and SO_2 process was proposed. • A thermodynamic model simulated the heat of absorption and the K_2SO_4 precipitation. • The CO_2 content can be regenerated in a stripper with lower heat of desorption. • The SO_2 content can be removed by K_2SO_4 precipitation from the lean NH_3 solvent. - Abstract: A new application of aqueous NH_3 based post-combustion CO_2 and SO_2 combined capture process was proposed to simultaneously capture CO_2 and SO_2, and remove sulfite by solid (K_2SO_4) precipitation method. The thermodynamic model of the NH_3-CO_2-SO_2-K_2SO_4-H_2O system for the combined CO_2 and SO_2 capture process was developed and validated in this work to analyze the heat of CO_2 and SO_2 absorption in the NH_3-CO_2-SO_2-H_2O system, and the K_2SO_4 precipitation characteristics in the NH_3-CO_2-SO_2-K_2SO_4-H_2O system. The average heat of CO_2 absorption in the NH_3-CO_2-H_2O system at 40 °C is around −73 kJ/mol CO_2 in 2.5 wt% NH_3 with CO_2 loading between 0.2 and 0.5 C/N. The average heat of SO_2 absorption in the NH_3-SO_2-H_2O system at 40 °C is around −120 kJ/mol SO_2 in 2.5 wt% NH_3 with SO_2 loading between 0 and 0.5 S/N. The average heat of CO_2 absorption in the NH_3-CO_2-SO_2-H_2O system at 40 °C is 77, 68, and 58 kJ/mol CO_2 in 2.5 wt% NH_3 with CO_2 loading between 0.2 and 0.5 C/N, when SO_2 loading is 0, 0.1, 0.2 S/N, respectively. The solubility of K_2SO_4 increases with temperature, CO_2 and SO_2 loadings, but decreases with NH_3 concentration in the CO_2 and SO_2 loaded aqueous NH_3. The thermodynamic evaluation indicates that the combined CO_2 and SO_2 capture process could employ the typical absorption/regeneration process to simultaneously capture CO_2 and SO_2 in an absorber, thermally desorb CO_2 in a stripper, and feasibly remove sulfite (oxidized to sulfate) content by precipitating K_2SO_4 from the lean NH_3 solvent after the lean/rich heat exchanger.

Infrared spectra of the ammonium ion in ammonium metavanadate NH 4VO 3

Science.gov (United States)

de Waal, D.; Heyns, A. M.; Range, K.-J.; Eglmeier, C.

The ND stretching modes of isotopically dilute NH 3D + ions in NH 4VO 3 are in agreement with the predicted splitting into C s, C s and C1(2) components under C s site symmetry for the NH +4 ion. The three bands observed represent the three NH bonding distances in the crystal, and the position, shape and low temperature behaviour of each band confirms the existence of two types of hydrogen bonding in NH 4VO 3. The low temperature infrared modes of NH +4 and ND +4 in NH 4VO 3 and ND 4VO 3, respectively, can be assigned under space group Pbcm. Temperature dependence of these modes also reflects the presence of both normal and bifurcated hydrogen bonds in NH 4VO 3.

Wet Mechanochemical Processing of Celestine using (NH42CO3

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Deniz Bingöl

2017-06-01

Full Text Available In this study, traditional (univariate method of processing to the wet mechanochemical treatment were applied to obtain both SrCO3 and (NH42SO4 from celestite (SrSO4-(NH42CO3-H2O mixtures in a planetary ball mill. X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and chemical analysis were used to analyze products formed during wet milling. A hydrometallurgical process was carried out to examine milling time, ball to grinding material mass ratio, (NH42CO3 to SrSO4 mole ratio and rotational speed of the mill in a planetary mill. Under optimum conditions, a conversion approaching 100% of SrCO3 was obtained.

Effects of atmospheric ammonia (NH{sub 3}) on terrestrial vegetation: a review

Energy Technology Data Exchange (ETDEWEB)

Krupa, S.V

2003-07-01

A review of atmospheric ammonia (NH{sub 3}) and ammonium (NH{sub 4}{sup +}) deposition and their effects on plants. - At the global scale, among all N (nitrogen) species in the atmosphere and their deposition on to terrestrial vegetation and other receptors, NH{sub 3} (ammonia) is considered to be the foremost. The major sources for atmospheric NH{sub 3} are agricultural activities and animal feedlot operations, followed by biomass burning (including forest fires) and to a lesser extent fossil fuel combustion. Close to its sources, acute exposures to NH{sub 3} can result in visible foliar injury on vegetation. NH{sub 3} is deposited rapidly within the first 4-5 km from its source. However, NH{sub 3} is also converted in the atmosphere to fine particle NH{sub 4}{sup +} (ammonium) aerosols that are a regional scale problem. Much of our current knowledge of the effects of NH{sub 3} on higher plants is predominantly derived from studies conducted in Europe. Adverse effects on vegetation occur when the rate of foliar uptake of NH{sub 3} is greater than the rate and capacity for in vivo detoxification by the plants. Most to least sensitive plant species to NH{sub 3} are native vegetation > forests > agricultural crops. There are also a number of studies on N deposition and lichens, mosses and green algae. Direct cause and effect relationships in most of those cases (exceptions being those locations very close to point sources) are confounded by other environmental factors, particularly changes in the ambient SO{sub 2} (sulfur dioxide) concentrations. In addition to direct foliar injury, adverse effects of NH{sub 3} on higher plants include alterations in: growth and productivity, tissue content of nutrients and toxic elements, drought and frost tolerance, responses to insect pests and disease causing microorganisms (pathogens), development of beneficial root symbiotic or mycorrhizal associations and inter species competition or biodiversity. In all these cases, the joint

[Effect of NH4(+) -N/NO3(-)-N ratio in applied supplementary fertilizer on nitrogen metabolism and main chemical composition of Pinellia ternata].

Science.gov (United States)

Hu, Long-Jiao; Wang, Kang-Cai; Li, Can-Wen

2013-07-01

To study the effect of nitrogen forms on nitrogen metabolism and main chemical composition of Pinellia ternate. Through the soilless cultivation experiment and based at the same nitrogen level and different NH4(+) -N/NO3(-) -N ratios, nitrate reductase (NR) activity, glutamine synthetase (GS) activity, the content of nitrate nitrogen and ammonium nitrogen in different parts of P. ternate were determined. The contents of total alkaloid, free total organic acids and guanosine in the tuber were determined. The yield of bulbil and tuber was calculated. The test results showed that, with the NH4(+) -N/NO3(-) -N ratio increasing, the activity of nitrate reductase decreased, the content of nitrate nitrogen in the leaves, petioles and tuber increasing initially, then decreased, and the content of nitrate nitrogen in the root decreased. Meanwhile, with the NH4(+) -N/NO3(-) -N ratio increasing, the activity of glutamine synthetase in the leaves, petioles and root increased, the activity of glutamine synthetase in the tuber increasing initially, then decreased. The contents of ammonium nitrogen in the leaves, tuber and root increased initially, then decreased, and the contents of ammonium nitrogen in the petioles increased with the NH4(+)(-N/NO3(-)-N ratio increasing. The yield of bulbil and tuber were the highest at the NH4(+)-N/NO3(-) -N ratio of 75: 25. The content of total alkaloid and guanosine in the tuber were the highest at the NH4(+)-N/NO3(-) -N ratio of 0: 100, and the contents were 0.245% and 0.0197% respectively. With the NH4(+)-N/NO3(-) -N ratio of 50: 50, the content of free total organic acids was the highest, it reached 0.7%, however, the content of free total organic acids was the lowest at the NH4(+) -N/NO3(-) -N ratio of 0: 100. Nitrogen fertilization significant influences the nitrogen metabolism, the yield and main chemical composition of P. ternate.

NO3-/NH4+ proportions affect cadmium bioaccumulation and tolerance of tomato.

Science.gov (United States)

Nogueirol, Roberta Corrêa; Monteiro, Francisco Antonio; de Souza Junior, João Cardoso; Azevedo, Ricardo Antunes

2018-05-01

With the growth of the world population, cadmium (Cd) concentration in the environment has increased considerably as a result of human activities such as foundry, battery disposal, mining, application of fertilizers containing toxic elements as impurities, and disposal of metal-containing waste. Higher plants uptake N as ammonium (NH 4 + ), nitrate (NO 3 - ), and many other water-soluble compounds such as urea and amino acids, and nourishing plants with N, providing part of it as NH 4 + , is an interesting alternative to the supply of this nutrient in the exclusive form of NO 3 - under Cd toxicity. The objective was to evaluate the influence of NO 3 - /NH 4 + proportions on the development and tolerance of tomato plants grown under the presence of Cd in the culture medium. The experiment was conducted in a completely randomized block design in a 3 × 3 factorial arrangement consisting of three Cd rates (0, 50, and 100 μmol L -1 ) and three NO 3 - /NH 4 + proportions (100/0, 70/30, and 50/50) in the nutrient solution. To this end, we quantified the responses of the antioxidant enzymatic system and productive and functional changes in Solanum lycopersicum var. esculentum (Calabash Rouge). Shoot biomass production decreased with the maximum Cd rate (100 μmol L -1 ) tested in the growth medium, whereas the NO 3 - /NH 4 + proportions and other Cd rates did not significantly influence this variable. The lowest SPAD values were observed at the 100/0 NO 3 - /NH 4 + proportion and in plants exposed to Cd. The largest accumulation of the metal occurred in the shoots at the NO 3 - /NH 4 + proportion of 70/30 and at 100 μmol L -1 Cd and in the roots at 100/0 NO 3 - /NH 4 + and with 50 and 100 μmol L -1 Cd. The concentration and accumulation of NO 3 - were highest at the NO 3 - /NH 4 + proportion of 100/0 in the shoots and at 50/50 NO 3 - /NH 4 + in the roots, whereas for NH 4 + , values were higher as the proportion of N supplied in the form of NH 4 + was

CH3NH3PbCl3 Single Crystals: Inverse Temperature Crystallization and Visible-Blind UV-Photodetector

KAUST Repository

Maculan, Giacomo; Sheikh, Arif D.; Abdelhady, Ahmed L.; Saidaminov, Makhsud I.; Haque, Mohammed; Banavoth, Murali; Alarousu, Erkki; Mohammed, Omar F.; Wu, Tao; Bakr, Osman

2015-01-01

a new method of sizeable CH3NH3PbCl3 single crystal growth based on retrograde solubility behavior of hybrid perovskites. We show, for the first time, the energy band structure, charge-carrier recombination and transport properties of single crystal

Mechanical response of CH3NH3PbI3 nanowires

Science.gov (United States)

Ćirić, L.; Ashby, K.; Abadie, T.; Spina, M.; Duchamp, M.; Náfrádi, B.; Kollár, M.; Forró, L.; Horváth, E.

2018-03-01

We report a systematic study of the mechanical response of methylammonium lead triiodide CH3NH3PbI3 nanowires by employing bending measurements using atomic force microscope on suspended wires over photo-lithographically patterned channels. Force-deflection curves measured at room temperature give a Young's modulus between 2 and 14 GPa. This broad range of values is attributed to the variations in the microcrystalline texture of halide perovskite nanowires. The mechanical response of a highly crystalline nanowire is linear with force and has a brittle character. The braking modulus of 48 ± 20 MPa corresponds to 100 μm of radius of curvature of the nanowires, rendering them much better structures for flexible devices than spin coated films. The measured moduli decrease rapidly if the NW is exposed to water vapor.

Rotational spectrum of the NH3–He van der Waals complex

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Surin L.

2017-01-01

Full Text Available The interaction between ammonia and helium has attracted considerable interest over many years, partly because of the observation of interstellar ammonia. The rate coefficients of NH3–He scattering are an important ingredient for numerical modeling of astrochemical environments. Another, though quite different application in which the NH3–He interaction can play an important role is the doping of helium clusters with NH3 molecules to perform high-resolution spectroscopy. Such experiments are directed on the detection of non-classical response of molecular rotation in helium clusters addressing fundamental questions related to the microscopic nature of superfluidity. High-resolution spectroscopy on the NH3–He complex is an important tool for increasing our understanding of intermolecular forces between NH3 and He.

CH3NH3PbCl3 Single Crystals: Inverse Temperature Crystallization and Visible-Blind UV-Photodetector

KAUST Repository

Maculan, Giacomo

2015-09-02

Single crystals of hybrid perovskites have shown remarkably improved physical properties compared to their polycrystalline film counterparts, underscoring their importance in the further development of advanced semiconductor devices. Here we present a new method of sizeable CH3NH3PbCl3 single crystal growth based on retrograde solubility behavior of hybrid perovskites. We show, for the first time, the energy band structure, charge-carrier recombination and transport properties of single crystal CH3NH3PbCl3. The chloride-based perovskite crystals exhibit trap-state density, charge carriers concentration, mobility and diffusion length comparable with the best quality crystals of methylammonium lead iodide or bromide perovskites reported so far. The high quality of the crystal along with its suitable optical bandgap enabled us to design and build an efficient visible-blind UV-photodetector, demonstrating the potential of this material to be employed in optoelectronic applications.

Structural study on cubic-tetragonal transition of CH3NH3PbI3

International Nuclear Information System (INIS)

Kawamura, Yukihiko; Mashiyama, Hiroyuki; Hasebe, Katsuhiko

2002-01-01

The cubic-tetragonal phase transition of CH 3 NH 3 PbI 3 was investigated by single crystal X-ray diffractometry. The crystal structure was refined at five temperatures in the tetragonal phase. The PbI 6 octahedron rotates around the c-axis alternatively to construct the SrTiO 3 -type tetragonal structure. A methylammonium ion is partially ordered; 24 disordered states in the cubic phase are reduced to 8. With decreasing temperature, the rotation angle of the octahedron increases monotonically, which indicates it is an order parameter of the cubic-tetragonal transition. (author)

Carrier injection and recombination processes in perovskite CH3NH3PbI3 solar cells studied by electroluminescence spectroscopy

Science.gov (United States)

Handa, Taketo; Okano, Makoto; Tex, David M.; Shimazaki, Ai; Aharen, Tomoko; Wakamiya, Atsushi; Kanemitsu, Yoshihiko

2016-02-01

Organic-inorganic hybrid perovskite materials, CH3NH3PbX3 (X = I and Br), are considered as promising candidates for emerging thin-film photovoltaics. For practical implementation, the degradation mechanism and the carrier dynamics during operation have to be clarified. We investigated the degradation mechanism and the carrier injection and recombination processes in perovskite CH3NH3PbI3 solar cells using photoluminescence (PL) and electroluminescence (EL) imaging spectroscopies. By applying forward bias-voltage, an inhomogeneous distribution of the EL intensity was clearly observed from the CH3NH3PbI3 solar cells. By comparing the PL- and EL-images, we revealed that the spatial inhomogeneity of the EL intensity is a result of the inhomogeneous luminescence efficiency in the perovskite layer. An application of bias-voltage for several tens of minutes in air caused a decrease in the EL intensity and the conversion efficiency of the perovskite solar cells. The degradation mechanism of perovskite solar cells under bias-voltage in air is discussed.

O3 fast and simple treatment-enhanced p-doped in Spiro-MeOTAD for CH3NH3I vapor-assisted processed CH3NH3PbI3 perovskite solar cells

Institute of Scientific and Technical Information of China (English)

En-Dong Jia; Xi Lou; Chun-Lan Zhou; Wei-Chang Hao; Wen-Jing Wang

2017-01-01

We demonstrate a simple and fast post-deposition treatment with high process compatibility on the hole transport material (HTM) Spiro-MeOTAD in vapor-assisted solution processed methylammonium lead triiodide (CH3NH3PbI3)-based solar cells.The prepared Co-doped p-type Spiro-MeOTAD films are treated by O3 at room temperature for 5 min,10 min,and 20 min,respectively,prior to the deposition of the metal electrodes.Compared with the traditional oxidation of Spiro-MeOTAD films overnight in dry air,our fast O3 treatment of HTM at room temperature only needs just 10 min,and a relative 40.3％ increment in the power conversion efficiency is observed with respect to the result of without-treated perovskite solar cells.This improvement of efficiency is mainly attributed to the obvious increase of the fill factor and short-circuit current density,despite a slight decrease in the open-circuit voltage.Ultraviolet photoelectron spectroscopy (UPS) and Hall effect measurement method are employed in our study to determine the changes of properties after O3 treatment in HTM.It is found that after the HTM is exposed to O3,its p-type doping level is enhanced.The enhancement of conductivity and Hall mobility of the film,resulting from the improvement in p-doping level of HTM,leads to better performances of perovskite solar cells.Best power conversion efficiencies (PCEs) of 13.05％ and 16.39％ are achieved with most properly optimized HTM via CH3NH3I vapor-assisted method and traditional single-step method respectively.

Preparation of planar CH3NH3PbI3 thin films with controlled size using 1-ethyl-2-pyrrolidone as solvent

International Nuclear Information System (INIS)

Hao, Qiuyan; Chu, Yixia; Zheng, Xuerong; Liu, Zhenya; Liang, Liming; Qi, Jiakun; Zhang, Xin; Liu, Gang; Liu, Hui; Chen, Hongjian; Liu, Caichi

2016-01-01

Recently, planar perovskite solar cells based on CH 3 NH 3 PbI 3 have attracted many researcher's interest due to their unique advantages such as simple cell architecture, easy fabrication and potential multijunction construction comparing to the initial mesoporous structure. However, the preparation of planar perovskite films with high quality is still in challenge. In this paper, we developed a vapor-assisted solution process using a novel and green solvent of 1-Ethyl-2-pyrrolidone (NEP) instead of the traditional N, N-dimethylformamide (DMF) to construct a high-quality perovskite CH 3 NH 3 PbI 3 thin film with pure phase, high compactness, small surface roughness and controlled size. The phase evolution and growth mechanism of the perovskite films are also discussed. Utilizing the NEP of low volatility and moderate boiling point as solvent, we dried the PbI 2 -NEP precursor films at different temperature under vacuum and then obtained PbI 2 thin films with different crystalline degree from amorphous to highly crystalline. The perovskite films with crystal size ranged from hundreds of nanometers to several micrometers can be prepared by reacting the PbI 2 films of different crystalline degree with CH 3 NH 3 I vapor. Moreover, planar-structured solar cells combining the perovskite film with TiO 2 and spiro-OMeTAD as the electron and holes transporting layer achieves a power conversion efficiency of 10.2%. - Highlights: • A novel and green solvent of 1-Ethyl-2-pyrrolidone (NEP) was used to construct high-quality perovskite CH 3 NH 3 PbI 3 thin film. • The CH 3 NH 3 PbI 3 grain with different sizes ranged from hundreds of nanometers to several micrometers can be obtained. • Planar-structured perovskite CH 3 NH 3 PbI 3 solar cells using NEP as solvent achieves a power conversion efficiency of 10.2%.

A Low Temperature Infrared Study Of Deuterated NH4VO3

Science.gov (United States)

de Waal, D.; Heyns, A. M.

1989-12-01

The existence of (NH4)2V6016 as an intermediate in the thermal decomposition of NH4V03 to V205 has been confirmed by vibrational spectroscopy, resulting in the following reaction in an open systeml: NH4VO3 1 bar, air, 50-200°C/(1) (NH4)2v6o16 1 bar, air, ca.360°C/(2) V205 The kinetics of reaction (1) was studied by means of Raman spectroscopy, and structural information on NH4V03 and (N114)V60 16 was required to obtain an accurate description of the reaction mechanism2. Information on the site symmetry of an ammonium ion and hydrogen bonding in a crystal can be obtained by considering the infrared spectra of isotopically dilute NH3D+ ions in the lattice at liquid nitrogen temperatures3, especially as the position of hydrogen atoms in (NHO2V6016 could not be determined by X-ray methods.

Effect of Different CH3NH3PbI3 Morphologies on Photovoltaic Properties of Perovskite Solar Cells

Science.gov (United States)

Chen, Lung-Chien; Lee, Kuan-Lin; Wu, Wen-Ti; Hsu, Chien-Feng; Tseng, Zong-Liang; Sun, Xiao Hong; Kao, Yu-Ting

2018-05-01

In this study, the perovskite layers were prepared by two-step wet process with different CH3NH3I (MAI) concentrations. The cell structure was glass/FTO/TiO2-mesoporous/CH3NH3PbI3 (MAPbI3)/spiro-OMeTAD/Ag. The MAPbI3 perovskite films were prepared using high and low MAI concentrations in a two-step process. The perovskite films were optimized at different spin coating speed and different annealing temperatures to enhance the power conversion efficiency (PCE) of perovskite solar cells. The PCE of the resulting device based on the different perovskite morphologies was discussed. The PCE of the best cell was up to 17.42%, open circuit voltage of 0.97 V, short current density of 24.06 mA/cm2, and fill factor of 0.747.

Single-crystal perovskite CH3NH3PbBr3 prepared by cast capping method for light-emitting diodes

Science.gov (United States)

Nguyen, Van-Cao; Katsuki, Hiroyuki; Sasaki, Fumio; Yanagi, Hisao

2018-04-01

In this study, electroluminescence from single crystals of CH3NH3PbBr3 perovskite is explored. The cast capping method was applied to fabricate simple devices with an ITO/CH3NH3PbBr3/ITO structure. The devices showed a low operation voltage of 2 V and a pure green luminescence with full width at half maximum of ∼20 nm. However, the emission occurring at the crystal edges demonstrated blinking with a subsecond time interval, which is similar to the previously reported photoluminescence behavior of nanocrystal perovskites. This electroluminescence blinking may provide new insight into the recombination processes depending on the carrier traps and defects of emission layers in perovskite light-emitting devices.

First principles study of NH3 molecular adsorption on LiH (100) surfaces

International Nuclear Information System (INIS)

Lu Xiaoxia; Chen Yuhong; Dong Xiao

2012-01-01

The adsorption of NH 3 on LiH (100) crystal surfaces was studied by first principles method. The preferred adsorption sites, adsorption energy, dissociation energy and electronic structure of the LiH (100)/NH 3 systems were calculated separately. It is found that chemical adsorption happened mainly when NH 3 molecules are on the LiH (100) crystal surfaces. When NH 3 is adsorbed on the Li top site, NH 2 is formed on the LiH (100) crystal surfaces after loss of H atom, the calculated adsorption energy, 0.511 eV, belongs to strong chemical adsorption, then the interaction is strongest. The interaction between NH 2 and the neighboring Li, H are ionic. The covalent bonds are formed between N and H atoms in NH 2 . One H 2 molecule is formed by another H atom in NH 3 and H atom from LiH (100) crystal sur- faces. The covalent bonds are formed between H and H atoms in H 2 . (authors)

A novel method of simultaneous NH4+ and NO3- removal using Fe cycling as a catalyst: Feammox coupled with NAFO.

Science.gov (United States)

Li, Xiang; Yuan, Yan; Huang, Yong; Liu, Heng-Wei; Bi, Zhen; Yuan, Yi; Yang, Peng-Bin

2018-08-01

The feasibility of using Feammox coupled with nitrate-dependent Fe(II) oxidizing (NAFO) to cause the simultaneous conversion of NH 4 + and NO 3 - was explored by inoculation with Feammox sludge and the use Fe cycling as catalyst. After 61days operation, the simultaneous conversion of NO 3 - and NH 4 + occurred with the presence of interconversion between Fe(III) and Fe(II). The conversion ratio of NH 4 + to NO 3 - stabilized at 0.9-1. The results of isotopic tracing and microbial diversity analysis indicated that NH 4 + was first oxidized to NO 2 - by Fe(III), then NO 3 - was reduced to NO 2 - and N 2 by the Fe(II) produced in Feammox process, and finally, the NO 2 - produced in NAFO process underwent an Anammox process with the remaining NH 4 + to yield N 2 . The results showed the simultaneous continuous conversion process of NO 3 - and NH 4 + with limited Fe as a catalyst was a coupled process of Feammox, Anammox, and NAFO under the anaerobic conditions. Copyright © 2018 Elsevier B.V. All rights reserved.

Using Low Temperature Photoluminescence Spectroscopy to Investigate CH3NH3PbI3 Hybrid Perovskite Degradation

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Khaoula Jemli

2016-07-01

Full Text Available Investigating the stability and evaluating the quality of the CH3NH3PbI3 perovskite structures is quite critical both to the design and fabrication of high-performance perovskite devices and to fundamental studies of the photophysics of the excitons. In particular, it is known that, under ambient conditions, CH3NH3PbI3 degrades producing some PbI2. We show here that low temperature Photoluminescence (PL spectroscopy is a powerful tool to detect PbI2 traces in hybrid perovskite layers and single crystals. Because PL spectroscopy is a signal detection method on a black background, small PbI2 traces can be detected, when other methods currently used at room temperature fail. Our study highlights the extremely high stability of the single crystals compared to the thin layers and defects and grain boundaries are thought to play an important role in the degradation mechanism.

Effects of GeI2 or ZnI2 addition to perovskite CH3NH3PbI3 photovoltaic devices

Science.gov (United States)

Tanaka, Hiroki; Ohishi, Yuya; Oku, Takeo

2018-01-01

CH3NH3PbI3 added with GeI2 or ZnI2 perovskite photovoltaic devices were fabricated characterized. The surface coverages of the perovskite layers were improved by the addition of GeI2 or ZnI2. Formation of PbI2 observed for the pristine CH3NH3PbI3 was suppressed by the GeI2 or ZnI2 addition, which resulted in the improvement of the conversion efficiencies of the perovskite photovoltaic devices.

Catalysts for selective hydrogenation of furfural derived from the double complex salt [Pd(NH 3 ) 4 ](ReO 4 ) 2 on γ-Al 2 O 3

Energy Technology Data Exchange (ETDEWEB)

Thompson, Simon T.; Lamb, H. Henry

2017-06-01

The double complex salt [Pd(NH3)4](ReO4)2 was employed as precursor of supported bimetallic catalysts for selective hydrogenation of furfural. Direct reduction of [Pd(NH3)4](ReO4)2 on γ-Al2O3 in flowing H2 at 400 °C yields bimetallic nanoparticles 1–2 nm in size that exhibit significant interaction between the metals, as evidenced by temperature-programmed hydride decomposition (complete suppression of β-PdHx formation), extended X-ray absorption fine structure spectroscopy at the Pd K and Re LIII edges (PdRe distance = 2.72 Å), and scanning transmission electron microscopy with energy dispersive X-ray analysis. In contrast, calcination of [Pd(NH3)4](ReO4)2 on γ-Al2O3 at 350 °C in air and subsequent reduction in H2 at 400 °C results in metal segregation and formation of large (>50 nm) supported Pd particles; Re species cover the Pd particles and γ-Al2O3 support. A PdRe 1:2 catalyst prepared by sequential impregnation and calcination using HReO4 and [Pd(NH3)4](NO3)2 has a similar morphology. The catalyst derived by direct reduction of [Pd(NH3)4](ReO4)2 on γ-Al2O3 exhibits remarkably high activity for selective hydrogenation of furfural to furfuryl alcohol (FAL) at 150 °C and 1 atm. Suppression of H2 chemisorption via elimination of Pd threefold sites, as evidenced by CO diffuse-reflectance infrared Fourier transform spectroscopy, correlates with increased FAL selectivity.

NH{sub 4}-doped anodic WO{sub 3} prepared through anodization and subsequent NH{sub 4}OH treatment for water splitting

Energy Technology Data Exchange (ETDEWEB)

Choi, Yong-Wook; Kim, Sunkyu; Seong, Mijeong; Yoo, Hyeonseok; Choi, Jinsub, E-mail: jinsub@inha.ac.kr

2015-01-01

Highlights: • NN{sub 4}-doped WO{sub 3} was successfully fabricated by a wet-based method using ammonium hydroxide (NH{sub 4}OH). • (NH{sub 4}){sub 10}W{sub 12}O{sub 41} phase was formed during the NH{sub 4}OH treatment. • Over-doped NH{sub 4} in WO{sub 3} led to reduced photo-electrochemical performance for OER. • The optimized surface was achieved by thermal treatment of anodic WO{sub 3} with 2 g of NH{sub 4}OH solution. - Abstract: Tungsten trioxide (WO{sub 3}) prepared by anodization of a W foil was doped with NH{sub 4} through NH{sub 4}OH treatment at 450 °C. Since aqueous NH{sub 4}OH was used during doping instead of NH{sub 3} gas, the treatment step does not require complicated annealing facilities. Moreover, the state of doped N is a form of NH{sub 3}-W instead of W{sub 2}N, which lowers the bandgap but increases photocorrosion. We found that incorporation of NH{sub 4} into WO{sub 3} leads to reduction of the bandgap from 2.9 eV to 2.2 eV, regardless of the amount of NH{sub 4}OH treatment, lowering the onset potential and increasing the current density at fixed potential for oxygen evolution reaction under illumination. Scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy were employed to investigate the surface morphologies, crystallinities of tungsten oxides and existence of NH{sub 4} doping, respectively. The bandgap energy was determined by UV–Vis spectroscopy to measure the transmittance and refraction. The water splitting performance of each sample was measured by electrochemical linear sweep voltammetry in a 3-electrode configuration under illumination.

Transparent and flexible photodetectors based on CH3NH3PbI3 perovskite nanoparticles

Science.gov (United States)

Jeon, Young Pyo; Woo, Sung Jun; Kim, Tae Whan

2018-03-01

Transparent and flexible photodetectors (PDs) based on CH3NH3PbI3 perovskite nanoparticles (NPs) were fabricated by using co-evaporation of methyl ammonium iodide and lead iodide. X-ray diffraction patterns and high-resolution transmission electron microscopy images demonstrated the formation of perovskite NPs. The optical transmittance of the perovskite NPs/glass was above 80% over the entire range of visible wavelengths, indicative of high transparency. The PDs based on CH3NH3PbI3 perovskite NPs were sensitive to a broad range of visible light from 450 to 650 nm. The currents in the PDs under exposure to red, green, and blue light-emitting diodes were enhanced to 5, 10, and 20 times that of the PD in the dark, respectively. The rise and the decay times of the PDs were 50 and 120 μs. The current in the perovskite NP PD on a polyethylene terephthalate substrate was enhanced by approximately 69% when the NP PD was exposed to a blue LED emitting at a wavelength of 459 nm. Despite multiple bending, the transparent and flexible PDs based on methyl ammonium iodide and lead iodide NPs showed reproducibility and high stability in performance.

Optical constants of CH3NH3PbBr3 perovskite thin films measured by spectroscopic ellipsometry

KAUST Repository

Alias, Mohd Sharizal; Dursun, Ibrahim; Saidaminov, Makhsud I.; Diallo, Elhadj Marwane; Mishra, Pawan; Ng, Tien Khee; Bakr, Osman; Ooi, Boon S.

2016-01-01

function) of CH3NH3PbBr3 perovskite thin films using spectroscopic ellipsometry. Due to the existence of voids, the refractive index of the thin films is around 8% less than the single crystals counterpart. The energy bandgap is around 2.309 eV as obtained

Effects of N source concentration and NH4(+)/NO3(-) ratio on phenylethanoid glycoside pattern in tissue cultures of Plantago lanceolata L.: a metabolomics driven full-factorial experiment with LC-ESI-MS(3.).

Science.gov (United States)

Gonda, Sándor; Kiss-Szikszai, Attila; Szűcs, Zsolt; Máthé, Csaba; Vasas, Gábor

2014-10-01

Tissue cultures of a medicinal plant, Plantago lanceolata L. were screened for phenylethanoid glycosides (PGs) and other natural products (NPs) with LC-ESI-MS(3). The effects of N source concentration and NH4(+)/NO3(-) ratio were evaluated in a full-factorial (FF) experiment. N concentrations of 10, 20, 40 and 60mM, and NH4(+)/NO3(-) ratios of 0, 0.11, 0.20 and 0.33 (ratio of NH4(+) in total N source) were tested. Several peaks could be identified as PGs, of which, 16 could be putatively identified from the MS/MS/MS spectra. N source concentration and NH4(+)/NO3(-) ratio had significant effects on the metabolome, their effects on individual PGs were different despite these metabolites were of the same biosynthethic class. Chief PGs were plantamajoside and acteoside (verbascoside), their highest concentrations were 3.54±0.83% and 1.30±0.40% of dry weight, on media 10(0.33) and 40(0.33), respectively. NH4(+)/NO3(-) ratio and N source concentration effects were examined on a set of 89 NPs. For most NPs, high increases in abundance were observed compared to Murashige-Skoog medium. Abundances of 42 and 10 NPs were significantly influenced by the N source concentration and the NH4(+)/NO3(-) ratio, respectively. Optimal media for production of different NP clusters were 10(0), 10(0.11) and 40(0.33). Interaction was observed between NH4(+)/NO3(-) ratio and N source concentration for many NPs. It was shown in simulated experiments, that one-factor at a time (OFAT) experimental designs lead to sub-optimal media compositions for production of many NPs, and alternative experimental designs (e.g. FF) should be preferred when optimizing medium N source for optimal yield of NPs. If using OFAT, the N source concentration is to be optimized first, followed by NH4(+)/NO3(-) ratio, as this reduces the likeliness of suboptimal yield results. Copyright © 2014 Elsevier Ltd. All rights reserved.

The Recombination Mechanism and True Green Amplified Spontaneous Emission in CH3NH3PbBr3 Perovskite

KAUST Repository

Priante, Davide

2015-01-01

. M. Bakr, and B. S. Ooi, "The recombination mechanisms leading to amplified spontaneous emission at the true-green wavelength in CH3NH3PbBr3 perovskites", Applied Physics Letters, 106, 081902, 2015. DOI: 10.1063/1.4913463

PENGARUH TEPUNG DAUN GAMAL DAN DAUN KELOR DALAM UREA CASSAVA BLOK (UCB TERHADAP KECERNAAN, KADAR VFA, DAN NH3 IN-VITRO

Directory of Open Access Journals (Sweden)

N M. WITARIADI

2012-09-01

Full Text Available ABSTRAK Penelitian telah dilakukan dengan tujuan untuk mendapatkan informasi tentang pengaruh tepung daun gamal dan daun kelor sebagai sumber protein dalam urea cassava blok (UCB terhadap kecernaan bahan kering, bahan organik, kadar VFA, dan NH3 cairan rumen pakan jerami padi secara invitro. Penelitian dilaksanakan dengan mempergunakan rancangan acak lengkap (RAL dengan 3 perlakuan dan 5 ulangan. Sehingga secara keseluruhan terdapat 15 unit penelitian. Adapun ketiga perlakuan tersebut adalah: Perlakuan A (jerami padi + UCB yang ditambah tepung daun kelor; B (jerami padi + UCB yang ditambah tepung daun gamal, dan C (jerami padi + UCB yang ditambah tepung daun kelor dan daun gamal. Varibel yang diamati adalah kecernaan bahan kering (KCBK , kecernaan bahan organik (KCBO in-vitro, produksi vollatile fatty acid (VFA, produksi NH3, dan pH supernatan. Hasil penelitian mendapatkan bahwa KCBK, KCBO invitro, VFA, NH3, dan pH supernatan pada ketiga perlakuan berbeda nyata (P<0,05. Penggunaan daun gamal sebagai sumber protein pada UCB menghasilkan KCBK, KCBO, VFA, NH3, tertinggi dibandingkan dengan daun kelor maupun kombinasi antara daun gamal dan daun kelor. EFFECT OF USING GLIRICIDIA (Gliricidia sepium AND MORINGA (Moringa oleifera LEAVES MEALS IN UREA CASSAVA BLOCK (UCB ON DIGESTIBILITY, VOLLATILE FATTY ACID, AND NH3 IN-VITRO. ABSTRACT The experiment has been conducted in order to now the effect of Gliricidia sepium and Moringa oleifera leaves meal a source of protein in urea cassava block (UCB to the digestibility dray matter and organic matter , VFA and ammonia concentration with rice straw diet. The experiment set in completely randomized design using three treatment. The treatment are: A (rise straw + UCB with Moringa; B (rise straw + UCB with Gliricidia sepium, and C (rise straw + UCB with Moringa and Gliricidia sepium. The observed variable are: dry matter, organic matter digestibility, volatile fatty acid, ammonia concentration, and pH rumen juice

The Effect of Solvents on the Performance of CH3NH3PbI3 Perovskite Solar Cells

Directory of Open Access Journals (Sweden)

Pao-Hsun Huang

2017-04-01

Full Text Available The properties of perovskite solar cells (PSCs fabricated using various solvents was studied. The devices had an indium tin oxide (ITO/poly(3,4-ethylenedioxythiophene: poly(styrenesulfonate (PEDOT:PSS/CH3NH3PbI3 (fabricated by using various solvents/fullerene (C60/bathocuproine (BCP/silver (Ag structure. The solvents used were dimethylformamide (DMF, γ-butyrolactone (GBL, dimethyl sulfoxide (DMSO, a mixture of DMSO and DMF (1:1 v/v, and a mixture of DMSO and GBL (DMSO: GBL, 1:1 v/v, respectively. The power conversion efficiency (PCE of the device fabricated using DMF is zero, which is attributed to the poor coverage of CH3NH3PbI3 film on the substrate. In addition, the PCE of the device made using GBL is only 1.74% due to the low solubility of PbI2 and CH3NH3I. In contrast, the PCE of the device fabricated using the solvents containing DMSO showed better performance. This is ascribed to the high solubilization properties and strong coordination of DMSO. As a result, a PCE of 9.77% was obtained using a mixed DMSO:GBL solvent due to the smooth surface, uniform film coverage on the substrate and the high crystallization of the perovskite structure. Finally, a mixed DMSO: DMF:GBL (5:2:3 v/v/v solvent that combined the advantages of each solvent was used to fabricate a device, leading to a further improvement of the PCE of the resulting PSC to 10.84%.

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.

THE c2d SPITZER SPECTROSCOPIC SURVEY OF ICES AROUND LOW-MASS YOUNG STELLAR OBJECTS. IV. NH3 AND CH3OH

International Nuclear Information System (INIS)

Bottinelli, Sandrine; Van Dishoeck, Ewine F.; Lahuis, Fred; Boogert, A. C. Adwin; Bouwman, Jordy; Beckwith, Martha; Oeberg, Karin I.; Linnartz, Harold; Pontoppidan, Klaus M.; Blake, Geoffrey A.; Evans, Neal J.

2010-01-01

NH 3 and CH 3 OH are key molecules in astrochemical networks leading to the formation of more complex N- and O-bearing molecules, such as CH 3 CN and CH 3 OCH 3 . Despite a number of recent studies, little is known about their abundances in the solid state. This is particularly the case for low-mass protostars, for which only the launch of the Spitzer Space Telescope has permitted high-sensitivity observations of the ices around these objects. In this work, we investigate the ∼8-10 μm region in the Spitzer IRS (InfraRed Spectrograph) spectra of 41 low-mass young stellar objects (YSOs). These data are part of a survey of interstellar ices in a sample of low-mass YSOs studied in earlier papers in this series. We used both an empirical and a local continuum method to correct for the contribution from the 10 μm silicate absorption in the recorded spectra. In addition, we conducted a systematic laboratory study of NH 3 - and CH 3 OH-containing ices to help interpret the astronomical spectra. We clearly detect a feature at ∼9 μm in 24 low-mass YSOs. Within the uncertainty in continuum determination, we identify this feature with the NH 3 ν 2 umbrella mode and derive abundances with respect to water between ∼2% and 15%. Simultaneously, we also revisited the case of CH 3 OH ice by studying the ν 4 C-O stretch mode of this molecule at ∼9.7 μm in 16 objects, yielding abundances consistent with those derived by Boogert et al. based on a simultaneous 9.75 and 3.53 μm data analysis. Our study indicates that NH 3 is present primarily in H 2 O-rich ices, but that in some cases, such ices are insufficient to explain the observed narrow FWHM. The laboratory data point to CH 3 OH being in an almost pure methanol ice, or mixed mainly with CO or CO 2 , consistent with its formation through hydrogenation on grains. Finally, we use our derived NH 3 abundances in combination with previously published abundances of other solid N-bearing species to find that up to 10%-20% of

GRP1 PH Domain, Like AKT1 PH Domain, Possesses a Sentry Glutamate Residue Essential for Specific Targeting to Plasma Membrane PI(3,4,5)P3

Science.gov (United States)

Pilling, Carissa; Landgraf, Kyle E.; Falke, Joseph J.

2011-01-01

During the appearance of the signaling lipid PI(3,4,5)P3, an important subset of pleckstrin homology (PH) domains target signaling proteins to the plasma membrane. To ensure proper pathway regulation, such PI(3,4,5)P3-specific PH domains must exclude the more prevalant, constitutive plasma membrane lipid PI(4,5)P2 and bind the rare PI(3,4,5)P3 target lipid with sufficiently high affinity. Our previous study of the E17K mutant of protein kinase B (AKT1) PH domain, together with evidence from Carpten et al (1), revealed that the native AKT1 E17 residue serves as a sentry glutamate that excludes PI(4,5)P2, thereby playing an essential role in specific PI(3,4,5)P3 targeting (2). The sentry glutamate hypothesis proposes that an analogous sentry glutamate residue is a widespread feature of PI(3,4,5)P3-specific PH domains, and that charge reversal mutation at the sentry glutamate position will yield both increased PI(4,5)P2 affinity and constitutive plasma membrane targeting. To test this hypothesis the present study investigates the E345 residue, a putative sentry glutamate, of General Receptor for Phosphoinositides 1 (GRP1) PH domain. The results show that incorporation of the E345K charge reversal mutation into GRP1 PH domain enhances PI(4,5)P2 affinity 8-fold and yields constitutive plasma membrane targeting in cells, reminiscent of the effects of the E17K mutation in AKT1 PH domain. Hydrolysis of plasma membrane PI(4,5)P2 releases E345K GRP1 PH domain into the cytoplasm and the efficiency of this release increases when target Arf6 binding is disrupted. Overall, the findings provide strong support for the sentry glutamate hypothesis and suggest that the GRP1 E345K mutation will be linked to changes in cell physiology and human pathologies, as demonstrated for AKT1 E17K (1, 3). Analysis of available PH domain structures suggests that a lone glutamate residue (or, in some cases an aspartate) is a common, perhaps ubiquitous, feature of PI(3,4,5)P3-specific binding

Orthorhombic fulleride (CH3NH2)K3C60 close to Mott-Hubbard instability: Ab initio study

Science.gov (United States)

Potočnik, Anton; Manini, Nicola; Komelj, Matej; Tosatti, Erio; Arčon, Denis

2012-08-01

We study the electronic structure and magnetic interactions in methylamine-intercalated orthorhombic alkali-doped fullerene (CH3NH2)K3C60 within the density functional theory. As in the simpler ammonia intercalated compound (NH3)K3C60, the orthorhombic crystal-field anisotropy Δ lifts the t1u triple degeneracy at the Γ point and drives the system deep into the Mott-insulating phase. However, the computed Δ and conduction electron bandwidth W cannot alone account for the abnormally low experimental Néel temperature, TN=11 K, of the methylamine compound, compared to the much higher value TN=40 K of the ammonia one. Significant interactions between CH3NH2 and C603- are responsible for the stabilization of particular fullerene-cage distortions and the ensuing low-spin S=1/2 state. These interactions also seem to affect the magnetic properties, as interfullerene exchange interactions depend on the relative orientation of deformations of neighboring C603- molecules. For the ferro-orientational order of CH3NH2-K+ groups we find an apparent reduced dimensionality in magnetic exchange interactions, which may explain the suppressed Néel temperature. The disorder in exchange interactions caused by orientational disorder of CH3NH2-K+ groups could further contribute to this suppression.

[CH(3)(CH(2))(11)NH(3)]SnI(3): a hybrid semiconductor with MoO(3)-type tin(II) iodide layers.

Science.gov (United States)

Xu, Zhengtao; Mitzi, David B

2003-10-20

The organic-inorganic hybrid [CH(3)(CH(2))(11)NH(3)]SnI(3) presents a lamellar structure with a Sn-I framework isotypic to that of MoO(3). The SnI(3)(-) layer consists of edge and corner-sharing SnI(6) octahedra in which one of the six Sn-I bonds is distinctly elongated (e.g., 3.62 A), indicating lone-pair stereoactivity for the Sn(II) atom. The overall electronic character remains comparable with that of the well-studied SnI(4)(2)(-)-based perovskite semiconductors, such as [CH(3)(CH(2))(11)NH(3)](2)SnI(4), with a red-shifted and broadened exciton peak associated with the band gap, apparently due to the increased dimensionality of the Sn-I framework. The title compound offers, aside from the hybrid perovskites, a new type of solution-processable Sn-I network for potential applications in semiconductive devices.

Impact of CH3NH3PbI3-PCBM bulk heterojunction active layer on the photovoltaic performance of perovskite solar cells

Science.gov (United States)

Chaudhary, Dhirendra K.; Kumar, Pankaj; Kumar, Lokendra

2017-10-01

We report here the impact of CH3NH3PbI3-PCBM bulk heterojunction (BHJ) active layer on the photovoltaic performance of perovskite solar cells. The solar cells were prepared in normal architecture on FTO coated glass substrates with compact TiO2 (c-TiO2) layer on FTO as electron transport layer (ETL) and poly(3-hexylthiophene) (P3HT) as hole transport layer (HTL). For comparison, a few solar cells were also prepared in planar heterojunction structure using CH3NH3PbI3 only as the active layer. The bulk heterojunction CH3NH3PbI3-PCBM active layer exhibited very large crystalline grains of 2-3 μm compared to ∼150 nm only in CH3NH3PbI3 active layer. Larger grains in bulk-heterojunction solar cells resulted in enhanced power conversion efficiency (PCE) through enhancement in all the photovoltaic parameters compared to planar heterojunction solar cells. The bulk-heterojunction solar cells exhibited ∼9.25% PCE with short circuit current density (Jsc) of ∼18.649 mA/cm2, open circuit voltage (Voc) of 0.894 V and Fill Factor (FF) of 0.554. There was ∼36.9% enhancement in the PCE of bulk-heterojunction solar cells compared to that of planar heterojunction solar cells. The larger grains are formed as a result of incorporation on PCBM in the active layer.

Hexamethylenetetramine-mediated growth of grain-boundary-passivation CH3NH3PbI3 for highly reproducible and stable perovskite solar cells

Science.gov (United States)

Zheng, Yan-Zhen; Li, Xi-Tao; Zhao, Er-Fei; Lv, Xin-Ding; Meng, Fan-Li; Peng, Chao; Lai, Xue-Sen; Huang, Meilan; Cao, Guozhong; Tao, Xia; Chen, Jian-Feng

2018-02-01

Simultaneously achieving the long-term device stability and reproducibility has proven challenging in perovskite solar cells because solution-processing produced perovskite film with grain boundary is sensitive to moisture. Herein, we develop a hexamethylenetetramine (HMTA)-mediated one-step solution-processing deposition strategy that leads to the formation of high-purity and grain-boundary-passivation CH3NH3PbI3 film and thereby advances cell optoelectronic performance. Through morphological and structural characterizations and theoretical calculations, we demonstrate that HMTA fully occupies the moisture-exposed surface to build a bridge across grain boundary and coordinates with Pb ions to inhibit the formation of detrimental PbI2. Such HMTA-mediated grown CH3NH3PbI3 films achieves a decent augmentation of power conversion efficiency (PCE) from 12.70% to 17.87%. A full coverage of PbI2-free CH3NH3PbI3 surface on ZnO also boosts the device's stability and reproducibility.

Polarisation properties of irradiated ammonia (NH3 and ND3) at 1 K and 25 kG

International Nuclear Information System (INIS)

Riechert, H.

1982-11-01

Dynamic Nuclear Polarisation (DNP) of irradiated ammonia was examined in some detail at 1 K and 25 kG. In continuation of earlier studies conducted in Bonn, it was attempted to gain information about the prevailing mechanism of DNP in this material. Therefore the frequency dependence of DNP in NH 3 , of deuterons and unsubstituted protons in ND 3 , as well as the polarising time tau and the relaxation time T 1 in NH 3 were measured. Also the shape of the deuteron polarisation signal observed in ND 3 is discussed. The polarisation measurements in ND 3 rule out the equal spin temperature (EST) behaviour of proton and deuteron DNP that is observed in most of the currently used target materials. It is attempted to explain the observations with a differential solid state effect model. Results of calculations for NH 3 and ND 3 incorporating the measured EPR-spectra are presented. (orig.)

Performance evaluation of poly-urethane foam packed-bed chemical scrubber for the oxidative absorption of NH3 and H2S gases.

Science.gov (United States)

Nisola, Grace M; Valdehuesa, Kris Niño G; Anonas, Alex V; Ramos, Kristine Rose M; Lee, Won-Keun; Chung, Wook-Jin

2018-01-02

The feasibility of open-pore polyurethane (PU) foam as packing material for wet chemical scrubber was tested for NH 3 and H 2 S removals. The foam is inexpensive, light-weight, highly porous (low pressure drop) and provides large surface area per unit volume, which are desirable properties for enhanced gas/liquid mass transfer. Conventional HCl/HOCl (for NH 3 ) and NaOH/NaOCl (for H 2 S) scrubbing solutions were used to absorb and oxidize the gases. Assessment of the wet chemical scrubbers reveals that pH and ORP levels are important to maintain the gas removal efficiencies >95%. A higher re-circulation rate of scrubbing solutions also proved to enhance the performance of the NH 3 and H 2 S columns. Accumulation of salts was confirmed by the gradual increase in total dissolved solids and conductivity values of scrubbing solutions. The critical elimination capacities at >95% gas removals were found to be 5.24 g NH 3 -N/m 3 -h and 17.2 g H 2 S-S/m 3 -h at an empty bed gas residence time of 23.6 s. Negligible pressure drops (scrubbers for NH 3 and H 2 S removals from high-volume dilute emissions.

Molecular beam epitaxy of GaN(0001) utilizing NH3 and/or NH+x ions: Growth kinetics and defect structure

International Nuclear Information System (INIS)

Lee, N.; Powell, R.C.; Kim, Y.; Greene, J.E.

1995-01-01

Gas-source molecular beam epitaxy (GS-MBE), utilizing Ga and NH 3 , and reactive-ion MBE (RIMBE), incorporating both thermal NH 3 and low-energy NH + x ions, were used to grow single crystal GaN(0001) layers on Al 2 O 3 (0001) at temperatures T s between 700 and 850 degree C with deposition rates of 0.2--0.5 μm h -1 . The RIMBE experiments were carried out with incident NH + x /Ga flux ratios J NH + x /J Ga =1.9--3.2 and NH + x acceleration energies E NH + x =45--90 eV. Plan-view and cross-sectional transmission electron microscopy analyses showed that the primary defects in the GS-MBE films were threading dislocations having either pure edge or mixed edge/screw characteristics with Burgers vectors bar b=1/3 left-angle 2 bar 1 bar 10 right-angle, basal-plane stacking faults with displacement vectors bar R=1/6 left-angle 02 bar 23 right-angle, and prismatic stacking faults with bar R=1/2 left-angle bar 1101 right-angle. In the case of RIMBE films, no stacking faults or residual ion-induced defects were observed with E NH + x =45 eV and T s ≥800 degree C. However, increasing E NH + x to ≥60 eV at T s =800 degree C gave rise to the formation of residual ion-induced point-defect clusters observable by transmission electron microscopy (TEM). Increasing T s to 850 degree C with E NH + x ≥60 eV resulted in the ion-induced defects aggregating to form interstitial basal and prismatic dislocation loops, whose number densities depended upon the ion flux, with Burgers vectors 1/2 left-angle 0001 right-angle and 1/3 left-angle 2 bar 1 bar 10 right-angle, respectively. (Abstract Truncated)

Facile And Reversible Co Insertion Into The Ir-ch3 Bond Of [ir4(ch3)(co)8(μ4- η3-ph2pccph)(μ-pph2)

OpenAIRE

Vargas M.D.; Pereira R.M.S.; Braga D.; Grepioni F.

1993-01-01

Reaction of [Ir4H(CO)10(mu-PPh2)) with BuLi, Ph2PC=CPh and then Mel gives [Ir4(CH3)(CO)8(mu4-eta3-Ph2PCCPh)(mu-PPh2)], which undergoes a reversible two-step CO insertion under extremely mild conditions to yield Ir4{(CH3C(O)}(CO)8-(mu4:eta3-Ph2PCCPh)(mu-PPh2)] as the final product; the structures of both species have been established by X-ray diffraction studies.

NH3 Abatement in Fluidized Bed Co-Gasification of RDF and Coal

Science.gov (United States)

Gulyurtlu, I.; Pinto, Filomena; Dias, Mário; Lopes, Helena; André, Rui Neto; Cabrita, I.

Gasification of wastes may come out as an alternative technology to produce a gas with many potential applications, from direct burning in a boiler or motor to the production of synthetic chemicals and hydrogen. High tar production and high operational costs are preventing gasification wider dissemination. Besides these problems, the presence of NH3 in the syngas may have a negative impact as it can be converted into nitrogen oxides if the gas is further burnt. To reduce NH3 formation it is required a full understanding of how operational parameters contribute to the formation/reduction of this pollutant. A full studyon the effect of fuel composition, temperature and equivalence ratio on the formation of NH3 is given. Experimental results are compared to theoretical ones obtained with FactSage software. It is also analyzed the effect of feedstock mineral matterin NH3 release during gasification. Toaccomplish a significant decrease in the release of NH3, different catalysts and sorbents were tested with the aim of achieving high energy conversions and low environmental impact.

Nanoscale charge localization induced by random orientations of organic molecules in hybrid perovskite CH3NH3PbI3

Science.gov (United States)

Ma, Jie; Wang, Lin-Wang

2015-03-01

Perovskite-based solar cells have achieved high solar-energy conversion efficiencies and attracted wide attentions nowadays. Despite the rapid progress in solar-cell devices, many fundamental issues of the hybrid perovskites have not been fully understood. Experimentally, it is well known that in CH3NH3PbI3, the organic molecules CH3NH3 are randomly orientated at the room temperature, but the impact of the random molecular orientation has not been investigated. Using linear-scaling ab-initiomethods, we have calculated the electronic structures of the tetragonal phase of CH3NH3PbI3 with randomly orientated organic molecules in large supercells up to ~20,000 atoms. Due to the dipole moment of the organic molecule, the random orientation creates a novel system with long-range potential fluctuations unlike alloys or other conventional disordered systems. We find that the charge densities of the conduction-band minimum and the valence-band maximum are localized separately in nanoscales due to the potential fluctuations. The charge localization causes electron-hole separation and reduces carrier recombination rates, which may contribute to the long carrier lifetime observed in experiments. We have also proposed a model to explain the charge localization.

The loss of NH2O from the N-hydroxyacetamide radical cation CH3C(O)NHOH+

Science.gov (United States)

Jobst, Karl J.; Burgers, Peter C.; Ruttink, Paul J. A.; Terlouw, Johan K.

2006-08-01

A previous study [Ch. Lifshitz, P.J.A. Ruttink, G. Schaftenaar, J.K. Terlouw, Rapid Commun. Mass Spectrom. 1 (1987) 61] shows that metastable N-hydroxyacetamide ions CH3C(O)NHOH+ (HA-1) do not dissociate into CH3CO+ + NHOH by direct bond cleavage but rather yield CH3CO+ + NH2OE The tandem mass spectrometry based experiments of the present study on the isotopologue CH3C(O)NDOD+ reveal that the majority of the metastable ions lose the NH2O radical as NHDO rather than ND2O. A mechanistic analysis using the CBS-QB3 model chemistry shows that the molecular ions HA-1 rearrange into hydrogen-bridged radical cations [OCC(H2)H...N(H)OH]+ whose acetyl cation component then catalyses the transformation NHOH --> NH2O prior to dissociation. The high barrier for the unassisted 1,2-H shift in the free radical, 43 kcal mol-1, is reduced to a mere 7 kcal mol-1 for the catalysed transformation which can be viewed as a quid-pro-quo reaction involving two proton transfers.

Conductivity of CH{sub 3}NH{sub 3}PbI{sub 3} thin film perovskite stored in ambient atmosphere

Energy Technology Data Exchange (ETDEWEB)

Gebremichael, Bizuneh, E-mail: bizunehme@gmail.com [Physics Department, Addis Ababa University, Addis Ababa, P.O. Box 1176 (Ethiopia); Alemu, Getachew [Physics Department, Addis Ababa University, Addis Ababa, P.O. Box 1176 (Ethiopia); Tessema Mola, Genene [School of Chemistry & Physics, University of KwaZulu-Nat al, Pietermaritzburg Campus, Private Bag X01, Scottsville 3209 (South Africa)

2017-06-01

Time dependent conductivity loss in CH{sub 3}NH{sub 3}PbI{sub 3} thin film perovskite stored in ambient atmosphere were studied based on electrical and optical measurements. Recent investigations on thin film perovskite solar cell suggest that in the steady state operation of the device, the V{sub oc} is unchanged by continuous illumination of light. Rather the reduction in the power conversion efficiency is caused by significant reduction of the short circuit current (J{sub sc}). In this paper, the effect of light on the optical absorption and electrical conductivity of the CH{sub 3}NH{sub 3}PbI{sub 3} thin film which is deposited on a glass substrate is investigated. The temperature dependent conductivity measurements indicated that the dominant conduction mechanism in the film perovskite is electronic rather than ionic.

Influence of hydration water on CH3NH3PbI3 perovskite films prepared through one-step procedure.

Science.gov (United States)

Wang, Ziyi; Yuan, Sijian; Li, Dahai; Jin, Feng; Zhang, Rongjun; Zhan, Yiqiang; Lu, Ming; Wang, Songyou; Zheng, Yuxiang; Guo, Junpeng; Fan, Zhiyong; Chen, Liangyao

2016-10-31

Organic-inorganic perovskites were fabricated through a one-step procedure with different levels of hydration water in precursor solutions. The optical properties of CH3NH3PbI3 films were investigated through spectroscopic ellipsometry and photoluminescence measurements. With the measured optical constants, the efficiency limit of perovskite solar cells is predicted with a detailed balance model. By comparing the optical measurement to that of planar heterojunction solar cells, we conclude that the radiative efficiency and porosity of the perovskite film significantly influence the performance of perovskite solar cells. An optimized hydration-water concentration is obtained for the 3CH3NH3I:1PbAc2•xH2O precursor solution. The results can provide guidance for further optimization of the device performance of perovskite solar cells by utilizing hydration water.

Chlorine Incorporation in the CH3NH3PbI3 Perovskite: Small Concentration, Big Effect.

Science.gov (United States)

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

2017-01-03

The role of chlorine doping in CH 3 NH 3 PbI 3 represents an important open issue in the use of hybrid perovskites for photovoltaic applications. In particular, even if a positive role of chlorine doping on perovskite film formation and on material morphology has been demonstrated, an inherent positive effect on the electronic and photovoltaic properties cannot be excluded. Here we carried out periodic density functional theory and Car-Parrinello molecular dynamics simulations, going down to ∼1% doping, to investigate the effect of chlorine on CH 3 NH 3 PbI 3 . We found that such a small doping has important effects on the dynamics of the crystalline structure, both with respect to the inorganic framework and with respect to the cation libration motion. Together, we observe a dynamic spatial localization of the valence and conduction states in separated spatial material regions, which takes place in the 10 -1 ps time scale and which could be the key to ease of exciton dissociation and, likely, to small charge recombination in hybrid perovskites. Moreover, such localization is enhanced by chlorine doping, demonstrating an inherent positive role of chlorine doping on the electronic properties of this class of materials.

Synthesis, P-31 NMR data and X-ray analysis of a ruthenium(II) dimethylphenylphosphine complex with dimerized phenylacetylene: The structure of [(PhMe(2)P)(4)Ru(eta(3)-PhC(3)CHPh)](PF6)

CSIR Research Space (South Africa)

Liles, DC

1996-09-06

Full Text Available Treatment of [RuHL (5)] (+) (L = PMe (2) Ph) with phenylacetylene in ethanol yielded the dimerization of HC=CPh to (Z)-1, 4-diphenylbut-3-en-1-yne. The molecular structure of [Ru(eta(3)-PhC(3)CHPh)L(4)](PF6) (L = PMe(2)Ph) (2) shows a seven...

Prediction on electronic structure of CH3NH3PbI3/Fe3O4 interfaces

Science.gov (United States)

Hou, Xueyao; Wang, Xiaocha; Mi, Wenbo; Du, Zunfeng

2018-01-01

The interfacial electronic structures of CH3NH3PbI3(MAPbI3)/Fe3O4 heterostructures are predicted by density functional theory. Four models (MAI/FeBO, PbI2/FeBO, MAI/FeA and PbI2/FeA) are included. Especially, a half-metal to semiconductor transition of Fe3O4 appears in PbI2/FeA model. A series of electric field is added to PbI2/FeA model, and a direct-indirect bandgap transition of Fe3O4 appears at a 500-kV/cm field. The electric field can control the bandgap of Fe3O4 in PbI2/FeA model by modulating the hybridization. The prediction of spin-related bandgap characteristic in MAPbI3/Fe3O4 is meaningful for further study.

Electron transport in NH3/NO2 sensed buckled antimonene

Science.gov (United States)

Srivastava, Anurag; Khan, Md. Shahzad; Ahuja, Rajeev

2018-04-01

The structural and electronic properties of buckled antimonene have been analysed using density functional theory based ab-initio approach. Geometrical parameters in terms of bond length and bond angle are found close to the single ruffle mono-layer of rhombohedral antimony. Inter-frontier orbital analyses suggest localization of lone pair electrons at each atomic centre. Phonon dispersion along with high symmetry point of Brillouin zone does not signify any soft mode. With an electronic band gap of 1.8eV, the quasi-2D nano-surface has been further explored for NH3/NO2 molecules sensing and qualities of interaction between NH3/NO2 gas and antimonene scrutinized in terms of electronic charges transfer. A current-voltage characteristic has also been analysed, using Non Equilibrium Green's function (NEGF), for antimonene, in presence of incoming NH3/NO2 molecules.

CH3NH3I treatment temperature of 70 °C in low-pressure vapor-assisted deposition for mesoscopic perovskite solar cells

Science.gov (United States)

Jin, Wenbin; Zou, Xiaoping; Bai, Xiao; Yang, Ying; Chen, Dan

2018-01-01

Herein, we report a modified vapor-assisted deposition method to fabricate CH3NH3PbI3 film at 70 °C in a vacuum drying oven. The modified method has excellent operability and expandability in preparing perovskite solar cells. The CH3NH3I treatment temperature is 130 °C or 150 °C in conventional method, but we reduced the temperature to 70 °C in the modified vapor-assisted method. Meanwhile, the quality of CH3NH3PbI3 films prepared via the modified method is superior to that of CH3NH3PbI3 films of solution-processed method.

The phytotoxic effects of present NH3 immissions

International Nuclear Information System (INIS)

Adaros, G.; Daemmgen, U.

1994-01-01

The phytotoxic effects of NH 3 have been known since the end of the previous century. The significance of ammonia as harmful substance or stressor even in ambient concentrations has been only realized and investigated during the last decades. This volume is aimed at accounting the effects produced by ambient doses of NH 3 . The entities relevant for the description of potential dose response relationships are discussed. The major source of potential dose response relationships are discussed. The major source of atmospheric pollution of ammonia and ammonium is intensive agriculture, in particular intensive cattle production. However, sources and transmission processes are not dealt with in this paper. Potential pathways of ammonia into the plants and the respective reaction mechanisms are discussed in detail. (orig./MG) [de

Study of various NH4+/NO3- mixtures for enhancing growth of potatoes

Science.gov (United States)

Cao, W.; Tibbitts, T. W.

1993-01-01

Two experiments were conducted to determine the effects of various NH4(+)-N/NO3(-)-N percentages on growth and mineral concentrations in potato (Solanum tuberosum L.) plants using a non-recirculating nutrient film system in a controlled environment. The first experiment included six NH4(+)-N/NO3(-)-N percentages at 0/100, 20/80, 40/60, 60/40, 80/20, and 100/0 with the same total N concentration of 4 mM. The second experiment included six NH4(+)-N/NO3(-)-N percentages at 0/100, 4/96, 8/92, 12/88, 16/84, and 20/80 again with the same total N of 4 mM. In each experiment, plants were harvested 35 days after transplanting when tubers had been initiated and started to enlarge. Dry weights of shoots, tubers, and whole plant at the harvest were increased significantly with all mixed nitrogen treatments as compared with single NH4+ or NO3- form. The enhanced growth with mixed nitrogen was greatest at 8% to 20% NH4(+)-N. Also, the concentrations and accumulation of total N in the shoots and roots were greater with mixed nitrogen than with separate NH4+ or NO3- nutrition. With NH4+ present in the solutions, the concentrations of P and Cl in the shoots were increased compared to NO3- alone, whereas the tissue concentrations of Ca and Mg were decreased. It was concluded that nitrogen fertilization provided with combined NH4+ and NO3- forms, even at small proportions of NH4+, can enhance nitrogen uptake and productivity in potato plants.

Thermal properties and phase transition in the fluoride, (NH4)3SnF7

International Nuclear Information System (INIS)

Kartashev, A.V.; Gorev, M.V.; Bogdanov, E.V.; Flerov, I.N.; Laptash, N.M.

2016-01-01

Calorimetric, dilatometric and differential thermal analysis studies were performed on (NH 4 ) 3 SnF 7 for a wide range of temperatures and pressures. Large entropy (δS 0 =22 J/mol K) and elastic deformation (δ(ΔV/V) 0 =0.89%) jumps have proven that the Pa-3↔Pm-3m phase transition is a strong first order structural transformation. A total entropy change of ΔS 0 =32.5 J/mol K is characteristic for the order–disorder phase transition, and is equal to the sum of entropy changes in the related material, (NH 4 ) 3 TiF 7 , undergoing transformation between the two cubic phases through the intermediate phases. Hydrostatic pressure decreases the stability of the high temperature Pm-3m phase in (NH 4 ) 3 SnF 7 , contrary to (NH 4 ) 3 TiF 7 , characterised by a negative baric coefficient. The effect of experimental conditions on the chemical stability of (NH 4 ) 3 SnF 7 was observed. - Graphical abstract: Strong first order structural transformation Pa-3↔Pm-3m in (NH 4 ) 3 SnF 7 is associated with very large total entropy change of ΔS 0 =32.5 J/mol K characteristic for the ordering processes and equal to the sum of entropy changes in the related (NH 4 ) 3 TiF 7 undergoing transformation between the same two cubic phases through the intermediate phases. - Highlights: • (NH 4 ) 3 SnF 7 undergoes strong first order Pa-3↔Pm-3m phase transition. • Anomalous behaviour of ΔC p and ΔV/V exists far below phase transition temperature. • Structural distortions are accompanied by huge total entropy change ΔS≈Rln50. • High pressure strongly increases the stability of Pa-3 phase in (NH 4 ) 3 SnF 7 . • Entropy of the Pa-3↔Pm-3m phase transition does not depend on pressure.

Fabrication and characterization of perovskite-based CH{sub 3}NH{sub 3}Pb{sub 1-x}Ge{sub x}I{sub 3}, CH{sub 3}NH{sub 3}Pb{sub 1-x}Tl{sub x}I{sub 3} and CH{sub 3}NH{sub 3}Pb{sub 1-x}In{sub x}I{sub 3} photovoltaic devices

Energy Technology Data Exchange (ETDEWEB)

Ohishi, Yuya; Oku, Takeo, E-mail: oku@mat.usp.ac.jp; Suzuki, Atsushi [Department of Materials Science, The University of Shiga Prefecture 2500 Hassaka, Hikone, Shiga 522-8533 (Japan)

2016-02-01

Perovskite-type CH{sub 3}NH{sub 3}PbI{sub 3}-based photovoltaic devices were fabricated and characterized. Doping effects of thallium (Tl), indium (In), or germanium (Ge) element on the photovoltaic properties and surface structures of the perovskite phase were investigated. The open circuit voltage increased by Ge addition, and fill factors were improved by adding a small amount of Ge, Tl or In. In addition, the wavelength range of incident photon conversion efficiencies was expanded by the Tl addition.

A straightforward and efficient synthesis of 3-(pyrimidinyl)propanoates from levulinic acid

International Nuclear Information System (INIS)

Flores, Alex F.C.; Malavolta, Juliana L.; Souto, Alynne A.; Goularte, Rayane B.; Flores, Darlene C.

2013-01-01

The cyclocondensation of methyl 7,7,7-trifluoro-4-methoxy-6-oxo-4-heptenoate and methyl 7,7,7-trichloro-4-methoxy-6-oxo-4-heptenoate, derived from levulinic acid with amidines [NH 2 CONH 2 , NH 2 CR(NH) (R = H, Me, Ph, NH 2 , SMe and 1H-pyrazol-1-yl), 5-amino-3-methyl-1H-pyrazol and 2-aminothiazole] into pyrimidine and pyrimidine-like derivatives as a new type of glutamate-like 3-(trihalomethylatedpyrimidinyl)propanoate is reported. Preparation of 3-(trihalomethylatedpyrimidinyl) propanohydrazides is also described. The synthetic potential of this straightforward protocol was established by the synthesis of fourteen new 3-(pyrimidinyl) propanoates in regular to good yields (38-92%). The structural assignments were based on the analysis of their 1 H and 13 C nuclear magnetic resonance (NMR) and gas chromatography-mass spectrometry (GC-MS) data. (author)

Efficiency enhancement of perovskite solar cells using structural and morphological improvement of CH3NH3PbI3 absorber layers

Science.gov (United States)

Alidaei, Maryam; Izadifard, Morteza; Ghazi, Mohammad E.; Ahmadi, Vahid

2018-01-01

Perovskite solar cells have been heavily investigated due to their unique properties such as high power conversion efficiency (PCE), low-cost fabrication by solution processes, high diffusion length, large absorption coefficient, and direct and tunable band gap. PCE of perovskite devices is strongly dependent on the absorber layer properties such as morphology, crystallinity, and compactness, which are required to be optimized. In this work, the CH3NH3PbI3 (170-480 nm) absorber layers with various methylammonium iodine (MAI) concentrations (7, 10, 20 and 40 mg ml-1) and perovskite solar cells with the fluorine-doped tin oxide (400 nm)/C-TiO2 (30 nm)/Meso-TiO2 (400 nm)/CH3NH3PbI3 (170-480 nm)/P3HT (30 nm)/Au (100 nm) structure were fabricated. A two-step solution process was used for deposition of the CH3NH3PbI3 absorber layers. The morphology, crystal structure, and optical properties of the perovskite layer grown on glass and also the photovoltaic properties of the fabricated solar cells were studied. The results obtained showed that by controlling the deposition conditions, due to the reduction in charge recombination, PCE enhancement of the perovskite solar cell (up to 11.6%) was accessible.

Ph effect on tricalcium phosphate (Ca3(PO4)2) thermoluminescence

International Nuclear Information System (INIS)

Barrera V, A.; Zarate M, J.; Lemus R, J.; Sanchez, A.; Rivera M, T.

2015-10-01

The study of the ph effect is presented on thermoluminescent response of calcium phosphates synthesized by precipitation process. For the synthesis by precipitation, were used: calcium nitrate (Ca(NO 3 ) 2 and ammonium phosphate dibasic ((NH 4 ) 2 HPO 4 ) as precursors. Samples were obtained at ph 7, 8, 9 and 10 and subjected to a calcination s temperature of 1100 C. Samples were also irradiated with X rays of 6 MV to a dose of 2 Gy. Samples prior to irradiation showed no luminescence, the irradiated samples displayed a luminescent curve which is due to the X-ray response. Powders synthesized at ph 7 showed a well-defined peak centered at 267 grades C. The rest of the prepared samples showed a luminescent curve composed of several peaks. By analyzing the curve at ph 7 by the method of the shape of the curve, was found to have an order of 1.7, with an activation energy, E = 1.44 ± 0.04 eV. (Author)

Sequence of phase transitions in (NH4)3SiF7.

Science.gov (United States)

Mel'nikova, S V; Molokeev, M S; Laptash, N M; Pogoreltsev, E I; Misyul, S V; Flerov, I N

2017-02-21

Single crystals of silicon double salt (NH 4 ) 3 SiF 7 = (NH 4 ) 2 SiF 6 ·NH 4 F = (NH 4 ) 3 [SiF 6 ]F were grown and studied by the methods of polarization optics, X-ray diffraction and calorimetry. A sequence of symmetry transformations with the temperature change was established: P4/mbm (Z = 2) (G 1 ) ↔ Pbam (Z = 4) (G 2 ) ↔ P2 1 /c (Z = 4) (G 3 ) ↔ P1[combining macron] (Z = 4) (G 4 ) ↔ P2 1 /c (Z = 8) (G 5 ). Crystal structures of different phases were determined. The experimental data were also interpreted by a group-theoretical analysis of the complete condensate of order parameters taking into account critical and noncritical atomic displacements. Strengthening of the N-HF hydrogen bonds can be a driving force of the observed phase transitions.

Study of NH3 Line Intensities in the THz and Far-IR Region

Science.gov (United States)

Yu, Shanshan

Ammonia (NH3) exists in the interstellar medium, late-type stars and giant planets of our solar system. Its temperature and abundance profiles in these environments, which are derived with its line parameters as fixed input , are commonly used to provide constraints on retrieving minor species. Therefore NH3 line parameters are essential for interpreting astrophysical and planetary spectra from Herschel, SOFIA, ALMA and JWST. However, our work under a predecessor grant with the APRA program revealed significant deficiencies in NH3 intensities in the terahertz and FIR region, including some weak Delta(K)=3 forbidden transitions predicted to be 100 times stronger. The Delta(K)=3 transitions are the ones connecting levels with different K values and therefore the only way other than collisions and l-doubled states to excite NH3 to K>0 levels. Their intensities have to be corrected to explain the observed high K excitation, such as the detection of NH3 (J,K) = (1,1), (2,2)&(14,14) and (18,18) transitions toward the galactic center star forming region Sgr B2, and to provide insights into the radiative- transfer vs. collision excitation mechanics of interstellar NH3. This proposal will remedy the serious deficiencies in the current databases involving NH3 line parameters in the terahertz and FIR region. We will target transitions with intensities greater than 10^{-23} cm-1/ (molecule/cm2) at 296 K, which will be among new astrophysical detections made by SOFIA, ALMA and JWST, and are 1000 times weaker than the strongest ground state transitions. We will retrieve new positions and intensities from existing laboratory spectra, use them to evaluate the current databases and ab initio calculations, and repair the line positions and intensities by replacing poorly calculated values with our new measurements. The proposed research will result in (1) a validated linelist containing the positions, intensities and lower state energies for the very important Delta(K)=3 NH3 FIR

Synthesis and structure of a 1,6-hexyldiamine heptaborate, [H3N(CH2)6NH3][B7O10(OH)3

International Nuclear Information System (INIS)

Yang Sihai; Li Guobao; Tian Shujian; Liao Fuhui; Xiong Ming; Lin Jianhua

2007-01-01

A new 1,6-hexyldiamine heptaborate, [H 3 N(CH 2 ) 6 NH 3 ][B 7 O 10 (OH) 3 ] (1), has been solvothermally synthesized and characterized by single-crystal X-ray diffraction, FTIR, elemental analysis, and thermogravimetric analysis. Compound 1 crystallizes in monoclinic system, space group P2 1 /n with a=8.042(2) A, b=20.004(4) A, c=10.103(2) A, and β=90.42(3) deg. The anionic [B 7 O 10 (OH) 3 ] n 2n- layers are interlinked via hydrogen bonding to form a 3D supramolecular network containing large channels, in which the templated [H 3 N(CH 2 ) 6 NH 3 ] 2+ cations are located. - Graphical abstract: A layered 1,6-hexyldiamine heptaborate, [H 3 N(CH 2 ) 6 NH 3 ][B 7 O 10 (OH) 3 ], was solvothermally synthesized at 150 deg. C. It is a layer borate and crystallized in monoclinic space group P2 1 /n with a=8.042(2) A, b=20.004(4) A, c=10.103(2) A, β=90.42(3) deg

A Highly Selective Room Temperature NH3 Gas Sensor based on Nanocrystalline a-Fe2O3

Directory of Open Access Journals (Sweden)

Priyanka A. PATIL

2017-05-01

Full Text Available Nanocrystalline a-Fe2O3 powder was synthesized by simple, inexpensive sol-gel method. The obtained powder was calcined at 700 0C in air atmosphere for 2 hours. The structural and morphological properties of calcined powder were studied by X-ray diffraction (XRD and Field Emission Scanning Electron Microscopy (FESEM respectively. Thermal properties of dried gel were studied by Thermogravimetric Analysis/Differential Scanning Calorimetry (TGA/DSC. The XRD pattern of the powder confirmed the a-Fe2O3 (hematite phase of iron oxide with average crystalline size of 30.87 nm calculated from Scherrer equation. The FESEM images showed uniform wormlike morphology of a-Fe2O3 powder. TGA result indicated that a-Fe2O3 is thermodynamically stable. Room temperature NH3 sensing characteristics of a-Fe2O3 were studied for various concentration levels (250-2500 ppm of NH3 at various humid conditions. The sensor based on a-Fe2O3 exhibited good selectivity and excellent sensitivity (S=92 towards 1000 ppm of NH3 with quick response of 4 sec and fast recovery of 9 sec. Room temperature sensing mechanism is also discussed.

Creation and annealing of metastable defect states in CH3NH3PbI3 at low temperatures

Science.gov (United States)

Lang, F.; Shargaieva, O.; Brus, V. V.; Rappich, J.; Nickel, N. H.

2018-02-01

Methylammonium lead iodide (CH3NH3PbI3), an organic-inorganic perovskite widely used for optoelectronic applications, is known to dissociate under illumination with light at photon energies around 2.7 eV and higher. Here, we show that photo-induced dissociation is not limited to ambient temperatures but can be observed even at 5 K. The photo-induced dissociation of N-H bonds results in the formation of metastable states. Photoluminescence (PL) measurements reveal the formation of defect states that are located 100 meV within the bandgap. This is accompanied by a quenching of the band-to-band PL by one order of magnitude. Defect generation is reversible and annealing at 30 K recovers the band-to-band PL, while the light-induced defect states disappear concurrently.

Comparison of NH4+-N and NO3--N nutrition in hybrid and conventional rice at the late growth stage

International Nuclear Information System (INIS)

Yang Xiaoe; Sun Xi

1990-01-01

The difference of NH 4 + -N/NO 3 - -N nutrition between hybrid and conventional rice varieties at the late growth stage was studied by using 15 N-tracer technique. The results showed that the nitrate fertilizer utilization efficiency by the hybrid rice after anthesis was 7.8% higher than that by the ordinary rice variety, and the nitrate fertilizer recovery fraction by the former was 13.2% greater than that by the latter. The varietal difference in NO 3 - -N uptake and utilization was almost twice as that in NH 4 + -N. It was also showed that 15 N distribution in ear of the hybrid rice was about 20% greater than that of the conventional variety, but there were no obvious differences between NO 3 - -N and NH 4 + -N. However, 15 N distribution in the lower node leaves and root was found to be significant higher with NO 3 - -N than that with NH 4 + -N in both rice varieties, particularly in the hybrid rice. Compared with NH 4 + -N, NO 3 - -N top-dressing before anthesis was observed to have much greater positive effects on the uptake of calcium and magnesium and the growth of the superficial root and the grain yield of the tested rice varieties, especially of the hybrid rice

Tunable far infrared laser spectroscopy of van der Waals bonds: Ar-NH3

International Nuclear Information System (INIS)

Gwo, Dz-Hung; California Univ., Berkeley, CA

1989-11-01

Hyperfine resolved vibration-rotation-tunneling spectra of Ar--NH 3 and (NH 3 ) 2 , generated in a planar supersonic jet, have been measured with the Berkeley tunable far infrared laser spectrometer. Among the seven rotationally assigned bands, one band belongs to Ar--NH 3 , and the other six belong to (NH 3 ) 2 . To facilitate the intermolecular vibrational assignment for Ar--NH 3 , a dynamics study aided by a permutation-inversion group theoretical treatment is performed on the rovibrational levels. The rovibrational quantum number correlation between the free internal rotor limit and the semi-rigid limit is established to provide a basic physical picture of the evolution of intermolecular vibrational component states. An anomalous vibronically allowed unique Q branch vibrational band structure is predicted to exist for a near prolate binary complex containing an inverting subunit. According to the model developed in this work, the observed band of Ar--NH 3 centered at 26.470633(17) cm -1 can correlate only to either the fundamental dimeric stretching band for the A 2 states with the NH 3 inversional quantum number v i = 1, or the K a = 0 left-arrow 0 subband of the lowest internal-rotation-inversion difference band. Although the estimated nuclear quadrupole coupling constant favors a tentative assignment in terms of the first possibility, a definitive assignment will require far infrared data and a dynamical model incorporating a potential surface

The international research progress of Ammonia(NH3) emissions and emissions reduction technology in farmland ecosystem

Science.gov (United States)

Yang, W. Z.; Jiao, Y.

2017-03-01

NH3 is the important factor leading to the grey haze, and one of the main causes of environmental problems of serious ecological imbalance, such as acid rain and air quality deterioration. The fertilizer excessive application of the current farmland results NH3 emissions intensity greatly. In order to clear the farmland NH3 emissions research status and achievements, the literature of farmland NH3 emission related were retrievaled by the SCI journals and Chinese science citation database. Some factors of NH3 emission were analyzed such as soil factors, climate factors and farmland management measures. The research progress was inductived on farmland NH3 emission reduction technology. The results will help to clarify farmland NH3 emissions research progress. The theoretical guidance was provided on the future of farmland NH3 emissions research.

Theoretical study on the mechanism of CH3NH2 and O3 ...

Indian Academy of Sciences (India)

CH3NH + OH + O2 adducts with one transition state is the most favoured path. Keywords. Ozone; calculation; reaction mechanism; potential energy profile; transition state. 1. Introduction ..... University of. Applied Science, Bielefeld, Germany.

Sterically crowded monomeric neutral bis(benzamidinato) compounds of aluminium, [PhC(NSiMe(3))(2)](2)AlX (X=Cl, H); X-ray crystal structure of [PhC(NSiMe(3))(2)]2AlH

NARCIS (Netherlands)

Duchateau, R; Meetsma, A; Teuben, JH

1996-01-01

AlCl3 reacts with [PhC(NSiMe(3))(2)]Li(OEt(2)) to afford the bis(N,N'-bis(trimethylsilyl)benzamidinato)aluminium chloro compound which, on treatment with KBEt(3)H, yields the structurally characterized monomeric hydride derivative, [PhC(NSiMe(3))(2)]2AlH, whose reactivity towards unsaturated

Trends of NO-, NO 2-, and NH 3-emissions from gasoline-fueled Euro-3- to Euro-4-passenger cars

Science.gov (United States)

Heeb, Norbert V.; Saxer, Christian J.; Forss, Anna-Maria; Brühlmann, Stefan

Vehicular emissions of reactive nitrogen compounds (RNCs) such as nitric oxide (NO), nitrogen dioxide (NO 2), and ammonia (NH 3) have a substantial impact on urban air quality. NO and NO 2 support the photochemical formation of ozone, and NH 3 is involved in the atmospheric formation of secondary aerosols. Vehicular NO is mainly formed during combustion, whereas NO 2 and NH 3 are both secondary pollutants of the catalytic converter systems. Herein we report on tail-pipe RNC emissions of gasoline-fueled Euro-3- and Euro-4-passenger cars at transient driving from 0 to 150 km h -1. Two sets of 10 in-use vehicles with comparable engine size and mileage were studied with time-resolved chemical ionization-mass spectrometry (CI-MS). Each vehicle was tested in 7 different driving cycles including the legislative European (EDC) and the US FTP-75 driving cycles. Mean emission factors (EFs) for different traffic situations are reported and effects of cold start, velocity, acceleration, and deceleration are discussed. Furthermore, critical operating conditions supporting the de novo formation of NH 3 have been identified. In the EDC, mean NO- and NH 3-EFs of 57±26 and 16±12 mg km -1 were obtained for Euro-3-vehicles; those of the Euro-4-technology were lower by about 25% and 33% at the levels of 43±46 and 10±7 mg km -1, respectively. NO 2 emissions of the investigated three-way catalyst (TWC) vehicles accounted for exhaust. Velocity and acceleration had pronounced effects on the RNC emission characteristics. Mean velocity-dependent EFs for NO and NH 3 varied by about one order of magnitude from 10 to 74 and 15 to 161 mg km -1 for Euro-3-vehicles and from 12 to 44 and 7 to 144 mg km -1 for the Euro-4 fleet. We conclude that the investigated Euro-3- and Euro-4-vehicles are mainly operated under slightly reducing conditions, where the NH 3 emissions dominate over those of the NO. Under these conditions, both vehicle fleets on an average fulfilled the valid Euro-3 and Euro-4

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

Science.gov (United States)

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

2017-10-18

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

Heterogeneous reactions between ions NH3+and NH+andhydrocarbons adsorbed on a tungsten surface.Formation of HCN+in NH+-surface hydrocarbon collisions

Czech Academy of Sciences Publication Activity Database

Harnisch, M.; Scheier, P.; Herman, Zdeněk

2015-01-01

Roč. 392, DEC 2015 (2015), s. 139-144 ISSN 1387-3806 Institutional support: RVO:61388955 Keywords : ion-surface collisions * NH3+ and NH+projectiles * surface hydrocarbons Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.183, year: 2015

Lead-free Perovskite Materials (NH4 )3 Sb2 Ix Br9-x.

Science.gov (United States)

Zuo, Chuantian; Ding, Liming

2017-06-01

A family of perovskite light absorbers (NH 4 ) 3 Sb 2 I x Br 9-x (0≤x≤9) was prepared. These materials show good solubility in ethanol, a low-cost, hypotoxic, and environmentally friendly solvent. The light absorption of (NH 4 ) 3 Sb 2 I x Br 9-x films can be tuned by adjusting I and Br content. The absorption onset for (NH 4 ) 3 Sb 2 I x Br 9-x films changes from 558 nm to 453 nm as x changes from 9 to 0. (NH 4 ) 3 Sb 2 I 9 single crystals were prepared, exhibiting a hole mobility of 4.8 cm 2  V -1  s -1 and an electron mobility of 12.3 cm 2  V -1  s -1 . (NH 4 ) 3 Sb 2 I 9 solar cells gave an open-circuit voltage of 1.03 V and a power conversion efficiency of 0.51 %. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High yielding mutants of blackgram variety 'PH-25'

International Nuclear Information System (INIS)

Misra, R.C.; Mohapatra, B.D.; Panda, B.S.

2001-01-01

Seeds of blackgram (Vigna mungo L.) variety 'PH-5' were treated with chemical mutagens ethyl methanesulfonate (EMS), nitrosoguanidine (NG), maleic hydrazide (MH) and sodium azide (NaN 3 ), each at 3 different concentrations. Thirty six mutant lines developed from mutagenic treatments along with parent varieties were tested in M 4 generation. The mutants showed wide variation in most of the traits and multivariante D 2 analysis showed genetic divergence among themselves. Twenty of the thirty mutants showed genetic divergence from parent. Ten selected high yielding mutants were tested in M 5 . Yield and other productive traits of five high yielding mutants in M 4 and M 5 are presented

Molecular modelling of the decomposition of NH{sub 3} over CoO(100)

Energy Technology Data Exchange (ETDEWEB)

Shojaee, Kambiz; Haynes, Brian S.; Montoya, Alejandro, E-mail: alejandro.montoya@sydney.edu.au

2015-04-15

Spin-polarised density functional theory using the PBE + U approach are used to determine reaction pathways of successive NH{sub 3} dehydrogenation on the CoO(100) surface. NH{sub 3} dehydrogenation promotes noticeable displacements of the surface CoO sites, in particular due to the binding of NH{sub 2} and H species. Surface lattice O has low activity towards dehydrogenation, reflected in energy barriers that are in the range of 292 kJ mol{sup −1} to 328 kJ mol{sup −1}. There is a preference of surface NH{sub 3} dehydrogenation to N{sub 2} rather than towards NO, due to a high-energy penalty of surface O vacancy formation. The presence of CoO in cobalt oxide catalysts not only may decline the ammonia conversion but also alter the selectivity towards N{sub 2} rather than NO. - Highlights: • Minimum reactions pathways of ammonia decomposition were studied using density functional theory. • The bonding characteristics of NH{sub x} and H on the CoO(100) surface were analysed using Layer-projected density of states. • Dehydrogenations of NH{sub 3}, NH{sub 2} and NH are highly activated. • The presence of strongly bound lattice oxygen favours the ammonia decomposition towards N{sub 2}.

An evaluation of IASI-NH3 with ground-based Fourier transform infrared spectroscopy measurements

Directory of Open Access Journals (Sweden)

E. Dammers

2016-08-01

Full Text Available Global distributions of atmospheric ammonia (NH3 measured with satellite instruments such as the Infrared Atmospheric Sounding Interferometer (IASI contain valuable information on NH3 concentrations and variability in regions not yet covered by ground-based instruments. Due to their large spatial coverage and (bi-daily overpasses, the satellite observations have the potential to increase our knowledge of the distribution of NH3 emissions and associated seasonal cycles. However the observations remain poorly validated, with only a handful of available studies often using only surface measurements without any vertical information. In this study, we present the first validation of the IASI-NH3 product using ground-based Fourier transform infrared spectroscopy (FTIR observations. Using a recently developed consistent retrieval strategy, NH3 concentration profiles have been retrieved using observations from nine Network for the Detection of Atmospheric Composition Change (NDACC stations around the world between 2008 and 2015. We demonstrate the importance of strict spatio-temporal collocation criteria for the comparison. Large differences in the regression results are observed for changing intervals of spatial criteria, mostly due to terrain characteristics and the short lifetime of NH3 in the atmosphere. The seasonal variations of both datasets are consistent for most sites. Correlations are found to be high at sites in areas with considerable NH3 levels, whereas correlations are lower at sites with low atmospheric NH3 levels close to the detection limit of the IASI instrument. A combination of the observations from all sites (Nobs = 547 give a mean relative difference of −32.4 ± (56.3 %, a correlation r of 0.8 with a slope of 0.73. These results give an improved estimate of the IASI-NH3 product performance compared to the previous upper-bound estimates (−50 to +100 %.

Gas-particle interactions above a Dutch heathland: I. Surface exchange fluxes of NH3, SO2, HNO3 and HCl

Directory of Open Access Journals (Sweden)

E. Nemitz

2004-01-01

Full Text Available A field measurement campaign was carried out over a Dutch heathland to investigate the effect of gas-to-particle conversion and ammonium aerosol evaporation on surface/atmosphere fluxes of ammonia and related species. Continuous micrometeorological measurements of the surface exchange of NH3, SO2, HNO3 and HCl were made and are analyzed here with regard to average fluxes, deposition velocities (Vd, canopy resistances (Rc and canopy compensation point for NH3. Gradients of SO2, HNO3 and HCl were measured with a novel wet-denuder system with online anion chromatography. Measurements of HNO3 and HCl indicate an Rc of 100 to 200 s m-1 during warm daytime periods, probably at least partly due to non-zero acid partial pressures above NH4NO3 and NH4Cl on the leaf surfaces. Although it is likely that this observation is exacerbated by the effect of the evaporation of airborne NH4+ on the gradient measurements, the findings nevertheless add to the growing evidence that HNO3 and HCl are not always deposited at the maximum rate. Ammonia (NH3 fluxes show mainly deposition, with some periods of significant daytime emission. The net exchange could be reproduced both with an Rc model (deposition fluxes only using resistance parameterizations from former measurements, as well as with the canopy compensation point model, using parameterizations derived from the measurements. The apoplastic ratio of ammonium and hydrogen concentration (Γs=[NH4+]/[H+] of 1200 estimated from the measurements is large for semi-natural vegetation, but smaller than indicated by previous measurements at this site.

Gas-particle interactions above a Dutch heathland: I. Surface exchange fluxes of NH3, SO2, HNO3 and HCl

Science.gov (United States)

Nemitz, E.; Sutton, M. A.; Wyers, G. P.; Jongejan, P. A. C.

2004-07-01

A field measurement campaign was carried out over a Dutch heathland to investigate the effect of gas-to-particle conversion and ammonium aerosol evaporation on surface/atmosphere fluxes of ammonia and related species. Continuous micrometeorological measurements of the surface exchange of NH3, SO2, HNO3 and HCl were made and are analyzed here with regard to average fluxes, deposition velocities (Vd), canopy resistances (Rc) and canopy compensation point for NH3. Gradients of SO2, HNO3 and HCl were measured with a novel wet-denuder system with online anion chromatography. Measurements of HNO3 and HCl indicate an Rc of 100 to 200 s m-1 during warm daytime periods, probably at least partly due to non-zero acid partial pressures above NH4NO3 and NH4Cl on the leaf surfaces. Although it is likely that this observation is exacerbated by the effect of the evaporation of airborne NH4+ on the gradient measurements, the findings nevertheless add to the growing evidence that HNO3 and HCl are not always deposited at the maximum rate. Ammonia (NH3) fluxes show mainly deposition, with some periods of significant daytime emission. The net exchange could be reproduced both with an Rc model (deposition fluxes only) using resistance parameterizations from former measurements, as well as with the canopy compensation point model, using parameterizations derived from the measurements. The apoplastic ratio of ammonium and hydrogen concentration (Γs=[NH4+]/[H+]) of 1200 estimated from the measurements is large for semi-natural vegetation, but smaller than indicated by previous measurements at this site.

Preparation of planar CH{sub 3}NH{sub 3}PbI{sub 3} thin films with controlled size using 1-ethyl-2-pyrrolidone as solvent

Energy Technology Data Exchange (ETDEWEB)

Hao, Qiuyan; Chu, Yixia [Engineering Laboratory of Functional Optoelectronic Crystalline Materials of Hebei Province, School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300132 (China); Zheng, Xuerong [Key Laboratory of Advanced Ceramics and Machining Technology of Ministry of Education, School of Materials Science and Engineering, Tianjin University, Tianjin 300072 (China); Liu, Zhenya; Liang, Liming [Engineering Laboratory of Functional Optoelectronic Crystalline Materials of Hebei Province, School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300132 (China); Qi, Jiakun [State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083 (China); Zhang, Xin [Engineering Laboratory of Functional Optoelectronic Crystalline Materials of Hebei Province, School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300132 (China); Liu, Gang [School of Chemical Engineering, Hebei University of Technology, Tianjin 300132 (China); Liu, Hui, E-mail: liuhuihebut@163.com [Engineering Laboratory of Functional Optoelectronic Crystalline Materials of Hebei Province, School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300132 (China); Chen, Hongjian [Engineering Laboratory of Functional Optoelectronic Crystalline Materials of Hebei Province, School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300132 (China); Liu, Caichi, E-mail: ccliu@hebut.edu.cn [Engineering Laboratory of Functional Optoelectronic Crystalline Materials of Hebei Province, School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300132 (China)

2016-06-25

Recently, planar perovskite solar cells based on CH{sub 3}NH{sub 3}PbI{sub 3} have attracted many researcher's interest due to their unique advantages such as simple cell architecture, easy fabrication and potential multijunction construction comparing to the initial mesoporous structure. However, the preparation of planar perovskite films with high quality is still in challenge. In this paper, we developed a vapor-assisted solution process using a novel and green solvent of 1-Ethyl-2-pyrrolidone (NEP) instead of the traditional N, N-dimethylformamide (DMF) to construct a high-quality perovskite CH{sub 3}NH{sub 3}PbI{sub 3} thin film with pure phase, high compactness, small surface roughness and controlled size. The phase evolution and growth mechanism of the perovskite films are also discussed. Utilizing the NEP of low volatility and moderate boiling point as solvent, we dried the PbI{sub 2}-NEP precursor films at different temperature under vacuum and then obtained PbI{sub 2} thin films with different crystalline degree from amorphous to highly crystalline. The perovskite films with crystal size ranged from hundreds of nanometers to several micrometers can be prepared by reacting the PbI{sub 2} films of different crystalline degree with CH{sub 3}NH{sub 3}I vapor. Moreover, planar-structured solar cells combining the perovskite film with TiO{sub 2} and spiro-OMeTAD as the electron and holes transporting layer achieves a power conversion efficiency of 10.2%. - Highlights: • A novel and green solvent of 1-Ethyl-2-pyrrolidone (NEP) was used to construct high-quality perovskite CH{sub 3}NH{sub 3}PbI{sub 3} thin film. • The CH{sub 3}NH{sub 3}PbI{sub 3} grain with different sizes ranged from hundreds of nanometers to several micrometers can be obtained. • Planar-structured perovskite CH{sub 3}NH{sub 3}PbI{sub 3} solar cells using NEP as solvent achieves a power conversion efficiency of 10.2%.

Electron motion in high-pressure polar gases: NH3

International Nuclear Information System (INIS)

Christophorou, L.G.; Carter, J.G.; Maxey, D.V.

1982-01-01

Drift velocities w for slow electrons in NH 3 vapor have been measured and are reported as a function of the density-reduced electric field E/N ( -17 V cm 2 ), density N (2.43--292 x 10 18 molecule cm -3 ), and temperature T (300--650 K). The w decreases with increasing N considerably and this decrease varies with T; for a fixed N it is higher the lower the T. Use is made of the T- and N-dependence of w to assess the role of the various processes which delay the electron drift. The density range above approx.2.5 x 10 19 molecules cm -3 seems (anionic) electron state. The number density N/sub L/ at which complete electron localization occurs, has been estimated at various T. At T = 300 K, N/sub L/approx. =3.3 x 10 20 molecule cm -3 or approx.0.01 g cm 3 . Estimates have also been made of the binding energy of the electron to the trapping species (possibly NH 3 clusters) which, depending on T, range from 0.11 to 0.15 eV

[Seasonal variation patterns of NH4(+) -N/NO3(-) -N ratio and delta 15 NH4(+) value in rainwater in Yangtze River Delta].

Science.gov (United States)

Xie, Ying-Xin; Zhang, Shu-Li; Zhao, Xu; Xiong, Zheng-Qin; Xing, Guang-Xi

2008-09-01

By using a customized manual rainwater sampler made of polyvinyl chloride plastic, the molar ratio of NH4(+) -N/NO3(-) -N and the natural 15N abundance of NH4(+) (delta 15 NH4(+) in rainwater was monitored all year round from June 2003 to July 2005 at three observation sites (Changshu, Nanjing, and Hangzhou) in the Yangtze River Delta. The results indicated that at the three sites, the NH4(+) -N/NO3(-) -N ratio and the delta 15 NH4(+) value in rainwater had the similar seasonal variation trend, being more obvious in Changshu (rural monitoring type) site than in Nanjing (urban monitoring type) and Hangzhou (urban-rural monitoring type) sites. The NH4(+) -N/NO3(-) -N ratio peaked from early June to early August, declined gradually afterwards, and reached the bottom in winter; while the delta 15 NH4(+) value was negative from late June to mid-August, turned positive from late August to mid or late November, became negative again when winter dominated from December to March, but turned positive again in next May and negative again in next July. These seasonal variation patterns of NH4(+) -N/NO3(-) -N ratio and delta 15 NH4(+) value were found in relation to the application of chemical nitrogen fertilizers during different crop growth periods, and also, the alternation of seasons and the NH3 volatilization from other NH3 emission sources (including excrements of human and animals, nitrogen- polluted water bodies, and organic nitrogen sources, etc.), which could be taken as an indicator of defining the sources and form composition of NH4(+) in atmospheric wet deposition and the intensity of various terrestrial NH3 emission sources.

Surface chemistry of PH 3, PF 3 and PCl 3 on Ru(0001)

Science.gov (United States)

Tao, H.-S.; Diebold, U.; Shinn, N. D.; Madey, T. E.

1994-06-01

The adsorption, desorption and decomposition of PH 3, PF 3 and PCl 3 on Ru(0001) have been studied by soft X-ray photoelectron spectroscopy (SXPS) using synchrotron radiation. Due to large chemical shifts in the P 2p core levels, different phosphorus containing surface species can be identified. We find that PF 3 adsorbs molecularly on Ru(0001) at 80 and 300 K. At 80 K, PH 3 saturates the surface with one layer of atomic hydrogen, elemental phosphorus, subhydride (i.e., PHx (0 PH 3, with a total phosphorus coverage of 0.4 ML. At 300 K, PH 3 decomposes into atomic hydrogen and elemental phosphorus with a phosphorus coverage of 0.8 ML. At 80 K, PCl 3 adsorbs dissociatively into atomic chlorine, elemental phosphorus, PCl and possibly PCl 2 and PCl 3 in the first monolayer. Formation of multilayers of PCl 3 is observed at 80 K. At 300 K, PCl 3 adsorbs dissociatively as atomic chlorine and elemental phosphorus with a saturation phosphorus coverage of 0.1 ML. The variation in total phosphorus uptake at 300 K from PX3 ( X = H, FandCl) adsorption is a result of competition between site blocking by dissociation fragments and displacement reactions. Annealing surfaces with adsorbed phosphorus to 1000 K results in formation of RuzP ( z = 1 or 2), which is manifested by the chemical shifts in the P2p core level, as well as the P LVV Auger transition. The recombination of adsorbed phosphorus and adsorbed X ( = H, FandCl) from decomposition is also observed, but is a minor reaction channel on the surface. Thermochemical data are used to analyze the different stabilities of PX 3 at 300 K, namely, PF 3 adsorbs molecularly and PH 3 and PCl 3 dissociate completely. First, we compare the heat of molecular adsorption and the heat of dissociative adsorption of PX 3 on Ru(0001), using an enthalpy approach, and find results consistent with experimental observations. Second, we compare the total bond energy difference between molecular adsorption and complete dissociation of PX 3 on Ru

Preparation and Study of NH3 Gas Sensing Behavior of Fe2O3 Doped ZnO Thick Film Resistors

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D. R. Patil

2006-08-01

Full Text Available The preparation, characterization and gas sensing properties of pure and Fe2O3-ZnO mixed oxide semiconductors have been investigated. The mixed oxides were obtained by mixing ZnO and Fe2O3 in the proportion 1:1, 1:0.5 and 0.5:1. Pure ZnO was observed to be insensitive to NH3 gas. However, mixed oxides (with ZnO: Fe2O3 =1:0.5 were observed to be highly sensitive to ammonia gas. Upon exposure to NH3 gas, the barrier height of Fe2O3-ZnO intergranular regions decreases markedly due to the chemical transformation of Fe2O3 into well conducting ferric ammonium hydroxide leading to a drastic decrease in resistance. The crucial gas response was found to NH3 gas at 3500C and no cross response was observed to other hazardous and polluting gases. The effects of microstructure and doping concentration on the gas response, selectivity, response and recovery of the sensor in the presence of NH3 gas were studied and discussed.

Nature of phase transitions in ammonium oxofluorovanadates, a vibrational spectroscopy study of (NH4)3VO2F4 and (NH4)3VOF5.

Science.gov (United States)

Gerasimova, Yu V; Oreshonkov, A S; Laptash, N M; Vtyurin, A N; Krylov, A S; Shestakov, N P; Ershov, A A; Kocharova, A G

2017-04-05

Two ammonium oxofluorovanadates, (NH 4 ) 3 VO 2 F 4 and (NH 4 ) 3 VOF 5 , have been investigated by temperature-dependent infrared and Raman spectroscopy methods to determine the nature of phase transitions (PT) in these compounds. Dynamics of quasioctahedral groups was simulated within the framework of semi-empirical approach, which justified the cis-conformation of VO 2 F 4 3- (C 2v ) and the C 4v geometry of VOF 5 3- . The observed infrared and Raman spectra of both compounds at room temperature (RT) revealed the presence at least of two crystallographically independent octahedral groups. The first order PT at elevated temperatures is connected with a complete dynamic disordering of these groups with only single octahedral state. At lower temperatures, the octahedra are ordered and several octahedral states appear. This PT is the most pronounced in the case of (NH 4 ) 3 VOF 5 , when at least seven independent VOF 5 3- octahedra are present in the structure below 50K, in accordance with the Raman spectra. Ammonium groups do not take part in PTs at higher and room temperatures but their reorientational motion freezes at lower temperatures. Copyright © 2017. Published by Elsevier B.V.

Effects of two litter amendments on air NH3 levels in broiler closed-houses

Science.gov (United States)

Atapattu, N. S. B. M; Lakmal, L. G. E.; Perera, P. W. A.

2017-01-01

Objective High NH3 emissions from poultry houses are reported to have negative impacts on health, welfare and safety of birds and humans, and on the environment. Objective of the present study was to determine the effects of two litter amendments on the NH3 levels in broiler closed houses under hot-humid conditions. Methods Giving a completely randomize design, nine closed houses, each housed 32,500 birds on paddy husk litter, were randomly allocated into two treatment (Mizuho; a bacterial culture mix and Rydall OE; an enzymatic biocatalyst) and control groups. NH3 levels were determined thrice a day (0600, 1200, and 1800 h), at three heights from the litter surface (30, 90, and 150 cm), at 20 predetermined locations of a house, from day 1 to 41. Results Rydall significantly reduced the NH3 level compared to control and Mizuho. NH3 levels at 30 cm were significantly higher than that of 90 and 150 cm. The NH3 levels at 30 cm height were higher than 25 ppm level from day 9, 11, and 13 in Mizuho, control, and Rydall groups, respectively to day 41. NH3 levels at 150 cm height were higher than maximum threshold limit of 50 ppm for human exposure from day 12, 14, and 15 in Mizuho, control, and Rydall groups, respectively to day 33. Being significantly different among each other, the NH3 level was highest and lowest at 0600 and 1800 h. Litter amendments had no significant effects on growth performance. Rydall significantly increased the litter N content on day 24. Conclusion It was concluded that the NH3 levels of closed house broiler production facilities under tropical condition are so high that both birds and workers are exposed to above recommended levels during many days of the growing period. Compared to microbial culture, the enzymatic biocatalyst was found to be more effective in reducing NH3 level. PMID:28423888

NQR and X-ray crystal structure studies of cadmium halide complexes: [C(NH2)3]CdI3 and [4-ClC6H5NH3]3CdBr5

International Nuclear Information System (INIS)

Gesing, Thorsten M.; Lork, Enno; Terao, Hiromitsu; Ishihara, Hideta

2016-01-01

The crystal structures of [C(NH 2 ) 3 ]CdI 3 (1) and [4-ClC 6 H 5 NH 3 ] 3 CdBr 5 (2) have been determined at 100 K: monoclinic, Cc, a = 828.75(3) pm, b = 1615.31(5) pm, c = 810.64(3) pm, and β = 106.5820(10) for 1; monoclinic, P2 1 /c, a = 1486.93(5) pm, b = 794.31(3) pm, c = 2290.59(7) pm, and β = 99.6830(10) for 2. The structure of 1 has an infinite chain of anions consisting of [CdI 4 ] tetrahedra sharing two corners. The structure of 2 has an infinite chain of anions consisting of [CdBr 6 ] octahedra sharing two corners in cis positions. In both structures, isolated cations are connected to the anion chains through weak hydrogen bonds Cd-X..H to result in three-dimensional network structures. In accordance with the crystal structures, three 127 I (m = ±1/2 <-> m = ±3/2), five 81 Br, and three 35 Cl nuclear quadrupole resonance (NQR) lines were observed for 1 and 2. The NQR spectra reflect the anion chain structures and their weak hydrogen bonds. The MO calculations of the models [Cd 5 I 16 ] 6- for 1 and [Cd 3 Br 16 ] 10- for 2 estimate only about half the values for the NQR frequencies but give accurate electric field gradient directions.

A straightforward and efficient synthesis of 3-(pyrimidinyl)propanoates from levulinic acid

Energy Technology Data Exchange (ETDEWEB)

Flores, Alex F.C.; Malavolta, Juliana L.; Souto, Alynne A.; Goularte, Rayane B.; Flores, Darlene C., E-mail: alex.fcf@ufsm.br [Universidade Federal de Santa Maria (UFSM/NUQUIMHE), RS (Brazil). Departamento de Quimica. Nucleo de Quimica de Heterociclos

2013-04-15

The cyclocondensation of methyl 7,7,7-trifluoro-4-methoxy-6-oxo-4-heptenoate and methyl 7,7,7-trichloro-4-methoxy-6-oxo-4-heptenoate, derived from levulinic acid with amidines [NH{sub 2}CONH{sub 2}, NH{sub 2}CR(NH) (R = H, Me, Ph, NH{sub 2}, SMe and 1H-pyrazol-1-yl), 5-amino-3-methyl-1H-pyrazol and 2-aminothiazole] into pyrimidine and pyrimidine-like derivatives as a new type of glutamate-like 3-(trihalomethylatedpyrimidinyl)propanoate is reported. Preparation of 3-(trihalomethylatedpyrimidinyl) propanohydrazides is also described. The synthetic potential of this straightforward protocol was established by the synthesis of fourteen new 3-(pyrimidinyl) propanoates in regular to good yields (38-92%). The structural assignments were based on the analysis of their {sup 1}H and {sup 13}C nuclear magnetic resonance (NMR) and gas chromatography-mass spectrometry (GC-MS) data. (author)

Crystallographic Investigations into Properties of Acentric Hybrid Perovskite Single Crystals NH(CH3)3SnX3(X = Cl, Br)

KAUST Repository

Dang, Yangyang; Zhong, Cheng; Zhang, Guodong; Ju, Dianxing; Wang, Lei; Xia, Shengqing; Xia, Haibing; Tao, Xutang

2016-01-01

substitute for the lead in the halides perovskites and solving the ambiguous crystal structures and phase transition of NH(CH3)3SnX3 (X = Cl, Br). Here, we report the bulk crystal growths and different crystal morphologies of orthorhombic hybrid perovskites

Morphology-photovoltaic property correlation in perovskite solar cells: One-step versus two-step deposition of CH3NH3PbI3

Directory of Open Access Journals (Sweden)

Jeong-Hyeok Im

2014-08-01

Full Text Available Perovskite CH3NH3PbI3 light absorber is deposited on the mesoporous TiO2 layer via one-step and two-step coating methods and their photovoltaic performances are compared. One-step coating using a solution containing CH3NH3I and PbI2 shows average power conversion efficiency (PCE of 7.5%, while higher average PCE of 13.9% is obtained from two-step coating method, mainly due to higher voltage and fill factor. The coverage, pore-filling, and morphology of the deposited perovskite are found to be critical in photovoltaic performance of the mesoporous TiO2 based perovskite solar cells.

Surface study of platinum decorated graphene towards adsorption of NH_3 and CH_4

International Nuclear Information System (INIS)

Rad, Ali Shokuhi; Pazoki, Hossein; Mohseni, Soheil; Zareyee, Daryoush; Peyravi, Majid

2016-01-01

To distinguish the potential of graphene sensors, there is a need to recognize the interaction between graphene sheet and adsorbing molecules. We used density functional theory (DFT) calculations to study the properties of pristine as well as Pt-decorated graphene sheet upon adsorption of NH_3 and CH_4 on its surface to exploit its potential to be as gas sensors for them. We found much higher adsorption, higher charge transfer, lower intermolecular distance, and higher orbital hybridizing upon adsorption of NH_3 and CH_4 gas molecules on Pt-decorated graphene compared to pristine graphene. Also our calculations reveal that the adsorption energies on Pt-decorated graphene sheet are in order of NH_3 >CH_4 which could be corresponded to the order of their sensitivity on this modified surface. We used orbital analysis including density of states as well as frontier molecular orbital study for all analyte-surface systems to more understanding the kind of interaction (physisorption or chemisorption). Consequently, the Pt-decorated graphene can transform the existence of NH_3 and CH_4 molecules into electrical signal and it may be potentially used as an ideal sensor for detection of NH_3 and CH_4 in ambient situation. - Highlights: • Pt-decorated graphene was investigated as an adsorbent for NH_3 and CH_4. • Much higher adsorption of NH_3 and CH_4 on Pt-decorated graphene than pristine graphene. • Higher adsorption of NH_3 compared to CH_4 on Pt-decorated graphene. • Pt influences the electronic structure of graphene.

Rotational Spectroscopy of the NH{sub 3}–H{sub 2} Molecular Complex

Energy Technology Data Exchange (ETDEWEB)

Surin, L. A.; Schlemmer, S. [I. Physikalisches Institut, University of Cologne, Zülpicher Str. 77, D-50937 Cologne (Germany); Tarabukin, I. V. [Institute of Spectroscopy of Russian Academy of Sciences, Fizicheskaya Str. 5, 108840 Troitsk, Moscow, Russia (Russian Federation); Breier, A. A.; Giesen, T. F. [Institute of Physics, University of Kassel, Heinrich-Plett-Str. 40, D-34132 Kassel (Germany); McCarthy, M. C. [Harvard-Smithsonian Center for Astrophysics, Cambridge, MA 02138 (United States); Avoird, A. van der, E-mail: surin@ph1.uni-koeln.de, E-mail: A.vanderAvoird@theochem.ru.nl [Theoretical Chemistry, Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen (Netherlands)

2017-03-20

We report the first high resolution spectroscopic study of the NH{sub 3}–H{sub 2} van der Waals molecular complex. Three different experimental techniques, a molecular beam Fourier transform microwave spectrometer, a millimeter-wave intracavity jet OROTRON spectrometer, and a submillimeter-wave jet spectrometer with multipass cell, were used to detect pure rotational transitions of NH{sub 3}–H{sub 2} in the wide frequency range from 39 to 230 GHz. Two nuclear spin species, ( o )-NH{sub 3}–( o )-H{sub 2} and ( p )-NH{sub 3}–( o )-H{sub 2}, have been assigned as carriers of the observed lines on the basis of accompanying rovibrational calculations performed using the ab initio intermolecular potential energy surface (PES) of Maret et al. The experimental spectra were compared with the theoretical bound state results, thus providing a critical test of the quality of the NH{sub 3}–H{sub 2} PES, which is a key issue for reliable computations of the collisional excitation and de-excitation of ammonia in the dense interstellar medium.

Selective Catalytic Reduction of NO with NH3 Over V-MCM-41 Catalyst.

Science.gov (United States)

Kwon, Woo Hyun; Park, Sung Hoon; Kim, Ji Man; Park, Su Bin; Jung, Sang-Chul; Kim, Sang Chai; Jeon, Jong-Ki; Park, Young-Kwon

2016-02-01

V-MCM-41, a mesoporous catalyst doped with V2O5, was applied for the first time to the removal of atmospheric NO. The quantity of V2O5 added was 10 wt% and 30 wt%. The characteristics of the synthesized catalysts were examined using XRD, N2 soprtion, and NH3-TPD. With increasing quantity of V2O5 added, specific surface area decreased and pore size increased. When the quantity of V2O5 was 10 wt%, the MCM-41 structure was retained, whereas considerable collapse of mesoporous structure was observed when 30 wt% V2O5 was added. The examination of acid characteristics using NH3-TPD showed that 30 wt% V-MCM-41 had the higher NH3 adsorption ability, implying that it would exhibit high activity for NH3 SCR reaction. In the NO removal experiments, 30 wt% V-MCM-41 showed much higher NO removal efficiency than 10 wt% V-MCM-41, which was attributed to its high NH3 adsorption ability.

Reactions of 11C recoil atoms in the systems H2O-NH3, H2O-CH4 and NH3-CH4

International Nuclear Information System (INIS)

Nebeling, B.

1988-11-01

In this study the chemical reactions of recoil carbon 11 in the binary gas mixtures H 2 O-NH 3 , H 2 O-CH 4 and NH 3 -CH 4 in different mixing ratios as well as in solid H 2 O and in a solid H 2 O-NH 3 mixture were analyzed in dependence of the dose. The analyses were to serve e.g. the simulation of chemical processes caused by solar wind, solar radiation and cosmic radiation in the coma and core of comets. They were to give further information about the role of the most important biogeneous element carbon, i.e. carbon, in the chemical evolution of the solar system. Besides the actual high energy processes resulting in the so-called primary products, also the radiation-chemical changes of the primary products were also observed in a wide range of dosing. The generation of the energetic 11 C atoms took place according to the target composition by the nuclear reactions 14 N(p,α) 11 C, 12 C( 3 He,α) 11 C or the 16 O(p,αpn) 11 C reaction. The identification of the products marked with 11 C was carried out by means of radio gas chromatography or radio liquid chromatography (HPLC). (orig./RB) [de

AMT1;1 transgenic rice plants with enhanced NH4(+) permeability show superior growth and higher yield under optimal and suboptimal NH4(+) conditions.

Science.gov (United States)

Ranathunge, Kosala; El-Kereamy, Ashraf; Gidda, Satinder; Bi, Yong-Mei; Rothstein, Steven J

2014-03-01

The major source of nitrogen for rice (Oryza sativa L.) is ammonium (NH4(+)). The NH4(+) uptake of roots is mainly governed by membrane transporters, with OsAMT1;1 being a prominent member of the OsAMT1 gene family that is known to be involved in NH4(+) transport in rice plants. However, little is known about its involvement in NH4(+) uptake in rice roots and subsequent effects on NH4(+) assimilation. This study shows that OsAMT1;1 is a constitutively expressed, nitrogen-responsive gene, and its protein product is localized in the plasma membrane. Its expression level is under the control of circadian rhythm. Transgenic rice lines (L-2 and L-3) overexpressing the OsAMT1;1 gene had the same root structure as the wild type (WT). However, they had 2-fold greater NH4(+) permeability than the WT, whereas OsAMT1;1 gene expression was 20-fold higher than in the WT. Analogous to the expression, transgenic lines had a higher NH4(+) content in the shoots and roots than the WT. Direct NH4(+) fluxes in the xylem showed that the transgenic lines had significantly greater uptake rates than the WT. Higher NH4(+) contents also promoted higher expression levels of genes in the nitrogen assimilation pathway, resulting in greater nitrogen assimilates, chlorophyll, starch, sugars, and grain yield in transgenic lines than in the WT under suboptimal and optimal nitrogen conditions. OsAMT1;1 also enhanced overall plant growth, especially under suboptimal NH4(+) levels. These results suggest that OsAMT1;1 has the potential for improving nitrogen use efficiency, plant growth, and grain yield under both suboptimal and optimal nitrogen fertilizer conditions.

AMT1;1 transgenic rice plants with enhanced NH4 + permeability show superior growth and higher yield under optimal and suboptimal NH4 + conditions

Science.gov (United States)

Rothstein, Steven J.

2014-01-01

The major source of nitrogen for rice (Oryza sativa L.) is ammonium (NH4 +). The NH4 + uptake of roots is mainly governed by membrane transporters, with OsAMT1;1 being a prominent member of the OsAMT1 gene family that is known to be involved in NH4 + transport in rice plants. However, little is known about its involvement in NH4 + uptake in rice roots and subsequent effects on NH4 + assimilation. This study shows that OsAMT1;1 is a constitutively expressed, nitrogen-responsive gene, and its protein product is localized in the plasma membrane. Its expression level is under the control of circadian rhythm. Transgenic rice lines (L-2 and L-3) overexpressing the OsAMT1;1 gene had the same root structure as the wild type (WT). However, they had 2-fold greater NH4 + permeability than the WT, whereas OsAMT1;1 gene expression was 20-fold higher than in the WT. Analogous to the expression, transgenic lines had a higher NH4 + content in the shoots and roots than the WT. Direct NH4 + fluxes in the xylem showed that the transgenic lines had significantly greater uptake rates than the WT. Higher NH4 + contents also promoted higher expression levels of genes in the nitrogen assimilation pathway, resulting in greater nitrogen assimilates, chlorophyll, starch, sugars, and grain yield in transgenic lines than in the WT under suboptimal and optimal nitrogen conditions. OsAMT1;1 also enhanced overall plant growth, especially under suboptimal NH4 + levels. These results suggest that OsAMT1;1 has the potential for improving nitrogen use efficiency, plant growth, and grain yield under both suboptimal and optimal nitrogen fertilizer conditions. PMID:24420570

Tunable bandgap in hybrid perovskite CH3NH3Pb(Br3−yXy single crystals and photodetector applications

Directory of Open Access Journals (Sweden)

L. Wang

2016-04-01

Full Text Available We report the synthesis of CH3NH3Pb(Br3−yXy (X=Cl and I single crystals via a stepwise temperature control approach. High-quality CH3NH3Pb(Br3−yXy crystals with a tunable bandgap from 1.92eV to 2.53eV have been prepared successfully in this way. And further experiments revealed the influence of halogen content and preparation temperature on the structural and optical properties of these crystals. It is observed that chlorine can lower the critical nucleation energy, which results in crystallizing at lower temperature with the chlorine content increasing, while the nucleation energy increases slowly with increasing iodine content. Moreover, in contrast to Frank–van der Merwe growth with low heating rate, high heating rate leads to a mass of small size single crystals and Stranski-Krastanov growth. The single crystals with tunable band gap and impressive characteristics enable us to fabricate high performance photodetectors for different wavelengths.

The GRP1 PH domain, like the AKT1 PH domain, possesses a sentry glutamate residue essential for specific targeting to plasma membrane PI(3,4,5)P(3).

Science.gov (United States)

Pilling, Carissa; Landgraf, Kyle E; Falke, Joseph J

2011-11-15

During the appearance of the signaling lipid PI(3,4,5)P(3), an important subset of pleckstrin homology (PH) domains target signaling proteins to the plasma membrane. To ensure proper pathway regulation, such PI(3,4,5)P(3)-specific PH domains must exclude the more prevalant, constitutive plasma membrane lipid PI(4,5)P(2) and bind the rare PI(3,4,5)P(3) target lipid with sufficiently high affinity. Our previous study of the E17K mutant of the protein kinase B (AKT1) PH domain, together with evidence from Carpten et al. [Carpten, J. D., et al. (2007) Nature 448, 439-444], revealed that the native AKT1 E17 residue serves as a sentry glutamate that excludes PI(4,5)P(2), thereby playing an essential role in specific PI(3,4,5)P(3) targeting [Landgraf, K. E., et al. (2008) Biochemistry 47, 12260-12269]. The sentry glutamate hypothesis proposes that an analogous sentry glutamate residue is a widespread feature of PI(3,4,5)P(3)-specific PH domains, and that charge reversal mutation at the sentry glutamate position will yield both increased PI(4,5)P(2) affinity and constitutive plasma membrane targeting. To test this hypothesis, we investigated the E345 residue, a putative sentry glutamate, of the general receptor for phosphoinositides 1 (GRP1) PH domain. The results show that incorporation of the E345K charge reversal mutation into the GRP1 PH domain enhances PI(4,5)P(2) affinity 8-fold and yields constitutive plasma membrane targeting in cells, reminiscent of the effects of the E17K mutation in the AKT1 PH domain. Hydrolysis of plasma membrane PI(4,5)P(2) releases the E345K GRP1 PH domain into the cytoplasm, and the efficiency of this release increases when Arf6 binding is disrupted. Overall, the findings provide strong support for the sentry glutamate hypothesis and suggest that the GRP1 E345K mutation will be linked to changes in cell physiology and human pathologies, as demonstrated for AKT1 E17K [Carpten, J. D., et al. (2007) Nature 448, 439-444; Lindhurst, M. J., et al

Tunable far infrared laser spectroscopy of van der Waals bonds: Ar-NH sub 3

Energy Technology Data Exchange (ETDEWEB)

Gwo, Dz-Hung (Lawrence Berkeley Lab., CA (USA) California Univ., Berkeley, CA (USA). Dept. of Chemistry)

1989-11-01

Hyperfine resolved vibration-rotation-tunneling spectra of Ar--NH{sub 3} and (NH{sub 3}){sub 2}, generated in a planar supersonic jet, have been measured with the Berkeley tunable far infrared laser spectrometer. Among the seven rotationally assigned bands, one band belongs to Ar--NH{sub 3}, and the other six belong to (NH{sub 3}){sub 2}. To facilitate the intermolecular vibrational assignment for Ar--NH{sub 3}, a dynamics study aided by a permutation-inversion group theoretical treatment is performed on the rovibrational levels. The rovibrational quantum number correlation between the free internal rotor limit and the semi-rigid limit is established to provide a basic physical picture of the evolution of intermolecular vibrational component states. An anomalous vibronically allowed unique Q branch vibrational band structure is predicted to exist for a near prolate binary complex containing an inverting subunit. According to the model developed in this work, the observed band of Ar--NH{sub 3} centered at 26.470633(17) cm{sup {minus}1} can correlate only to either the fundamental dimeric stretching band for the A{sub 2} states with the NH{sub 3} inversional quantum number v{sub i} = 1, or the K{sub a} = 0 {l arrow} 0 subband of the lowest internal-rotation-inversion difference band. Although the estimated nuclear quadrupole coupling constant favors a tentative assignment in terms of the first possibility, a definitive assignment will require far infrared data and a dynamical model incorporating a potential surface.

Increase in Ice Nucleation Efficiency of Feldspars, Kaolinite and Mica in Dilute NH3 and NH4+-containing Solutions

Science.gov (United States)

Kumar, A.; Marcolli, C.; Luo, B.; Krieger, U. K.; Peter, T.

2017-12-01

Semivolatile species present in the atmosphere are prone to adhere to mineral dust particle surfaces during long range transport, and could potentially change the particle surface properties and its ice nucleation (IN) efficiency. Immersion freezing experiments were performed with microcline (K-feldspar), known to be highly IN active, suspended in aqueous solutions of ammonia, (NH4)2SO4, NH4HSO4, NH4NO3, NH4Cl, Na2SO4, H2SO4, K2SO4 and KCl to investigate the effect of solutes on the IN efficiency. Freezing of emulsified droplets investigated with a differential scanning calorimeter (DSC) showed that the heterogeneous ice nucleation temperatures deviate from the water activity-based IN theory, describing heterogeneous ice nucleation temperatures as a function of solution water activity by a constant offset with respect to the ice melting point curve (Zobrist et al. 2008). IN temperatures enhanced up to 4.5 K were observed for very dilute NH3 and NH4+-containing solutions while a decrease was observed as the concentration was further increased. For all solutes with cations other than NH4+, the IN efficiency decreased. An increase of the IN efficiency in very dilute NH3 and NH4+-containing solutions followed by a decrease with increasing concentration was also observed for sanidine (K-feldspar) and andesine (Na/Ca-feldspar). This is an important indication towards specific chemical interactions between solutes and the feldspar surface which is not captured by the water activity-based IN theory. A similar trend is present but less pronounced in case of kaolinite and mica, while quartz is barely affected. We hypothesize that the hydrogen bonding of NH3 molecules with surface -OH groups could be the reason for the enhanced freezing temperatures in dilute ammonia and ammonium containing solutions as they could form an ice-like overlayer providing hydrogen bonding groups for ice to nucleate on top of it. This implies to possibilities of enhanced IN efficiency, especially

In situ attenuated total reflection infrared (ATR-IR) study of the adsorption of NO2-, NH2OH, and NH4+ on Pd/Al2O3 and Pt/Al2O3.

NARCIS (Netherlands)

Ebbesen, S.D.; Mojet, Barbara; Lefferts, Leonardus

2008-01-01

In relation to the heterogeneous hydrogenation of nitrite, adsorption of NO2-, NH4+, and NH2OH from the aqueous phase was examined on Pt/Al2O3, Pd/Al2O3, and Al2O3. None of the investigated inorganic nitrogen compounds adsorb on alumina at conditions presented in this study. NO2-(aq) and NH4+(aq) on

Formulation of an inhibitor radiopharmaceutical of prostatic antigen of 177Lu-Glu-Nh-CO-Nh-Lys membrane

International Nuclear Information System (INIS)

Ortega S, D.

2015-01-01

The prostate specific membrane antigen (PSMA) is a zinc metalloenzyme that is expressed on the cell membrane and highly expressed in prostate cancer. Recently, it has been demonstrated that the peptide sequence Glu-Nh-CO-Nh-Lys inhibit PSMA activity through an electrostatic interaction with the Zn. Several theragnostic radiopharmaceuticals with base in 177 Lu have been developed for radiotherapy of specific molecular targets because gamma and beta emissions of the radionuclide (β = 0.498 MeV and γ= 0.133 MeV). However, there is currently no label a formulation for preparing a radiopharmaceutical of 177 Lu-Glu-Nh-CO-Nh-Lys useful treatment of prostate cancer. The aim of this research was to optimize and document the process of production of the radiopharmaceutical 177 Lu-Glu-Nh-CO-Nh-Lys for sanitary registration application before the Comision Federal para la Proteccion contra Riesgos Sanitarios (COFEPRIS). The optimization of the production process was assessed a factorial design of three variables with mixed levels (3 x 3 x 2) where the dependent variable is the radiochemical purity, the analytical method was validated by UV-Vis spectrophotometry. Next, process validation was carried out by labeling 3 lots of the optimized formulation of the radiopharmaceutical (5.55 GBq (2.16 μg) of 177 LuCl 3 , 90 mg peptide PSMA, 50 mg ascorbic acid and 150 μL of acetate buffer 1 M ph 5), long-term stability was performed by high resolution liquid chromatography) to determine its useful shelf life. 3 validation batches were prepared under protocols of Good Manufacturing Practice (GMP) in the Production Plant of Radiopharmaceuticals of the Instituto Nacional de Investigaciones Nucleares (ININ), meet specifications preset by obtaining a sterile and free development of bacterial endotoxin yields of labeled 100% and which retains its quality characteristics radiochemical purity greater than 90% for at least 15 days. (Author)

CH3NH3PbI3 and CsPbI3 Supramolecular Clusters in 1D: Do They Evolve with the Same Principle of Cooperative Binding?

Science.gov (United States)

Varadwaj, Arpita; Varadwaj, Pradeep R.; Yamashita, Koichi

Development of novel semiconductor-based photo-catalytic and -voltaic systems is a major area of research in nanoscience and technologies, and engineering. The process can be either direct or indirect in converting the light energy into electricity. Some of the photovoltaics include the organic, dye-sensitized, and halide perovskite solar cells, among others. Methylammonium lead iodide (CH3NH3PbI3) inorganic-organic hybrid perovskite is one among the many highly valued semiconductors reported till date, comparable with the inorganic cesium lead iodide (CsPbI3) perovskite. These are competitive candidates in the solar energy race. Nevertheless, this study was concentrated on the fundamental understanding of the rational designs of the CH3NH3PbI3 and CsPbI3 supramolecular materials using first-principles calculations, emerged though the self-assembly of the respective building blocks. It therefore addresses the question whether the (CH3NH3PbI3)n and (CsPbI3)n (n =1-10) supramolecular clusters are the consequences of additivity, or non-additive cooperative binding? For addressing this question, the supramolecular properties such as the polarizability, the intermolecular charge transfer, and the binding energy, etc., all w.r.t the cluster size n, are exploited. CREST-JST, 7 Gobancho, Chiyoda-ku, Tokyo, Japan 102-0076.

Theoretical study of the properties of BH3NH3

International Nuclear Information System (INIS)

Binkley, J.S.; Thorne, L.R.

1983-01-01

Borane monoammoniate (BH 3 NH 3 ) has been studied using several ab initio electronic structure methods and Gaussian basis sets. Equilibrium geometries have been computed at the Hartree--Fock level and, using the electron-correlated Moller--Plesset perturbation method, carried out to third order (MP3) with double-zeta polarized quality basis sets. The computed MP3 geometry is in close agreement with recent microwave data; electron correlation is found to be necessary for a proper description of the B--N distance. Hartree--Fock dipole moments and harmonic vibrational frequencies are presented and discussed. Moller--Plesset perturbation theory carried out to fourth order with triple-zeta plus polarization basis sets is used to compute a B--N dissociation energy of 34.7 kcal mol -1 and a (Hartree--Fock zero-point corrected) rotational barrier of 2.065 kcal mol -1 , which is in excellent agreement with the experimental value. Analysis of the dissociation energy as a function of perturbation order indicates that terms involving triple and quadruple substitutions are required in the dissociation energy

Encapsulation of a trinuclear silver(I) cluster by two imido-nitrido metalloligands [{Ti(eta5-C5Me5)(micro-NH)}3(micro3-N)].

Science.gov (United States)

Martín, Avelino; Martínez-Espada, Noelia; Mena, Miguel; Yélamos, Carlos

2007-07-28

Treatment of the metalloligand [{Ti(eta(5)-C(5)Me(5))(micro-NH)}(3)(micro(3)-N)] with silver(i) trifluoromethanesulfonate in different molar ratios gives the ionic compounds [Ag{(micro(3)-NH)(3)Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)}(2)][O(3)SCF(3)] and [Ag{(micro(3)-NH)(3)Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)}][O(3)SCF(3)] or the triangular silver cluster [(CF(3)SO(2)O)(3)Ag(3){(micro(3)-NH)(3)Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)}(2)] in which each face is capped by a metalloligand.

The recombination mechanisms leading to amplified spontaneous emission at the true-green wavelength in CH3NH3PbBr3 perovskites

KAUST Repository

Priante, Davide; Dursun, Ibrahim; Alias, M. S.; Shi, Dong; Melnikov, V. A.; Ng, Tien Khee; Mohammed, Omar F.; Bakr, Osman; Ooi, Boon S.

2015-01-01

We investigated the mechanisms of radiative recombination in a CH3NH3PbBr3 hybrid perovskite material using low-temperature, power-dependent (77K), and temperature-dependent photoluminescence (PL) measurements. Two bound-excitonic radiative

Kinetics of gas to particle conversion in the NH/sub 3/-Chl system

Energy Technology Data Exchange (ETDEWEB)

Luria, M; Cohen, B

1980-01-01

Particle formation in the reaction of NH/sub 3/ and Chl under 1 atm of N/sub 2/ and at 25/sup 0/C was studied in a flow reactor. The critical concentration below which NO particle can be formed was found to be 3.5 x 10/sup +14/ molecule/CM/sup 3/ for (NH/sub 3/)=(HCl). Above this concentration, gas-particle conversion percentage increases rapidly to approach 100%.

Stability and carrier mobility of organic-inorganic hybrid perovskite CH3NH3PbI3 in two-dimensional limit

Science.gov (United States)

Huang, Kui; Lai, Kang; Yan, Chang-Lin; Zhang, Wei-Bing

2017-10-01

Recently, atomically thin organic-inorganic hybrid perovskites have been synthesized experimentally, which opens up new opportunities for exploring their novel properties in the 2D limit. Based on the comparative density functional theory calculation with and without spin-orbit coupling effects, the stability, electronic structure, and carrier mobility of the two-dimensional organic-inorganic hybrid perovskites MAPbI3 (MA = CH3NH3) have been investigated systemically. Two single-unit-cell-thick 2D MAPbI3 terminated by PbI2 and CH3NH3I are constructed, and their thermodynamic stabilities are also evaluated using the first-principles constrained thermodynamics method. Our results indicate that both 2D MAPbI3 with different terminations can be stable under certain conditions and have a suitable direct bandgap. Moreover, they are also found to have termination-dependent band edge and carrier mobility. The acoustic-phonon-limited carrier mobilities estimated using the deformation theory and effective mass approximation are on the order of thousands of square centimeters per volt per second and also highly anisotropic. These results indicate that 2D MAPbI3 are competitive candidates for low-dimensional photovoltaic applications.

Electron pairing analysis of the Fischer-type chromium-carbene complexes (CO){sub 5}Cr=C(X)R (X=H, OH, OCH{sub 3}, NH{sub 2}, NHCH{sub 3} and R=H, CH{sub 3}, CH=CH{sub 2}, Ph, C-CH )

Energy Technology Data Exchange (ETDEWEB)

Poater, Jordi; Cases, Montserrat; Fradera, Xavier; Duran, Miquel; Sola, Miquel

2003-10-15

The electron-pair density distributions of a series of 25 Fischer carbene complexes of the type (CO){sub 5}Cr=C(X)R (X=H, OH, OCH{sub 3}, NH{sub 2}, NHCH{sub 3} and R=H, CH{sub 3}, CH=CH{sub 2}, Ph, C-CH) are analyzed using the Atoms in Molecules theory. Localization and delocalization indices are used to characterize the electron pairing taking place in the Cr=C---X moiety in these complexes. Electron delocalization between the Cr and C atoms and between the C atom and the X group are related to the {pi}-donor strength of the X group and the degree of back-donation between the chromium pentacarbonyl and the carbene fragments. The results obtained with the Atoms in Molecules theory complement those obtained in a previous study by means of energy and charge decomposition analyses. Electron delocalization between the Cr atom and the X group is consistent with the hypothesis of a weak 3-center 4-electron bonding interaction in the Cr=C-X group of atoms. Except for X=H, {delta}(Cr,X) increases with the decrease of the {pi}-donor character of the X group.

Role of hydrogen-bonding and its interplay with octahedral tilting in CH3NH3PbI3

OpenAIRE

Lee, Paul David; Bristowe, Nicholas C; Bristowe, Paul D; Cheetham, Anthony Kevin

2015-01-01

First principles calculations on the hybrid perovskite CH3NH3PbI3 predict strong hydrogen-bonding which influences the structure and dynamics of the methylammonium cation and reveal its interaction with the tilting of the PbI6 octahedra. The calculated atomic coordinates are in excellent agreement with neutron diffraction results. [Image - see article] Funding from the Winton Programme for the Physics of Sustainability at the University of Cambridge is gratefully acknowledged. NCB acknowle...

Extractability of plutonium-238 and curium-242 from a contaminated soil as a function of pH and certain soil components. CH3COOH-NH4OH system

International Nuclear Information System (INIS)

Nishita, H.

1978-01-01

Extractability of 238 Pu and 242 Cm from an artificially contaminated soil as a function of pH and certain soil components was examined with an equilibrium batch technique by the use of a CH 3 COOH--NH 4 OH extracting system. The influence of various soil components on 238 Pu and 242 Cm extractability was determined indirectly by selective removal of the components from the soil. The soil organic matter appeared to have a major influence on the extractability of these radionuclides. Though to a lesser extent, free iron oxides exerted an influence also. Before removal of soil organic matter, the extractability curves for these radionuclides were qualitatively similar in general form. The nature of this form is discussed. Within the contaminated, untreated soil, the 238 Pu and 242 Cm extractability ranged from 0.60 to 30.8% and 0.11 to 14.83% of dose, respectively, depending on the pH of the extracting solution. The liquid-to soild-phase ratio (K'/sub d/) values ranged from 3.5 x 10 -4 to 2.7 x 10 -2 for 238 Pu and 0.9 x 10 -4 to 1.4 x 10 -2 for 242 Cm. Very low extractability occurred in the pH range from approx. 8.6 to approx. 9.7 for 238 Pu and from 7.6 to approx. 9.7 for 242 Cm

Shallow trapping vs. deep polarons in a hybrid lead halide perovskite, CH3NH3PbI3.

Science.gov (United States)

Kang, Byungkyun; Biswas, Koushik

2017-10-18

There has been considerable speculation over the nature of charge carriers in organic-inorganic hybrid perovskites, i.e., whether they are free and band-like, or they are prone to self-trapping via short range deformation potentials. Unusually long minority-carrier diffusion lengths and moderate-to-low mobilities, together with relatively few deep defects add to their intrigue. Here we implement density functional methods to investigate the room-temperature, tetragonal phase of CH 3 NH 3 PbI 3 . We compare charge localization behavior at shallow levels and associated lattice relaxation versus those at deep polaronic states. The shallow level originates from screened Coulomb interaction between the perturbed host and an excited electron or hole. The host lattice has a tendency towards forming these shallow traps where the electron or hole is localized not too far from the band edge. In contrast, there is a considerable potential barrier that must be overcome in order to initiate polaronic hole trapping. The formation of a hole polaron (I 2 - center) involves strong lattice relaxation, including large off-center displacement of the organic cation, CH 3 NH 3 + . This type of deep polaron is energetically unfavorable, and active shallow traps are expected to shape the carrier dynamics in this material.

The recombination mechanisms leading to amplified spontaneous emission at the true-green wavelength in CH3NH3PbBr3 perovskites

Science.gov (United States)

Priante, D.; Dursun, I.; Alias, M. S.; Shi, D.; Melnikov, V. A.; Ng, T. K.; Mohammed, O. F.; Bakr, O. M.; Ooi, B. S.

2015-02-01

We investigated the mechanisms of radiative recombination in a CH3NH3PbBr3 hybrid perovskite material using low-temperature, power-dependent (77 K), and temperature-dependent photoluminescence (PL) measurements. Two bound-excitonic radiative transitions related to grain size inhomogeneity were identified. Both transitions led to PL spectra broadening as a result of concurrent blue and red shifts of these excitonic peaks. The red-shifted bound-excitonic peak dominated at high PL excitation led to a true-green wavelength of 553 nm for CH3NH3PbBr3 powders that are encapsulated in polydimethylsiloxane. Amplified spontaneous emission was eventually achieved for an excitation threshold energy of approximately 350 μJ/cm2. Our results provide a platform for potential extension towards a true-green light-emitting device for solid-state lighting and display applications.

The recombination mechanisms leading to amplified spontaneous emission at the true-green wavelength in CH3NH3PbBr3 perovskites

KAUST Repository

Priante, Davide

2015-02-23

We investigated the mechanisms of radiative recombination in a CH3NH3PbBr3 hybrid perovskite material using low-temperature, power-dependent (77K), and temperature-dependent photoluminescence (PL) measurements. Two bound-excitonic radiative transitions related to grain size inhomogeneity were identified. Both transitions led to PL spectra broadening as a result of concurrent blue and red shifts of these excitonic peaks. The red-shifted bound-excitonic peak dominated at high PL excitation led to a true-green wavelength of 553nm for CH3NH3PbBr3 powders that are encapsulated in polydimethylsiloxane. Amplified spontaneous emission was eventually achieved for an excitation threshold energy of approximately 350μJ/cm2. Our results provide a platform for potential extension towards a true-green light-emitting device for solid-state lighting and display applications.

Isotopically decoupled vibrational spectra and proton exchange rates for crystalline NH3 and ammonia hydrate

Science.gov (United States)

Thornton, Cynthia; Khatkale, M. S.; Devlin, J. Paul

1981-12-01

Codeposits of NH3 with ND3 or D2O have been prepared at liquid nitrogen temperatures in the absence of proton exchange. Vibrational data for the anhydrous cubic crystalline ammonia, containing isolated NH3 or ND3, confirm that, relative to water ice, intermolecular coupling in ammonia ice exerts a relatively minor influence on the infrared and Raman spectra. Nevertheless, sizeable decoupling shifts, particularly for ν1, have been observed and attributed to a combination of factors including correlation field and Fermi resonance effects. The Raman polarization data has also affirmed long standing assignments of ν1 and ν3 for ammonia ice. Warming of the ammonia thin films resulted in limited isotopic scrambling at 130 K, apparently possible only through the agency of trace concentrations of water. The vibrational coupling pattern for the resultant NHD2 and NH2D molecules suggest that proton (deuteron) migration away from the exchange centers is impossible at temperatures up to 150 K. By contrast, isotopic scrambling was rapid and complete at 140 K for amorphous ammonia hydrate films (˜35% NH3, ˜65% D2O) which were also prepared without exchange at ˜90 K. The proton (deuteron) exchange rate is much greater for the amorphous ammonia hydrate at 140 K than for pure water ice. Such exchange requires both ion-pair defect formation and proton mobility. Since the NH3 suppresses the H3O+ concentration via formation of NH+4, a suppression the likes of which has been shown to stop proton exchange in water ice, the evidence strongly suggests that NH4+ in ammonia, like H3O+ in water, is an effective proton transfer agent, probably acting through a tunneling mechanism (i.e., H3N+-HṡṡṡNH3→H3NṡṡṡH-N+H3 etc.) to render the proton mobile in the ammonia hydrate. This mobility combined with the greater NH4+ concentration, relative to the H3O+ concentration in H2O ice Ic, results in isotopic scrambling at the reduced temperature.