Characterization of copper-zinc mixed oxide system in relation to different precursor structure and morphology

Energy Technology Data Exchange (ETDEWEB)

Porta, P; De Rossi, S; Ferraris, G [Centro del CNR su ' Struttura e Attivia Catalitica di Sistemi di Ossidi' (SACSO), Rome (Italy); Pompa, F [ENEA, TIB Scienza dei Materiali, Rome (Italy)

1991-03-01

Hydroxycarbonate and hydroxynitrate precursors of CuO-ZnO catalysts (Cu/Zn atomic ratio=67/33) have been prepared by two different methods; the precursor obtained by precipitation at 333 K and constant pH=8 from mixed nitrate solution with excess of sodium bicarbonate consisted of zincian malachite and aurichalcite, while that obtained by addition of sodium carbonate solution to Cu-Zn nitrate solution is essentially copper hydroxynitrate plus some amount of aurichalcite. By thermal decomposition at 623 K both types of precursor gave a mixture of CuO and ZnO. The mixed oxides were then treated at 873, 1073 and 1273 K in air. X-ray diffraction, diffuse reflectance spectroscopy, scanning electron microscopy and surface area determination were used to characterize the mixed oxide systems. The precursor containing zincian malachite plus aurichalcite, after calcination at 623 K gave rise to well dispersed and much smaller particles of CuO and ZnO than the precursor containing copper hydroxynitrate plus aurichalcite. No Cu{sup 2+} in solid solution in the ZnO zincite structure Zn{sup 2+} in the CuO tenorite lattice were detected by reflectance spectroscopy up to 873 K; the presence of tetrahedral copper (Cu{sub x}Zn{sub 1-x}O solid solution formation at least at the surface) was evident only in samples calcined at temperatures higher than 1073 K. X-ray diffraction analysis for lattice parameter determination showed that only for samples treated at 1273 K both Cu{sub x}Zn{sub 1-x}O and Zn{sub y}Cu{sub 1-y}O solid solution formations are detectable. An unexpected volume decrease of Zn{sub y}Cu{sub 1-y}O with respect to pure CuO was revealed; the introduction of zinc in the tenorite structure probably changes the local metal symmetry from nearly square planar towards octahedral, producing an overall less distorted and more compact structure. (orig.).

Designing high performance precursors for atomic layer deposition of silicon oxide

Energy Technology Data Exchange (ETDEWEB)

Mallikarjunan, Anupama, E-mail: mallika@airproducts.com; Chandra, Haripin; Xiao, Manchao; Lei, Xinjian; Pearlstein, Ronald M.; Bowen, Heather R.; O' Neill, Mark L. [Air Products and Chemicals, Inc., 1969 Palomar Oaks Way, Carlsbad, California 92011 (United States); Derecskei-Kovacs, Agnes [Air Products and Chemicals, Inc., 7201 Hamilton Blvd., Allentown, Pennsylvania 18195 (United States); Han, Bing [Air Products and Chemicals, Inc., 2 Dongsanhuan North Road, Chaoyang District, Beijing 100027 (China)

2015-01-15

Conformal and continuous silicon oxide films produced by atomic layer deposition (ALD) are enabling novel processing schemes and integrated device structures. The increasing drive toward lower temperature processing requires new precursors with even higher reactivity. The aminosilane family of precursors has advantages due to their reactive nature and relative ease of use. In this paper, the authors present the experimental results that reveal the uniqueness of the monoaminosilane structure [(R{sub 2}N)SiH{sub 3}] in providing ultralow temperature silicon oxide depositions. Disubstituted aminosilanes with primary amines such as in bis(t-butylamino)silane and with secondary amines such as in bis(diethylamino)silane were compared with a representative monoaminosilane: di-sec-butylaminosilane (DSBAS). DSBAS showed the highest growth per cycle in both thermal and plasma enhanced ALD. These findings show the importance of the arrangement of the precursor's organic groups in an ALD silicon oxide process.

Alkoxide-based precursors for direct drawing of metal oxide micro- and nanofibres

Energy Technology Data Exchange (ETDEWEB)

Taette, Tanel; Hussainov, Medhat; Paalo, Madis; Part, Marko; Talviste, Rasmus; Kiisk, Valter; Maendar, Hugo; Pohako, Kaija; Reivelt, Kaido; Lohmus, Ants [Institute of Physics, University of Tartu, Riia 142, Tartu 51014 (Estonia); Pehk, Tonis [National Institute of Chemical and Biological Physics, Akadeemia tee 23, Tallinn 12618 (Estonia); Natali, Marco [ICIS-CNR, Corso Stati Uniti 4, Padova 35127 (Italy); Gurauskis, Jonas [Instituto de Ciencia de Materiales de Aragon C.S.I.C., University of Zaragoza Fac. De Ciencias, c/Pedro Cerbuna 12, Zaragoza 50009 (Spain); Maeeorg, Uno, E-mail: tanelt@fi.tartu.ee [Institute of Chemistry, University of Tartu, Ravila 14a, Tartu 50411 (Estonia)

2011-06-15

The invention of electrospinning has solved the problem of producing micro- and nanoscaled metal oxide fibres in bulk quantities. However, until now no methods have been available for preparing a single nanofibre of a metal oxide. In this work, the direct drawing method was successfully applied to produce metal oxide (SnO{sub 2}, TiO{sub 2}, ZrO{sub 2}, HfO{sub 2} and CeO{sub 2}) fibres with a high aspect ratio (up to 10 000) and a diameter as small as 200 nm. The sol-gel processing includes consumption of precursors obtained from alkoxides by aqueous or non-aqueous polymerization. Shear thinning of the precursors enables pulling a material into a fibre. This rheological behaviour can be explained by sliding of particles owing to external forces. Transmission (propagation) of light along microscaled fibres and their excellent surface morphology suggest that metal oxide nanofibres can be directly drawn from sol precursors for use in integrated photonic systems.

V6O13 films by control of the oxidation state from aqueous precursor to crystalline phase.

Science.gov (United States)

Peys, Nick; Ling, Yun; Dewulf, Daan; Gielis, Sven; De Dobbelaere, Christopher; Cuypers, Daniel; Adriaensens, Peter; Van Doorslaer, Sabine; De Gendt, Stefan; Hardy, An; Van Bael, Marlies K

2013-01-28

An aqueous deposition process for V(6)O(13) films is developed whereby the vanadium oxidation state is continuously controlled throughout the entire process. In the precursor stage, a controlled wet chemical reduction of the vanadium(V) source with oxalic acid is achieved and monitored by (51)Vanadium Nuclear Magnetic Resonance ((51)V-NMR) and Ultraviolet-Visible (UV-Vis) spectroscopy. The resulting vanadium(IV) species in the aqueous solution are identified as mononuclear citrato-oxovanadate(IV) complexes by Electron Paramagnetic Resonance (EPR) and Fourier Transform Infra-Red (FTIR) spectroscopy. This precursor is successfully employed for the deposition of uniform, thin films. The optimal deposition and annealing conditions for the formation of crystalline V(6)O(13), including the control of the vanadium oxidation state, are determined through an elaborate study of processing temperature and O(2) partial pressure. To ensure a sub 100 nm adjustable film thickness, a non-oxidative intermediate thermal treatment is carried out at the end of each deposition cycle, allowing maximal precursor decomposition while still avoiding V(IV) oxidation. The resulting surface hydrophilicity, indispensable for the homogeneous deposition of the next layer, is explained by an increased surface roughness and the increased availability of surface vanadyl groups. Crystalline V(6)O(13) with a preferential (002) orientation is obtained after a post deposition annealing in a 0.1% O(2) ambient for thin films with a thickness of 20 nm.

Synergy of iron and copper oxides in the catalytic formation of PCDD/Fs from 2-monochlorophenol.

Science.gov (United States)

Potter, Phillip M; Guan, Xia; Lomnicki, Slawomir M

2018-07-01

Transition metal oxides present in waste incineration systems have the ability to catalyze the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) through surface reactions involving organic dioxin precursors. However, studies have concentrated on the catalytic effects of individual transition metal oxides, while the complex elemental composition of fly ash introduces the possibility of synergistic or inhibiting effects between multiple, catalytically active components. In this study, we have tested fly ash surrogates containing different ratios (by weight) of iron (III) oxide and copper (II) oxide. Such Fe 2 O 3 /CuO mixed-oxide surrogates (in the Fe:Cu ratio of 3.5, 0.9 and 0.2 ) were used to study the cooperative effects between two transition metals that are present in high concentrations in most combustion systems and are known to individually catalyze the formation of PCDD/Fs. The presence of both iron and copper oxides increased the oxidative power of the fly ash surrogates in oxygen rich conditions and led to extremely high PCDD/F yields under pyrolytic conditions (up to >5% yield) from 2-monochlorophenol precursor. PCDD/F congener profiles from the mixed oxide samples are similar to results obtained from only CuO, however the total PCDD/F yield increases with increasing Fe 2 O 3 content. Careful analysis of the reaction products and changes to the oxidation states of active metals indicate the CuO surface sites are centers for reaction while the Fe 2 O 3 is affecting the bonds in CuO and increasing the ability of copper centers to form surface-bound radicals that are precursors to PCDD/Fs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Preparation of iron molybdate catalysts for methanol to formaldehyde oxidation based on ammonium molybdoferrate(II precursor

Directory of Open Access Journals (Sweden)

N.V. Nikolenko

2018-03-01

Full Text Available It was demonstrated that iron molybdate catalysts for methanol oxidation can be prepared using Fe(II as a precursor instead of Fe(III. This would allow for reduction of acidity of preparation solutions as well as elimination of Fe(III oxide impurities which are detrimental for the process selectivity. The system containing Fe(II and Mo(VI species in aqueous solution was investigated using UV–Vis spectroscopy. It was demonstrated that three types of chemical reactions occur in the Fe(II–Mo(VI system: (i formation of complexes between Fe(II and molybdate(VI ions, (ii inner sphere oxidation of coordinated Fe(II by Mo(VI and (iii decomposition of the Fe–Mo complexes to form scarcely soluble Fe(III molybdate, Mo(VI hydrous trioxide and molybdenum blue. Solid molybdoferrate(II prepared by interaction of Fe(II and Mo(VI in solution was characterized by EDXA, TGA, DTA and XRD and a scheme of its thermal evolution proposed. The iron molybdate catalyst prepared from Fe(II precursor was tested in methanol-to-formaldehyde oxidation in a continuous flow fixed-bed reactor to show similar activity and selectivity to the conventional catalyst prepared with the use of Fe(III.

Formation of Nano-crystalline Todorokite from Biogenic Mn Oxides

Energy Technology Data Exchange (ETDEWEB)

Feng, X.; Zhu, M; Ginder-Vogel, M; Ni, C; Parikh, S; Sparks, D

2010-01-01

Todorokite, as one of three main Mn oxide phases present in oceanic Mn nodules and an active MnO{sub 6} octahedral molecular sieve (OMS), has garnered much interest; however, its formation pathway in natural systems is not fully understood. Todorokite is widely considered to form from layer structured Mn oxides with hexagonal symmetry, such as vernadite ({delta}-MnO{sub 2}), which are generally of biogenic origin. However, this geochemical process has not been documented in the environment or demonstrated in the laboratory, except for precursor phases with triclinic symmetry. Here we report on the formation of a nanoscale, todorokite-like phase from biogenic Mn oxides produced by the freshwater bacterium Pseudomonas putida strain GB-1. At long- and short-range structural scales biogenic Mn oxides were transformed to a todorokite-like phase at atmospheric pressure through refluxing. Topotactic transformation was observed during the transformation. Furthermore, the todorokite-like phases formed via refluxing had thin layers along the c* axis and a lack of c* periodicity, making the basal plane undetectable with X-ray diffraction reflection. The proposed pathway of the todorokite-like phase formation is proposed as: hexagonal biogenic Mn oxide {yields} 10-{angstrom} triclinic phyllomanganate {yields} todorokite. These observations provide evidence supporting the possible bio-related origin of natural todorokites and provide important clues for understanding the transformation of biogenic Mn oxides to other Mn oxides in the environment. Additionally this method may be a viable biosynthesis route for porous, nano-crystalline OMS materials for use in practical applications.

A study on the polymer precursor formation and microstructure evolution of square-shaped (La{sub 0.5}Ba{sub 0.5})(Mn{sub 0.5}Fe{sub 0.5})O{sub 3} ceramic nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Romero, M.; Pardo, H.; Faccio, R.; Suescun, L.; Fernandez-Werner, L.; Mombru, A.W. [Univ. de la Republica, Montevideo (Uruguay). Cryssmat-Lab/Centro NanoMat; Univ. de la Republica, Montevideo (Uruguay). Centro Interdisciplinario de Nanotecnologia, Quimica y Fisica de Materiales; Vazquez, S.; Laborda, I. [Univ. de la Republica, Montevideo (Uruguay). Cryssmat-Lab/Centro NanoMat; Acosta, A. [Univ. de la Republica, Montevideo (Uruguay). Catedra de Quimica Inorganica; Castiglioni, J. [Univ. de la Republica, Montevideo (Uruguay). Catedra de Fisicoquimica

2015-07-01

The polymer precursor formation and the growth mechanism of (La{sub 0.5}Ba{sub 0.5})(Mn{sub 0.5}Fe{sub 0.5})O{sub 3} ceramic nanoparticles have been studied. First, we focused on the influence of isolated metals (La, Ba, Mn, Fe) on the polymer precursor formation by means of Raman, FT-IR, scanning electron microscopy and differential scanning calorimetry, showing that the presence of metal ions, especially iron, increases the oxidation rate of the polymer precursor, while the presence of barium leads to a higher degree of polymerization, preventing partial oxidation of the polymer at low temperatures and allowing the presence of nitrates at the combustion stage. Nevertheless, when all metals are present, the polymer precursor showed a largely homogeneous microstructure with a global average influence from all cations. Finally,we studied the microstructure evolution of nanoparticles obtained after calcination above 700 C. SAXS and TEM analysis suggests that the formation of square-shaped nanoparticles below 900 C and coalescence leads to the formation of larger-sized and round-shaped nanoparticles at 900 C.

Polymeric precursors method for obtaining pigments based on Inorganic oxides of chromium and iron deposited on TiO2

International Nuclear Information System (INIS)

Silva, Everlania M. da; Galvao, Sheila B.; Paskocimas, C.A.

2011-01-01

The case study was the use of chromium oxides and iron, as a precursor in the synthesis of inorganic pigments. The synthesis was based on the dissolution of citric acid as a complexing agent, addition of metal oxides, such as ion chromophores; polymerization with ethylene glycol and doping with titanium oxide. Going through pre-calcination, breakdown, calcination at different temperatures (700, 900 and 1100 deg C resulting in pigments: green for pigment and chromium deposited on TiO2, orange for iron on TiO2. The thermal analysis (TG and DTA), evaluated their thermal decompositions, the XRD revealed the formation of crystalline phases such as iron titanate and chrome titanate; SEM showed the formation of hexagonal particles for both oxides. Under the different analysis, one can see the potential stability of pigments and powders, can be proposed its use as pigments in polymers. (author)

Contribution towards ALD and MOCVD of rare earth oxides and hafnium oxide. From precursor evaluation to process development and thin film characterization

International Nuclear Information System (INIS)

Xu, Ke

2013-01-01

This PhD thesis is consisted of two major parts: precursor development for ALD and MOCVD applications as well as thin film deposition using ALD and MOCVD with self developed precursors. The first part of this work presents the synthesis, characterization and detailed thermal property investigations of different novel group IV and rare earth precursor classes (guandinate, guanidine and ketoiminate). The second part of this work presents the ALD and MOCVD depositions using various guanidinate precursors for forming corresponding metal oxide thin films. The overall motivation of this work is to fulfill the lack of precursors of rare earth and group IV elements for ALD and MOCVD applications that satisfy the stringent requirements for the modern microelectronic and optoelectronic technologies. The aspect of the precursor engineering part is focusing on influence of ligand sphere on precursors' chemical and thermal properties. In this way, we successfully introduced guanidine and ketoiminate as potential ligands for the precursor design. The thin film deposition part of this work is ALD of rare earth oxides and group IV oxides employing literature known compounds which were previously developed in our research group. The main focus was dedicated to the process optimization, the characterization of the structural, morphological, compositional and functional properties of the deposited thin films. Certain film properties were discussed comparatively with the corresponding thin films deposited with literature known precursors. It was already shortly demonstrated in Chapter 6 that the guanidine ligand showed potential interest as suitable ligand for precursor engineering. This titan guanidine precursor [Ti(NC(NMe 2 ) 2 ) 4 ] (GD1) possesses higher thermal stability compared to its parent amide, [Ti(NMe 2 ) 4 ], while reactivity against water is not significantly affected. It could be very interesting to transfer this ligand for the precursor development of rare earth

Study of hafnium (IV) oxide nanoparticles synthesized by polymerized complex and polymer precursor derived sol-gel methods

KAUST Repository

Ramos-Gonzá lez, R.; Garcí a-Cerda, L. A.; Alshareef, Husam N.; Gnade, Bruce E.; Quevedo-Ló pez, Manuel Angel Quevedo

2010-01-01

This work reports the preparation and characterization of hafnium (IV) oxide (HfO2) nanoparticles grown by derived sol-gel routes that involves the formation of an organic polymeric network. A comparison between polymerized complex (PC) and polymer precursor (PP) methods is presented. For the PC method, citric acid (CA) and ethylene glycol (EG) are used as the chelating and polymerizable reagents, respectively. In the case of PP method, poly(acrylic acid) (PAA) is used as the chelating reagent. In both cases, different precursor gels were prepared and the hafnium (IV) chloride (HfCl4) molar ratio was varied from 0.1 to 1.0 for the PC method and from 0.05 to 0.5 for the PP method. In order to obtain the nanoparticles, the precursors were heat treated at 500 and 800 °C. The thermal characterization of the precursor gels was carried out by thermogravimetric analysis (TGA) and the structural and morphological characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns of the samples obtained by both methods shows the formation of HfO2 at 500 °C with monoclinic crystalline phase. The PC method exhibited also the cubic phase. Finally, the HfO2 nanoparticles size (4 to 11 nm) was determined by TEM and XRD patterns. © (2010) Trans Tech Publications.

Study of hafnium (IV) oxide nanoparticles synthesized by polymerized complex and polymer precursor derived sol-gel methods

KAUST Repository

Ramos-González, R.

2010-03-01

This work reports the preparation and characterization of hafnium (IV) oxide (HfO2) nanoparticles grown by derived sol-gel routes that involves the formation of an organic polymeric network. A comparison between polymerized complex (PC) and polymer precursor (PP) methods is presented. For the PC method, citric acid (CA) and ethylene glycol (EG) are used as the chelating and polymerizable reagents, respectively. In the case of PP method, poly(acrylic acid) (PAA) is used as the chelating reagent. In both cases, different precursor gels were prepared and the hafnium (IV) chloride (HfCl4) molar ratio was varied from 0.1 to 1.0 for the PC method and from 0.05 to 0.5 for the PP method. In order to obtain the nanoparticles, the precursors were heat treated at 500 and 800 °C. The thermal characterization of the precursor gels was carried out by thermogravimetric analysis (TGA) and the structural and morphological characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns of the samples obtained by both methods shows the formation of HfO2 at 500 °C with monoclinic crystalline phase. The PC method exhibited also the cubic phase. Finally, the HfO2 nanoparticles size (4 to 11 nm) was determined by TEM and XRD patterns. © (2010) Trans Tech Publications.

Sonochemically synthesized iron-doped zinc oxide nanoparticles: Influence of precursor composition on characteristics

International Nuclear Information System (INIS)

Roy, Anirban; Maitra, Saikat; Ghosh, Sobhan; Chakrabarti, Sampa

2016-01-01

Highlights: • Sonochemical synthesis of iron-doped zinc oxide nanoparticles. • Green synthesis without alkali at room temperature. • Characterization by UV–vis spectroscopy, FESEM, XRD and EDX. • Influence of precursor composition on characteristics. • Composition and characteristics are correlated. - Abstract: Iron-doped zinc oxide nanoparticles have been synthesized sonochemically from aqueous acetyl acetonate precursors of different proportions. Synthesized nanoparticles were characterized with UV–vis spectroscopy, X-ray diffraction and microscopy. Influences of precursor mixture on the characteristics have been examined and modeled. Linear correlations have been proposed between dopant dosing, extent of doping and band gap energy. Experimental data corroborated with the proposed models.

In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

Science.gov (United States)

Palm, Brett B.; Campuzano-Jost, Pedro; Ortega, Amber M.; Day, Douglas A.; Kaser, Lisa; Jud, Werner; Karl, Thomas; Hansel, Armin; Hunter, James F.; Cross, Eben S.; Kroll, Jesse H.; Peng, Zhe; Brune, William H.; Jimenez, Jose L.

2016-03-01

An oxidation flow reactor (OFR) is a vessel inside which the concentration of a chosen oxidant can be increased for the purpose of studying SOA formation and aging by that oxidant. During the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen-Rocky Mountain Biogenic Aerosol Study) field campaign, ambient pine forest air was oxidized by OH radicals in an OFR to measure the amount of SOA that could be formed from the real mix of ambient SOA precursor gases, and how that amount changed with time as precursors changed. High OH concentrations and short residence times allowed for semicontinuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative timescales of condensation of low-volatility organic compounds (LVOCs) onto particles; condensational loss to the walls; and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 3 µg m-3 when LVOC fate corrected) compared to daytime (average 0.9 µg m-3 when LVOC fate corrected), with maximum formation observed at 0.4-1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene+p-cymene concentrations, including a substantial increase just after sunrise at 07:00 local time. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254-70), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic

In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

Directory of Open Access Journals (Sweden)

B. B. Palm

2016-03-01

Full Text Available An oxidation flow reactor (OFR is a vessel inside which the concentration of a chosen oxidant can be increased for the purpose of studying SOA formation and aging by that oxidant. During the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen–Rocky Mountain Biogenic Aerosol Study field campaign, ambient pine forest air was oxidized by OH radicals in an OFR to measure the amount of SOA that could be formed from the real mix of ambient SOA precursor gases, and how that amount changed with time as precursors changed. High OH concentrations and short residence times allowed for semicontinuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq. atmospheric aging. A simple model is derived and used to account for the relative timescales of condensation of low-volatility organic compounds (LVOCs onto particles; condensational loss to the walls; and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 3 µg m−3 when LVOC fate corrected compared to daytime (average 0.9 µg m−3 when LVOC fate corrected, with maximum formation observed at 0.4–1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene+p-cymene concentrations, including a substantial increase just after sunrise at 07:00 local time. Higher photochemical aging (> 10 eq. days led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254-70, similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production

Relationship between organic precursors and N-nitrosodimethylamine (NDMA) formation in tropical water sources.

Science.gov (United States)

Qi, Wang; Fang Yee, Lim; Jiangyong, Hu

2014-12-01

The presence of organic compounds in water sources is one of the concerns in water treatment. They are potential precursors of disinfection byproducts (DBPs) and thus induce health problems in humans. Among the emerging DBPs, carcinogenic compound N-nitrosodimethylamine (NDMA) has been receiving attention during the last decade. This study examined the characteristics of organic components in various water sources and investigated their relationships with NDMA formation. Experiments were carried out on selected water samples from both natural water and wastewater. Results showed similar NDMA formation kinetics for both water sources. However, more contribution of NDMA precursors was found to be from the wastewater due to its higher organic nitrogen content. NDMA formation potential (NDMAFP) of secondary effluent ranged from 264 to 530 ng/L. A correlation study between organic compound characteristics and NDMAFP indicated that the majority of NDMA precursors came from dissolved organic nitrogen (DON) compound with small molecular weight (smaller than 500 Da), with correlation R(2) = 0.898. Although secondary treatment removed more than 90% of NDMA precursors, the remaining precursors in secondary effluent would still pose a challenge for water quality.

Nanostructured manganese oxides as highly active water oxidation catalysts: a boost from manganese precursor chemistry.

Science.gov (United States)

Menezes, Prashanth W; Indra, Arindam; Littlewood, Patrick; Schwarze, Michael; Göbel, Caren; Schomäcker, Reinhard; Driess, Matthias

2014-08-01

We present a facile synthesis of bioinspired manganese oxides for chemical and photocatalytic water oxidation, starting from a reliable and versatile manganese(II) oxalate single-source precursor (SSP) accessible through an inverse micellar molecular approach. Strikingly, thermal decomposition of the latter precursor in various environments (air, nitrogen, and vacuum) led to the three different mineral phases of bixbyite (Mn2 O3 ), hausmannite (Mn3 O4 ), and manganosite (MnO). Initial chemical water oxidation experiments using ceric ammonium nitrate (CAN) gave the maximum catalytic activity for Mn2 O3 and MnO whereas Mn3 O4 had a limited activity. The substantial increase in the catalytic activity of MnO in chemical water oxidation was demonstrated by the fact that a phase transformation occurs at the surface from nanocrystalline MnO into an amorphous MnOx (1oxidizing agent. Photocatalytic water oxidation in the presence of [Ru(bpy)3 ](2+) (bpy=2,2'-bipyridine) as a sensitizer and peroxodisulfate as an electron acceptor was carried out for all three manganese oxides including the newly formed amorphous MnOx . Both Mn2 O3 and the amorphous MnOx exhibit tremendous enhancement in oxygen evolution during photocatalysis and are much higher in comparison to so far known bioinspired manganese oxides and calcium-manganese oxides. Also, for the first time, a new approach for the representation of activities of water oxidation catalysts has been proposed by determining the amount of accessible manganese centers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Powder of a copper oxide superconductor precursor, fabrication process and use for the preparation of superconducting oxide

International Nuclear Information System (INIS)

Dehaudt, P.

1990-01-01

The precursor powder comprises at least a copper compound (hydroxide, oxide and hydroxynitrates), at least a rare earth and/or yttrium compound (nitrates, hydroxides and hydroxynitrates) or bismuth oxide and at least an alkaline earth nitrate. It can be prepared by atomization drying of a suspension a copper precipitate or coprecipitate and other elements of the superconducting oxide in solution [fr

High formation of secondary organic aerosol from the photo-oxidation of toluene

OpenAIRE

L. Hildebrandt; N. M. Donahue; S. N. Pandis

2009-01-01

Toluene and other aromatics have long been viewed as the dominant anthropogenic secondary organic aerosol (SOA) precursors, but the SOA mass yields from toluene reported in previous studies vary widely. Experiments conducted in the Carnegie Mellon University environmental chamber to study SOA formation from the photo-oxidation of toluene show significantly larger SOA production than parameterizations employed in current air-quality models. Aerosol mass yields depend on experimental co...

Role of Chlorine Dioxide in N-Nitrosodimethylamine Formation from Oxidation of Model Amines.

Science.gov (United States)

Gan, Wenhui; Bond, Tom; Yang, Xin; Westerhoff, Paul

2015-10-06

N-Nitrosodimethylamine (NDMA) is an emerging disinfection byproduct, and we show that use of chlorine dioxide (ClO2) has the potential to increase NDMA formation in waters containing precursors with hydrazine moieties. NDMA formation was measured after oxidation of 13 amines by monochloramine and ClO2 and pretreatment with ClO2 followed by postmonochloramination. Daminozide, a plant growth regulator, was found to yield 5.01 ± 0.96% NDMA upon reaction with ClO2, although no NDMA was recorded during chloramination. The reaction rate was estimated to be ∼0.0085 s(-1), and on the basis of our identification by mass spectrometry of the intermediates, the reaction likely proceeds via the hydrolytic release of unsymmetrical dimethylhydrazine (UDMH), with the hydrazine structure a key intermediate in NDMA formation. The presence of UDMH was confirmed by gas chromatography-mass spectrometry analysis. For 10 of the 13 compounds, ClO2 preoxidation reduced NDMA yields compared with monochloramination alone, which is explained by our measured release of dimethylamine. This work shows potential preoxidation strategies to control NDMA formation may not impact all organic precursors uniformly, so differences might be source specific depending upon the occurrence of different precursors in source waters. For example, daminozide is a plant regulator, so drinking water that is heavily influenced by upstream agricultural runoff could be at risk.

Laboratory Studies of the Formation of Carbonaceous Cosmic Dust from PAH Precursors

Science.gov (United States)

Salama, Farid; Contreras, C. S.

2012-05-01

The study of the formation and destruction processes of cosmic dust is essential to understand and to quantify the budget of extraterrestrial organic molecules. Although dust with all its components plays an important role in the evolution of interstellar chemistry and in the formation of organic molecules, little is known on the formation and destruction processes of carbonaceous dust. PAHs are important chemical building blocks of interstellar dust. They are detected in interplanetary dust particles and in meteoritic samples and are an important, ubiquitous component of the interstellar medium. The formation of PAHs from smaller molecules has not been extensively studied. Therefore, it is imperative that laboratory experiments be conducted to study the dynamic processes of carbon grain formation from PAH precursors. Studies of interstellar dust analogs formed from a variety of PAH and hydrocarbon precursors as well as species that include O, N, and S, have recently been performed using the COSmIC facility in our laboratory under conditions that simulate interstellar and circumstellar environments. The species formed in the pulsed discharge nozzle (PDN) plasma source are detected and characterized with high-sensitivity cavity ringdown spectroscopy coupled to a Reflectron time-of-flight mass spectrometer (ReTOF-MS), thus providing both spectroscopic and ion mass information in-situ. We report the measurements obtained in these experiments. Studies with hydrocarbon precursors show the feasibility of specific molecules to form PAHs, while studies with carbon ring systems (benzene and derivatives, PAHs) precursors provide information on pathways toward larger carbonaceous molecules. From these unique measurements, we derive information on the size and the structure of interstellar dust grain particles, the growth and the destruction processes of interstellar dust and the resulting budget of extraterrestrial organic molecules. Acknowledgements: This research is

Observations and Explicit Modeling of Summertime Carbonyl Formation in Beijing: Identification of Key Precursor Species and Their Impact on Atmospheric Oxidation Chemistry

Science.gov (United States)

Yang, Xue; Xue, Likun; Wang, Tao; Wang, Xinfeng; Gao, Jian; Lee, Shuncheng; Blake, Donald R.; Chai, Fahe; Wang, Wenxing

2018-01-01

Carbonyls are an important group of volatile organic compounds (VOCs) that play critical roles in tropospheric chemistry. To better understand the formation mechanisms of carbonyl compounds, extensive measurements of carbonyls and related parameters were conducted in Beijing in summer 2008. Formaldehyde (11.17 ± 5.32 ppbv), acetone (6.98 ± 3.01 ppbv), and acetaldehyde (5.27 ± 2.24 ppbv) were the most abundant carbonyl species. Two dicarbonyls, glyoxal (0.68 ± 0.26 ppbv) and methylglyoxal (MGLY; 1.10 ± 0.44 ppbv), were also present in relatively high concentrations. An observation-based chemical box model was used to simulate the in situ production of formaldehyde, acetaldehyde, glyoxal, and MGLY and quantify their contributions to ozone formation and ROx budget. All four carbonyls showed similar formation mechanisms but exhibited different precursor distributions. Alkenes (mainly isoprene and ethene) were the dominant precursors of formaldehyde, while both alkenes (e.g., propene, i-butene, and cis-2-pentene) and alkanes (mainly i-pentane) were major precursors of acetaldehyde. For dicarbonyls, both isoprene and aromatic VOCs were the dominant parent hydrocarbons of glyoxal and MGLY. Photolysis of oxygenated VOCs was the dominant source of ROx radicals (approximately >80% for HO2 and approximately >70% for RO2) in Beijing. Ozone production occurred under a mixed-control regime with carbonyls being the key VOC species. Overall, this study provides some new insights into the formation mechanisms of carbonyls, especially their parent hydrocarbon species, and underlines the important role of carbonyls in radical chemistry and ozone pollution in Beijing. Reducing the emissions of alkenes and aromatics would be an effective way to mitigate photochemical pollution in Beijing.

Formation of Hydroxylamine on Dust Grains via Ammonia Oxidation

Science.gov (United States)

He, Jiao; Vidali, Gianfranco; Lemaire, Jean-Louis; Garrod, Robin T.

2015-01-01

The quest to detect prebiotic molecules in space, notably amino acids, requires an understanding of the chemistry involving nitrogen atoms. Hydroxylamine (NH2OH) is considered a precursor to the amino acid glycine. Although not yet detected, NH2OH is considered a likely target of detection with ALMA. We report on an experimental investigation of the formation of hydroxylamine on an amorphous silicate surface via the oxidation of ammonia. The experimental data are then fed into a simulation of the formation of NH2OH in dense cloud conditions. On ices at 14 K and with a modest activation energy barrier, NH2OH is found to be formed with an abundance that never falls below a factor 10 with respect to NH3. Suggestions of conditions for future observations are provided.

Factors affecting the formation of iodo-trihalomethanes during oxidation with chlorine dioxide.

Science.gov (United States)

Guo, Wanhong; Shan, Yingchun; Yang, Xin

2014-01-15

Effects of water characteristics, reaction time, temperature, bromide and iodide ion concentrations, oxidant doses, and pH on formation of iodinated trihalomethanes (I-THM) during oxidation of iodide-containing water with chlorine dioxide (ClO2) were investigated. Among the water samples collected from ten water sources, iodoform (CHI3) was the predominant I-THM and trace amount of chlorodiiodomethane (CHClI2) was occasionally found. CHI3 yields correlated moderately with specific UV absorbance (SUVA) (R(2)=0.79), indicating that hydrophobic aromatic content were important precursors. Longer reaction time led to continued formation of CHI3. I-THM containing bromide was also found in waters containing both bromide and iodide, but CHI3 was dominant. The formation of CHI3 was higher at 25°C than 5°C and 35°C. CHI3 formation showed an increase followed by a decrease trend with increasing ClO2 doses and iodide concentrations and the highest yields occurred at iodide to ClO2 molar ratios of 1-2. pH 8 resulted in the highest CHI3 formation. It should be noted that a high iodide concentration was spiked to waters before adding ClO2 and the results may not reflect the formation yields of iodinated THMs in real conditions, but they provide information about formation trend of I-THM during oxidation of ClO2. Copyright © 2013 Elsevier B.V. All rights reserved.

Atomic layer deposition of calcium oxide and calcium hafnium oxide films using calcium cyclopentadienyl precursor

International Nuclear Information System (INIS)

Kukli, Kaupo; Ritala, Mikko; Sajavaara, Timo; Haenninen, Timo; Leskelae, Markku

2006-01-01

Calcium oxide and calcium hafnium oxide thin films were grown by atomic layer deposition on borosilicate glass and silicon substrates in the temperature range of 205-300 o C. The calcium oxide films were grown from novel calcium cyclopentadienyl precursor and water. Calcium oxide films possessed refractive index 1.75-1.80. Calcium oxide films grown without Al 2 O 3 capping layer occurred hygroscopic and converted to Ca(OH) 2 after exposure to air. As-deposited CaO films were (200)-oriented. CaO covered with Al 2 O 3 capping layers contained relatively low amounts of hydrogen and re-oriented into (111) direction upon annealing at 900 o C. In order to examine the application of CaO in high-permittivity dielectric layers, mixtures of Ca and Hf oxides were grown by alternate CaO and HfO 2 growth cycles at 230 and 300 o C. HfCl 4 was used as a hafnium precursor. When grown at 230 o C, the films were amorphous with equal amounts of Ca and Hf constituents (15 at.%). These films crystallized upon annealing at 750 o C, showing X-ray diffraction peaks characteristic of hafnium-rich phases such as Ca 2 Hf 7 O 16 or Ca 6 Hf 19 O 44 . At 300 o C, the relative Ca content remained below 8 at.%. The crystallized phase well matched with rhombohedral Ca 2 Hf 7 O 16 . The dielectric films grown on Si(100) substrates possessed effective permittivity values in the range of 12.8-14.2

Secondary organic aerosol formation from in situ OH, O3, and NO3 oxidation of ambient forest air in an oxidation flow reactor

Science.gov (United States)

Palm, Brett B.; Campuzano-Jost, Pedro; Day, Douglas A.; Ortega, Amber M.; Fry, Juliane L.; Brown, Steven S.; Zarzana, Kyle J.; Dube, William; Wagner, Nicholas L.; Draper, Danielle C.; Kaser, Lisa; Jud, Werner; Karl, Thomas; Hansel, Armin; Gutiérrez-Montes, Cándido; Jimenez, Jose L.

2017-04-01

Ambient pine forest air was oxidized by OH, O3, or NO3 radicals using an oxidation flow reactor (OFR) during the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen - Rocky Mountain Biogenic Aerosol Study) campaign to study biogenic secondary organic aerosol (SOA) formation and organic aerosol (OA) aging. A wide range of equivalent atmospheric photochemical ages was sampled, from hours up to days (for O3 and NO3) or weeks (for OH). Ambient air processed by the OFR was typically sampled every 20-30 min, in order to determine how the availability of SOA precursor gases in ambient air changed with diurnal and synoptic conditions, for each of the three oxidants. More SOA was formed during nighttime than daytime for all three oxidants, indicating that SOA precursor concentrations were higher at night. At all times of day, OH oxidation led to approximately 4 times more SOA formation than either O3 or NO3 oxidation. This is likely because O3 and NO3 will only react with gases containing C = C bonds (e.g., terpenes) to form SOA but will not react appreciably with many of their oxidation products or any species in the gas phase that lacks a C = C bond (e.g., pinonic acid, alkanes). In contrast, OH can continue to react with compounds that lack C = C bonds to produce SOA. Closure was achieved between the amount of SOA formed from O3 and NO3 oxidation in the OFR and the SOA predicted to form from measured concentrations of ambient monoterpenes and sesquiterpenes using published chamber yields. This is in contrast to previous work at this site (Palm et al., 2016), which has shown that a source of SOA from semi- and intermediate-volatility organic compounds (S/IVOCs) 3.4 times larger than the source from measured VOCs is needed to explain the measured SOA formation from OH oxidation. This work suggests that those S/IVOCs typically do not contain C = C bonds. O3 and NO3 oxidation produced SOA with elemental O : C and H : C

Comparison of the reactivity of alkyl and alkyl amine precursors with native oxide GaAs(100) and InAs(100) surfaces

Energy Technology Data Exchange (ETDEWEB)

Henegar, A.J., E-mail: henegar1@umbc.edu; Gougousi, T., E-mail: gougousi@umbc.edu

2016-12-30

Graphical abstract: The interaction of the native oxides of GaAs(100) and InAs(100) with alkyl (trimethyl aluminum) and alkyl amine (tetrakis dimethylamino titanium) precursors during thermal atomic layer deposition (ALD) of Al{sub 2}O{sub 3} and TiO{sub 2} is compared. Al{sub 2}O{sub 3} if found to be a significantly better barrier against the transport of the surface native oxide during the film deposition as well as after post-deposition heat treatment. This superior blocking ability also limits the removal of the native oxides during the Al{sub 2}O{sub 3} ALD process. - Highlights: • Native oxide diffusion is required for continuous native oxide removal. • The diffusion barrier capabilities of Al{sub 2}O{sub 3} limits native oxide removal during ALD. • Arsenic oxide exhibits higher mobility from InAs compared to GaAs substrates. • Oxygen scavenging from the surface by trimethyl aluminum is confirmed. - Abstract: In this manuscript we compare the interaction of alkyl (trimethyl aluminum) and alkyl amine (tetrakis dimethylamino titanium) precursors during thermal atomic layer deposition with III-V native oxides. For that purpose we deposit Al{sub 2}O{sub 3} and TiO{sub 2}, using H{sub 2}O as the oxidizer, on GaAs(100) and InAs(100) native oxide surfaces. We find that there are distinct differences in the behavior of the two films. For the Al{sub 2}O{sub 3} ALD very little native oxide removal happens after the first few ALD cycles while the interaction of the alkyl amine precursor for TiO{sub 2} and the native oxides continues well after the surface has been covered with 2 nm of TiO{sub 2}. This difference is traced to the superior properties of Al{sub 2}O{sub 3} as a diffusion barrier. Differences are also found in the behavior of the arsenic oxides of the InAs and GaAs substrates. The arsenic oxides from the InAs surface are found to mix more efficiently in the growing dielectric film than those from the GaAs surface. This difference is attributed to

Comparison of the reactivity of alkyl and alkyl amine precursors with native oxide GaAs(100) and InAs(100) surfaces

International Nuclear Information System (INIS)

Henegar, A.J.; Gougousi, T.

2016-01-01

Graphical abstract: The interaction of the native oxides of GaAs(100) and InAs(100) with alkyl (trimethyl aluminum) and alkyl amine (tetrakis dimethylamino titanium) precursors during thermal atomic layer deposition (ALD) of Al_2O_3 and TiO_2 is compared. Al_2O_3 if found to be a significantly better barrier against the transport of the surface native oxide during the film deposition as well as after post-deposition heat treatment. This superior blocking ability also limits the removal of the native oxides during the Al_2O_3 ALD process. - Highlights: • Native oxide diffusion is required for continuous native oxide removal. • The diffusion barrier capabilities of Al_2O_3 limits native oxide removal during ALD. • Arsenic oxide exhibits higher mobility from InAs compared to GaAs substrates. • Oxygen scavenging from the surface by trimethyl aluminum is confirmed. - Abstract: In this manuscript we compare the interaction of alkyl (trimethyl aluminum) and alkyl amine (tetrakis dimethylamino titanium) precursors during thermal atomic layer deposition with III-V native oxides. For that purpose we deposit Al_2O_3 and TiO_2, using H_2O as the oxidizer, on GaAs(100) and InAs(100) native oxide surfaces. We find that there are distinct differences in the behavior of the two films. For the Al_2O_3 ALD very little native oxide removal happens after the first few ALD cycles while the interaction of the alkyl amine precursor for TiO_2 and the native oxides continues well after the surface has been covered with 2 nm of TiO_2. This difference is traced to the superior properties of Al_2O_3 as a diffusion barrier. Differences are also found in the behavior of the arsenic oxides of the InAs and GaAs substrates. The arsenic oxides from the InAs surface are found to mix more efficiently in the growing dielectric film than those from the GaAs surface. This difference is attributed to lower native oxide stability as well as an initial diffusion path formation by the indium oxides.

Direct preparation of Al-base alloys from their oxides/metal precursors in the eutectic LiCl–KCl melt

International Nuclear Information System (INIS)

Gao, Bingliang; Zhu, Hao; Xia, Yuxiang; Shi, Zhongning; Hu, Xianwei; Wang, Zhaowen

2016-01-01

A study was carried out on the preparation of Al–Cu–Li alloy from their oxides/metal precursors using the method of electro-deoxidation in the eutectic LiCl–KCl melt at 648 K. Cyclic voltammetry was used to characterize the system. The samples were prepared by potentiostatic electrolysis at −1.0 V to −2.0 V (vs. Ag + /Ag) for 5 h. XRD analysis shows that Li 2 O is not electrochemically reduced to Li at −1.0 V (vs. Ag + /Ag) or more negative potential. During the preparation process of Al–Cu–Li alloy, lithium peroxide is formed as an intermediate compound. Al–Cu–Li alloy is chemically prepared through the reaction between aluminum and lithium peroxide by heating of Al–Cu–Li 2 O precursors in KCl–LiCl–LiF melt at 1023 K. Eelectro-deoxidation in LiCl–KCl melt can increase the lithium content in the final alloy product. Al–Mg and Al–Nd alloy were also prepared by using the same method from their mixture of aluminum and corresponding oxide, respectively. Al–Nd alloy can only be obtained at the temperature above 773 K. Al–Li alloy could not be obtained in eutectic CaCl 2 –LiCl melt because of formation of calcium aluminates. - Highlights: • Al–Cu–Li alloy was prepared using electrochemical deoxidation of Al–Cu–Li 2 O precursor in eutectic KCl–LiCl melt at 648 K. • Al–Nd alloy was successfully produced by the same method at 773 K. • CaCl 2 –LiCl melt is not a good choice for preparing Al–Li alloy because of formation of calcium aluminate.

Direct preparation of Al-base alloys from their oxides/metal precursors in the eutectic LiCl–KCl melt

Energy Technology Data Exchange (ETDEWEB)

Gao, Bingliang, E-mail: blgao@mail.neu.edu.cn; Zhu, Hao; Xia, Yuxiang; Shi, Zhongning; Hu, Xianwei; Wang, Zhaowen

2016-04-25

A study was carried out on the preparation of Al–Cu–Li alloy from their oxides/metal precursors using the method of electro-deoxidation in the eutectic LiCl–KCl melt at 648 K. Cyclic voltammetry was used to characterize the system. The samples were prepared by potentiostatic electrolysis at −1.0 V to −2.0 V (vs. Ag{sup +}/Ag) for 5 h. XRD analysis shows that Li{sub 2}O is not electrochemically reduced to Li at −1.0 V (vs. Ag{sup +}/Ag) or more negative potential. During the preparation process of Al–Cu–Li alloy, lithium peroxide is formed as an intermediate compound. Al–Cu–Li alloy is chemically prepared through the reaction between aluminum and lithium peroxide by heating of Al–Cu–Li{sub 2}O precursors in KCl–LiCl–LiF melt at 1023 K. Eelectro-deoxidation in LiCl–KCl melt can increase the lithium content in the final alloy product. Al–Mg and Al–Nd alloy were also prepared by using the same method from their mixture of aluminum and corresponding oxide, respectively. Al–Nd alloy can only be obtained at the temperature above 773 K. Al–Li alloy could not be obtained in eutectic CaCl{sub 2}–LiCl melt because of formation of calcium aluminates. - Highlights: • Al–Cu–Li alloy was prepared using electrochemical deoxidation of Al–Cu–Li{sub 2}O precursor in eutectic KCl–LiCl melt at 648 K. • Al–Nd alloy was successfully produced by the same method at 773 K. • CaCl{sub 2}–LiCl melt is not a good choice for preparing Al–Li alloy because of formation of calcium aluminate.

FORMATION OF HYDROXYLAMINE ON DUST GRAINS VIA AMMONIA OXIDATION

Energy Technology Data Exchange (ETDEWEB)

He, Jiao; Vidali, Gianfranco [Physics Department, Syracuse University, Syracuse, NY 13244 (United States); Lemaire, Jean-Louis [Paris Observatory, F-75014 Paris (France); Garrod, Robin T., E-mail: gvidali@syr.edu [Center for Radiophysics and Space Research, Cornell University, Ithaca, NY 14853 (United States)

2015-01-20

The quest to detect prebiotic molecules in space, notably amino acids, requires an understanding of the chemistry involving nitrogen atoms. Hydroxylamine (NH{sub 2}OH) is considered a precursor to the amino acid glycine. Although not yet detected, NH{sub 2}OH is considered a likely target of detection with ALMA. We report on an experimental investigation of the formation of hydroxylamine on an amorphous silicate surface via the oxidation of ammonia. The experimental data are then fed into a simulation of the formation of NH{sub 2}OH in dense cloud conditions. On ices at 14 K and with a modest activation energy barrier, NH{sub 2}OH is found to be formed with an abundance that never falls below a factor 10 with respect to NH{sub 3}. Suggestions of conditions for future observations are provided.

Isotopic Studies of O-O Bond Formation During Water Oxidation (SISGR)

Energy Technology Data Exchange (ETDEWEB)

Roth, Justine P. [Johns Hopkins Univ., Baltimore, MD (United States)

2015-03-03

Isotopic Studies of O-O Bond Formation During Water Oxidation (SISGR) Research during the project period focused primarily on mechanisms of water oxidation by structurally defined transition metal complexes. Competitive oxygen isotope fractionation of water, mediated by oxidized precursors or reduced catalysts together with ceric, Ce(IV), ammonium nitrate in aqueous media, afforded oxygen-18 kinetic isotope effects (O-18 KIEs). Measurement, calculation, and interpretation of O-18 KIEs, described in the accompanying report has important ramifications for the production of electricity and solar hydrogen (as fuel). The catalysis division of BES has acknowledged that understanding mechanisms of transition metal catalyzed water oxidation has major ramifications, potentially leading to transformation of the global economy and natural environment in years to come. Yet, because of program restructuring and decreased availability of funds, it was recommended that the Solar Photochemistry sub-division of BES would be a more appropriate parent program for support of continued research.

Summary of ceramic pigments by polymer precursors Pechini method; Sintese de pigmentos ceramicos pelo metodo dos precursores polimericos

Energy Technology Data Exchange (ETDEWEB)

Silva, E.M. da; Galvao, S.B.; Paskocimas, C.A., E-mail: everlania_siva@yahoo.com.b [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil)

2010-07-01

In this work were synthesized nitrate chromium nitrate and iron-doped titanium oxide by the polymeric precursor method, for application as ceramic pigments. The stains were developed between the temperatures 700 deg C to 1000 deg C, in green for chromium oxide and orange for iron. Noticing an increase of its opacity by increasing temperature. Characterization by thermogravimetry (TG) showed strong thermo decomposition from 355 deg C for the chromium oxide and thermo decomposition gradual for the iron. By analysis of X-ray diffraction revealed the formation of crystalline phases as Iron Titanate (FeTiO3) and Chrome Titanate (CrTiO3), respectively. The scanning electron microscopy showed the formation of rounded particles for both oxides. Thus, the synthesized oxides were within the requirements to be applied as pigments and shown to be possible to propose its use in ceramic materials. (author)

Direct imprinting of indium-tin-oxide precursor gel and simultaneous formation of channel and source/drain in thin-film transistor

Science.gov (United States)

Haga, Ken-ichi; Kamiya, Yuusuke; Tokumitsu, Eisuke

2018-02-01

We report on a new fabrication process for thin-film transistors (TFTs) with a new structure and a new operation principle. In this process, both the channel and electrode (source/drain) are formed simultaneously, using the same oxide material, using a single nano-rheology printing (n-RP) process, without any conventional lithography process. N-RP is a direct thermal imprint technique and deforms oxide precursor gel. To reduce the source/drain resistance, the material common to the channel and electrode is conductive indium-tin-oxide (ITO). The gate insulator is made of a ferroelectric material, whose high charge density can deplete the channel of the thin ITO film, which realizes the proposed operation principle. First, we have examined the n-RP conditions required for the channel and source/drain patterning, and found that the patterning properties are strongly affected by the cooling rate before separating the mold. Second, we have fabricated the TFTs as proposed and confirmed their TFT operation.

Phase formation of V2O5.xNb2O5 compounds via gels and freeze-dried precursors

International Nuclear Information System (INIS)

Langbein, Hubert; Mayer-Uhma, Tobias

2009-01-01

An X-ray powder diffraction study of the phase formation in the system V 2 O 5 /Nb 2 O 5 is performed. Freeze-dried ammonium vanadate and ammonium oxalato niobate, alkoxide-derived xerogels and a mixture of active oxides are used as precursors to compare the resulting phase composition. Thermal decomposition of the freeze-dried precursor is monitored with DTA/TG and mass spectrometry. In the quasi-binary system V 2 O 5 -Nb 2 O 5 metastable VNbO 5 , V 4 Nb 18 O 55 , VNb 9 O 25 and solid solutions of V 2 O 5 in TT-Nb 2 O 5 as also thermodynamically stable VNb 9 O 25 exist. The thermal decomposition of freeze-dried vanadate-oxalatoniobate solution allows the synthesis of all these phases in a relative simple manner. Structural relationships between an intermediate phase and the product, or, in the case of solid-state reactions, between one of the starting oxide and the product, favour the desired reaction. Therefore, the structure of a former phase influences or directs the structure of the product similar to a topotactic reaction

The route of liquid precursor to ZnO nanoparticles in premixed combustion spray pyrolysis

Science.gov (United States)

Widiyastuti, W.; Machmudah, Siti; Nurtono, Tantular; Winardi, Sugeng

2018-04-01

Zinc oxide nanoparticles had been successfully synthesized by premixed combustion spray pyrolysis. Zinc acetate was dissolved in distilled water was selected as a liquid precursor. Zinc nitrate was also used for comparison the effect of precursor type on the generated particles morphology and the crystallinity. The premixed combustion reaction used liquefied petroleum gas (LPG) mainly consisting of butane and propane as a fuel and compressed air used as an oxidizer. The liquid precursor was atomized using a custom two fluid nozzle to generate droplets. Then, the droplets were sprayed by the flow of air as a carrier gas into the premixed combustion reactor. The zinc precursor was decomposed to zinc oxide due to the high temperature as a result of combustion reaction inside the reactor resulting in nanoparticles formation. The particle size decreased with the increase of the fuel flow rate. In addition, it can be found that at the same flow rate of fuel, the particle size of zinc oxide synthesized using zinc nitrate is larger than that of the use of zinc acetate as a precursor.

Antarctic new particle formation from continental biogenic precursors

Directory of Open Access Journals (Sweden)

E.-M. Kyrö

2013-04-01

Full Text Available Over Antarctica, aerosol particles originate almost entirely from marine areas, with minor contribution from long-range transported dust or anthropogenic material. The Antarctic continent itself, unlike all other continental areas, has been thought to be practically free of aerosol sources. Here we present evidence of local aerosol production associated with melt-water ponds in continental Antarctica. We show that in air masses passing such ponds, new aerosol particles are efficiently formed and these particles grow up to sizes where they may act as cloud condensation nuclei (CCN. The precursor vapours responsible for aerosol formation and growth originate very likely from highly abundant cyanobacteria Nostoc commune (Vaucher communities of local ponds. This is the first time freshwater vegetation has been identified as an aerosol precursor source. The influence of the new source on clouds and climate may increase in future Antarctica, and possibly elsewhere undergoing accelerating summer melting of semi-permanent snow cover.

Antarctic new particle formation from continental biogenic precursors

Science.gov (United States)

Kyrö, E.-M.; Kerminen, V.-M.; Virkkula, A.; Dal Maso, M.; Parshintsev, J.; Ruíz-Jimenez, J.; Forsström, L.; Manninen, H. E.; Riekkola, M.-L.; Heinonen, P.; Kulmala, M.

2013-04-01

Over Antarctica, aerosol particles originate almost entirely from marine areas, with minor contribution from long-range transported dust or anthropogenic material. The Antarctic continent itself, unlike all other continental areas, has been thought to be practically free of aerosol sources. Here we present evidence of local aerosol production associated with melt-water ponds in continental Antarctica. We show that in air masses passing such ponds, new aerosol particles are efficiently formed and these particles grow up to sizes where they may act as cloud condensation nuclei (CCN). The precursor vapours responsible for aerosol formation and growth originate very likely from highly abundant cyanobacteria Nostoc commune (Vaucher) communities of local ponds. This is the first time freshwater vegetation has been identified as an aerosol precursor source. The influence of the new source on clouds and climate may increase in future Antarctica, and possibly elsewhere undergoing accelerating summer melting of semi-permanent snow cover.

The competing oxide and sub-oxide formation in metal-oxide molecular beam epitaxy

International Nuclear Information System (INIS)

Vogt, Patrick; Bierwagen, Oliver

2015-01-01

The hetero-epitaxial growth of the n-type semiconducting oxides β-Ga 2 O 3 , In 2 O 3 , and SnO 2 on c- and r-plane sapphire was performed by plasma-assisted molecular beam epitaxy. The growth-rate and desorbing flux from the substrate were measured in-situ under various oxygen to metal ratios by laser reflectometry and quadrupole mass spectrometry, respectively. These measurements clarified the role of volatile sub-oxide formation (Ga 2 O, In 2 O, and SnO) during growth, the sub-oxide stoichiometry, and the efficiency of oxide formation for the three oxides. As a result, the formation of the sub-oxides decreased the growth-rate under metal-rich growth conditions and resulted in etching of the oxide film by supplying only metal flux. The flux ratio for the exclusive formation of the sub-oxide (e.g., the p-type semiconductor SnO) was determined, and the efficiency of oxide formation was found to be the highest for SnO 2 , somewhat lower for In 2 O 3 , and the lowest for Ga 2 O 3 . Our findings can be generalized to further oxides that possess related sub-oxides

Factors Affecting Pro- and Anti-Oxidant Properties of Fragments of the b-Protein Precursor (bPP): Implication for Alzheimer's Disease.

Science.gov (United States)

Andorn, Anne C.; Kalaria, Rajesh N.

2000-06-01

Oxidative stress may have a key pathogenetic role in neurodegenerative diseases including Alzheimer's disease (AD). While there is evidence that some amyloid-b (Ab) peptides can initiate oxidative stress at micromolar doses, there is also some evidence that oxidative stress increases the concentration of the b-protein precursor (bPP) and the potential for increased formation of the Ab peptides. The following studies were performed to test the hypothesis that fragments of bPP could be antioxidants and hence that oxidative stress might be an early event in AD. We found that several fragments of bPP, including the Ab peptides, inhibit ascorbate-stimulated lipid peroxidation (ASLP) in membrane fragment preparations of postmortem human brain. In contrast, other fragments of bPP enhance ASLP. These data indicate that bPP or fragments of bPP could play a key role in the redox status of cells and that alterations in bPP processing could have profound effects on the cellular response to oxidative stress.

Spinel formation for stabilizing simulated nickel-laden sludge with aluminum-rich ceramic precursors.

Science.gov (United States)

Shih, Kaimin; White, Tim; Leckie, James O

2006-08-15

The feasibility of stabilizing nickel-laden sludge from commonly available Al-rich ceramic precursors was investigated and accomplished with high nickel incorporation efficiency. To simulate the process, nickel oxide was mixed alternatively with gamma-alumina, corundum, kaolinite, and mullite and was sintered from 800 to 1480 degrees C. The nickel aluminate spinel (NiAl2O4) was confirmed as the stabilization phase for nickel and crystallized with efficiencies greater than 90% for all precursors above 1250 degrees C and 3-h sintering. The nickel-incorporation reaction pathways with these precursors were identified, and the microstructure and spinel yield were investigated as a function of sintering temperature with fixed sintering time. This study has demonstrated a promising process for forming nickel spinel to stabilize nickel-laden sludge from a wide range of inexpensive ceramic precursors, which may provide an avenue for economically blending waste metal sludges via the building industry processes to reduce the environmental hazards of toxic metals. The correlation of product textures and nickel incorporation efficiencies through selection of different precursors also provides the option of tailoring property-specific products.

Kinetics of 25-hydroperoxycholesterol formation during photo-oxidation of crystalline cholesterol.

Science.gov (United States)

Medina-Meza, Ilce Gabriela; Rodriguez-Estrada, Maria Teresa; Lercker, Giovanni; Barnaba, Carlo; García, Hugo Sergio

2014-06-01

25-Hydroxycholesterol (25-OH), a side-chain product of cholesterol oxidation, has emerged as one of the important issues in food chemistry and biochemistry, because of its involvement in several human pathologies. This oxysterol is derived from both enzymatic and non-enzymatic pathways. However, the latter mechanism has been scarcely studied in either food or model systems. In this work, a kinetic model was developed to evaluate the formation of 25-OH and its precursor 25-hydroperoxycholesterol (25-OOH) during photo-oxidation of cholesterol for 28 days under fluorescent light. 25-OOH was estimated by an indirect method, using thin-layer chromatography coupled with gas chromatography-mass spectrometry. Peroxide value (POV) and cholesterol oxidation products (COPs) were determined. POV showed a hyperbolic behavior, typical of a crystalline system in which the availability of cholesterol is the limiting factor. Further reactions of hydroperoxides were followed; in particular, after photo-oxidation, 25-OOH (0.55 mg g(-1) ) and 25-OH (0.08 mg g(-1) ) were found in cholesterol, as well as seven other oxysterols, including 7-hydroxy and 5,6-epoxy derivatives. The application of kinetic models to the data showed good correlation with theoretical values, allowing derivation of the kinetic parameters for each oxidation route. The results of this work confirm that cholesterol in the crystalline state involves different oxidation patterns as compared to cholesterol in solution. Moreover, the numerical fit proved that hydroperoxidation is the rate-limiting step in 25-OH formation. © 2013 Society of Chemical Industry.

Self-propagating high-temperature synthesis of LaMO{sub 3} perovskite-type oxide using heteronuclearcyano metal complex precursors

Energy Technology Data Exchange (ETDEWEB)

Sánchez-Rodríguez, Daniel, E-mail: daniel.sanchez@udg.edu [GRMT, Department of Physics, University of Girona, Campus Montilivi, Edif.PII, E17071 Girona, Catalonia (Spain); Wada, Hiroki; Yamaguchi, Syuhei [Department of Materials Science and Biotechnology, Graduate School of Science and Engineering, Ehime University, Matsuyama 790-8577 (Japan); Farjas, Jordi [GRMT, Department of Physics, University of Girona, Campus Montilivi, Edif.PII, E17071 Girona, Catalonia (Spain); Yahiro, Hidenori, E-mail: yahiro.hidenori.me@ehime-u.ac.jp [Department of Materials Science and Biotechnology, Graduate School of Science and Engineering, Ehime University, Matsuyama 790-8577 (Japan)

2015-11-15

The decomposition of La[Fe(CN){sub 6}]·5H{sub 2}O and La[Co(CN){sub 6}]·5H{sub 2}O under different atmospheres has been analyzed by thermogravimetry (TG) and differential thermal analysis (DTA). In addition, the decomposition temperature at different sample locations was monitored for sample masses around 2 g of La[Fe(CN){sub 6}]·5H{sub 2}O and La[Co(CN){sub 6}]·5H{sub 2}O, when they were calcined for 1 h at temperatures ranging from 200 to 400 °C in a controlled gas-flow system. Results showed that, the large enough of the cyano complex precursors undergo combustion when they are decomposed under oxygen atmosphere. X-ray diffraction results revealed that perovskite-type oxides crystallize due to the overheating of the process. As a result, it has been possible to produce LaFeO{sub 3} and LaCoO{sub 3} perovskite-type oxide powders by SHS under oxygen atmosphere using La[Fe(CN){sub 6}]·5H{sub 2}O and La[Co(CN){sub 6}]·5H{sub 2}O as a precursor. The effect of the ignition temperature has been investigated. The specific surface area of the perovskite-type oxides produced via SHS using heteronuclearcyano metal complex as a precursor is significantly higher than that of other LaMO{sub 3} produced using the same technique but obtained from other type of precursors. - Highlights: • The decomposition of La[Fe(CN){sub 6}] and La[Co(CN){sub 6}] precursors was analyzed. • The combustion process proceeded under oxygen when sample was large enough. • Perovskite oxides via SHS from the cyano complex precursors were synthesized. • LaMO{sub 3} perovskite oxides via SHS was obtained with high specific surface area.

Novel precursors for the deposition of rare earth oxides

International Nuclear Information System (INIS)

Ahlers, Mareike

2010-01-01

During this work rare earth solvates with nitrate and perchlorate anions have been investigated. All compounds have been structurally characterized and analyzed using thermal gravimetric analysis. The decomposition residues were analyzed using powder diffraction methods. Almost all compounds showed a characteristically intense exothermic decomposition step during the thermal decomposition, most likely caused by an intramolecular redox reaction between the nitrate or perchlorate anion respectively and the organic solvent molecules. The nitrates RE(NO 3 ) 3 (CH(OCH 3 ) 3 ) 2 (RE = Sm, Eu) were isolated and characterized for the first time as the intermediate of the dehydration reaction with trimethyl orthoformate. The known compound group of dimethoxyethane solvates was then expanded with RE(NO 3 ) 3 (O 2 C 4 H 10 ) (RE = La, Sm, Eu). Considering the possible use as precursor material the already described neodymium compound is also discussed. The thermal decomposition of these compounds yields the respective cubic rare earth oxide and shows the typical intense exothermic decomposition reaction. A variety of different precursor system based on nitrate solvates for the deposition of rare earth oxide layers on a silicon surface was developed and investigated in collaboration with the group of Prof. Dr. Al-Shamery (Univ. Oldenburg). Ultra thin films on a H-Si(111) surface were obtained via the deposition of the precursor, which was dissolved in organic solvents. An oxide layer was detected after the heating of the sample. The film thickness was measured as < 10 nm, whereas the thickness of the film was controlled by the concentration of the precursor solution. Sm(ClO 4 ) 3 (CH(OCH 3 ) 3 ) 3 was isolated and characterized for the first time as the intermediate of the dehydration reaction with trimethyl orthoformate. Eu(ClO 4 ) 3 (CH(OCH 3 ) 3 ) 2 (MeOH) 2 was obtained without recrystallization. The methanol molecules, formed during the hydrolysis of the trimethyl

Low-temperature Synthesis of Tin(II) Oxide From Tin(II) ketoacidoximate Precursor

KAUST Repository

Alshankiti, Buthainah

2015-01-01

Sn (II) oxide finds numerous applications in different fields such as thin film transistors1, solar cells2 and sensors.3 In this study we present the fabrication of tin monoxide SnO by using Sn (II) ketoacid oximate complexes as precursors. Tin (II

Facile and sustainable synthesis of shaped iron oxide nanoparticles: effect of iron precursor salts on the shapes of iron oxides.

Science.gov (United States)

Sayed, Farheen N; Polshettiwar, Vivek

2015-05-05

A facile and sustainable protocol for synthesis of six different shaped iron oxides is developed. Notably, all the six shapes of iron oxides can be synthesised using exactly same synthetic protocol, by simply changing the precursor iron salts. Several of the synthesised shapes are not reported before. This novel protocol is relatively easy to implement and could contribute to overcome the challenge of obtaining various shaped iron oxides in economical and sustainable manner.

High formation of secondary organic aerosol from the photo-oxidation of toluene

Directory of Open Access Journals (Sweden)

L. Hildebrandt

2009-05-01

Full Text Available Toluene and other aromatics have long been viewed as the dominant anthropogenic secondary organic aerosol (SOA precursors, but the SOA mass yields from toluene reported in previous studies vary widely. Experiments conducted in the Carnegie Mellon University environmental chamber to study SOA formation from the photo-oxidation of toluene show significantly larger SOA production than parameterizations employed in current air-quality models. Aerosol mass yields depend on experimental conditions: yields are higher under higher UV intensity, under low-NO_x conditions and at lower temperatures. The extent of oxidation of the aerosol also varies with experimental conditions, consistent with ongoing, progressive photochemical aging of the toluene SOA. Measurements using a thermodenuder system suggest that the aerosol formed under high- and low-NO_x conditions is semi-volatile. These results suggest that SOA formation from toluene depends strongly on ambient conditions. An approximate parameterization is proposed for use in air-quality models until a more thorough treatment accounting for the dynamic nature of this system becomes available.

Polymeric precursors method for obtaining pigments based on Inorganic oxides of chromium and iron deposited on TiO{sub 2}; Metodo dos precursores polimericos para obtencao de pigmentos inorganicos a base de oxidos de cromo e de ferro, depositados sobre TiO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

NONE

2011-07-01

The case study was the use of chromium oxides and iron, as a precursor in the synthesis of inorganic pigments. The synthesis was based on the dissolution of citric acid as a complexing agent, addition of metal oxides, such as ion chromophores; polymerization with ethylene glycol and doping with titanium oxide. Going through pre-calcination, breakdown, calcination at different temperatures (700, 900 and 1100 deg C resulting in pigments: green for pigment and chromium deposited on TiO2, orange for iron on TiO2. The thermal analysis (TG and DTA), evaluated their thermal decompositions, the XRD revealed the formation of crystalline phases such as iron titanate and chrome titanate; SEM showed the formation of hexagonal particles for both oxides. Under the different analysis, one can see the potential stability of pigments and powders, can be proposed its use as pigments in polymers. (author)

Rare earth [beta]-diketonate and carboxylate metal complexes as precursors for MOCVD of oxide films

Energy Technology Data Exchange (ETDEWEB)

Kuzmina, N.P. (Dept. of Chemistry, Moscow State Univ. (Russian Federation)); Martynenko, L.I. (Dept. of Chemistry, Moscow State Univ. (Russian Federation)); Tu, Z.A. (Dept. of Chemistry, Moscow State Univ. (Russian Federation)); Kaul, A.R. (Dept. of Chemistry, Moscow State Univ. (Russian Federation)); Girichev, G.V. (Dept. of Chemistry, Moscow State Univ. (Russian Federation)); Giricheva, N.I. (Dept. of Chemistry, Moscow State Univ. (Russian Federation)); Rykov, A.N. (Dept. of Chemistry, Moscow State Univ. (Russian Federation)); Korenev, Y.M. (Dept. of Chemistry, Moscow State Univ. (Russian Federation))

1993-08-01

Volatile and thermostable complexes of lanthanide acetylacetonates and pivalates were obtained and investigated by different methods. These compounds were used for lanthanide oxide containing film producing and for fabrication of silica optical fibers doped by lanthanide oxide. The properties of these and already known volatile precursors are compared. (orig.).

Rare earth β-diketonate and carboxylate metal complexes as precursors for MOCVD of oxide films

International Nuclear Information System (INIS)

Kuzmina, N.P.; Martynenko, L.I.; Tu, Z.A.; Kaul, A.R.; Girichev, G.V.; Giricheva, N.I.; Rykov, A.N.; Korenev, Y.M.

1993-01-01

Volatile and thermostable complexes of lanthanide acetylacetonates and pivalates were obtained and investigated by different methods. These compounds were used for lanthanide oxide containing film producing and for fabrication of silica optical fibers doped by lanthanide oxide. The properties of these and already known volatile precursors are compared. (orig.)

Summary of ceramic pigments by polymer precursors Pechini method

International Nuclear Information System (INIS)

Silva, E.M. da; Galvao, S.B.; Paskocimas, C.A.

2010-01-01

In this work were synthesized nitrate chromium nitrate and iron-doped titanium oxide by the polymeric precursor method, for application as ceramic pigments. The stains were developed between the temperatures 700 deg C to 1000 deg C, in green for chromium oxide and orange for iron. Noticing an increase of its opacity by increasing temperature. Characterization by thermogravimetry (TG) showed strong thermo decomposition from 355 deg C for the chromium oxide and thermo decomposition gradual for the iron. By analysis of X-ray diffraction revealed the formation of crystalline phases as Iron Titanate (FeTiO3) and Chrome Titanate (CrTiO3), respectively. The scanning electron microscopy showed the formation of rounded particles for both oxides. Thus, the synthesized oxides were within the requirements to be applied as pigments and shown to be possible to propose its use in ceramic materials. (author)

Plasma-enhanced chemical vapor deposition of aluminum oxide using ultrashort precursor injection pulses

NARCIS (Netherlands)

Dingemans, G.; Sanden, van de M.C.M.; Kessels, W.M.M.

2012-01-01

An alternative plasma-enhanced chemical vapor deposition (PECVD) method is developed and applied for the deposition of high-quality aluminum oxide (AlOx) films. The PECVD method combines a continuous plasma with ultrashort precursor injection pulses. We demonstrate that the modulation of the

N-nitrosodimethylamine (NDMA) formation potential of amine-based water treatment polymers: Effects of in situ chloramination, breakpoint chlorination, and pre-oxidation.

Science.gov (United States)

Park, Sang Hyuck; Padhye, Lokesh P; Wang, Pei; Cho, Min; Kim, Jae-Hong; Huang, Ching-Hua

2015-01-23

Recent studies show that cationic amine-based water treatment polymers may be important precursors that contribute to formation of the probable human carcinogen N-nitrosodimethylamine (NDMA) during water treatment and disinfection. To better understand how water treatment parameters affect NDMA formation from the polymers, the effects of in situ chloramination, breakpoint chlorination, and pre-oxidation on the NDMA formation from the polymers were investigated. NDMA formation potential (NDMA-FP) as well as dimethylamine (DMA) residual concentration were measured from poly(epichlorohydrin dimethylamine) (polyamine) and poly(diallyldimethylammonium chloride) (polyDADMAC) solutions upon reactions with oxidants including free chlorine, chlorine dioxide, ozone, and monochloramine under different treatment conditions. The results supported that dichloramine (NHCl2) formation was the critical factor affecting NDMA formation from the polymers during in situ chloramination. The highest NDMA formation from the polymers occurred near the breakpoint of chlorination. Polymer chain breakdown and transformation of the released DMA and other intermediates were important factors affecting NDMA formation from the polymers in pre-oxidation followed by post-chloramination. Pre-oxidation generally reduced NDMA-FP of the polymers; however, the treatments involving pre-ozonation increased polyDADMAC's NDMA-FP and DMA release. The strategies for reducing NDMA formation from the polymers may include the avoidance of the conditions favorable to NHCl2 formation and the avoidance of polymer exposure to strong oxidants such as ozone. Copyright © 2014 Elsevier B.V. All rights reserved.

Laser-driven coating of vertically aligned carbon nanotubes with manganese oxide from metal organic precursors for energy storage

Science.gov (United States)

Pérez del Pino, A.; György, E.; Alshaikh, I.; Pantoja-Suárez, F.; Andújar, J. L.; Pascual, E.; Amade, R.; Bertran-Serra, E.

2017-09-01

Carbon nanotubes-transition metal oxide systems are intensively studied due to their excellent properties for electrochemical applications. In this work, an innovative procedure is developed for the synthesis of vertically aligned multi-walled carbon nanotubes (VACNTs) coated with transition metal oxide nanostructures. VACNTs are grown by plasma enhanced chemical vapor deposition and coated with a manganese-based metal organic precursor (MOP) film based on manganese acetate solution. Subsequent UV pulsed laser irradiation induces the effective heating-decomposition of the MOP leading to the crystallization of manganese oxide nanostructures on the VACNT surface. The study of the morphology, structure and composition of the synthesized materials shows the formation of randomly oriented MnO2 crystals, with few nanometers in size, and to their alignment in hundreds of nm long filament-like structures, parallel to the CNT’s long axis. Electrochemical measurements reveal a significant increase of the specific capacitance of the MnO2-VACNT system (100 F g-1) as compared to the initial VACNT one (21 F g-1).

Low-temperature Synthesis of Tin(II) Oxide From Tin(II) ketoacidoximate Precursor

KAUST Repository

Alshankiti, Buthainah

2015-04-01

Sn (II) oxide finds numerous applications in different fields such as thin film transistors1, solar cells2 and sensors.3 In this study we present the fabrication of tin monoxide SnO by using Sn (II) ketoacid oximate complexes as precursors. Tin (II) ketoacidoximates of the type [HON=CRCOO]2Sn where R= Me 1, R= CH2Ph 2, and [(MeON=CMeCOO)3Sn]- NH4 +.2H2O 3 were synthesized by in situ formation of the ketoacid oximate ligand. The crystal structures were determined via single crystal X- ray diffraction of the complexes 1-3 revealed square planar and square pyramidal coordination environments for the Sn atom. Intramolecular hydrogen bonding is observed in all the complexes. Furthermore, the complexes were characterized by Infrared (IR), Nuclear Magnetic Resonance (NMR) and elemental analysis. From thermogravimetric analysis of 1-3, it was found that the complexes decomposed in the range of 160 – 165 oC. Analysis of the gases evolved during decomposition indicated complete loss of the oximato ligand in one step and the formation of SnO. Spin coating of 1 on silicon or glass substrate show uniform coating of SnO. Band gaps of SnO films were measured and found to be in the range of 3.0 – 3.3 eV by UV-Vis spectroscopy. X-ray photoelectron spectroscopy indicated surface oxidation of the SnO film. Heating 1 above 140 oC in air gives SnO of size ranging from 10 – 500 nm and is spherical in shape. The SnO nanomaterial is characterized by powder X-ray diffraction(XRD), Raman spectroscopy, Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM).

Ionospheric earthquake precursors

International Nuclear Information System (INIS)

Bulachenko, A.L.; Oraevskij, V.N.; Pokhotelov, O.A.; Sorokin, V.N.; Strakhov, V.N.; Chmyrev, V.M.

1996-01-01

Results of experimental study on ionospheric earthquake precursors, program development on processes in the earthquake focus and physical mechanisms of formation of various type precursors are considered. Composition of experimental cosmic system for earthquake precursors monitoring is determined. 36 refs., 5 figs

Reactive oxidation products promote secondary organic aerosol formation from green leaf volatiles

Directory of Open Access Journals (Sweden)

J. F. Hamilton

2009-06-01

Full Text Available Green leaf volatiles (GLVs are an important group of chemicals released by vegetation which have emission fluxes that can be significantly increased when plants are damaged or stressed. A series of simulation chamber experiments has been conducted at the European Photoreactor in Valencia, Spain, to investigate secondary organic aerosol (SOA formation from the atmospheric oxidation of the major GLVs cis-3-hexenylacetate and cis-3-hexen-1-ol. Liquid chromatography-ion trap mass spectrometry was used to identify chemical species present in the SOA. Cis-3-hexen-1-ol proved to be a more efficient SOA precursor due to the high reactivity of its first generation oxidation product, 3-hydroxypropanal, which can hydrate and undergo further reactions with other aldehydes resulting in SOA dominated by higher molecular weight oligomers. The lower SOA yields produced from cis-3-hexenylacetate are attributed to the acetate functionality, which inhibits oligomer formation in the particle phase. Based on observed SOA yields and best estimates of global emissions, these compounds may be calculated to be a substantial unidentified global source of SOA, contributing 1–5 TgC yr⁻¹, equivalent to around a third of that predicted from isoprene. Molecular characterization of the SOA, combined with organic mechanistic information, has provided evidence that the formation of organic aerosols from GLVs is closely related to the reactivity of their first generation atmospheric oxidation products, and indicates that this may be a simple parameter that could be used in assessing the aerosol formation potential for other unstudied organic compounds in the atmosphere.

N-nitrosamine formation by monochloramine, free chlorine, and peracetic acid disinfection with presence of amine precursors in drinking water system.

Science.gov (United States)

West, Danielle M; Wu, Qihua; Donovan, Ariel; Shi, Honglan; Ma, Yinfa; Jiang, Hua; Wang, Jianmin

2016-06-01

In this study, the formation of eight N-nitrosamines, N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine, N-nitrosomethylamine, N-nitrosodi-n-propylamine, N-nitrosodi-n-butylamine, N-Nitrosopiperidine, N-Nitrosopyrrolidine, N-Nitrosomorpholine, were systematically evaluated with respect to seven N-nitrosamine precursors (dimethylamine, trimethylamine, 3-(dimethylaminomethyl)indole, 4-dimethylaminoantipyrine, ethylmethylamine, diethylamine, dipropylamine) and three disinfectants (monochloramine, free chlorine, peracetic acid) under variable dosages, exposure times, and pH in a drinking water system. Without the presence of the seven selected N-nitrosamine precursors N-nitrosamine formation was not observed under any tested condition except very low levels of N-Nitrosopyrrolidine under some conditions. With selected N-nitrosamine precursors present N-nitrosamines formed at different levels under different conditions. The highest N-nitrosamine formation was NDMA with a maximum concentration of 1180 ng/L by monochloramine disinfection with precursors present; much lower levels of N-nitrosamines were formed by free chlorine disinfection; and no detectable level of N-nitrosamines were observed by peracetic acid disinfection except low level of N-Nitrosodi-n-propylamine under some conditions. NDMA formation was not affected by pH while four other N-nitrosamine formations were slightly affected by sample pH tested between 7 and 9, with formation decreasing with increasing pH. Monochloramine exposure time study displayed fast formation of N-nitrosamines, largely formed in four hours of exposure and maximized after seven days. This was a systematic study on the N-nitrosamine formation with the seven major N-nitrosamine precursors presence and absence under different conditions, including peracetic acid disinfection which has not been studied elsewhere. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ultrahighly Dispersed Titanium Oxide on Silica : Effect of Precursors on the Structure and Photocatalysis

OpenAIRE

Yoshida , S.; Takenaka , S.; Tanaka , T.; Funabiki , T.

1997-01-01

The effect of precursor on the dispersion and catalytic performance of titanium oxide supported on silica has ben investigated. The catalysts were prepared by a simple impregnation method with three kinds of titanium complexes of different ligands (bis(isopropyato)-bis(pivaroylmethanato) : DPM, acetylacetonato : ACAC, tetrakis(isopropylato) : IPRO) with the aim of preparing ultrahighly dispersed titanium oxide on silica. The XAFS study revealed that titanium species in the catalyst prepared f...

Revealing the Formation of Copper Nanoparticles from a Homogeneous Solid Precursor by Electron Microscopy

DEFF Research Database (Denmark)

van den Berg, Roy; Elkjær, Christian Fink; Gommes, Cedric J.

2016-01-01

The understanding of processes leading to the formation of nanometer-sized particles is important for tailoring of their size, shape and location. The growth mechanisms and kinetics of nanoparticles from solid precursors are, however, often poorly described. Here we employ transmission electron...... microscopy (TEM) to examine the formation of copper nanoparticles on a silica support during the reduction by H2 of homogeneous copper phyllosilicate platelets, as a prototype precursor for a coprecipitated catalyst. Specifically, time-lapsed TEM image series acquired of the material during the reduction...... process provide a direct visualization of the growth dynamics of an ensemble of individual nanoparticles and enable a quantitative evaluation of the nucleation and growth of the nanoparticles. This quantitative information is compared with kinetic models and found to be best described by a nucleation...

Positronium formation studies in crystalline molecular complexes: Triphenylphosphine oxide - Acetanilide

Science.gov (United States)

Oliveira, F. C.; Denadai, A. M. L.; Guerra, L. D. L.; Fulgêncio, F. H.; Windmöller, D.; Santos, G. C.; Fernandes, N. G.; Yoshida, M. I.; Donnici, C. L.; Magalhães, W. F.; Machado, J. C.

2013-04-01

Hydrogen bond formation in the triphenylphosphine oxide (TPPO), acetanilide (ACN) supramolecular heterosynton system, named [TPPO0.5·ACN0.5], has been studied by Positron Annihilation Lifetime Spectroscopy (PALS) and supported by several analytical techniques. In toluene solution, Isothermal Titration Calorimetry (ITC) presented a 1:1 stoichiometry and indicated that the complexation process is driven by entropy, with low enthalpy contribution. X-ray structure determination showed the existence of a three-dimensional network of hydrogen bonds, allowing also the confirmation of the existence of a 1:1 crystalline molecular complex in solid state. The results of thermal analysis (TGA, DTA and DSC) and FTIR spectroscopy showed that the interactions in the complex are relatively weaker than those found in pure precursors, leading to a higher positronium formation probability at [TPPO0.5·ACN0.5]. These weak interactions in the complex enhance the possibility of the n- and π-electrons to interact with positrons and consequently, the probability of positronium formation is higher. Through the present work is shown that PALS is a sensible powerful tool to investigate intermolecular interactions in solid heterosynton supramolecular systems.

The role of aromatic precursors in the formation of haloacetamides by chloramination of dissolved organic matter

KAUST Repository

Le Roux, Julien

2015-10-21

Water treatment utilities are diversifying their water sources and often rely on waters enriched in nitrogen-containing compounds (e.g., ammonia, organic nitrogen such as amino acids). The disinfection of waters exhibiting high levels of nitrogen has been associated with the formation of nitrogenous disinfection byproducts (N-DBPs) such as haloacetonitriles (HANs) and haloacetamides (HAcAms). While the potential precursors of HANs have been extensively studied, only few investigations are available regarding the nature of HAcAm precursors. Previous research has suggested that HAcAms are hydrolysis products of HANs. Nevertheless, it has been recently suggested that HAcAms can be formed independently, especially during chloramination of humic substances. When used as a disinfectant, monochloramine can also be a source of nitrogen for N-DBPs. This study investigated the role of aromatic organic matter in the formation of N-DBPs (HAcAms and HANs) upon chloramination. Formation kinetics were performed from various fractions of organic matter isolated from surface waters or treated wastewater effluents. Experiments were conducted with 15N-labeled monochloramine (15NH2Cl) to trace the origin of nitrogen. N-DBP formation showed a two-step profile: (1) a rapid formation following second-order reaction kinetics and incorporating nitrogen atom originating from the organic matrix (e.g., amine groups); and (2) a slower and linear increase correlated with exposure to chloramines, incorporating inorganic nitrogen (15N) from 15NH2Cl into aromatic moieties. Organic matter isolates showing high aromatic character (i.e., high SUVA) exhibited high reactivity characterized by a major incorporation of 15N in N-DBPs. A significantly lower incorporation was observed for low-aromatic-content organic matter. 15N-DCAcAm and 15N-DCAN formations exhibited a linear correlation, suggesting a similar behavior of 15N incorporation as SUVA increases. Chloramination of aromatic model compounds (i

The Effect of Precursor Ligands and Oxidation State in the Synthesis of Bimetallic Nano-Alloys

KAUST Repository

LaGrow, Alec P.

2015-05-12

The characteristics of bimetallic nanomaterials are dictated by their size, shape and elemental distribution. Solution synthesis is widely utilized to form nanomaterials, such as nanoparticles, with controlled size and shape. However, the effects of variables on the characteristics of bimetallic nanomaterials are not completely understood. In this study, we used a continuous-flow synthetic strategy to explore the effects of the ligands and the oxidation state of a metal precursor in a shape-controlled synthesis on the final shape of the nanomaterials and the elemental distribution within the alloy. We demonstrate that this strategy can tune the size of monodisperse PtM (M=Ni or Cu) alloy nanocrystals ranging from 3 to 16 nm with an octahedral shape using acetylacetonate or halide precursors of Pt(II), Pt(IV) and Ni or Cu (II). The nanoparticles formed from halide precursors showed an enrichment of platinum on their surfaces, and the bromides could oxidatively etch the nanoparticles during synthesis with the O2/Br- pair. The two nanocrystal precursors can be uti-lized independently and can control the size with a trend of Pt(acac)2precursor during the synthesis of alloy nanoparticles as well as to control, in a scalable manner, the nanomaterial size and surface chemistry.

Formation of Poultry Meat Flavor by Heating Process and Lipid Oxidation

Directory of Open Access Journals (Sweden)

Maijon Purba

2014-09-01

Full Text Available Flavor is an important factor in the acceptance of food. Flavor of poultry meat is naturally formed through a specific process of heating, where various chemical reactions complex occurred among nonvolatile precursors in fatty tissue or in lean tissue. The main flavor in the form of volatile and nonvolatile components play a major influence on the acceptance of various processed meat, especially the taste. Removal of sulfur components decreases meat flavor (meaty, while removal of carbonyl compounds decrease the specific flavor and increases common flavor of the meat. Poultry meat has a fairly high fat content that easily generates lipid oxidation. Lipid oxidation in poultry meat is a sign that the meat was damaged and caused off odor. Addition of antioxidants in the diet can inhibit lipid oxidation in the meat. Lipids interaction with proteins and carbohydrates is unavoidable during the thermal processing of food, causing the appearance of volatile components. The main reaction in meat flavor formation mechanism is Maillard reaction followed by Stecker reaction and degradation of lipids and thiamine. They involve in the reaction between carbonyl and amine components to form flavor compounds, which enhance the flavor of poultry meat.

Novel precursors for the deposition of rare earth oxides; Neuartige Precursor zur Abscheidung von Selten-Erd-Oxiden

Energy Technology Data Exchange (ETDEWEB)

Ahlers, Mareike

2010-02-22

During this work rare earth solvates with nitrate and perchlorate anions have been investigated. All compounds have been structurally characterized and analyzed using thermal gravimetric analysis. The decomposition residues were analyzed using powder diffraction methods. Almost all compounds showed a characteristically intense exothermic decomposition step during the thermal decomposition, most likely caused by an intramolecular redox reaction between the nitrate or perchlorate anion respectively and the organic solvent molecules. The nitrates RE(NO{sub 3}){sub 3}(CH(OCH{sub 3}){sub 3}){sub 2} (RE = Sm, Eu) were isolated and characterized for the first time as the intermediate of the dehydration reaction with trimethyl orthoformate. The known compound group of dimethoxyethane solvates was then expanded with RE(NO{sub 3}){sub 3}(O{sub 2}C{sub 4}H{sub 10}) (RE = La, Sm, Eu). Considering the possible use as precursor material the already described neodymium compound is also discussed. The thermal decomposition of these compounds yields the respective cubic rare earth oxide and shows the typical intense exothermic decomposition reaction. A variety of different precursor system based on nitrate solvates for the deposition of rare earth oxide layers on a silicon surface was developed and investigated in collaboration with the group of Prof. Dr. Al-Shamery (Univ. Oldenburg). Ultra thin films on a H-Si(111) surface were obtained via the deposition of the precursor, which was dissolved in organic solvents. An oxide layer was detected after the heating of the sample. The film thickness was measured as < 10 nm, whereas the thickness of the film was controlled by the concentration of the precursor solution. Sm(ClO{sub 4}){sub 3}(CH(OCH{sub 3}){sub 3}){sub 3} was isolated and characterized for the first time as the intermediate of the dehydration reaction with trimethyl orthoformate. Eu(ClO{sub 4}){sub 3}(CH(OCH{sub 3}){sub 3}){sub 2}(MeOH){sub 2} was obtained without

The Effect of Precursor Ligands and Oxidation State in the Synthesis of Bimetallic Nano-Alloys

KAUST Repository

LaGrow, Alec P.; Knudsen, Kristian; AlYami, Noktan; Anjum, Dalaver H.; Bakr, Osman

2015-01-01

of variables on the characteristics of bimetallic nanomaterials are not completely understood. In this study, we used a continuous-flow synthetic strategy to explore the effects of the ligands and the oxidation state of a metal precursor in a shape

Constraints on superoxide mediated formation of manganese oxides

Directory of Open Access Journals (Sweden)

Deric R. Learman

2013-09-01

Full Text Available Manganese (Mn oxides are among the most reactive sorbents and oxidants within the environment, where they play a central role in the cycling of nutrients, metals, and carbon. Recent discoveries have identified superoxide (O2- (both of biogenic and abiogenic origin as an effective oxidant of Mn(II leading to the formation of Mn oxides. Here we examined the conditions under which abiotically produced superoxide led to oxidative precipitation of Mn and the solid-phases produced. Oxidized Mn, as both aqueous Mn(III and Mn(III/IV oxides, was only observed in the presence of active catalase, indicating that hydrogen peroxide, a product of the reaction of O2- with Mn(II, inhibits the oxidation process presumably through the reduction of Mn(III. Citrate and pyrophosphate increased the yield of oxidized Mn but decreased the amount of Mn oxide produced via formation of Mn(III-ligand complexes. While complexing ligands played a role in stabilizing Mn(III, they did not eliminate the inhibition of net Mn(III formation by H2O2. The Mn oxides precipitated were highly disordered colloidal hexagonal birnessite, similar to those produced by biotically generated superoxide. Yet, in contrast to the large particulate Mn oxides formed by biogenic superoxide, abiotic Mn oxides did not ripen to larger, more crystalline phases. This suggests that the deposition of crystalline Mn oxides within the environment requires a biological, or at least organic, influence. This work provides the first direct evidence that, under conditions relevant to natural waters, oxidation of Mn(II by superoxide can occur and lead to formation of Mn oxides. For organisms that oxidize Mn(II by producing superoxide, these findings may also point to other microbially mediated processes, in particular enzymatic hydrogen peroxide degradation and/or production of organic ligand metabolites, that allow for Mn oxide formation.

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

Directory of Open Access Journals (Sweden)

Kai Rückriem

2016-06-01

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

N-nitrosodimethylamine (NDMA) formation from the ozonation of model compounds.

Science.gov (United States)

Marti, Erica J; Pisarenko, Aleksey N; Peller, Julie R; Dickenson, Eric R V

2015-04-01

Nitrosamines are a class of toxic disinfection byproducts commonly associated with chloramination, of which several were included on the most recent U.S. EPA Contaminant Candidate List. Nitrosamine formation may be a significant barrier to ozonation in water reuse applications, particularly for direct or indirect potable reuse, since recent studies show direct formation during ozonation of natural water and treated wastewaters. Only a few studies have identified precursors which react with ozone to form N-nitrosodimethylamine (NDMA). In this study, several precursor compound solutions, prepared in ultrapure water and treated wastewater, were subjected to a 10 M excess of ozone. In parallel experiments, the precursor solutions in ultrapure water were exposed to gamma radiation to determine NDMA formation as a byproduct of reactions of precursor compounds with hydroxyl radicals. The results show six new NDMA precursor compounds that have not been previously reported in the literature, including compounds with hydrazone and carbamate moieties. Molar yields in deionized water were 61-78% for 3 precursors, 12-23% for 5 precursors and NDMA formation for the other precursors. NDMA formation due to chloramination was minimal compared to formation due to ozonation, suggesting distinct groups of precursor compounds for these two oxidants. Hydroxyl radical reactions with the precursors will produce NDMA, but formation is much greater in the presence of molecular ozone. Also, hydroxyl radical scavenging during ozonation leads to increased NDMA formation. Molar conversion yields were higher for several precursors in wastewater as compared to deionized water, which could be due to catalyzed reactions with constituents found in wastewater or hydroxyl radical scavenging. Copyright © 2014 Elsevier Ltd. All rights reserved.

A versatile single molecular precursor for the synthesis of layered oxide cathode materials for Li-ion batteries.

Science.gov (United States)

Li, Maofan; Liu, Jiajie; Liu, Tongchao; Zhang, Mingjian; Pan, Feng

2018-02-01

A carbonyl-bridged single molecular precursor LiTM(acac) 3 [transition metal (TM) = cobalt/manganese/nickel (Co/Mn/Ni), acac = acetylacetone], featuring a one-dimensional chain structure, was designed and applied to achieve the layered oxide cathode materials: LiTMO 2 (TM = Ni/Mn/Co, NMC). As examples, layered oxides, primary LiCoO 2 , binary LiNi 0.8 Co 0.2 O 2 and ternary LiNi 0.5 Mn 0.3 Co 0.2 O 2 were successfully prepared to be used as cathode materials. When they are applied to lithium-ion batteries (LIBs), all exhibit good electrochemical performance because of their unique morphology and great uniformity of element distribution. This versatile precursor is predicted to accommodate many other metal cations, such as aluminum (Al 3+ ), iron (Fe 2+ ), and sodium (Na + ), because of the flexibility of organic ligand, which not only facilitates the doping-modification of the NMC system, but also enables synthesis of Na-ion layered oxides. This opens a new direction of research for the synthesis of high-performance layered oxide cathode materials for LIBs.

Effect of precursor solutions stirring on deep level defects concentration and spatial distribution in low temperature aqueous chemical synthesis of zinc oxide nanorods

Energy Technology Data Exchange (ETDEWEB)

Alnoor, Hatim, E-mail: hatim.alnoor@liu.se; Chey, Chan Oeurn; Pozina, Galia; Willander, Magnus; Nur, Omer [Department of Science and Technology (ITN), Campus Norrköping, Linköping University, SE-601 74 Norrköping (Sweden); Liu, Xianjie; Khranovskyy, Volodymyr [Department of Physics, Chemistry and Biology (IFM), Linköping University, SE-583 81 Linköping (Sweden)

2015-08-15

Hexagonal c-axis oriented zinc oxide (ZnO) nanorods (NRs) with 120-300 nm diameters are synthesized via the low temperature aqueous chemical route at 80 °C on silver-coated glass substrates. The influence of varying the precursor solutions stirring durations on the concentration and spatial distributions of deep level defects in ZnO NRs is investigated. Room temperature micro-photoluminesnce (μ-PL) spectra were collected for all samples. Cathodoluminescence (CL) spectra of the as-synthesized NRs reveal a significant change in the intensity ratio of the near band edge emission (NBE) to the deep-level emission (DLE) peaks with increasing stirring durations. This is attributed to the variation in the concentration of the oxygen-deficiency with increasing stirring durations as suggested from the X-ray photoelectron spectroscopy analysis. Spatially resolved CL spectra taken along individual NRs revealed that stirring the precursor solutions for relatively short duration (1-3 h), which likely induced high super saturation under thermodynamic equilibrium during the synthesis process, is observed to favor the formation of point defects moving towards the tip of the NRs. In contrary, stirring for longer duration (5-15 h) will induce low super saturation favoring the formation of point defects located at the bottom of the NRs. These findings demonstrate that it is possible to control the concentration and spatial distribution of deep level defects in ZnO NRs by varying the stirring durations of the precursor solutions.

Effect of precursor solutions stirring on deep level defects concentration and spatial distribution in low temperature aqueous chemical synthesis of zinc oxide nanorods

Directory of Open Access Journals (Sweden)

Hatim Alnoor

2015-08-01

Full Text Available Hexagonal c-axis oriented zinc oxide (ZnO nanorods (NRs with 120-300 nm diameters are synthesized via the low temperature aqueous chemical route at 80 °C on silver-coated glass substrates. The influence of varying the precursor solutions stirring durations on the concentration and spatial distributions of deep level defects in ZnO NRs is investigated. Room temperature micro-photoluminesnce (μ-PL spectra were collected for all samples. Cathodoluminescence (CL spectra of the as-synthesized NRs reveal a significant change in the intensity ratio of the near band edge emission (NBE to the deep-level emission (DLE peaks with increasing stirring durations. This is attributed to the variation in the concentration of the oxygen-deficiency with increasing stirring durations as suggested from the X-ray photoelectron spectroscopy analysis. Spatially resolved CL spectra taken along individual NRs revealed that stirring the precursor solutions for relatively short duration (1-3 h, which likely induced high super saturation under thermodynamic equilibrium during the synthesis process, is observed to favor the formation of point defects moving towards the tip of the NRs. In contrary, stirring for longer duration (5-15 h will induce low super saturation favoring the formation of point defects located at the bottom of the NRs. These findings demonstrate that it is possible to control the concentration and spatial distribution of deep level defects in ZnO NRs by varying the stirring durations of the precursor solutions.

Formation of brominated disinfection byproducts from natural organic matter isolates and model compounds in a sulfate radical-based oxidation process

KAUST Repository

Wang, Yuru; Le Roux, Julien; Zhang, Tao; Croue, Jean-Philippe

2014-01-01

A sulfate radical-based advanced oxidation process (SR-AOP) has received increasing application interest for the removal of water/wastewater contaminants. However, limited knowledge is available on its side effects. This study investigated the side effects in terms of the production of total organic bromine (TOBr) and brominated disinfection byproducts (Br-DBPs) in the presence of bromide ion and organic matter in water. Sulfate radical was generated by heterogeneous catalytic activation of peroxymonosulfate. Isolated natural organic matter (NOM) fractions as well as low molecular weight (LMW) compounds were used as model organic matter. Considerable amounts of TOBr were produced by SR-AOP, where bromoform (TBM) and dibromoacetic acid (DBAA) were identified as dominant Br-DBPs. In general, SR-AOP favored the formation of DBAA, which is quite distinct from bromination with HOBr/OBr- (more TBM production). SR-AOP experimental results indicate that bromine incorporation is distributed among both hydrophobic and hydrophilic NOM fractions. Studies on model precursors reveal that LMW acids are reactive TBM precursors (citric acid > succinic acid > pyruvic acid > maleic acid). High DBAA formation from citric acid, aspartic acid, and asparagine was observed; meanwhile aspartic acid and asparagine were the major precursors of dibromoacetonitrile and dibromoacetamide, respectively.

Formation of brominated disinfection byproducts from natural organic matter isolates and model compounds in a sulfate radical-based oxidation process

KAUST Repository

Wang, Yuru

2014-12-16

A sulfate radical-based advanced oxidation process (SR-AOP) has received increasing application interest for the removal of water/wastewater contaminants. However, limited knowledge is available on its side effects. This study investigated the side effects in terms of the production of total organic bromine (TOBr) and brominated disinfection byproducts (Br-DBPs) in the presence of bromide ion and organic matter in water. Sulfate radical was generated by heterogeneous catalytic activation of peroxymonosulfate. Isolated natural organic matter (NOM) fractions as well as low molecular weight (LMW) compounds were used as model organic matter. Considerable amounts of TOBr were produced by SR-AOP, where bromoform (TBM) and dibromoacetic acid (DBAA) were identified as dominant Br-DBPs. In general, SR-AOP favored the formation of DBAA, which is quite distinct from bromination with HOBr/OBr- (more TBM production). SR-AOP experimental results indicate that bromine incorporation is distributed among both hydrophobic and hydrophilic NOM fractions. Studies on model precursors reveal that LMW acids are reactive TBM precursors (citric acid > succinic acid > pyruvic acid > maleic acid). High DBAA formation from citric acid, aspartic acid, and asparagine was observed; meanwhile aspartic acid and asparagine were the major precursors of dibromoacetonitrile and dibromoacetamide, respectively.

MECHANICAL VIBRATION INHIBITS OSTEOCLAST FORMATION BY REDUCING DC-STAMP RECEPTOR EXPRESSION IN OSTEOCLAST PRECURSOR CELLS

Science.gov (United States)

Kulkarni, R.N.; Voglewede, P.A.; Liu, D.

2014-01-01

It is well known that physical inactivity leads to loss of muscle mass, but it also causes bone loss. Mechanistically, osteoclastogenesis and bone resorption have recently been shown to be regulated by vibration. However, the underlying mechanism behind the inhibition of osteoclast formation is yet unknown. Therefore, we investigated whether mechanical vibration of osteoclast precursor cells affects osteoclast formation by the involvement of fusion-related molecules such as dendritic cell-specific transmembrane protein (DC-STAMP), and P2X7 receptor (P2X7R). RAW264.7 (a murine osteoclastic-like cell line) cells were treated with 20 ng/ml receptor activator of NF-κB ligand (RANKL). For 3 consecutive days, the cells were subjected to 1 hour of mechanical vibration with 20 µm displacement at a frequency of 4 Hz and compared to the control cells that were treated under the same condition but without the vibration. After 5 days of culture, osteoclast formation was determined. Gene expression of DC-STAMP and P2X7R by RAW264.7 cells were determined after 1 hour mechanical vibration, while protein production of the DC-STAMP was determined after 6 hours of post incubation after vibration. As a result, mechanical vibration of RAW264.7 cells inhibited the formation of osteoclasts. Vibration down-regulated DC-STAMP gene expression by 1.6-fold in the presence of RANKL and by 1.4-fold in the absence of RANKL. Additionally, DC-STAMP protein production was also down-regulated by 1.4-fold in the presence of RANKL and by 1.2-fold in the absence of RANKL in RAW264.7 cells in response to mechanical vibration. However, vibration did not affect P2X7R gene expression. Mouse anti-DC-STAMP antibody inhibited osteoclast formation in the absence of vibration. Our results suggest that mechanical vibration of osteoclast precursor cells reduce DC-STAMP expression in osteoclast precursor cells leading to the inhibition of osteoclast formation. PMID:23994170

Mechanical vibration inhibits osteoclast formation by reducing DC-STAMP receptor expression in osteoclast precursor cells.

Science.gov (United States)

Kulkarni, Rishikesh N; Voglewede, Philip A; Liu, Dawei

2013-12-01

It is well known that physical inactivity leads to loss of muscle mass, but it also causes bone loss. Mechanistically, osteoclastogenesis and bone resorption have recently been shown to be regulated by vibration. However, the underlying mechanism behind the inhibition of osteoclast formation is yet unknown. Therefore, we investigated whether mechanical vibration of osteoclast precursor cells affects osteoclast formation by the involvement of fusion-related molecules such as dendritic cell-specific transmembrane protein (DC-STAMP) and P2X7 receptor (P2X7R). RAW264.7 (a murine osteoclastic-like cell line) cells were treated with 20ng/ml receptor activator of NF-κB ligand (RANKL). For 3 consecutive days, the cells were subjected to 1h of mechanical vibration with 20μm displacement at a frequency of 4Hz and compared to the control cells that were treated under the same condition but without the vibration. After 5days of culture, osteoclast formation was determined. Gene expression of DC-STAMP and P2X7R by RAW264.7 cells was determined after 1h of mechanical vibration, while protein production of the DC-STAMP was determined after 6h of postincubation after vibration. As a result, mechanical vibration of RAW264.7 cells inhibited the formation of osteoclasts. Vibration down-regulated DC-STAMP gene expression by 1.6-fold in the presence of RANKL and by 1.4-fold in the absence of RANKL. Additionally, DC-STAMP protein production was also down-regulated by 1.4-fold in the presence of RANKL and by 1.2-fold in the absence of RANKL in RAW264.7 cells in response to mechanical vibration. However, vibration did not affect P2X7R gene expression. Mouse anti-DC-STAMP antibody inhibited osteoclast formation in the absence of vibration. Our results suggest that mechanical vibration of osteoclast precursor cells reduces DC-STAMP expression in osteoclast precursor cells leading to the inhibition of osteoclast formation. © 2013 Elsevier Inc. All rights reserved.

Development of a redox-free Mitsunobu reaction exploiting phosphine oxides as precursors to dioxyphosphoranes.

Science.gov (United States)

Tang, Xiaoping; Chapman, Charlotte; Whiting, Matthew; Denton, Ross

2014-07-14

The development of the first redox-free protocol for the Mitsunobu reaction is described. This has been achieved by exploiting triphenylphosphine oxide--the unwanted by-product in the conventional Mitsunobu reaction--as the precursor to the active P(V) coupling reagent. Multinuclear NMR studies are consistent with hydroxyl activation via an alkoxyphosphonium salt.

High-quality CdTe films from nanoparticle precursors

Energy Technology Data Exchange (ETDEWEB)

Schulz, D.L.; Pehnt, M.; Urgiles, E. [National Renewable Energy Lab., Golden, CO (United States)] [and others

1996-05-01

In this paper the authors demonstrate that nanoparticulate precursors coupled with spray deposition offers an attractive route into electronic materials with improved smoothness, density, and lower processing temperatures. Employing a metathesis approach, cadmium iodide was reacted with sodium telluride in methanol solvent, resulting in the formation of soluble NaI and insoluble CdTe nanoparticles. After appropriate chemical workup, methanol-capped CdTe colloids were isolated. CdTe thin film formation was achieved by spray depositing the nanoparticle colloids (25-75 {Angstrom} diameter) onto substrates at elevated temperatures (T = 280-440{degrees}C) with no further thermal treatment. These films were characterized by x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). Cubic CdTe phase formation was observed by XRD, with a contaminant oxide phase also detected. XPS analysis showed that CdTe films produced by this one-step method contained no Na or C and substantial O. AFM gave CdTe grain sizes of {approx}0.1-0.3 {mu}m for film sprayed at 400{degrees}C. A layer-by-layer film growth mechanism proposed for the one-step spray deposition of nanoparticle precursors will be discussed.

MECHANICAL VIBRATION INHIBITS OSTEOCLAST FORMATION BY REDUCING DC-STAMP RECEPTOR EXPRESSION IN OSTEOCLAST PRECURSOR CELLS

OpenAIRE

Kulkarni, R.N.; Voglewede, P.A.; Liu, D.

2013-01-01

It is well known that physical inactivity leads to loss of muscle mass, but it also causes bone loss. Mechanistically, osteoclastogenesis and bone resorption have recently been shown to be regulated by vibration. However, the underlying mechanism behind the inhibition of osteoclast formation is yet unknown. Therefore, we investigated whether mechanical vibration of osteoclast precursor cells affects osteoclast formation by the involvement of fusion-related molecules such as dendritic cell-spe...

Effect of ultrasonic waves on the water turbidity during the oxidation of phenol. Formation of (hydro)peroxo complexes.

Science.gov (United States)

Villota, Natalia; Lomas, Jose M; Camarero, Luis M

2017-11-01

Analysis of the kinetics of aqueous phenol oxidation by a sono-Fenton process reveals that the via involving ortho-substituted intermediates prevails: catechol (25.0%), hydroquinone (7.7%) and resorcinol (0.6%). During the oxidation, water rapidly acquires color that reaches its maximum intensity at the maximum concentration of p-benzoquinone. Turbidity formation occurs at a slower rate. Oxidant dosage determines the nature of the intermediates, being trihydroxylated benzenes (pyrogallol, hydroxyhydroquinone) and muconic acid the main precursors causing turbidity. It is found that the concentration of iron species and ultrasonic waves affects the intensity of the turbidity. The pathway of (hydro)peroxo-iron(II) complexes formation is proposed. Operating with 20.0-27.8mgFe 2+ /kW rates leads to formation of (hydro)peroxo-iron(II) complexes, which induce high turbidity levels. These species would dissociate into ZZ-muconic acid and ferrous ions. Applying relationships around 13.9mgFe 2+ /kW, the formation of (hydro)peroxo-iron(III) complexes would occur, which could react with carboxylic acids (2,5-dioxo-3-hexenedioic acid). That reaction induces turbidity slower. This is due to the organic substrate reacting with two molecules of the (hydro)peroxo complex. Therefore, it is necessary to accelerate the iron regeneration, intensifying the ultrasonic irradiation. Afterwards, this complex would dissociate into maleic acid and ferric ions. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermal decomposition and spectroscopic investigation of a new aqueous glycolato(-peroxo) Ti(IV) solution-gel precursor

International Nuclear Information System (INIS)

De Dobbelaere, Christopher; Mullens, Jules; Hardy, An; Van Bael, Marlies K.

2011-01-01

Highlights: → A totally water based glycolato-Ti(IV) precursor is presented and characterized. → The precursors' thermal decomposition profile depends on the ligand to metal ratio. → Titanium is coordinated in an unidentate fashion by the glycolate anion. → Smooth and uniform TiO 2 films can be prepared from the precursor solution. - Abstract: A new aqueous solution-gel precursor based on water soluble glycolato(-peroxo)-Ti(IV) complexes is developed for the preparation of TiO 2 films. With regard to the decomposition of complexes towards oxide formation, it is important to gain insight in the chemical transformations inside the precursor during thermal treatment. Therefore, the thermo-oxidative decomposition pathway of a gel obtained by slow evaporation of the precursor solution is described based on hyphenated thermogravimetric analysis with Fourier transform infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS). Pure glycolic acid is used as a reference system for this study. By varying the molar glycolic acid to Ti(IV) ratio, the thermal decomposition of the gel can be drastically shortened and the profile's course changed. Gel structure and chemical changes in the gel upon heating are also studied by means of off-line FTIR. A unidentate coordination of the titanium(IV) ion by the carboxylate group of the glycolato ligands and the involvement of the hydroxyl group is confirmed. Phase formation at certain points in the thermal decomposition is studied by X-ray diffraction and Raman spectroscopy. Finally, it is proven that the new precursor is a valuable candidate for the deposition of low carbon containing solution-gel films which can ultimately be converted into smooth and uniform TiO 2 films.

Photochemically consumed hydrocarbons and their relationship with ozone formation in two megacities of China

Science.gov (United States)

Chang, C.; Wang, J.; Liu, S.; Shao, M.; Zhang, Y.; Zhu, T.; Shiu, C.; Lai, C.

2010-12-01

Two on-site continuous measurements of ozone and its precursors in two megacities of China were carried out in an urban site of Beijing and a suburban site near Guangzhou in the Pearl River Delta (PRD) to estimate precursor consumption and to assess its relationship with oxidant (O3+NO2) formation level. An observation-based method (OBM) with the precursor consumption concept was adopted to assess the relationship between oxidant production and amounts of photochemically consumed non-methane hydrocarbons (NMHCs). In this approach, the ratio of ethylbenzene to m,p-xylenes was used to estimate the degree of photochemical processing, as well as the amounts of photochemically consumed NMHCs by reacting with OH. By trying to correlate the observed oxidant with the observed NMHC concentration, the two areas both revealed nearly no to low correlation between them. However, it existed fair to good correlations (R2=0.68 for Beijing, 0.53 for PRD) between the observed oxidant level and the degree of photochemical processing (ethylbenzene/m,p-xylenes). Furthermore, after taking the approach of consumption to estimate the consumed amounts of NMHCs, an interesting finding reveals that the definite correlation existed between the observed oxidant level and the total consumed NMHCs. The good correlations (R2=0.83 for Beijing, 0.81 for PRD) implies that the ambient oxidant level correlated to the amount of consumed NMHCs. The results of the two megacities in China by using the OBM with the precursor consumption concept can provide another pathway to explore the relationship between photochemically produced oxidant and consumed precursors, and will be helpful to validate model results and to reduce uncertainty of model predictions. However, the method has some room for uncertainty, as injection of fresh precursor emissions and additional boundary ozone involved, etc. could affect the estimation of consumed NMHCs and observed oxidant levels. Assistance of approaches in assessing the

Phase transitions during formation of Ag nanoparticles on In{sub 2}S{sub 3} precursor layers

Energy Technology Data Exchange (ETDEWEB)

Liu, Yang, E-mail: yang.liu@helmholtz-berlin.de; Fu, Yanpeng; Dittrich, Thomas; Sáez-Araoz, Rodrigo; Schmid, Martina; Hinrichs, Volker; Lux-Steiner, Martha Ch.; Fischer, Christian-Herbert

2015-09-01

Phase transitions have been investigated for silver deposition onto In{sub 2}S{sub 3} precursor layers by spray chemical vapor deposition from a trimethylphosphine (hexafluoroacetylacetonato) silver (Ag(hfacac)(PMe{sub 3})) solution. The formation of Ag nanoparticles (Ag NPs) on top of the semiconductor layer set on concomitant with the formation of AgIn{sub 5}S{sub 8}. The increase of the diameter of Ag NPs was accompanied by the evolution of orthorhombic AgInS{sub 2}. The formation of Ag{sub 2}S at the interface between Ag NPs and the semiconductor layer was observed. Surface photovoltage spectroscopy indicated charge separation and electronic transitions in the ranges of corresponding band gaps. The phase transition approach is aimed to be applied for the formation of plasmonic nanostructures on top of extremely thin semiconducting layers. - Highlights: • Silver nanoparticles were deposited onto In{sub 2}S{sub 3} precursor layer by spray pyrolysis. • The silver nanoparticle size and density could be controlled by deposition time. • Phase transitions during deposition and material properties were investigated. • The layers still show semiconducting properties after phase transitions. • Plasmonic absorption enhancement has been demonstrated.

In situ characterization of uranium and americium oxide solid solution formation for CRMP process: first combination of in situ XRD and XANES measurements.

Science.gov (United States)

Caisso, Marie; Picart, Sébastien; Belin, Renaud C; Lebreton, Florent; Martin, Philippe M; Dardenne, Kathy; Rothe, Jörg; Neuville, Daniel R; Delahaye, Thibaud; Ayral, André

2015-04-14

Transmutation of americium in heterogeneous mode through the use of U1-xAmxO2±δ ceramic pellets, also known as Americium Bearing Blankets (AmBB), has become a major research axis. Nevertheless, in order to consider future large-scale deployment, the processes involved in AmBB fabrication have to minimize fine particle dissemination, due to the presence of americium, which considerably increases the risk of contamination. New synthesis routes avoiding the use of pulverulent precursors are thus currently under development, such as the Calcined Resin Microsphere Pelletization (CRMP) process. It is based on the use of weak-acid resin (WAR) microspheres as precursors, loaded with actinide cations. After two specific calcinations under controlled atmospheres, resin microspheres are converted into oxide microspheres composed of a monophasic U1-xAmxO2±δ phase. Understanding the different mechanisms during thermal conversion, that lead to the release of organic matter and the formation of a solid solution, appear essential. By combining in situ techniques such as XRD and XAS, it has become possible to identify the key temperatures for oxide formation, and the corresponding oxidation states taken by uranium and americium during mineralization. This paper thus presents the first results on the mineralization of (U,Am) loaded resin microspheres into a solid solution, through in situ XAS analysis correlated with HT-XRD.

Experimental evidence on formation of imminent and short-term hydrochemical precursors for earthquakes

International Nuclear Information System (INIS)

Du Jianguo; Amita, Kazuhiro; Ohsawa, Shinji; Zhang Youlian; Kang Chunli; Yamada, Makoto

2010-01-01

The formation of imminent hydrochemical precursors of earthquakes is investigated by the simulation for water-rock reaction in a brittle aquifer. Sixty-one soaking experiments were carried out with granodiorite and trachyandesite grains of different sizes and three chemically-distinct waters for 6 to 168 h. The experimental data demonstrate that water-rock reaction can result in both measurable increases and decreases of ion concentrations in short times and that the extents of hydrochemical variations are controlled by the grain size, dissolution and secondary mineral precipitation, as well as the chemistry of the rock and groundwater. The results indicate that water-rock reactions in brittle aquifers and aquitards may be an important genetic mechanism of hydrochemical seismic precursors when the aquifers and aquitards are fractured in response to tectonic stress.

Thin films by metal-organic precursor plasma spray

International Nuclear Information System (INIS)

Schulz, Douglas L.; Sailer, Robert A.; Payne, Scott; Leach, James; Molz, Ronald J.

2009-01-01

While most plasma spray routes to coatings utilize solids as the precursor feedstock, metal-organic precursor plasma spray (MOPPS) is an area that the authors have investigated recently as a novel route to thin film materials. Very thin films are possible via MOPPS and the technology offers the possibility of forming graded structures by metering the liquid feed. The current work employs metal-organic compounds that are liquids at standard temperature-pressure conditions. In addition, these complexes contain chemical functionality that allows straightforward thermolytic transformation to targeted phases of interest. Toward that end, aluminum 3,5-heptanedionate (Al(hd) 3 ), triethylsilane (HSi(C 2 H 5 ) 3 or HSiEt 3 ), and titanium tetrakisdiethylamide (Ti(N(C 2 H 5 ) 2 ) 4 or Ti(NEt 2 ) 4 ) were employed as precursors to aluminum oxide, silicon carbide, and titanium nitride, respectively. In all instances, the liquids contain metal-heteroatom bonds envisioned to provide atomic concentrations of the appropriate reagents at the film growth surface, thus promoting phase formation (e.g., Si-C bond in triethylsilane, Ti-N bond in titanium amide, etc.). Films were deposited using a Sulzer Metco TriplexPro-200 plasma spray system under various experimental conditions using design of experiment principles. Film compositions were analyzed by glazing incidence x-ray diffraction and elemental determination by x-ray spectroscopy. MOPPS films from HSiEt 3 showed the formation of SiC phase but Al(hd) 3 -derived films were amorphous. The Ti(NEt 2 ) 4 precursor gave MOPPS films that appear to consist of nanosized splats of TiOCN with spheres of TiO 2 anatase. While all films in this study suffered from poor adhesion, it is anticipated that the use of heated substrates will aid in the formation of dense, adherent films.

Self-assembly of metal–organic frameworks and graphene oxide as precursors for lithium-ion battery applications

Energy Technology Data Exchange (ETDEWEB)

Yang, Xia [Southwest University, Key Laboratory of Luminescent and Real-Time Analytical Chemistry, Ministry of Education, College of Chemistry and Chemical Engineering (China); Liu, Linlin [City University of Hong Kong, Department of Physics and Materials Science, Center of Super-Diamond and Advanced Films (COSDAF) (Hong Kong); Yuan, Ruo, E-mail: yuanruo@swu.edu.cn [Southwest University, Key Laboratory of Luminescent and Real-Time Analytical Chemistry, Ministry of Education, College of Chemistry and Chemical Engineering (China); Lee, Chun-Sing, E-mail: apcslee@cityu.edu.hk [City University of Hong Kong, Department of Physics and Materials Science, Center of Super-Diamond and Advanced Films (COSDAF) (Hong Kong)

2016-10-15

We fabricated composites of Fe{sub 2}O{sub 3}/reduced graphene oxide as lithium-ion batteries anode material with controlled structures by employing self-assembly of metal–organic frameworks (MOFs) and polymer-functionalized graphene oxide as precursors. By electrostatic interaction, the negatively charged MOFs, Prussian Blue (PB), are assembled on poly(diallyldimethylammonium chloride) (PDDA)-functionalized graphene oxide (positive charge). Then the PB cubes become FeOOH nanosheets when treated with sodium hydroxide. Upon further annealing, the FeOOH nanosheets transform to Fe{sub 2}O{sub 3} nanoparticles while the graphene oxide become reduced graphene oxide simultaneously. It was found that the composites have good performance as anode of lithium-ion battery. This work shows a new way for self-assembling MOFs and 2D materials.

Increased formate overflow is a hallmark of oxidative cancer.

Science.gov (United States)

Meiser, Johannes; Schuster, Anne; Pietzke, Matthias; Vande Voorde, Johan; Athineos, Dimitris; Oizel, Kristell; Burgos-Barragan, Guillermo; Wit, Niek; Dhayade, Sandeep; Morton, Jennifer P; Dornier, Emmanuel; Sumpton, David; Mackay, Gillian M; Blyth, Karen; Patel, Ketan J; Niclou, Simone P; Vazquez, Alexei

2018-04-10

Formate overflow coupled to mitochondrial oxidative metabolism\\ has been observed in cancer cell lines, but whether that takes place in the tumor microenvironment is not known. Here we report the observation of serine catabolism to formate in normal murine tissues, with a relative rate correlating with serine levels and the tissue oxidative state. Yet, serine catabolism to formate is increased in the transformed tissue of in vivo models of intestinal adenomas and mammary carcinomas. The increased serine catabolism to formate is associated with increased serum formate levels. Finally, we show that inhibition of formate production by genetic interference reduces cancer cell invasion and this phenotype can be rescued by exogenous formate. We conclude that increased formate overflow is a hallmark of oxidative cancers and that high formate levels promote invasion via a yet unknown mechanism.

Preparation of molybdenum oxide thin films by MOCVD

International Nuclear Information System (INIS)

Guerrero, R. Martinez; Garcia, J.R. Vargas; Santes, V.; Gomez, E.

2007-01-01

In this study, molybdenum oxide films were prepared in a horizontal hot-wall MOCVD apparatus using molybdenum dioxide acetylacetonate as precursor. The molybdenum precursor was synthesized from acetylacetone and molybdenum oxide powder. Thermal gravimetric (TG) and differential thermal analyses (DTA) of the precursor suggested the formation of molybdenum oxides around 430 o C (703 K). Thus, a range of deposition temperatures varying from 350 to 630 o C (623-903 K) was explored to investigate the effects on the nature of the molybdenum oxide films. X-ray diffraction (XRD) results showed that the films consisted of α-MoO 3 phase at deposition temperatures ranging from 400 to 560 o C (673-833 K). Crystalline α-MoO 3 films can be obtained from molybdenum dioxide acetylacetonate precursor, without need of a post-annealing treatment. The best crystalline quality was found in films having needle-like crystallites grown at deposition temperature of about 560 o C (833 K), which exhibit a strong (0 1 0) preferred orientation and a transparent visual appearance

Preparation of molybdenum oxide thin films by MOCVD

Energy Technology Data Exchange (ETDEWEB)

Guerrero, R. Martinez [Depto. de Ingenieria Metalurgica, ESIQIE-IPN, Mexico 07300, D.F. (Mexico); Garcia, J.R. Vargas [Depto. de Ingenieria Metalurgica, ESIQIE-IPN, Mexico 07300, D.F. (Mexico)]. E-mail: rvargasga@ipn.mx; Santes, V. [CIIEMAD-IPN, Miguel Othon de Mendizabal 485, Mexico 07700, D.F. (Mexico); Gomez, E. [Instituto de Quimica-UNAM, Circuito Exterior-Ciudad Universitaria, Mexico 04510, D.F. (Mexico)

2007-05-31

In this study, molybdenum oxide films were prepared in a horizontal hot-wall MOCVD apparatus using molybdenum dioxide acetylacetonate as precursor. The molybdenum precursor was synthesized from acetylacetone and molybdenum oxide powder. Thermal gravimetric (TG) and differential thermal analyses (DTA) of the precursor suggested the formation of molybdenum oxides around 430 {sup o}C (703 K). Thus, a range of deposition temperatures varying from 350 to 630 {sup o}C (623-903 K) was explored to investigate the effects on the nature of the molybdenum oxide films. X-ray diffraction (XRD) results showed that the films consisted of {alpha}-MoO{sub 3} phase at deposition temperatures ranging from 400 to 560 {sup o}C (673-833 K). Crystalline {alpha}-MoO{sub 3} films can be obtained from molybdenum dioxide acetylacetonate precursor, without need of a post-annealing treatment. The best crystalline quality was found in films having needle-like crystallites grown at deposition temperature of about 560 {sup o}C (833 K), which exhibit a strong (0 1 0) preferred orientation and a transparent visual appearance.

A single-source precursor route to anisotropic halogen-doped zinc oxide particles as a promising candidate for new transparent conducting oxide materials

Directory of Open Access Journals (Sweden)

Daniela Lehr

2015-11-01

Full Text Available Numerous applications in optoelectronics require electrically conducting materials with high optical transparency over the entire visible light range. A solid solution of indium oxide and substantial amounts of tin oxide for electronic doping (ITO is currently the most prominent example for the class of so-called TCOs (transparent conducting oxides. Due to the limited, natural occurrence of indium and its steadily increasing price, it is highly desired to identify materials alternatives containing highly abundant chemical elements. The doping of other metal oxides (e.g., zinc oxide, ZnO is a promising approach, but two problems can be identified. Phase separation might occur at the required high concentration of the doping element, and for successful electronic modification it is mandatory that the introduced heteroelement occupies a defined position in the lattice of the host material. In the case of ZnO, most attention has been attributed so far to n-doping via substitution of Zn2+ by other metals (e.g., Al3+. Here, we present first steps towards n-doped ZnO-based TCO materials via substitution in the anion lattice (O2− versus halogenides. A special approach is presented, using novel single-source precursors containing a potential excerpt of the target lattice 'HalZn·Zn3O3' preorganized on the molecular scale (Hal = I, Br, Cl. We report about the synthesis of the precursors, their transformation into halogene-containing ZnO materials, and finally structural, optical and electronic properties are investigated using a combination of techniques including FT-Raman, low-T photoluminescence, impedance and THz spectroscopies.

Thermal decomposition and spectroscopic investigation of a new aqueous glycolato(-peroxo) Ti(IV) solution-gel precursor

Energy Technology Data Exchange (ETDEWEB)

De Dobbelaere, Christopher, E-mail: christopher.dedobbelaere@uhasselt.be [Hasselt University, Institute for Materials Research, Inorganic and Physical Chemistry, Agoralaan Building D, B-3590 Diepenbeek (Belgium); Mullens, Jules, E-mail: jules.mullens@uhasselt.be [Hasselt University, Institute for Materials Research, Inorganic and Physical Chemistry, Agoralaan Building D, B-3590 Diepenbeek (Belgium); Hardy, An, E-mail: an.hardy@uhasselt.be [Hasselt University, Institute for Materials Research, Inorganic and Physical Chemistry, Agoralaan Building D, B-3590 Diepenbeek (Belgium); IMEC vzw, Division IMOMEC, Agoralaan Building D, B-3590 Diepenbeek (Belgium); Van Bael, Marlies K., E-mail: marlies.vanbael@uhasselt.be [Hasselt University, Institute for Materials Research, Inorganic and Physical Chemistry, Agoralaan Building D, B-3590 Diepenbeek (Belgium); IMEC vzw, Division IMOMEC, Agoralaan Building D, B-3590 Diepenbeek (Belgium)

2011-06-10

Highlights: {yields} A totally water based glycolato-Ti(IV) precursor is presented and characterized. {yields} The precursors' thermal decomposition profile depends on the ligand to metal ratio. {yields} Titanium is coordinated in an unidentate fashion by the glycolate anion. {yields} Smooth and uniform TiO{sub 2} films can be prepared from the precursor solution. - Abstract: A new aqueous solution-gel precursor based on water soluble glycolato(-peroxo)-Ti(IV) complexes is developed for the preparation of TiO{sub 2} films. With regard to the decomposition of complexes towards oxide formation, it is important to gain insight in the chemical transformations inside the precursor during thermal treatment. Therefore, the thermo-oxidative decomposition pathway of a gel obtained by slow evaporation of the precursor solution is described based on hyphenated thermogravimetric analysis with Fourier transform infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS). Pure glycolic acid is used as a reference system for this study. By varying the molar glycolic acid to Ti(IV) ratio, the thermal decomposition of the gel can be drastically shortened and the profile's course changed. Gel structure and chemical changes in the gel upon heating are also studied by means of off-line FTIR. A unidentate coordination of the titanium(IV) ion by the carboxylate group of the glycolato ligands and the involvement of the hydroxyl group is confirmed. Phase formation at certain points in the thermal decomposition is studied by X-ray diffraction and Raman spectroscopy. Finally, it is proven that the new precursor is a valuable candidate for the deposition of low carbon containing solution-gel films which can ultimately be converted into smooth and uniform TiO{sub 2} films.

Formation of iron (hydr)oxides during the abiotic oxidation of Fe(II) in the presence of arsenate.

Science.gov (United States)

Song, Jia; Jia, Shao-Yi; Yu, Bo; Wu, Song-Hai; Han, Xu

2015-08-30

Abiotic oxidation of Fe(II) is a common pathway in the formation of Fe (hydr)oxides under natural conditions, however, little is known regarding the presence of arsenate on this process. In hence, the effect of arsenate on the precipitation of Fe (hydr)oxides during the oxidation of Fe(II) is investigated. Formation of arsenic-containing Fe (hydr)oxides is constrained by pH and molar ratios of As:Fe during the oxidation Fe(II). At pH 6.0, arsenate inhibits the formation of lepidocrocite and goethite, while favors the formation of ferric arsenate with the increasing As:Fe ratio. At pH 7.0, arsenate promotes the formation of hollow-structured Fe (hydr)oxides containing arsenate, as the As:Fe ratio reaches 0.07. Arsenate effectively inhibits the formation of magnetite at pH 8.0 even at As:Fe ratio of 0.01, while favors the formation of lepidocrocite and green rust, which can be latterly degenerated and replaced by ferric arsenate with the increasing As:Fe ratio. This study indicates that arsenate and low pH value favor the slow growth of dense-structured Fe (hydr)oxides like spherical ferric arsenate. With the rapid oxidation rate of Fe(II) at high pH, ferric (hydr)oxides prefer to precipitate in the formation of loose-structured Fe (hydr)oxides like lepidocrocite and green rust. Copyright © 2015 Elsevier B.V. All rights reserved.

Precursors for formation of copper selenide, indium selenide, copper indium diselenide, and/or copper indium gallium diselenide films

Science.gov (United States)

Curtis, Calvin J; Miedaner, Alexander; Van Hest, Maikel; Ginley, David S

2014-11-04

Liquid-based precursors for formation of Copper Selenide, Indium Selenide, Copper Indium Diselenide, and/or copper Indium Galium Diselenide include copper-organoselenides, particulate copper selenide suspensions, copper selenide ethylene diamine in liquid solvent, nanoparticulate indium selenide suspensions, and indium selenide ethylene diamine coordination compounds in solvent. These liquid-based precursors can be deposited in liquid form onto substrates and treated by rapid thermal processing to form crystalline copper selenide and indium selenide films.

Chemical fingerprint of iron oxides related to iron enrichment of banded iron formation from the Cauê Formation - Esperança Deposit, Quadrilátero Ferrífero, Brazil: a laser ablation ICP-MS study

Directory of Open Access Journals (Sweden)

Lucilia Aparecida Ramos de Oliveira

Full Text Available Chemical signatures of iron oxides from dolomitic itabirite and high-grade iron ore from the Esperança deposit, located in the Quadrilátero Ferrífero, indicate that polycyclic processes involving changing of chemical and redox conditions are responsible for the iron enrichment on Cauê Formation from Minas Supergroup. Variations of Mn, Mg and Sr content in different generations of iron oxides from dolomitic itabirite, high-grade iron ore and syn-mineralization quartz-carbonate-hematite veins denote the close relationship between high-grade iron ore formation and carbonate alteration. This indicates that dolomitic itabirite is the main precursor of the iron ore in that deposit. Long-lasting percolation of hydrothermal fluids and shifts in the redox conditions have contributed to changes in the Y/Ho ratio, light/heavy rare earth elements ratio and Ce anomaly with successive iron oxide generations (martite-granular hematite, as well as lower abundance of trace elements including rare earth elements in the younger specularite generations.

Method for continuous synthesis of metal oxide powders

Science.gov (United States)

Berry, David A.; Haynes, Daniel J.; Shekhawat, Dushyant; Smith, Mark W.

2015-09-08

A method for the rapid and continuous production of crystalline mixed-metal oxides from a precursor solution comprised of a polymerizing agent, chelated metal ions, and a solvent. The method discharges solution droplets of less than 500 .mu.m diameter using an atomizing or spray-type process into a reactor having multiple temperature zones. Rapid evaporation occurs in a first zone, followed by mixed-metal organic foam formation in a second zone, followed by amorphous and partially crystalline oxide precursor formation in a third zone, followed by formation of the substantially crystalline mixed-metal oxide in a fourth zone. The method operates in a continuous rather than batch manner and the use of small droplets as the starting material for the temperature-based process allows relatively high temperature processing. In a particular embodiment, the first zone operates at 100-300.degree. C., the second zone operates at 300-700.degree. C., and the third operates at 700-1000.degree. C., and fourth zone operates at at least 700.degree. C. The resulting crystalline mixed-metal oxides display a high degree of crystallinity and sphericity with typical diameters on the order of 50 .mu.m or less.

Characterizing oxidative flow reactor SOA production and OH radical exposure from laboratory experiments of complex mixtures (engine exhaust) and simple precursors (monoterpenes)

Science.gov (United States)

Michael Link, M. L.; Friedman, B.; Ortega, J. V.; Son, J.; Kim, J.; Park, G.; Park, T.; Kim, K.; Lee, T.; Farmer, D.

2016-12-01

Recent commercialization of the Oxidative Flow Reactor (OFR, occasionally described in the literature as a "Potential Aerosol Mass") has created the opportunity for many researchers to explore the mechanisms behind OH-driven aerosol formation on a wide range of oxidative timescales (hours to weeks) in both laboratory and field measurements. These experiments have been conducted in both laboratory and field settings, including simple (i.e. single component) and complex (multi-component) precursors. Standard practices for performing OFR experiments, and interpreting data from the measurements, are still being developed. Measurement of gas and particle phase chemistry, from oxidation products generated in the OFR, through laboratory studies on single precursors and the measurement of SOA from vehicle emissions on short atmospheric timescales represent two very different experiments in which careful experimental design is essential for exploring reaction mechanisms and SOA yields. Two parameters essential in experimental design are (1) the role of seed aerosol in controlling gas-particle partitioning and SOA yields, and (2) the accurate determination of OH exposure during any one experiment. We investigated the role of seed aerosol surface area in controlling the observed SOA yields and gas/particle composition from the OH-initiated oxidation of four monoterpenes using an aerosol chemical ionization time-of-flight mass spectrometer and scanning mobility particle sizer. While the OH exposure during laboratory experiments is simple to constrain, complex mixtures such as diesel exhaust have high estimated OH reactivity values, and thus require careful consideration. We developed methods for constraining OH radical exposure in the OFR during vehicle exhaust oxidation experiments. We observe changes in O/C ratios and highly functionalized species over the temperature gradient employed in the aerosol-CIMS measurement. We relate this observed, speciated chemistry to the

Formate Formation and Formate Conversion in Biological Fuels Production

Directory of Open Access Journals (Sweden)

Bryan R. Crable

2011-01-01

Full Text Available Biomethanation is a mature technology for fuel production. Fourth generation biofuels research will focus on sequestering CO2 and providing carbon-neutral or carbon-negative strategies to cope with dwindling fossil fuel supplies and environmental impact. Formate is an important intermediate in the methanogenic breakdown of complex organic material and serves as an important precursor for biological fuels production in the form of methane, hydrogen, and potentially methanol. Formate is produced by either CoA-dependent cleavage of pyruvate or enzymatic reduction of CO2 in an NADH- or ferredoxin-dependent manner. Formate is consumed through oxidation to CO2 and H2 or can be further reduced via the Wood-Ljungdahl pathway for carbon fixation or industrially for the production of methanol. Here, we review the enzymes involved in the interconversion of formate and discuss potential applications for biofuels production.

Hydrothermal oxidation in the Biwabik Iron Formation, MN, USA

Science.gov (United States)

Losh, Steven; Rague, Ryan

2018-02-01

Precambrian iron formations throughout the world, notably in Australia, Brazil, and South Africa, show evidence of hypogene (≥ 110 °C, mostly > 250 °C) oxidation, alteration, and silica dissolution as a result of tectonic or magmatic activity. Although hydrothermal oxidation has been proposed for the prototype Lake Superior-type iron formation, the Biwabik Iron Formation in Minnesota (USA), it has not been documented there. By examining oxidized and unoxidized Biwabik Iron Formation in three mines, including material from high-angle faults that are associated with oxidation, we document an early hypogene oxidation event ( 175 °C) involving medium-salinity aqueous fluids (8.4 ± 4.9 wt% NaCl equiv) that infiltrated iron formation along high-angle faults. At the Hibbing Taconite Mine, hydrothermal fluids oxidized iron carbonates and silicates near faults, producing goethite ± quartz. In contrast with much of the oxidized iron ores on the Mesabi Range, silica was not removed but rather recrystallized during this event, perhaps lying in a rock-dominated system at low cumulative fluid flux. During the hydrothermal oxidation event in the Hibbing Taconite deposit, quartz-filled microfractures and irregular inclusions commonly formed in coarse variably oxidized magnetite, currently the ore mineral: these inclusions degrade the ore by introducing excess silica in magnetic concentrate. Hydrothermal oxidation at Hibbing Taconite Mine is overprinted by later, relatively minor supergene oxidation both along faults and near the surface, which locally dissolved quartz. At the Fayal Reserve Mine, widespread silicate and carbonate gangue dissolution and iron oxidation was followed by precipitation of pyrite, Mn-siderite, apatite, and other minerals in void spaces, which prevented post-oxidation compaction and significant volume loss in the sampled rocks. Although definitive temperature data for this assemblage are needed, the weight of evidence indicates that this

Tungsten oxide coatings deposited by plasma spray using powder and solution precursor for detection of nitrogen dioxide gas

Energy Technology Data Exchange (ETDEWEB)

Zhang, Chao, E-mail: zhangc@yzu.edu.cn [College of Mechanical Engineering, Yangzhou University, Yangzhou 225127 (China); Wang, Jie [College of Mechanical Engineering, Yangzhou University, Yangzhou 225127 (China); Geng, Xin [College of Mechanical Engineering, Yangzhou University, Yangzhou 225127 (China); College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002 (China)

2016-05-25

Increasing attention has been paid on preparation methods for resistive-type gas sensors based on semiconductor metal oxides. In this work, tungsten oxide (WO{sub 3}) coatings were prepared on alumina substrates and used as gas sensitive layers. The coatings were deposited by atmospheric plasma spray using powder, solution precursor, or a combination of both. Tungsten oxide powder through a powder port and ammonium tungstate aqueous solution through a liquid port were injected into plasma stream respectively or together to deposit WO{sub 3} coatings. Phase structures in the coatings were characterized by X-ray diffraction analyzer. The field-emission scanning electron microscopy images confirmed that the coatings were in microstructure, nanostructure or micro-nanostructure. The sensing properties of the sensors based on the coatings exposed to 1 ppm nitrogen dioxide gas were characterized in a home-made instrument. Sensing properties of the coatings were compared and discussed. The influences of gas humidity and working temperature on the sensor responses were further studied. - Highlights: • Porous gas sensitive coatings were deposited by plasma spray using powder and solution precursor. • Crystallized WO{sub 3} were obtained through hybrid plasma spray plus a pre-conditioned step. • Plasma power had an important influence on coating microstructure. • The particle size of atmospheric plasma-sprayed microstructured coating was stable. • Solution precursor plasma-sprayed WO{sub 3} coatings had nanostructure and showed good responses to 1 ppm NO{sub 2}.

Effect of Au Precursor and Support on the Catalytic Activity of the Nano-Au-Catalysts for Propane Complete Oxidation

Directory of Open Access Journals (Sweden)

Arshid M. Ali

2015-01-01

Full Text Available Catalytic activity of nano-Au-catalyst(s for the complete propane oxidation was investigated. The results showed that the nature of both Au precursor and support strongly influences catalytic activity of the Au-catalyst(s for the propane oxidation. Oxidation state, size, and dispersion of Au nanoparticles in the Au-catalysts, surface area, crystallinity, phase structure, and redox property of the support are the key aspects for the complete propane oxidation. Among the studied Au-catalysts, the AuHAuCl4-Ce catalyst is found to be the most active catalyst.

Dopamine Oxidation and Autophagy

Directory of Open Access Journals (Sweden)

Patricia Muñoz

2012-01-01

Full Text Available The molecular mechanisms involved in the neurodegenerative process of Parkinson's disease remain unclear. Currently, there is a general agreement that mitochondrial dysfunction, α-synuclein aggregation, oxidative stress, neuroinflammation, and impaired protein degradation are involved in the neurodegeneration of dopaminergic neurons containing neuromelanin in Parkinson's disease. Aminochrome has been proposed to play an essential role in the degeneration of dopaminergic neurons containing neuromelanin by inducing mitochondrial dysfunction, oxidative stress, the formation of neurotoxic α-synuclein protofibrils, and impaired protein degradation. Here, we discuss the relationship between the oxidation of dopamine to aminochrome, the precursor of neuromelanin, autophagy dysfunction in dopaminergic neurons containing neuromelanin, and the role of dopamine oxidation to aminochrome in autophagy dysfunction in dopaminergic neurons. Aminochrome induces the following: (i the formation of α-synuclein protofibrils that inactivate chaperone-mediated autophagy; (ii the formation of adducts with α- and β-tubulin, which induce the aggregation of the microtubules required for the fusion of autophagy vacuoles and lysosomes.

Formation of cerussite and hydrocerussite during adsorption of lead from aqueous solution on oxidized carbons by cold oxygen plasma

Energy Technology Data Exchange (ETDEWEB)

De Velasco Maldonado, Paola S. [Instituto Tecnologico de Aguascalientes, Av. Adolfo López Mateos No. 1801 Ote. C.P, Aguascalientes, Ags, 20256 (Mexico); Hernández-Montoya, Virginia, E-mail: virginia.hernandez@yahoo.com.mx [Instituto Tecnologico de Aguascalientes, Av. Adolfo López Mateos No. 1801 Ote. C.P, Aguascalientes, Ags, 20256 (Mexico); Concheso, A.; Montes-Morán, Miguel A. [Instituto Nacional del Carbon, INCAR-CSIC, Apartado 73, E-33080, Oviedo (Spain)

2016-11-15

Highlights: • The formation of cerussite and hydrocerussite was observed on the carbon surface. • Occurrence of CaCO{sub 3} on the carbons surface plays a crucial role in the formation. • The carbons were prepared by carbonization and oxidation with cold oxygen plasma. • Oxidation with cold oxygen plasma increases the formation of these compounds. - Abstract: A new procedure of elimination of Pb{sup 2+} from aqueous solution using carbon adsorbents, in which high amounts of cerussite and hydrocerussite are deposited on the carbon surfaces, is reported. The procedure includes the preparation of carbons from selected lignocellulosic wastes (pecan nut shells and peach stones) by single carbonization and further oxidation with cold oxygen plasma. The materials prior and after the oxidation treatment were characterized using elemental analysis, FT-IR spectroscopy, SEM/EDX analysis, adsorption of N{sub 2} at −196 °C and X-ray photoelectron spectroscopy. The adsorption of Pb{sup 2+} was carried out in batch systems under constant agitation. The formation of cerussite and hydrocerussite on the spent carbon surfaces was confirmed by XRD, SEM/EDX and FT-IR. A Pb{sup 2+} removal mechanism is proposed in which a co-precipitation of lead nitrate and calcium carbonate would render the formation of the lead carbonates. In such mechanism, the occurrence of CaCO{sub 3} on the surface of the adsorbents plays a crucial role. The presence of calcium carbonate on the precursors is understood on the basis of the thermal evolution of calcium oxalate originally present in the biomass. The oxygen plasma treatment helps to expose the calcium carbonate nanocrystals thus improving dramatically the removal capacity of Pb{sup 2+}. Accordingly, retention capacities as high as 63 mg of Pb{sup 2+} per gram of adsorbent have been attained.

Formation of cerussite and hydrocerussite during adsorption of lead from aqueous solution on oxidized carbons by cold oxygen plasma

International Nuclear Information System (INIS)

De Velasco Maldonado, Paola S.; Hernández-Montoya, Virginia; Concheso, A.; Montes-Morán, Miguel A.

2016-01-01

Highlights: • The formation of cerussite and hydrocerussite was observed on the carbon surface. • Occurrence of CaCO_3 on the carbons surface plays a crucial role in the formation. • The carbons were prepared by carbonization and oxidation with cold oxygen plasma. • Oxidation with cold oxygen plasma increases the formation of these compounds. - Abstract: A new procedure of elimination of Pb"2"+ from aqueous solution using carbon adsorbents, in which high amounts of cerussite and hydrocerussite are deposited on the carbon surfaces, is reported. The procedure includes the preparation of carbons from selected lignocellulosic wastes (pecan nut shells and peach stones) by single carbonization and further oxidation with cold oxygen plasma. The materials prior and after the oxidation treatment were characterized using elemental analysis, FT-IR spectroscopy, SEM/EDX analysis, adsorption of N_2 at −196 °C and X-ray photoelectron spectroscopy. The adsorption of Pb"2"+ was carried out in batch systems under constant agitation. The formation of cerussite and hydrocerussite on the spent carbon surfaces was confirmed by XRD, SEM/EDX and FT-IR. A Pb"2"+ removal mechanism is proposed in which a co-precipitation of lead nitrate and calcium carbonate would render the formation of the lead carbonates. In such mechanism, the occurrence of CaCO_3 on the surface of the adsorbents plays a crucial role. The presence of calcium carbonate on the precursors is understood on the basis of the thermal evolution of calcium oxalate originally present in the biomass. The oxygen plasma treatment helps to expose the calcium carbonate nanocrystals thus improving dramatically the removal capacity of Pb"2"+. Accordingly, retention capacities as high as 63 mg of Pb"2"+ per gram of adsorbent have been attained.

Design and synthesis of single-source molecular precursors to homogeneous multi-component oxide materials

Science.gov (United States)

Fujdala, Kyle Lee

This dissertation describes the syntheses of single-source molecular precursors to multi-component oxide materials. These molecules possess a core metal or element with various combinations of -OSi(O tBu)3, -O2P(OtBu) 2, and -OB[OSi(OtBu)3] 2 ligands. Such molecules decompose under mild thermolytic conditions (models for oxide-supported metal species and multi-component oxides. Significantly, the first complexes to contain three or more heteroelements suitable for use in the TMP method have been synthesized. Compounds for use as single-source molecular precursors have been synthesized containing Al, B, Cr, Hf, Mo, V, W, and Zr, and their thermal transformations have been examined. Heterogeneous catalytic reactions have been examined for selected materials. Also, cothermolyses of molecular precursors and additional molecules (i.e., metal alkoxides) have been utilized to provide materials with several components for potential use as catalysts or catalyst supports. Reactions of one and two equivs of HOSi(OtBu) 3 with Cr(OtBu)4 afforded the first Cr(IV) alkoxysiloxy complexes (tBuO) 3CrOSi(OtBu)3 and ( tBuO)2Cr[OSi(OtBu) 3]2, respectively. The high-yielding, convenient synthesis of (tBuO)3CrOSi(O tBu)3 make this complex a useful single-source molecular precursor, via the TMP method, to Cr/Si/O materials. The thermal transformations of (tBuO)3CrOSi(O tBu)3 and (tBuO) 2Cr[OSi(OtBu)3]2 to chromia-silica materials occurr at low temperatures (≤180°C), to give isobutene as the major carbon-containing product. The material generated from the solid-state conversion of (tBuO) 3CrOSi(OtBu)3 (CrOS ss) has an unexpectedly high surface area of 315 m2 g-1 that is slightly reduced to 275 m2 g-1 after calcination at 500°C in O2. The xerogel obtained by the thermolysis of an n-octane solution of (tBuO)3CrOSi(O tBu)3 (CrOSixg) has a surface area of 315 m2 g-1 that is reduced to 205 m2 g-1 upon calcination at 500°C. Powder X-ray diffraction (PXRD) analysis revealed that Cr2O 3 is

The formation of non-oxidic oxygen phases on Ru(0001). From the first stages of the oxygen take-up to oxidation

International Nuclear Information System (INIS)

Blume, R.

2005-01-01

K. With further increasing oxygen contents underneath the topmost ruthenium layer the bond of the chemisorbed oxygen is reduced leading to an additional desorption feature at a lower temperature of 950 K. The ''subsurface''phases formed that way can be considered as a precursor to the oxide formation. In an intermediate preparation range in between 550 and 600 K for very high oxygen exposures the formation of oxidic phases are observed whose spacial dimensions cannot be resolved with SPEM. The onset of oxide formation is characterized by the growth of RuO2(110) oxide domains in dependence of oxygen exposure and sample temperature. The areas in between the oxide domains do not spectroscopically resemble either the chemisorbed layer or the oxide. In fact they show the features of a strongly distorted and oxygen enriched surface. (orig.)

Gas atomized precursor alloy powder for oxide dispersion strengthened ferritic stainless steel

Energy Technology Data Exchange (ETDEWEB)

Rieken, Joel [Iowa State Univ., Ames, IA (United States)

2011-12-13

Gas atomization reaction synthesis (GARS) was employed as a simplified method for producing precursor powders for oxide dispersion strengthened (ODS) ferritic stainless steels (e.g., Fe-Cr-Y-(Ti,Hf)-O), departing from the conventional mechanical alloying (MA) process. During GARS processing a reactive atomization gas (i.e., Ar-O₂) was used to oxidize the powder surfaces during primary break-up and rapid solidification of the molten alloy. This resulted in envelopment of the powders by an ultra-thin (t < 150 nm) metastable Cr-enriched oxide layer that was used as a vehicle for solid-state transport of O into the consolidated microstructure. In an attempt to better understand the kinetics of this GARS reaction, theoretical cooling curves for the atomized droplets were calculated and used to establish an oxidation model for this process. Subsequent elevated temperature heat treatments, which were derived from Rhines pack measurements using an internal oxidation model, were used to promote thermodynamically driven O exchange reactions between trapped films of the initial Cr-enriched surface oxide and internal Y-enriched intermetallic precipitates. This novel microstructural evolution process resulted in the successful formation of nano-metric Y-enriched dispersoids, as confirmed using high energy X-ray diffraction and transmission electron microscopy (TEM), equivalent to conventional ODS alloys from MA powders. The thermal stability of these Y-enriched dispersoids was evaluated using high temperature (1200°C) annealing treatments ranging from 2.5 to 1,000 hrs of exposure. In a further departure from current ODS practice, replacing Ti with additions of Hf appeared to improve the Y-enriched dispersoid thermal stability by means of crystal structure modification. Additionally, the spatial distribution of the dispersoids was found to depend strongly on the original rapidly solidified microstructure. To exploit this, ODS microstructures were engineered from

Precursor Mediated Synthesis of Nanostructured Silicas: From Precursor-Surfactant Ion Pairs to Structured Materials.

Science.gov (United States)

Hesemann, Peter; Nguyen, Thy Phung; Hankari, Samir El

2014-04-11

The synthesis of nanostructured anionic-surfactant-templated mesoporous silica (AMS) recently appeared as a new strategy for the formation of nanostructured silica based materials. This method is based on the use of anionic surfactants together with a co-structure-directing agent (CSDA), mostly a silylated ammonium precursor. The presence of this CSDA is necessary in order to create ionic interactions between template and silica forming phases and to ensure sufficient affinity between the two phases. This synthetic strategy was for the first time applied in view of the synthesis of surface functionalized silica bearing ammonium groups and was then extended on the formation of materials functionalized with anionic carboxylate and bifunctional amine-carboxylate groups. In the field of silica hybrid materials, the "anionic templating" strategy has recently been applied for the synthesis of silica hybrid materials from cationic precursors. Starting from di- or oligosilylated imidazolium and ammonium precursors, only template directed hydrolysis-polycondensation reactions involving complementary anionic surfactants allowed accessing structured ionosilica hybrid materials. The mechanistic particularity of this approach resides in the formation of precursor-surfactant ion pairs in the hydrolysis-polycondensation mixture. This review gives a systematic overview over the various types of materials accessed from this cooperative ionic templating approach and highlights the high potential of this original strategy for the formation of nanostructured silica based materials which appears as a complementary strategy to conventional soft templating approaches.

Synthesis of organometallic hydroxides of titanium, vanadium, cobalt and chromium as precursors of thin films type MaOb

International Nuclear Information System (INIS)

Montero Villalobos, Mavis

2001-01-01

This study shows the results obtained from a general objective that was the synthesis and characterization of precursors of thin films of metallic oxides, two different routes of synthesis have been practiced: route molecular precursors and route Sol-Gel technic. In the first route one of the objectives of the investigation is to obtain a molecular precursor of material type M a O b a route of synthesis have been tried proved that involves anhydrous chlorides of the transition metals and linked R that are alcoxides of metal such as silicon, titanium and zirconium. In the second route the general objective to create thin films of metallic oxide has been maintained but the way to resolve the problem has changed, not giving so much emphasis to the molecular precursors as it was originally presented (this due mainly to its instability and difficulty of synthesis), but being supported in the sun-gel chemistry. It was started a new synthesis line through the sun-gel chemistry that is more versatile and simplifies the process in the film formation [es

Microencapsulation of silicon nitride particles with yttria and yttria-alumina precursors

International Nuclear Information System (INIS)

Garg, A.K.; De Jonghe, L.C.

1990-01-01

Procedures are described to deposit uniform layers of yttria and yttria-alumina precursors on fine powders and whiskers of silicon nitride. The coatings were produced by aging at elevated temperatures aqueous systems containing the silicon nitride core particles, yttrium and aluminum nitrates, and urea. Optimum concentrations of the core particles, in relation to the reactants, were established to promote surface deposition of the oxide precursors. Polymeric dispersants were used effectively to prevent agglomeration of the solids during the microencapsulation process. The morphology of the powders was characterized using scanning and transmission electron microscopy. The mechanisms for the formation of the coated layers are discussed. A description is provided that allows qualitative assessment of the experimental factors that determine microencapsulation by a slurry method

Oxidation of monolayers of partly converted dimethoxy-substituted poly(p-phenylenevinylene) precursor polymers at the air-water interface

NARCIS (Netherlands)

Hagting, J.G.; Schouten, A.J.; Hagting, A

2000-01-01

We observed that the poly(p-phenylenevinylene) units in Langmuir monolayers of partly converted dimethoxy-substituted poly(p-phenylenevinylene) precursor polymers oxidize at the air-water interface. This reaction even happened in the dark and therefore can not be attributed to a photooxygenation

Gas-phase Precursors to Anthropogenic SOA: Using the MCM to Probe Detailed Observations of Aromatic Photo-oxidation

Science.gov (United States)

Rickard, A. R.; Wyche, K. P.; Metzger, A.; Monks, P. S.; Ellis, A. M.; Baltensperger, U.; Pilling, M. J.; Jenkin, M. E.

2008-12-01

The formation of photochemical ozone and particulate matter are major priorities in the determination of European air quality policies. Predictions of the future state of the atmosphere and the development of appropriate mitigation strategies rely on models, which necessarily incorporate chemistry. The Master Chemical Mechanism (MCM, http://mcm.leeds.ac.uk/MCM) is a near-explicit chemical mechanism originally conceived to model ozone formation in Europe but now also employed as a benchmark mechanism in a wide variety of applications where chemical detail is required. The MCM currently describes the detailed gas- phase tropospheric degradation of a 135 primary emitted volatile organic compounds (VOCs) leading to a mechanism containing ca. 5900 species and 13500 reactions. In order that the MCM continues to be a state-of-the-art resource for the atmospheric science community it resides under a constant regime of evaluation, development and improvement. Individual VOC photochemical mechanisms are evaluated using data obtained, under a variety of atmospheric conditions, from highly instrumented smog chambers. Smog chamber experiments are crucial, not only for mechanism evaluation, but also for mechanism development. Findings obtained from combined model and chamber studies can additionally provide key insight for guiding the directions of future laboratory experiments. Recently, the MCM was updated to MCMv3.1 in order to take into account recent advancements in the understanding of aromatic photo-oxidation, an important class of anthropogenic VOCs. As well as constituting precursors to secondary organic aerosol (SOA), aromatics generally have high photochemical ozone creation potentials (POCPs) and hence contribute significantly towards tropospheric ozone formation. In the work presented, a detailed gas-phase photochemical chamber box model, incorporating the MCMv3.1 degradation mechanism for 1,3,5-trimethylbenzene (TMB), has been used to simulate data measured during

Sol-gel precursors and products thereof

Science.gov (United States)

Warren, Scott C.; DiSalvo, Jr., Francis J.; Weisner, Ulrich B.

2017-02-14

The present invention provides a generalizable single-source sol-gel precursor capable of introducing a wide range of functionalities to metal oxides such as silica. The sol-gel precursor facilitates a one-molecule, one-step approach to the synthesis of metal-silica hybrids with combinations of biological, catalytic, magnetic, and optical functionalities. The single-source precursor also provides a flexible route for simultaneously incorporating functional species of many different types. The ligands employed for functionalizing the metal oxides are derived from a library of amino acids, hydroxy acids, or peptides and a silicon alkoxide, allowing many biological functionalities to be built into silica hybrids. The ligands can coordinate with a wide range of metals via a carboxylic acid, thereby allowing direct incorporation of inorganic functionalities from across the periodic table. Using the single-source precursor a wide range of functionalized nanostructures such as monolith structures, mesostructures, multiple metal gradient mesostructures and Stober-type nanoparticles can be synthesized. ##STR00001##

Effects of precursor and sulfation on OMS-2 catalyst for oxidation of ethanol and acetaldehyde at low temperatures.

Science.gov (United States)

Wang, Renhu; Li, Junhua

2010-06-01

Volatile organic compounds (VOCs) emitted from many industrial processes and transportation activities are major organic pollutants in the atmosphere and toxic to human health. Octahedral molecular sieve (OMS-2) catalysts with different precursors and sulfate-acidified OMS-2 catalysts were synthesized using refluxing methods. The catalysts were investigated on complete oxidation of ethanol and acetaldehyde, and both demonstrated good reactivity. However, acidification resulted in a decrease in activity. OMS-2 catalyst using MnSO(4) as precursor exhibited the best catalytic performance and, thus, was selected for catalyst deactivation by sulfur dioxide. The results of this study suggested that the Mn-O bond of OMS-2 catalysts was the main determinant of the catalytic activity toward oxygenated VOC oxidation and weaker acid sites benefited higher acetaldehyde selectivity. Catalyst deactivation resulted from a strong but slow chemical interaction between the Mn-O bond and sulfur dioxide, probably forming manganese sulfate.

Degradation of typical N-nitrosodimethylamine (NDMA) precursors and its formation potential in anoxic-aerobic (AO) activated sludge system.

Science.gov (United States)

Wang, Lin; Li, Yongmei; He, Guodong

2014-01-01

N-nitrosodimethylamine (NDMA) is an emerging disinfection byproduct. Removal of its potential precursors is considered as an effective method to control NDMA. In this study, four typical NDMA precursors (dimethylamine (DMA), trimethylamine (TMA), dimethylformamide (DMFA) and dimethylaminobenzene (DMAB)) were selected, and their removal capacities by activated sludge were investigated. Batch experiments indicated that removal of NDMA precursors was better under aerobic condition than anoxic condition; and their specific degradation rates follow the order of DMA > TMA > DMFA > DMAB. In anoxic-aerobic (AO) activated sludge system, the optimal hydraulic retention time and sludge retention time were 10 h and 20 d, respectively, for the removal of both NDMA precursors (four selected NDMA precursors and NDMA formation potential (NDMA FP)) and nutrients. Our results also suggested that there was a positive correlation between NDMA FP and dissolved organic nitrogen (DON) in wastewater. The removal efficiency of NDMA FP was in the range of 46.8-72.5% in the four surveyed wastewater treatment plants except the one which adopted chemically enhanced primary process. The results revealed that the AO system had the advantage of removing NDMA FP. Our results are helpful for the knowledge of the removals of NDMA precursors during activated sludge treatment processes.

Metallorganic routes to nanoscale iron and titanium oxide particles encapsulated in mesoporous alumina: formation, physical properties, and chemical reactivity.

Science.gov (United States)

Schneider, J J; Czap, N; Hagen, J; Engstler, J; Ensling, J; Gütlich, P; Reinoehl, U; Bertagnolli, H; Luis, F; de Jongh, L J; Wark, M; Grubert, G; Hornyak, G L; Zanoni, R

2000-12-01

Iron and titanium oxide nanoparticles have been synthesized in parallel mesopores of alumina by a novel organometallic "chimie douce" approach that uses bis(toluene)iron(0) (1) and bis(toluene)titanium(0) (2) as precursors. These complexes are molecular sources of iron and titanium in a zerovalent atomic state. In the case of 1, core shell iron/iron oxide particles with a strong magnetic coupling between both components, as revealed by magnetic measurements, are formed. Mössbauer data reveal superparamagnetic particle behavior with a distinct particle size distribution that confirms the magnetic measurements. The dependence of the Mössbauer spectra on temperature and particle size is explained by the influence of superparamagnetic relaxation effects. The coexistence of a paramagnetic doublet and a magnetically split component in the spectra is further explained by a distribution in particle size. From Mössbauer parameters the oxide phase can be identified as low-crystallinity ferrihydrite oxide. In agreement with quantum size effects observed in UV-visible studies, TEM measurements determine the size of the particles in the range 5-8 nm. The particles are mainly arranged alongside the pore walls of the alumina template. TiO2 nanoparticles are formed by depositing 2 in mesoporous alumina template. This produces metallic Ti, which is subsequently oxidized to TiO2 (anatase) within the alumina pores. UV-visible studies show a strong quantum confinement effect for these particles. From UV-visible investigations the particle size is determined to be around 2 nm. XPS analysis of the iron- and titania- embedded nanoparticles reveal the presence of Fe2O3 and TiO2 according to experimental binding energies and the experimental line shapes. Ti4+ and Fe3+ are the only oxidation states of the particles which can be determined by this technique. Hydrogen reduction of the iron/iron-oxide nanoparticles at 500 degrees C under flowing H2/N2 produces a catalyst, which is active

Heating subsurface formations by oxidizing fuel on a fuel carrier

Science.gov (United States)

Costello, Michael; Vinegar, Harold J.

2012-10-02

A method of heating a portion of a subsurface formation includes drawing fuel on a fuel carrier through an opening formed in the formation. Oxidant is supplied to the fuel at one or more locations in the opening. The fuel is combusted with the oxidant to provide heat to the formation.

Aromatics oxidation and soot formation in flames

Energy Technology Data Exchange (ETDEWEB)

Howard, J.B.; Pope, C.J.; Shandross, R.A.; Yadav, T. [Massachusetts Institute of Technology, Cambridge (United States)

1993-12-01

This project is concerned with the kinetics and mechanisms of aromatics oxidation and soot and fullerenes formation in flames. The scope includes detailed measurements of profiles of stable and radical species concentrations in low-pressure one-dimensional premixed flames. Intermediate species identifications and mole fractions, fluxes, and net reaction rates calculated from the measured profiles are used to test postulated reaction mechanisms. Particular objectives are to identify and to determine or confirm rate constants for the main benzene oxidation reactions in flames, and to characterize fullerenes and their formation mechanisms and kinetics.

Potential of secondary aerosol formation from Chinese gasoline engine exhaust.

Science.gov (United States)

Du, Zhuofei; Hu, Min; Peng, Jianfei; Guo, Song; Zheng, Rong; Zheng, Jing; Shang, Dongjie; Qin, Yanhong; Niu, He; Li, Mengren; Yang, Yudong; Lu, Sihua; Wu, Yusheng; Shao, Min; Shuai, Shijin

2018-04-01

Light-duty gasoline vehicles have drawn public attention in China due to their significant primary emissions of particulate matter and volatile organic compounds (VOCs). However, little information on secondary aerosol formation from exhaust for Chinese vehicles and fuel conditions is available. In this study, chamber experiments were conducted to quantify the potential of secondary aerosol formation from the exhaust of a port fuel injection gasoline engine. The engine and fuel used are common in the Chinese market, and the fuel satisfies the China V gasoline fuel standard. Substantial secondary aerosol formation was observed during a 4-5hr simulation, which was estimated to represent more than 10days of equivalent atmospheric photo-oxidation in Beijing. As a consequence, the extreme case secondary organic aerosol (SOA) production was 426±85mg/kg-fuel, with high levels of precursors and OH exposure. The low hygroscopicity of the aerosols formed inside the chamber suggests that SOA was the dominant chemical composition. Fourteen percent of SOA measured in the chamber experiments could be explained through the oxidation of speciated single-ring aromatics. Unspeciated precursors, such as intermediate-volatility organic compounds and semi-volatile organic compounds, might be significant for SOA formation from gasoline VOCs. We concluded that reductions of emissions of aerosol precursor gases from vehicles are essential to mediate pollution in China. Copyright © 2017. Published by Elsevier B.V.

Precursor Mediated Synthesis of Nanostructured Silicas: From Precursor-Surfactant Ion Pairs to Structured Materials

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Peter Hesemann

2014-04-01

Full Text Available The synthesis of nanostructured anionic-surfactant-templated mesoporous silica (AMS recently appeared as a new strategy for the formation of nanostructured silica based materials. This method is based on the use of anionic surfactants together with a co-structure-directing agent (CSDA, mostly a silylated ammonium precursor. The presence of this CSDA is necessary in order to create ionic interactions between template and silica forming phases and to ensure sufficient affinity between the two phases. This synthetic strategy was for the first time applied in view of the synthesis of surface functionalized silica bearing ammonium groups and was then extended on the formation of materials functionalized with anionic carboxylate and bifunctional amine-carboxylate groups. In the field of silica hybrid materials, the “anionic templating” strategy has recently been applied for the synthesis of silica hybrid materials from cationic precursors. Starting from di- or oligosilylated imidazolium and ammonium precursors, only template directed hydrolysis-polycondensation reactions involving complementary anionic surfactants allowed accessing structured ionosilica hybrid materials. The mechanistic particularity of this approach resides in the formation of precursor-surfactant ion pairs in the hydrolysis-polycondensation mixture. This review gives a systematic overview over the various types of materials accessed from this cooperative ionic templating approach and highlights the high potential of this original strategy for the formation of nanostructured silica based materials which appears as a complementary strategy to conventional soft templating approaches.

Formation of the 67-kDa laminin receptor by acylation of the precursor.

Science.gov (United States)

Butò, S; Tagliabue, E; Ardini, E; Magnifico, A; Ghirelli, C; van den Brûle, F; Castronovo, V; Colnaghi, M I; Sobel, M E; Ménard, S

1998-06-01

Even though the involvement of the 67-kDa laminin receptor (67LR) in tumor invasiveness has been clearly demonstrated, its molecular structure remains an open problem, since only a full-length gene encoding a 37-kDa precursor protein (37LRP) has been isolated so far. A pool of recently obtained monoclonal antibodies directed against the recombinant 37LRP molecule was used to investigate the processing that leads to the formation of the 67-kDa molecule. In soluble extracts of A431 human carcinoma cells, these reagents recognize the precursor molecule as well as the mature 67LR and a 120-kDa molecule. The recovery of these proteins was found to be strikingly dependent upon the cell solubilization conditions: the 67LR is soluble in NP-40-lysis buffer whereas the 37LRP is NP-40-insoluble. Inhibition of 67LR formation by cerulenin indicates that acylation is involved in the processing of the receptor. It is likely a palmitoylation process, as indicated by sensitivity of NP-40-soluble extracts to hydroxylamine treatment. Immunoblotting assays performed with a polyclonal serum directed against galectin3 showed that both the 67- and the 120-kDa proteins carry galectin3 epitopes whereas the 37LRP does not. These data suggest that the 67LR is a heterodimer stabilized by strong intramolecular hydrophobic interactions, carried by fatty acids bound to the 37LRP and to a galectin3 cross-reacting molecule.

Kinetic removal of haloacetonitrile precursors by photo-based advanced oxidation processes (UV/H2O2, UV/O3, and UV/H2O2/O3).

Science.gov (United States)

Srithep, Sirinthip; Phattarapattamawong, Songkeart

2017-06-01

The objective of the study is to evaluate the performance of conventional treatment process (i.e., coagulation, flocculation, sedimentation and sand filtration) on the removals of haloacetonitrile (HAN) precursors. In addition, the removals of HAN precursors by photo-based advanced oxidation processes (Photo-AOPs) (i.e., UV/H 2 O 2 , UV/O 3 , and UV/H 2 O 2 /O 3 ) are investigated. The conventional treatment process was ineffective to remove HAN precursors. Among Photo-AOPs, the UV/H 2 O 2 /O 3 was the most effective process for removing HAN precursors, followed by UV/H 2 O 2 , and UV/O 3 , respectively. For 20min contact time, the UV/H 2 O 2 /O 3 , UV/H 2 O 2 , and UV/O 3 suppressed the HAN formations by 54, 42, and 27% reduction. Increasing ozone doses from 1 to 5 mgL -1 in UV/O 3 systems slightly improved the removals of HAN precursors. Changes in pH (6-8) were unaffected most of processes (i.e., UV, UV/H 2 O 2 , and UV/H 2 O 2 /O 3 ), except for the UV/O 3 system that its efficiency was low in the weak acid condition. The pseudo first-order kinetic constant for removals of dichloroacetonitrile precursors (k' DCANFP ) by the UV/H 2 O 2 /O 3 , UV/H 2 O 2 and standalone UV systems were 1.4-2.8 orders magnitude higher than the UV/O 3 process. The kinetic degradation of dissolved organic nitrogen (DON) tended to be higher than the k' DCANFP value. This study firstly differentiates the kinetic degradation between DON and HAN precursors. Copyright © 2017 Elsevier Ltd. All rights reserved.

Generalized trends in the formation energies of perovskite oxides.

Science.gov (United States)

Zeng, ZhenHua; Calle-Vallejo, Federico; Mogensen, Mogens B; Rossmeisl, Jan

2013-05-28

Generalized trends in the formation energies of several families of perovskite oxides (ABO3) and plausible explanations to their existence are provided in this study through a combination of DFT calculations, solid-state physics analyses and simple physical/chemical descriptors. The studied elements at the A site of perovskites comprise rare-earth, alkaline-earth and alkaline metals, whereas 3d and 5d metals were studied at the B site. We also include ReO3-type compounds, which have the same crystal structure of cubic ABO3 perovskites except without A-site elements. From the observations we extract the following four conclusions for the perovskites studied in the present paper: for a given cation at the B site, (I) perovskites with cations of identical oxidation state at the A site possess close formation energies; and (II) perovskites with cations of different oxidation states at the A site usually have quite different but ordered formation energies. On the other hand, for a given A-site cation, (III) the formation energies of perovskites vary linearly with respect to the atomic number of the elements at the B site within the same period of the periodic table, and the slopes depend systematically on the oxidation state of the A-site cation; and (IV) the trends in formation energies of perovskites with elements from different periods at the B site depend on the oxidation state of A-site cations. Since the energetics of perovskites is shown to be the superposition of the individual contributions of their constituent oxides, the trends can be rationalized in terms of A-O and B-O interactions in the ionic crystal. These findings reveal the existence of general systematic trends in the formation energies of perovskites and provide further insight into the role of ion-ion interactions in the properties of ternary compounds.

Microstructure evolution in nanoporous gold thin films made from sputter-deposited precursors

International Nuclear Information System (INIS)

Gwak, Eun-Ji; Kang, Na-Ri; Baek, Un Bong; Lee, Hae Moo; Nahm, Seung Hoon; Kim, Ju-Young

2013-01-01

We fabricate almost crack-free 1.5 μm thick nanoporous gold thin films using free-corrosion dealloying and transfer processes from sputter-deposited precursors. By controlling the temperature and the concentration of the nitric acid solution during free-corrosion dealloying, we obtain ligament sizes in nanoporous gold between 22 and 155 nm. We investigate the effects of dissolution rate of Ag atoms, surface diffusivity of Au atoms and formation of Ag oxide on nanoporosity evolution

Effect of Precursor Concentration on Structural Optical and Electrical Properties of NiO Thin Films Prepared by Spray Pyrolysis

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Rafia Barir

2017-01-01

Full Text Available Undoped nickel oxide (NiO thin films were deposited on 500°C heated glass substrates using spray pyrolysis method at (0.015–0.1 M range of precursor. The latter was obtained by decomposition of nickel nitrate hexahydrate in double distilled water. Effect of precursor concentration on structural, optical, and electrical properties of NiO thin films was investigated. X-ray diffraction (XRD shows the formation of NiO under cubic structure with single diffraction peak along (111 plane at 2θ=37.24°. When precursor concentration reaches 0.1 M, an increment in NiO crystallite size over 37.04 nm was obtained indicating the product nano structure. SEM images reveal that beyond 0.04 M as precursor concentration the substrate becomes completely covered with NiO and thin films exhibit formation of nano agglomerations at the top of the sample surface. Ni-O bonds vibrations modes in the product of films were confirmed by FT-IR analysis. Transparency of the films ranged from 57 to 88% and band gap energy of the films decreases from 3.68 to 3.60 eV with increasing precursor concentration. Electrical properties of the elaborated NiO thin films were correlated to the precursor concentration.

Methanol oxidation reaction on Ti/RuO{sub 2(x)}Pt{sub (1-x)} electrodes prepared by the polymeric precursor method

Energy Technology Data Exchange (ETDEWEB)

Freitas, R.G.; Marchesi, L.F.; Mattos-Costa, F.I.; Pereira, E.C. [Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Centro Multidisciplinar para o Desenvolvimento de Materiais Ceramicos, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13560-905 Sao Carlos, SP (Brazil); Oliveira, R.T.S. [Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Centro Multidisciplinar para o Desenvolvimento de Materiais Ceramicos, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13560-905 Sao Carlos, SP (Brazil); Grupo de Materiais Eletroquimicos e Metodos Eletroanaliticos, Instituto de Quimica de Sao Carlos, Universidade de Sao Paulo, Caixa Postal 780, 13566-590 Sao Carlos, SP (Brazil); LEMN, Laboratorio de Eletroquimica e Materiais Nanoestruturados, CCNH-Centro de Ciencias Naturais e Humanas, UFABC-Universidade Federal do ABC, CEP 09.210-170, Rua Santa Adelia 166, Bairro Bangu, Santo Andre, SP (Brazil); Bulhoes, L.O.S. [Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Centro Multidisciplinar para o Desenvolvimento de Materiais Ceramicos, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13560-905 Sao Carlos, SP (Brazil); CENIP, Centro Universitario Central Paulista, UNICEP, Rua Miguel Petroni, 5111, CEP 13563-470, Sao Carlos, SP (Brazil); Santos, M.C. [Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Centro Multidisciplinar para o Desenvolvimento de Materiais Ceramicos, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13560-905 Sao Carlos, SP (Brazil); LEMN, Laboratorio de Eletroquimica e Materiais Nanoestruturados, CCNH-Centro de Ciencias Naturais e Humanas, UFABC-Universidade Federal do ABC, CEP 09.210-170, Rua Santa Adelia 166, Bairro Bangu, Santo Andre, SP (Brazil)

2007-09-27

In this work, ruthenium oxide films containing platinum nanoparticles were prepared using the polymeric precursor method on Ti substrates with several molar ratios. This paper aims at presenting the characterization of the Pt content effect in the methanol electrochemical oxidation reaction. The films were physically characterized using X-ray diffraction and both Pt and RuO{sub 2} (rutile) phases were observed. The mean crystallite sizes were 6 nm for Pt and 25 nm for RuO{sub 2}. The X-ray photoelectronic results indicated that on the electrodes surfaces, depending on the substrate, there was RuO{sub 2}, Ru metal and Pt metal. Besides, it was not observed the formation of PtRu alloys. The atomic force microscopy images of the films showed highly rough surfaces. A decrease in the roughness mean square values is observed as the Pt content increases. These last results are similar to electroactive surface area values calculated by redox-couple (K{sub 4}FeCN{sub 6}/K{sub 3}FeCN{sub 6}). There was an increase in the globular size observed on the electrode surface and lower particle dispersion as the Pt content is increased from 12.5 to 75 mol%. Regarding the eletrode electrocatalytical behavior for methanol oxidation, it was observed that the onset oxidation overpotential is displaced towards more negative values as Pt content is decreased. Besides, an increase has been shown in the current density for methanol oxidation of 600% using a Ti/RuO{sub 2}-Pt (87.5:12.5) electrode compared to polycrystalline Pt. (author)

Formation of secondary organic aerosol from isoprene oxidation over Europe

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M. Karl

2009-09-01

Full Text Available The role of isoprene as a precursor to secondary organic aerosol (SOA over Europe is studied with the two-way nested global chemistry transport model TM5. The inclusion of the formation of SOA from isoprene oxidation in our model almost doubles the atmospheric burden of SOA over Europe compared to SOA formation from terpenes and aromatics. The reference simulation, which considers SOA formation from isoprene, terpenes and aromatics, predicts a yearly European production rate of 1.0 Tg SOA yr⁻¹ and an annual averaged atmospheric burden of about 50 Gg SOA over Europe. A fraction of 35% of the SOA produced in the boundary layer over Europe is transported to higher altitudes or to other world regions. Summertime measurements of organic matter (OM during the extensive EMEP OC/EC campaign 2002/2003 are better reproduced when SOA formation from isoprene is taken into account, reflecting also the strong seasonality of isoprene and other biogenic volatile organic compounds (BVOC emissions from vegetation. However, during winter, our model strongly underestimates OM, likely caused by missing wood burning in the emission inventories. Uncertainties in the parameterisation of isoprene SOA formation have been investigated. Maximum SOA production is found for irreversible sticking (non-equilibrium partitioning of condensable vapours on particles, with tropospheric SOA production over Europe increased by a factor of 4 in summer compared to the reference case. Completely neglecting SOA formation from isoprene results in the lowest estimate (0.51 Tg SOA yr⁻¹. The amount and the nature of the absorbing matter are shown to be another key uncertainty when predicting SOA levels. Consequently, smog chamber experiments on SOA formation should be performed with different types of seed aerosols and without seed aerosols in order to derive an improved treatment of the absorption of SOA in the models. Consideration of a number of recent insights

Topotactic Synthesis of Porous Cobalt Ferrite Platelets from a Layered Double Hydroxide Precursor and Their Application in Oxidation Catalysis.

Science.gov (United States)

Ortega, Klaus Friedel; Anke, Sven; Salamon, Soma; Özcan, Fatih; Heese, Justus; Andronescu, Corina; Landers, Joachim; Wende, Heiko; Schuhmann, Wolfgang; Muhler, Martin; Lunkenbein, Thomas; Behrens, Malte

2017-09-12

Monocrystalline, yet porous mosaic platelets of cobalt ferrite, CoFe 2 O 4 , can be synthesized from a layered double hydroxide (LDH) precursor by thermal decomposition. Using an equimolar mixture of Fe 2+ , Co 2+ , and Fe 3+ during co-precipitation, a mixture of LDH, (Fe II Co II ) 2/3 Fe III 1/3 (OH) 2 (CO 3 ) 1/6 ⋅m H 2 O, and the target spinel CoFe 2 O 4 can be obtained in the precursor. During calcination, the remaining Fe II fraction of the LDH is oxidized to Fe III leading to an overall Co 2+ :Fe 3+ ratio of 1:2 as required for spinel crystallization. This pre-adjustment of the spinel composition in the LDH precursor suggests a topotactic crystallization of cobalt ferrite and yields phase pure spinel in unusual anisotropic platelet morphology. The preferred topotactic relationship in most particles is [111] Spinel ∥[001] LDH . Due to the anion decomposition, holes are formed throughout the quasi monocrystalline platelets. This synthesis approach can be used for different ferrites and the unique microstructure leads to unusual chemical properties as shown by the application of the ex-LDH cobalt ferrite as catalyst in the selective oxidation of 2-propanol. Compared to commercial cobalt ferrite, which mainly catalyzes the oxidative dehydrogenation to acetone, the main reaction over the novel ex-LDH cobalt is dehydration to propene. Moreover, the oxygen evolution reaction (OER) activity of the ex-LDH catalyst was markedly higher compared to the commercial material. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Features of the theories of the formation of oxide films on aluminum alloys piston diesel engines with micro-arc oxidation

Directory of Open Access Journals (Sweden)

Skryabin M.L.

2017-12-01

Full Text Available The article considers one of the promising methods of surface hardening of piston aluminum alloy – microarc oxidation. Described fundamental differences from the micro-arc oxidation anodizing and similar electrochemical processes. The schemes of formation of the barrier and outer layers surface treatment in aqueous electrolytes. Shows the mechanism of formation of the interface. Considers the formation of layers with high porosity and method of exposure. Also describes the exponential dependence of the current density from the electric field in the surface film of the base metal. The role of discharges in the formation of oxide layers on the treated surface. Proposed and described features of the three main theories of formation of oxide films on the surface of the piston: physical and geometrical model of Keller; models of formation of oxide films as a colloid formations and plasma theory (theory of oxidation with the formation of plasma in the zone of oxidation. The features of formation of films in each of the models. For the model of Keller porous oxide film is a close-Packed oxide cell, having the shape of a prism. They are based on a hexagonal prism. These cells have normal orientation to the surface of the metal. In the center of the unit cell there is one season that is a channel, whose size is determined by the composition of the electrolyte, the chemical composition of the base metal and the electrical parameters of the process of oxidation. In the micro-arc oxidation process according to this model, the beginning of the formation of cells occurs with the formation of the barrier layer, passing in the porous layer and, over time, the elonga-tion of the pores, due to the constant etching electrolyte. In the theory of formation of the oxide films as kolloidnyh formations revealed that formation of pores in the film is a result of their growth. The anodic oxide is represented by a directed electric field, the alumina gel colloidal and

Products of BVOC oxidation: ozone and organic aerosols

Science.gov (United States)

Wildt, Jürgen; Andres, Stefanie; Carriero, Giulia; Ehn, Mikael; Fares, Silvano; Hoffmann, Thorsten; Hacker, Lina; Kiendler-Scharr, Astrid; Kleist, Einhard; Paoletti, Elena; Pullinen, Iida; Rohrer, Franz; Rudich, Yinon; Springer, Monika; Tillmann, Ralf; Wahner, Andreas; Wu, Cheng; Mentel, Thomas

2015-04-01

Biogenic Volatile Organic Compounds (BVOC) are important precursors in photochemical O3 and secondary organic aerosol (SOA) formation. We conducted a series of laboratory experiments with OH-induced oxidation of monoterpenes to elucidate pathways and efficiencies of O3 and SOA formation. At high NOx conditions ([BVOC] / [NOx] monoterpene mixes emitted from different plant species we observed increasing ozone formation with increasing [NOX]. Between 2 and 3 O3-molecules were formed from 1 monoterpene when ozone formation was BVOC limited. Under such high NOX conditions, new particle formation was suppressed. Increasing [BVOC] / [NOX] ratios caused increasing efficiency of new particle formation indicating that peroxy radicals are the key intermediates in both, photochemical ozone- and new particle formation. The classical chemistry of peroxy radicals is well established (e.g. Master Chemical Mechanism). Peroxy radicals are produced by addition of molecular oxygen to the alkyl radical formed after OH attack at the BVOC. They either react with NO which leads to ozone formation or they react with other peroxy radicals and form chemically stable products (hydroperoxides, alkoholes and ketones). Much less knowledge exists on such reactions for Highly Oxidized Peroxy Radicals, (HOPR). Such HOPR were observed during ozonolysis of several volatiles and, in case of monoterpenes as precursors, they can contain more than 12 Oxygen atoms (Mentel et al., 2015). Although the OH-initiated formation of HOPR is yet not fully understood, their basic gas phase reactions seem to follow classical photochemical rules. In reactions with NO they can act as precursor for O3 and in reactions with other HOPR or with classical less oxidized peroxy radicals they can form highly oxidized stable products and alkoxy radicals. In addition, HOPR-HOPR reactions lead to the formation of dimers that, in case of monoterpenes as reactants, consist of a skeleton with 20 carbon atoms. These dimers seem to

Effect of temperature on the reaction pathway of calcium carbonate formation via precursor phases

Science.gov (United States)

Purgstaller, Bettina; Mavromatis, Vasileios; Konrad, Florian; Dietzel, Martin

2016-04-01

It has been earlier postulated that some biogenic and sedimentary calcium carbonate (CaCO3) minerals (e.g. calcite and aragonite) are secondary in origin and have originally formed via a metastable calcium carbonate precursor phase (e.g. amorphous CaCO3, [1-2]). Such formation pathways are likely affected by various physicochemical parameters including aqueous Mg and temperature. In an effort to improve our understanding on the formation mechanism of CaCO3 minerals, precipitation experiments were carried out by the addition of a 0.6 M (Ca,Mg)Cl2 solution at distinct Mg/Ca ratios (1/4 and 1/8) into a 1 M NaHCO3 solution under constant pH conditions(8.3 ±0.1). The formation of CaCO3 was systematically examined as a function of temperature (6, 12, 18 and 25 ±0.3° C). During the experimental runs mineral precipitation was monitored by in situ Raman spectroscopy as well as by continuous sampling and analyzing of precipitates and reactive solutions. The results revealed two pathways of CaCO3 formation depending on the initial Mg/Ca ratio and temperature: (i) In experiments with a Mg/Ca ratio of 1/4 at ≤ 12° C as well as in experiments with a Mg/Ca ratio of 1/8 at ≤ 18° C, ikaite (CaCO3 6H2O) acts as a precursor phase for aragonite formation. (ii) In contrast higher temperatures induced the formation of Mg-rich amorphous CaCO3 (Mg-ACC) which was subsequently transformed to Mg-rich calcite. In situ Raman spectra showed that the transformation of Mg-ACC to Mg-calcite occurs at a higher rate (˜ 8 min) compared to that of ikaite to aragonite (> 2 h). Thus, the formation of aragonite rather than of Mg-calcite occurs due to the slower release of Ca2+and CO32- ions into the Mg-rich reactive solution during retarded ikaite dissolution. This behavior is generally consistent with the observation that calcite precipitation is inhibited at elevated aqueous Mg/Ca ratios. [1] Addadi L., Raz S. and Weiner S. (2003) Advanced Materials 15, 959-970. [2] Rodriguez-Blanco J. D

Effect of precursor concentration on the growth of zinc oxide nanorod arrays on pre-treated substrates

International Nuclear Information System (INIS)

Urgessa, Z.N.; Oluwafemi, O.S.; Botha, J.R.

2012-01-01

Well aligned zinc oxide nanorod arrays (ZNAs) synthesized by a simple chemical bath deposition method were fabricated on pre-treated Si substrates. By keeping the molar VI/II ratio constant, the effect of precursor concentration on the growth and optical quality of the ZNAs was investigated. The as-synthesized ZNAs were characterized by field emission scanning electron microscopy (FESEM), x-ray diffraction (XRD) and photoluminescence spectroscopy (PL). FESEM images show that both the diameter and aspect ratio of the ZNAs increase dramatically as the precursor concentration increases. The XRD analysis indicates that all the as-grown ZNAs are crystalline and are preferentially oriented along the c-axis. The high intensity ratio of the UV emission to visible emission in the room temperature PL spectra illustrate that high optical quality ZNAs were produced.

Effect of precursor concentration on the growth of zinc oxide nanorod arrays on pre-treated substrates

Energy Technology Data Exchange (ETDEWEB)

Urgessa, Z.N. [Department of Physics, P.O. Box 77000, Nelson Mandela Metropolitan University, Port Elizabeth 6031 (South Africa); Oluwafemi, O.S., E-mail: oluwafemi.oluwatobi@gmail.com [Department of Chemistry and Chemical Technology, Walter Sisulu University, Mthatha Campus, Private Bag XI, 5117 (South Africa); Botha, J.R. [Department of Physics, P.O. Box 77000, Nelson Mandela Metropolitan University, Port Elizabeth 6031 (South Africa)

2012-05-15

Well aligned zinc oxide nanorod arrays (ZNAs) synthesized by a simple chemical bath deposition method were fabricated on pre-treated Si substrates. By keeping the molar VI/II ratio constant, the effect of precursor concentration on the growth and optical quality of the ZNAs was investigated. The as-synthesized ZNAs were characterized by field emission scanning electron microscopy (FESEM), x-ray diffraction (XRD) and photoluminescence spectroscopy (PL). FESEM images show that both the diameter and aspect ratio of the ZNAs increase dramatically as the precursor concentration increases. The XRD analysis indicates that all the as-grown ZNAs are crystalline and are preferentially oriented along the c-axis. The high intensity ratio of the UV emission to visible emission in the room temperature PL spectra illustrate that high optical quality ZNAs were produced.

Iron Oxide Doped Alumina-Zirconia Nanoparticle Synthesis by Liquid Flame Spray from Metal Organic Precursors

OpenAIRE

Juha-Pekka Nikkanen; Helmi Keskinen; Mikko Aromaa; Mikael Järn; Tomi Kanerva; Erkki Levänen; Jyrki M. Mäkelä; Tapio Mäntylä

2008-01-01

The liquid flame spray (LFS) method was used to make iron oxide doped alumina-zirconia nanoparticles. Nanoparticles were generated using a turbulent, high-temperature (Tmax⁡∼3000 K) H2-O2 flame. The precursors were aluminium-isopropoxide, zirconium-n-propoxide, and ferrocene in xylene solution. The solution was atomized into micron-sized droplets by high velocity H2 flow and introduced into the flame where nanoparticles were formed. The particle morphology, size, phase, and chemical compositi...

Investigation of the Surface Properties of an Oxide of Interest in the Field of a Conductive Oxide System: Influence of Precursor and Purification

Directory of Open Access Journals (Sweden)

Gomes Gilmar de Almeida

1999-01-01

Full Text Available The surface properties of commercial TiO2 and samples synthesized by the thermal decomposition procedure using several precursor salts were investigated by a microelectrophoresis technique. The iep was determined as a function of the ionic strength which was controlled with KNO3 or KCl. The experimental results showed: 1 The commercial sample and the ones synthesized from the chloride salt dissolved in HCl 1:1 (v/v show low iep?s due to chloride inclusion; 2 The purification methods explored (oxide suspension at pH~12 and dialysis are inefficient; 3 TiO2 samples synthesized from an organic precursor salt under totally chloride-free conditions furnished an iep of 5.9 in excellent agreement with literature data; 4 Chloride specific adsorption on TiO2 is weak.

Meat flavor precursors and factors influencing flavor precursors--A systematic review.

Science.gov (United States)

Khan, Muhammad Issa; Jo, Cheorun; Tariq, Muhammad Rizwan

2015-12-01

Flavor is the sensory impression sensed by taste and smell buds and is a leading factor determining the meat quality and purchasing decision of the consumer. Meat flavor is characteristic of volatiles produced as a result of reactions of non-volatile components that are induced thermally. The water soluble compounds having low molecular weight and meat lipids are important precursors of cooked meat flavor. The Maillard reaction, lipid oxidation, and vitamin degradation are leading reactions during cooking which develop meat flavor from uncooked meat with little aroma and bloody taste. The pre-slaughter and postmortem factors like animal breed, sex, age, feed, aging and cooking conditions contribute to flavor development of cooked meat. The objective of this review is to highlight the flavor chemistry, meat flavor precursors and factors affecting meat flavor precursors. Copyright © 2015 Elsevier Ltd. All rights reserved.

Experimental Determination of the Formation Enthalpy of Calcium Cobaltate from Sol–Gel Precursors

DEFF Research Database (Denmark)

Holgate, Tim C.; Wu, NingYu; Van Nong, Ngo

2017-01-01

Calcium cobaltate (Ca3Co4O9) remains one of the most promising p-type oxide materials for high-temperature thermoelectric energy conversion. While much progress has been made in refining our understanding of the unique structure of the material, as well as optimization of the transport properties...... as observations of its decomposition into the Ca3Co2O6 phase. The reaction enthalpy of forming Ca3Co4O9 from CaCO3 and Co3O4 sol–gel precursors was determined to be +284 (±2%) kJ/mol, leading to a standard enthalpy of Ca3Co4O9 of −3307 (±3.5%) kJ/mol....

Mechanistic Study of Monodisperse Iron Oxide Nanocrystals ...

African Journals Online (AJOL)

To gain better insight into the formation of iron oxide nanocrystals from the solution phase thermal decomposition of iron (III) oleate complex, different reaction conditions including time, heating ramp, as well as concentrations of iron oleate precursor and oleic acid ligand were systematically varied and the resulting ...

Ex situ formation of metal selenide quantum dots using bacterially derived selenide precursors

International Nuclear Information System (INIS)

Fellowes, J W; Pattrick, R A D; Lloyd, J R; Charnock, J M; Coker, V S; Mosselmans, J F W; Weng, T-C; Pearce, C I

2013-01-01

Luminescent quantum dots were synthesized using bacterially derived selenide (Se II− ) as the precursor. Biogenic Se II− was produced by the reduction of Se IV by Veillonella atypica and compared directly against borohydride-reduced Se IV for the production of glutathione-stabilized CdSe and β-mercaptoethanol-stabilized ZnSe nanoparticles by aqueous synthesis. Biological Se II− formed smaller, narrower size distributed QDs under the same conditions. The growth kinetics of biologically sourced CdSe phases were slower. The proteins isolated from filter sterilized biogenic Se II− included a methylmalonyl-CoA decarboxylase previously characterized in the closely related Veillonella parvula. XAS analysis of the glutathione-capped CdSe at the S K-edge suggested that sulfur from the glutathione was structurally incorporated within the CdSe. A novel synchrotron based XAS technique was also developed to follow the nucleation of biological and inorganic selenide phases, and showed that biogenic Se II− is more stable and more resistant to beam-induced oxidative damage than its inorganic counterpart. The bacterial production of quantum dot precursors offers an alternative, ‘green’ synthesis technique that negates the requirement of expensive, toxic chemicals and suggests a possible link to the exploitation of selenium contaminated waste streams. (paper)

Ex Situ Formation of Metal Selenide Quantum Dots Using Bacterially Derived Selenide Precursors

Energy Technology Data Exchange (ETDEWEB)

Fellowes, Jonathan W.; Pattrick, Richard; Lloyd, Jon; Charnock, John M.; Coker, Victoria S.; Mosselmans, JFW; Weng, Tsu-Chien; Pearce, Carolyn I.

2013-04-12

Luminescent quantum dots were synthesized using bacterially derived selenide (SeII-) as the precursor. Biogenic SeII- was produced by the reduction of Se-IV by Veillonella atypica and compared directly against borohydride-reduced Se-IV for the production of glutathione-stabilized CdSe and beta-mercaptoethanol-stabilized ZnSe nanoparticles by aqueous synthesis. Biological SeII- formed smaller, narrower size distributed QDs under the same conditions. The growth kinetics of biologically sourced CdSe phases were slower. The proteins isolated from filter sterilized biogenic SeII- included a methylmalonyl-CoA decarboxylase previously characterized in the closely related Veillonella parvula. XAS analysis of the glutathione-capped CdSe at the S K-edge suggested that sulfur from the glutathione was structurally incorporated within the CdSe. A novel synchrotron based XAS technique was also developed to follow the nucleation of biological and inorganic selenide phases, and showed that biogenic SeII- is more stable and more resistant to beam-induced oxidative damage than its inorganic counterpart. The bacterial production of quantum dot precursors offers an alternative, 'green' synthesis technique that negates the requirement of expensive, toxic chemicals and suggests a possible link to the exploitation of selenium contaminated waste streams.

Aromatics Oxidation and Soot Formation in Flames

Energy Technology Data Exchange (ETDEWEB)

Howard, J. B.; Richter, H.

2005-03-29

This project is concerned with the kinetics and mechanisms of aromatics oxidation and the growth process to polycyclic aromatic hydrocarbons (PAH) of increasing size, soot and fullerenes formation in flames. The overall objective of the experimental aromatics oxidation work is to extend the set of available data by measuring concentration profiles for decomposition intermediates such as phenyl, cyclopentadienyl, phenoxy or indenyl radicals which could not be measured with molecular-beam mass spectrometry to permit further refinement and testing of benzene oxidation mechanisms. The focus includes PAH radicals which are thought to play a major role in the soot formation process while their concentrations are in many cases too low to permit measurement with conventional mass spectrometry. The radical species measurements are used in critical testing and improvement of a kinetic model describing benzene oxidation and PAH growth. Thermodynamic property data of selected species are determined computationally, for instance using density functional theory (DFT). Potential energy surfaces are explored in order to identify additional reaction pathways. The ultimate goal is to understand the conversion of high molecular weight compounds to nascent soot particles, to assess the roles of planar and curved PAH and relationships between soot and fullerenes formation. The specific aims are to characterize both the high molecular weight compounds involved in the nucleation of soot particles and the structure of soot including internal nanoscale features indicative of contributions of planar and/or curved PAH to particle inception.

Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid and methylglyoxal

Directory of Open Access Journals (Sweden)

Y. Tan

2012-01-01

Full Text Available Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including pyruvate, oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA. Acetic acid plays a central role in the aqueous oxidation of methylglyoxal and it is a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid (20 μM–10 mM was oxidized by OH radicals, and pyruvic acid and methylglyoxal experimental samples were analyzed using new analytical methods, in order to better understand the formation of SOA from acetic acid and methylglyoxal. Glyoxylic, glycolic, and oxalic acids formed from acetic acid and OH radicals. In contrast to the aqueous OH radical oxidation of methylglyoxal, the aqueous OH radical oxidation of acetic acid did not produce succinic acid and oligomers. This suggests that the methylgloxal-derived oligomers do not form through the acid catalyzed esterification pathway proposed previously. Using results from these experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

Formation of 14C-asparagine from 14C-precursor in mulberry leaves

International Nuclear Information System (INIS)

Yamashita, Tadaaki

1981-01-01

Since a remarkable accumulation of asparagine in the young leaves of mulberry has been observed, the formation of 14 C-asparagine from 14 C-labeled substrates in young leaves was examined in comparison with that in the mature leaves. 14 C-aspartic acid and 14 C-succinic acid expected as active precursors for asparagine biosynthesis, and 14 C-sucrose as respiratory substrates were fed respectively to the disks of young or mature leaves of mulberry. Although 14 C-succinic acid was actively converted to 14 C-asparagine, no significant amount of 14 C-asparagine was formed from 14 C-aspartic acid in two hours of feeding period. The rate of formation of 14 C-asparagine from 14 C-succinic acid in the mature leaves was slightly higher than that in the young leaves. Amino acids other than asparagine acquired 14 C from 14 C-labeled substrates were mainly aspartic acid, glutamic acid, alanine and ν-amino butyric acid in both of the leaves. Intending to accelerate the formation of asparagine in the leaves, ammonium ion was supplied to culturing solution as only source of nitrogen and plants were grown for two weeks in that solution before 14 C-labeled substrates feeding experiments. Supplying of ammonium ion brought about enhanced accumulation of asparagine in the young leaves, and caused remarkable formation of 14 C-asparagine from 14 C-aspartic acid in both of the leaves. However, the rate of 14 C-asparagine formation from 14 C-aspartic acid in the young leaves did not exceed that in the mature leaves. (author)

Precursor directed synthesis - ``molecular'' mechanisms in the Soft Chemistry approaches and their use for template-free synthesis of metal, metal oxide and metal chalcogenide nanoparticles and nanostructures

Science.gov (United States)

Seisenbaeva, Gulaim A.; Kessler, Vadim G.

2014-05-01

This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials.This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials. To Professor David Avnir on his 65th birthday.

Control of aliphatic halogenated DBP precursors with multiple drinking water treatment processes: Formation potential and integrated toxicity.

Science.gov (United States)

Zhang, Yimeng; Chu, Wenhai; Yao, Dechang; Yin, Daqiang

2017-08-01

The comprehensive control efficiency for the formation potentials (FPs) of a range of regulated and unregulated halogenated disinfection by-products (DBPs) (including carbonaceous DBPs (C-DBPs), nitrogenous DBPs (N-DBPs), and iodinated DBPs (I-DBPs)) with the multiple drinking water treatment processes, including pre-ozonation, conventional treatment (coagulation-sedimentation, pre-sand filtration), ozone-biological activated carbon (O 3 -BAC) advanced treatment, and post-sand filtration, was investigated. The potential toxic risks of DBPs by combing their FPs and toxicity values were also evaluated. The results showed that the multiple drinking water treatment processes had superior performance in removing organic/inorganic precursors and reducing the formation of a range of halogenated DBPs. Therein, ozonation significantly removed bromide and iodide, and thus reduced the formation of brominated and iodinated DBPs. The removal of organic carbon and nitrogen precursors by the conventional treatment processes was substantially improved by O 3 -BAC advanced treatment, and thus prevented the formation of chlorinated C-DBPs and N-DBPs. However, BAC filtration leads to the increased formation of brominated C-DBPs and N-DBPs due to the increase of bromide/DOC and bromide/DON. After the whole multiple treatment processes, the rank order for integrated toxic risk values caused by these halogenated DBPs was haloacetonitriles (HANs)≫haloacetamides (HAMs)>haloacetic acids (HAAs)>trihalomethanes (THMs)>halonitromethanes (HNMs)≫I-DBPs (I-HAMs and I-THMs). I-DBPs failed to cause high integrated toxic risk because of their very low FPs. The significant higher integrated toxic risk value caused by HANs than other halogenated DBPs cannot be ignored. Copyright © 2017. Published by Elsevier B.V.

Synthesis of encapsulated pigments based on Fe, Co and Si by route of polymeric precursors

International Nuclear Information System (INIS)

Macedo, D.S.S.M.; Macedo Neto, O.C.; Paskocimas, C.A.; Varela, M.L.N.

2012-01-01

The objective is to apply the polymeric precursor method to obtain encapsulated pigments, the basis of oxides of iron and cobalt deposited on silica. The method has advantages such as reduction of time and reproducibility in the conventional methods, and also improves optical properties, thermal stability and morphology. The synthesis was based on the dissolution of the citric acid (complexing agent), addition of oxides of iron and cobalt (ions chromophores) polymerization of ethylene glycol and silica coating. The mixture was pre-calcined to form the precursor powder was analyzed by TG and DTA. Was then split, and calcined at different temperatures (700 ° C - 900 ° C) and analyzed by BET, DRX, MEV and UV-Visible. The pigments were stable thermally, with surface area ranging between 3,09 and 7,65 m² / g, formation of crystalline phases of cobalt ferrite (CoFe 2 O 4 ) and Cristobalite (SiO 2 ) and agglomerates of particles slightly rounded. (author)

The formation of CuInSe{sub 2}-based thin-film solar cell absorbers from alternative low-cost precursors

Energy Technology Data Exchange (ETDEWEB)

Jost, S.

2008-01-18

This work deals with real-time investigations concerning the crystallisation process of CuInSe{sub 2}-based thin-film solar cell absorbers while annealing differently produced and composed ''low-cost'' precursors. Various types of precursors have been investigated concerning their crystallisation behaviour. Three groups of experiments have been performed: (i) Investigations concerning the crystallisation process of the quaternary chalcopyrite Cu(In,Al)Se{sub 2} and Cu(In,Al)S{sub 2}, (ii) investigations concerning the formation process of the compound semiconductor CuInSe{sub 2} from electroplated precursors, and (iii) investigations concerning the crystallisation of Cu(In,Ga)Se{sub 2} using precursors with thermally evaporated indium. A specific sample surrounding has been constructed, which enables to perform time-resolved angle-dispersive X-ray powder diffraction experiments during the annealing process of precursor samples. A thorough analysis of subsequently recorded diffraction patterns using the Rietveld method provides a detailed knowledge about the semiconductor crystallisation process while annealing. Based on these fundamental investigations, conclusions have been drawn concerning an adaptation of the precursor deposition process in order to optimise the final solar cell results. The investigations have shown, that one class of electroplated precursors shows a crystallisation behaviour identical to the one known for vacuum-deposited precursors. The investigations concerning the crystallisation process of the quaternary chalcopyrite Cu(In,Al)Se{sub 2} revealed, that the chalcopyrite forms from the ternary selenide (Al,In){sub 2}Se{sub 3} and Cu{sub 2}Se at elevated process temperatures. This result is used to explain the separation of the absorber layer into an aluminum-rich and an indium-rich chalcopyrite phase, which has been observed at processed Cu(In,Al)Se{sub 2} absorbers from several research groups. In addition, differences

In Situ X-ray Diffraction Study of the Formation of Fe(Se,Te) from Various Precursors

DEFF Research Database (Denmark)

Grivel, Jean-Claude; Yue, Zhao; Wulff, Anders Christian

2012-01-01

The formation of the FeSe0.5Te0.5 phase was studied by means of high energy synchrotron x-ray diffraction. The precursors consisted of Fe, Se and Te or Se0.5Te0.5 powder mixtures and were encased in a metal (Cu/Nb) composite sheath to prevent evaporation of Se and Te during high temperature...... equilibria of the Se – Te system. The grain size of the starting Fe powder has no influence on the reaction path for the grain sizes used in the present study. However, the reaction rate for Fe(Se,Te) formation is clearly sensitive to this parameter....

Formation of inorganic nanocomposites by filling TiO{sub 2} nanopores with indium and antimony sulfide precursor aerosols

Energy Technology Data Exchange (ETDEWEB)

Juma, Albert, E-mail: jumalberto@yahoo.com [Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Azarpira, Anahita [Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Fischer, Ch.-H. [Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Free University Berlin, Institute of Chemistry and Biochemistry, Fabeckstr. 34-36, 14195 Berlin (Germany); Wendler, Elke [Friedrich-Schiller-Universität Jena, Institut für Festkörperphysik, Max-Wien-Platz 1, 07743 Jena (Germany); Dittrich, Thomas [Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109 Berlin (Germany)

2014-09-01

Nanocomposites of nanoporous-TiO{sub 2}/In{sub 2}S{sub 3} and np-TiO{sub 2}/Sb{sub 2}S{sub 3} were formed by deposition of In{sub 2}S{sub 3} or Sb{sub 2}S{sub 3} using spray ion layer gas reaction technique from their precursor solutions onto nanoporous TiO{sub 2} substrates at temperatures of 150, 175 and 200 °C. The least penetration of the precursor into np-TiO{sub 2} was achieved for np-TiO{sub 2}/In{sub 2}S{sub 3} nanocomposites from indium acetylacetonate salt. The deepest penetration was obtained for both np-TiO{sub 2}/In{sub 2}S{sub 3}(Cl) and np-TiO{sub 2}/Sb{sub 2}S{sub 3} nanocomposites with effective diffusion coefficients of 3.3 × 10{sup −3} cm{sup 2}/s and 3.2 × 10{sup −3} cm{sup 2}/s, respectively. The transport of the precursors in np-TiO{sub 2} and the formation of different nanocomposites were described the regime of the Knudsen diffusion model. - Highlights: • Deposition of metal sulfides by ion layer gas reaction technique • Penetration and diffusion depend on precursor characteristics. • Pore transport described by Knudsen diffusion model • InCl{sub 3} precursor penetrates more than In(acac){sub 3}.

Water formation via HCl oxidation on Cu(1 0 0)

Energy Technology Data Exchange (ETDEWEB)

Suleiman, Ibrahim A., E-mail: isuleman@taibahu.edu.sa [College of Engineering, Taibah University, Yanbu 41911 (Saudi Arabia); Radny, Marian W. [School of Mathematical and Physical Sciences, The University of Newcastle, Callaghan, NSW 2308 (Australia); Institute of Physics, Poznan University of Technology, 62-956 Poznan (Poland); Gladys, Michael J.; Smith, Phillip V. [School of Mathematical and Physical Sciences, The University of Newcastle, Callaghan, NSW 2308 (Australia); Mackie, John C. [School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); School of Chemistry, The University of Sydney (Australia); Stockenhuber, Michael; Kennedy, Eric M. [School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Dlugogorski, Bogdan Z. [School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); School of Engineering and Information Technology, Murdoch University, Perth (Australia)

2014-04-01

Graphical abstract: This work investigates water formation on the Cu(1 0 0) surface via HCl oxidation using density functional theory and periodic slabs. We show that there are two different pathways for water formation on the surface depending on the temperature and oxygen coverage. - Highlights: • Pre-adsorbed chlorine increases the stability of water on Cu(1 0 0). • Two different pathways describe water formation on Cu(1 0 0) via HCl oxidation. • The mechanism of H{sub 2}O formation depends on the temperature and oxygen coverage. - Abstract: Using density functional theory and periodic slabs, we have studied water formation via HCl oxidation on the Cu(1 0 0) surface. We show that while adsorbed chlorine increases the stability of water on the Cu(1 0 0) surface, water molecules dissociate immediately when located next to an oxygen atom. We also show that these competing interactions, when arising from HCl reacting with oxygen on Cu(1 0 0), lead to water formation according to two different pathways depending on the temperature and oxygen coverage.

Synthesis and characterization of titanium and yttrium precursors with unsaturated ligands: application to the doping of low-density micro-molecular materials oxides

International Nuclear Information System (INIS)

Gamet-Cauro, L.-C.

2001-01-01

The laser-matter interaction experiments for high-power pulsed lasers require doped micro-targets. The ablator is a Low-Density Microcellular Material,foam namely a styrene-divinylbenzene copolymer obtained by a HIPE process (High Internal Polymerisation Emulsion). The spectroscopic tracers selected for doping are titanium, yttrium and aluminium as oxides. For obtaining these hybrid organic-inorganic materials, precursors with polymerizable ligands were introduced during the emulsification step since the unsaturation of the ligands could participate in the copolymerization reaction. We report here in the synthesis and characterization of titanium and yttrium precursors with polymerizable ligands. The structures of [Ti(O i Pr) 3 (AMP)] 2 (HAMP allyl-methylphenol), [Ti(OEt) 3 (AAA)] 2 (HAAA allylacetoacetate), Y 8 O 2 (OH) 4 (OEt) 6 (AAA) 10 were established by X-ray diffraction. Ti 4 O 3 (OR) 8 (AAA) 2 (R Et, i Pr).[TiO(O i Pr)(oleate)] m , Y 4 (OH) 2 (AAA) 5 , Y 4 O(O i Pr) 5 (AAA) 5 , Y 4 (OH) 4 Cl 5 (AAA) 3 (THF) 3 have been prepared as well and characterized by FT-IR, 1 HNMR and elemental analysis. Micro-hydrolysis reactions of titanium derivatives were investigated. The rates of polymerisation and copolymerization with styrene were evaluated for the titanium precursors with polymerizable ligands. The parameters of the HIPE process were adapted to the fabrication of doped foams, only the dopant and initiator change. We discuss incorporation mechanisms of titanium oxide and yttrium oxo-hydroxides: precursor-surfactant interaction, copolymerization of precursors with unsaturated ligands and physical or chemical retention. The foams have been characterized by scanning electron microscopy (morphology), elemental analysis and fluorescence X cartography (amount, distribution of metal oxide), adsorption isotherms (BET, texture), compression tests (mechanical strength). Due to this systematic study, a good control of doping has become possible and allowed us to develop

Relative importance and interactions of furan precursors in sterilised, vegetable-based food systems.

Science.gov (United States)

Palmers, Stijn; Grauwet, Tara; Buvé, Carolien; Vanratingen, Koen; Kebede, Biniam T; Goos, Peter; Hendrickx, Marc E; Van Loey, Ann

2016-01-01

Mitigation strategies aimed at an intervention in the reaction pathways for furan formation (e.g., by adjusting precursor concentrations) might offer an additional route for furan reduction in sterilised, vegetable-based foods, without adverse effects on other food safety or quality attributes. As a first step towards product reformulation, the aim of the present study was to determine the relative importance and interactions of possible furan precursors in these types of foods. Based on an I-optimal experimental design, potato purée (naturally low in furan precursors) was spiked with known amounts of sugars, ascorbic acid, olive oil and β-carotene, and subjected to a thermal sterilisation. Significant correlations were observed between furan concentrations after thermal treatment and starting concentrations of ascorbic acid and monosaccharides (i.e., fructose and glucose). Ascorbic acid had a clear furan-reducing effect as an antioxidant by protecting (polyunsaturated) fatty acids against oxidative degradation. Fructose and glucose were the main precursors, which can most probably be attributed to their high, but realistic, concentrations in the product. The contributions of fatty acids and β-carotene were strongly dependent on redox interactions with other food constituents. In the same potato purées, only low concentrations (0-2 ng g(-1) purée) of 2-methylfuran were detected, indicating that the direct importance of the spiked food constituents as a precursor for methylfuran formation was rather small. Based on the results of this study, reducing the amount of monosaccharides or adjusting the redox conditions of the matrix are suggested as two possible approaches for furan mitigation on the product side.

Bismuth oxide aqueous colloidal nanoparticles inhibit Candida albicans growth and biofilm formation

Directory of Open Access Journals (Sweden)

Hernandez-Delgadillo R

2013-04-01

Full Text Available Rene Hernandez-Delgadillo,1 Donaji Velasco-Arias,3 Juan Jose Martinez-Sanmiguel,2 David Diaz,3 Inti Zumeta-Dube,3 Katiushka Arevalo-Niño,1 Claudio Cabral-Romero2 1Facultad de Ciencias Biológicas, Instituto de Biotecnologia, Universidad Autonoma de Nuevo Leon, UANL, Monterrey, Mexico; 2Facultad de Odontología, Universidad Autonoma de Nuevo Leon, UANL, Monterrey, México; 3Facultad de Quimica, Universidad Nacional Autonoma de Mexico, UNAM, Distrito Federal, México Abstract: Multiresistance among microorganisms to common antimicrobials has become one of the most significant concerns in modern medicine. Nanomaterials are a new alternative to successfully treat the multiresistant microorganisms. Nanostructured materials are used in many fields, including biological sciences and medicine. Recently, it was demonstrated that the bactericidal activity of zero-valent bismuth colloidal nanoparticles inhibited the growth of Streptococcus mutans; however the antimycotic potential of bismuth nanostructured derivatives has not yet been studied. The main objective of this investigation was to analyze the fungicidal activity of bismuth oxide nanoparticles against Candida albicans, and their antibiofilm capabilities. Our results showed that aqueous colloidal bismuth oxide nanoparticles displayed antimicrobial activity against C. albicans growth (reducing colony size by 85% and a complete inhibition of biofilm formation. These results are better than those obtained with chlorhexidine, nystatin, and terbinafine, the most effective oral antiseptic and commercial antifungal agents. In this work, we also compared the antimycotic activities of bulk bismuth oxide and bismuth nitrate, the precursor metallic salt. These results suggest that bismuth oxide colloidal nanoparticles could be a very interesting candidate as a fungicidal agent to be incorporated into an oral antiseptic. Additionally, we determined the minimum inhibitory concentration for the synthesized

High-performance zno transistors processed via an aqueous carbon-free metal oxide precursor route at temperatures between 80-180 °c

KAUST Repository

Lin, Yenhung; Faber, Hendrik; Zhao, Kui; Wang, Qingxiao; Amassian, Aram; McLachlan, Martyn A.; Anthopoulos, Thomas D.

2013-01-01

An aqueous and carbon-free metal-oxide precursor route is used in combination with a UV irradiation-assisted low-temperature conversion method to fabricate low-voltage ZnO transistors with electron mobilities exceeding 10 cm2/Vs at temperatures <

Degradation of natural organic matter by UV/chlorine oxidation: Molecular decomposition, formation of oxidation byproducts and cytotoxicity.

Science.gov (United States)

Wang, Wen-Long; Zhang, Xue; Wu, Qian-Yuan; Du, Ye; Hu, Hong-Ying

2017-11-01

The degradation of natural organic matters (NOMs) by the combination of UV and chlorine (UV/chlorine) was investigated in this study. UV/chlorine oxidation can effectively degrade NOMs, with the degradation of chromophores (∼80%) and fluorophores (76.4-80.8%) being more efficient than that of DOC (15.1-18.6%). This effect was attributed to the chromophores and fluorophores (double bonds, aromatic groups and phenolic groups) being preferentially degraded by UV/chlorine oxidation, particularly reactive groups with high electron donating capacity. Radical species •OH and •Cl were generated during UV/chlorine oxidation, with the contribution of •OH 1.4 times as high as that of •Cl. The degradation kinetics of different molecular weight (MW) fractions suggests that UV/chlorine oxidation degrades high MW fractions into low MW fractions, with the degradation rates of high MW fractions (>3000 Da) 4.5 times of those of medium MW fractions (1000-3000 Da). In comparison with chlorination alone, UV/chlorine oxidation did not increase the formation (30 min) and formation potential (24 h) of trihalomethanes, but instead promoted the formation and formation potential of haloacetic acids and chloral hydrate. Adsorbable organic halogen (AOX) formed from UV/chlorine oxidation of NOM were 0.8 times higher than those formed from chlorination. Cytotoxicity studies indicated that the cytotoxicity of NOM increased after both chlorination and UV/chlorine oxidation, which may be due to the formation of AOX. Copyright © 2017 Elsevier Ltd. All rights reserved.

Planar half-cell shaped precursor body

DEFF Research Database (Denmark)

2015-01-01

The invention relates to a half-cell shaped precursor body of either anode type or cathode type, the half-cell shaped precursor body being prepared to be free sintered to form a sintered or pre-sintered half-cell being adapted to be stacked in a solid oxide fuel cell stack. The obtained half......-cell has an improved planar shape, which remains planar also after a sintering process and during temperature fluctuations....

NDMA formation from amine-based pharmaceuticals--impact from prechlorination and water matrix.

Science.gov (United States)

Shen, Ruqiao; Andrews, Susan A

2013-05-01

The presence of N-nitrosodimethylamine (NDMA) in drinking water is most commonly associated with the chloramination of amine-based precursors. One option to control the NDMA formation is to remove the precursors via pre-oxidation, and prechlorination is among the most effective options in reducing NDMA formation. However, most of the findings to-date are based on single-precursor scenarios using the model precursor dimethylamine (DMA) and natural organic matter (NOM), while few studies have considered the potential interactions between water matrix components and the target precursors when investigating the prechlorination impact. Specifically, little is known for the behaviour of amine-based pharmaceuticals which have recently been reported to contribute to NDMA formation upon chloramination. This work demonstrates that prechlorination can affect both the ultimate NDMA conversion and the reaction kinetics from selected pharmaceuticals, and the nature and extent of the impact was compound-specific and matrix-specific. In the absence of NOM, the NDMA formation from most pharmaceuticals was reduced upon prechlorination, except for sumatriptan which showed a consistent increase in NDMA formation with increasing free chlorine contact time. In the presence of NOM, prechlorination was shown to enhance initial reactions by reducing the binding between NOM and pharmaceuticals, but prolonged prechlorination broke down NOM into smaller products which could then form new bonds with pharmaceuticals and thus inhibit their further conversion into NDMA. Copyright © 2013 Elsevier Ltd. All rights reserved.

Imbalance of heterologous protein folding and disulfide bond formation rates yields runaway oxidative stress

Directory of Open Access Journals (Sweden)

Tyo Keith EJ

2012-03-01

Full Text Available Abstract Background The protein secretory pathway must process a wide assortment of native proteins for eukaryotic cells to function. As well, recombinant protein secretion is used extensively to produce many biologics and industrial enzymes. Therefore, secretory pathway dysfunction can be highly detrimental to the cell and can drastically inhibit product titers in biochemical production. Because the secretory pathway is a highly-integrated, multi-organelle system, dysfunction can happen at many levels and dissecting the root cause can be challenging. In this study, we apply a systems biology approach to analyze secretory pathway dysfunctions resulting from heterologous production of a small protein (insulin precursor or a larger protein (α-amylase. Results HAC1-dependent and independent dysfunctions and cellular responses were apparent across multiple datasets. In particular, processes involving (a degradation of protein/recycling amino acids, (b overall transcription/translation repression, and (c oxidative stress were broadly associated with secretory stress. Conclusions Apparent runaway oxidative stress due to radical production observed here and elsewhere can be explained by a futile cycle of disulfide formation and breaking that consumes reduced glutathione and produces reactive oxygen species. The futile cycle is dominating when protein folding rates are low relative to disulfide bond formation rates. While not strictly conclusive with the present data, this insight does provide a molecular interpretation to an, until now, largely empirical understanding of optimizing heterologous protein secretion. This molecular insight has direct implications on engineering a broad range of recombinant proteins for secretion and provides potential hypotheses for the root causes of several secretory-associated diseases.

Enhanced CO2 Adsorption by Nitrogen-Doped Graphene Oxide Sheets (N-GOs Prepared by Employing Polymeric Precursors

Directory of Open Access Journals (Sweden)

Abdulaziz Ali Alghamdi

2018-04-01

Full Text Available Nitrogen-doped graphene oxide sheets (N-GOs are prepared by employing N-containing polymers such as polypyrrole, polyaniline, and copolymer (polypyrrole-polyaniline doped with acids such as HCl, H2SO4, and C6H5-SO3-K, which are activated using different concentrations of KOH and carbonized at 650 °C; characterized using SEM, TEM, BET, TGA-DSC, XRD, and XPS; and employed for the removal of environmental pollutant CO2. The porosity of the N-GOs obtained were found to be in the range 1–3.5 nm when the KOH employed was in the ratio of 1:4, and the XRD confirmed the formation of the layered like structure. However, when the KOH employed was in the ratio of 1:2, the pore diameter was found to be in the range of 50–200 nm. The SEM and TEM analysis reveal the porosity and sheet-like structure of the products obtained. The nitrogen-doped graphene oxide sheets (N-GOs prepared by employing polypyrrole doped with C6H5-SO3-K were found to possess a high surface area of 2870 m2/g. The N-GOs displayed excellent CO2 capture property with the N-GOs; PPy/Ar-1 displayed ~1.36 mmol/g. The precursor employed, the dopant used, and the activation process were found to affect the adsorption property of the N-GOs obtained. The preparation procedure is simple and favourable for the synthesis of N-GOs for their application as adsorbents in greenhouse gas removal and capture.

Directed synthesis of bio-inorganic vanadium oxide composites using genetically modified filamentous phage

International Nuclear Information System (INIS)

Mueller, Michael; Baik, Seungyun; Jeon, Hojeong; Kim, Yuchan; Kim, Jungtae; Kim, Young Jun

2015-01-01

Highlights: • Phage is an excellent seeding for bio-templates for environmentally benign vanadium oxide nanocomposite synthesis. • The synthesized bio-inorganic vanadium oxide showed photodegradation activities. • The fabricated wt phage/vanadium oxide composite exhibited bundle-like structure. • The fabricated RSTB-phage/vanadium oxide composite exhibited a ball with a fiber-like nanostructure. • The virus/vanadium oxide composite could be applied in photocatalysts, sensors and nanoelectronic applications. - Abstract: The growth of crystalline vanadium oxide using a filamentous bacteriophage template was investigated using sequential incubation in a V 2 O 5 precursor. Using the genetic modification of the bacteriophage, we displayed two cysteines that constrained the RSTB-1 peptide on the major coat protein P8, resulting in vanadium oxide crystallization. The phage-driven vanadium oxide crystals with different topologies, microstructures, photodegradation and vanadium oxide composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), quartz microbalance and dissipation (QCM-D) and X-ray photoelectron spectroscopy (XPS). Non-specific electrostatic attraction between a wild-type phage (wt-phage) and vanadium cations in the V 2 O 5 precursor caused phage agglomeration and fiber formation along the length of the viral scaffold. As a result, the addition of recombinant phage (re-phage) in V 2 O 5 precursors formed heterogeneous structures, which led to efficient condensation of vanadium oxide crystal formation in lines, shown by QCM-D analysis. Furthermore, re-phage/V x O x composites showed significantly enhanced photodegradation activities compared with the synthesized wt-phage-V 2 O 5 composite under illumination. This study demonstrates that peptide-mediated vanadium oxide mineralization is governed by a complicated interplay of peptide sequence, local structure, kinetics and the presence of a mineralizing

SPH based modelling of oxide and oxide film formation in gravity die castings

International Nuclear Information System (INIS)

Ellingsen, K; M'Hamdi, M; Coudert, T

2015-01-01

Gravity die casting is an important casting process which has the capability of making complicated, high-integrity components for e.g. the automotive industry. Oxides and oxide films formed during filling affect the cast product quality. The Smoothed particle hydrodynamics (SPH) method is particularly suited to follow complex flows. The SPH method has been used to study filling of a gravity die including the formation and transport of oxides and oxide films for two different filling velocities. A low inlet velocity leads to a higher amount of oxides and oxide films in the casting. The study demonstrates the usefulness of the SPH method for an increased understanding of the effect of different filling procedures on the cast quality. (paper)

Hafnium carbide formation in oxygen deficient hafnium oxide thin films

Energy Technology Data Exchange (ETDEWEB)

Rodenbücher, C. [Forschungszentrum Jülich GmbH, Peter Grünberg Institute (PGI-7), JARA-FIT, 52425 Jülich (Germany); Hildebrandt, E.; Sharath, S. U.; Kurian, J.; Komissinskiy, P.; Alff, L. [Technische Universität Darmstadt, Institute of Materials Science, 64287 Darmstadt (Germany); Szot, K. [Forschungszentrum Jülich GmbH, Peter Grünberg Institute (PGI-7), JARA-FIT, 52425 Jülich (Germany); University of Silesia, A. Chełkowski Institute of Physics, 40-007 Katowice (Poland); Breuer, U. [Forschungszentrum Jülich GmbH, Central Institute for Engineering, Electronics and Analytics (ZEA-3), 52425 Jülich (Germany); Waser, R. [Forschungszentrum Jülich GmbH, Peter Grünberg Institute (PGI-7), JARA-FIT, 52425 Jülich (Germany); RWTH Aachen, Institute of Electronic Materials (IWE 2), 52056 Aachen (Germany)

2016-06-20

On highly oxygen deficient thin films of hafnium oxide (hafnia, HfO{sub 2−x}) contaminated with adsorbates of carbon oxides, the formation of hafnium carbide (HfC{sub x}) at the surface during vacuum annealing at temperatures as low as 600 °C is reported. Using X-ray photoelectron spectroscopy the evolution of the HfC{sub x} surface layer related to a transformation from insulating into metallic state is monitored in situ. In contrast, for fully stoichiometric HfO{sub 2} thin films prepared and measured under identical conditions, the formation of HfC{sub x} was not detectable suggesting that the enhanced adsorption of carbon oxides on oxygen deficient films provides a carbon source for the carbide formation. This shows that a high concentration of oxygen vacancies in carbon contaminated hafnia lowers considerably the formation energy of hafnium carbide. Thus, the presence of a sufficient amount of residual carbon in resistive random access memory devices might lead to a similar carbide formation within the conducting filaments due to Joule heating.

The influences of microwave irradiation and polyol precursor pH on Cu/AC catalyst and its CO oxidation performance

Science.gov (United States)

Chuang, Kui-Hao; Shih, Kaimin; Wey, Ming-Yen

2012-10-01

This study evaluated the effects of microwave irradiation parameters and the pH of the polyol precursor on the morphological features and catalytic performances of Cu/activated carbon (AC) catalysts. Experimental results of carbon monoxide (CO) oxidation indicated that the highest catalytic activity is achieved when the Cu/AC catalyst is prepared with microwave irradiation at 700 W for 60 s. Scanning electron microscopy revealed the presence of beneficial small copper aciculae on the Cu/AC catalyst under such a microwave irradiation scheme. Further investigation of operational parameters found that the performance of Cu/AC catalysts is enhanced by adopting a pH = 12 polyol precursor solution. With the observation that small cube copper ( 16 nm) aggregates form when a pH = 12 polyol precursor solution is used, this study also demonstrated the importance of controlling the morphology of metal nanoparticles on Cu/AC catalysts when using the microwave-assisted polyol method.

The influences of microwave irradiation and polyol precursor pH on Cu/AC catalyst and its CO oxidation performance

International Nuclear Information System (INIS)

Chuang, Kui-Hao; Shih, Kaimin; Wey, Ming-Yen

2012-01-01

This study evaluated the effects of microwave irradiation parameters and the pH of the polyol precursor on the morphological features and catalytic performances of Cu/activated carbon (AC) catalysts. Experimental results of carbon monoxide (CO) oxidation indicated that the highest catalytic activity is achieved when the Cu/AC catalyst is prepared with microwave irradiation at 700 W for 60 s. Scanning electron microscopy revealed the presence of beneficial small copper aciculae on the Cu/AC catalyst under such a microwave irradiation scheme. Further investigation of operational parameters found that the performance of Cu/AC catalysts is enhanced by adopting a pH = 12 polyol precursor solution. With the observation that small cube copper (∼16 nm) aggregates form when a pH = 12 polyol precursor solution is used, this study also demonstrated the importance of controlling the morphology of metal nanoparticles on Cu/AC catalysts when using the microwave-assisted polyol method.

Synthesis engineering of iron oxide raspberry-shaped nanostructures.

Science.gov (United States)

Gerber, O; Pichon, B P; Ihiawakrim, D; Florea, I; Moldovan, S; Ersen, O; Begin, D; Grenèche, J-M; Lemonnier, S; Barraud, E; Begin-Colin, S

2017-01-07

Magnetic porous nanostructures consisting of oriented aggregates of iron oxide nanocrystals display very interesting properties such as a lower oxidation state of magnetite, and enhanced saturation magnetization in comparison with individual nanoparticles of similar sizes and porosity. However, the formation mechanism of these promising nanostructures is not well understood, which hampers the fine tuning of their magnetic properties, for instance by doping them with other elements. Therefore the formation mechanism of porous raspberry shaped nanostructures (RSNs) synthesized by a one-pot polyol solvothermal method has been investigated in detail from the early stages by using a wide panel of characterization techniques, and especially by performing original in situ HR-TEM studies in temperature. A time-resolved study showed the intermediate formation of an amorphous iron alkoxide phase with a plate-like lamellar structure (PLS). Then, the fine investigation of PLS transformation upon heating up to 500 °C confirmed that the synthesis of RSNs involves two iron precursors: the starting one (hydrated iron chlorides) and the in situ formed iron alkoxide precursor which decomposes with time and heating and contributes to the growth step of nanostructures. Such an understanding of the formation mechanism of RSNs is necessary to envision efficient and rational enhancement of their magnetic properties.

From cation to oxide: hydroxylation and condensation of aqueous complexes

International Nuclear Information System (INIS)

Jolivet, J.P.

1997-01-01

Hydroxylation, condensation and precipitation of metal cations in aqueous solution are briefly reviewed. Hydroxylation of aqueous complexes essentially depends on the format charge (oxidation state), the size and the pH of the medium. It is the step allowing the condensation reaction. Depending on the nature of complexes (aqua-hydroxo, oxo-hydroxo), the. mechanism of condensation is different, olation or ox-olation respectively. The first one leads to poly-cations or hydroxides more or less stable against dehydration. The second one leads to poly-anions or oxides. Oligomeric species (poly-cations, poly-anions) are form from charged monomer complexes while the formation of solid phases requires non-charged precursors. Because of their high lability, charged oligomers are never the precursors of solids phases. The main routes for the formation of solid phases from solution are studied with two important and representative elements, Al and Si. For Al 3+ ions, different methods (base addition in solution, thermo-hydrolysis, hydrothermal synthesis) are discussed in relation to the crystal structure of the solid phase obtained. For silicic species condensing by ox-olation, the role of acid or base catalysis on the morphology of gels is studied. The influence of complexing ligands on the processes and on the characteristics of solids (morphology of particles, basic salts and polymetallic oxides formation) is studied. (author)

Nitrogen-doped graphene: effect of graphite oxide precursors and nitrogen content on the electrochemical sensing properties.

Science.gov (United States)

Megawati, Monica; Chua, Chun Kiang; Sofer, Zdenek; Klímová, Kateřina; Pumera, Martin

2017-06-21

Graphene, produced via chemical methods, has been widely applied for electrochemical sensing due to its structural and electrochemical properties as well as its ease of production in large quantity. While nitrogen-doped graphenes are widely studied materials, the literature showing an effect of graphene oxide preparation methods on nitrogen quantity and chemical states as well as on defects and, in turn, on electrochemical sensing is non-existent. In this study, the properties of nitrogen-doped graphene materials, prepared via hydrothermal synthesis using graphite oxide produced by various classical methods using permanganate or chlorate oxidants Staudenmaier, Hummers, Hofmann and Brodie oxidation methods, were studied; the resulting nitrogen-doped graphene oxides were labeled as ST-GO, HU-GO, HO-GO and BR-GO, respectively. The electrochemical oxidation of biomolecules, such as ascorbic acid, uric acid, dopamine, nicotinamide adenine nucleotide and DNA free bases, was carried out using cyclic voltammetry and differential pulse voltammetry techniques. The nitrogen content in doped graphene oxides increased in the order ST-GO graphene followed this trend, as shown in the cyclic voltammograms. This is a very important finding that provides insight into the electrocatalytic effect of N-doped graphene. The nitrogen-doped graphene materials exhibited improved sensitivity over bare glassy carbon for ascorbic acid, uric acid and dopamine detection. These studies will enhance our understanding of the effects of graphite oxide precursors on the electrochemical sensing properties of nitrogen-doped graphene materials.

Formation of methane and nitrous oxide in plants

Science.gov (United States)

Keppler, Frank; Lenhart, Katharina

2017-04-01

and mosses, so called cryptogamic covers, were recently identified to release substantial amounts of nitrous oxide (Lenhart et al. 2015). In this presentation we will give a brief overview of recent observations of aerobic methane formation and nitrous oxide emissions from terrestrial vegetation. Furthermore, we will present new results from laboratory incubation experiments that provide further insights into the formation of methane and nitrous oxide from plants. References: Bruhn, D. et al.: Leaf surface wax is a source of plant methane formation under UV radiation and in the presence of oxygen. Plant Biology 16, 512-516, 2014. Chang, C. et al.: Nitrous Oxide Emission through Plants. Soil Science Society of America Journal 62, 35-38, 1998. Dean, J. V., Harper, J. E.: Nitric oxide and nitrous oxide production by soybean and winged bean during the in vivo nitrate reductase assay. Plant Physiology 82, 718-723, 1986. Keppler, F., Boros, M., Frankenberg, C., Lelieveld, J., McLeod, A., Pirttilä, A. M., Röckmann, T., Schnitzler, J.: Methane formation in aerobic environments, Environmental Chemistry, 6, 459-465, 2009. Lenhart, K. et al.: Nitrous oxide and methane emissions from cryptogamic covers. Global Change Biology 21, 3889-3900, 2015. Pihlatie, M., Ambus, P., Rinne, J., Pilegaard, K., Vesala, T.: Plant-mediated nitrous oxide emissions from beech (Fagus sylvatica) leaves. New Phytologist 168, 93-98, 2005. Wang, Z.-P., Chang, S. X., Chen, H., Han, X.-G.: Widespread non-microbial methane production by organic compounds and the impact of environmental stresses, Earth-Science Reviews, 127, 193-202, 2013.

Analysis and Chemistry of Novel Protein Oxidation Markers in Vivo.

Science.gov (United States)

Henning, Christian; Liehr, Kristin; Girndt, Matthias; Ulrich, Christof; Glomb, Marcus A

2018-05-09

Proteins continually undergo spontaneous oxidation reactions, which lead to changes in structure and function. The quantitative assessment of protein oxidation adducts provides information on the level of exposure to reactive precursor compounds with a high oxidizing potential and reactive oxygen species (ROS). In the present work, we introduce N 6 -(2-hydroxyethyl)lysine as a novel marker based on the ratio of glycolaldehyde and its oxidized form glyoxal. The high analytical potential was proven with a first set of patients undergoing hemodialysis versus healthy controls, in comparison with well-established parameters for oxidative stress. In vitro experiments with N 1 - t-BOC-lysine and N 1 - t-BOC-arginine enlightened the mechanistic relationship of glycolaldehyde and glyoxal. Oxidation was strongly dependent on the catalytic action of the ε-amino moiety of lysine. Investigations on the formation of N 6 -carboxymethyl lysine revealed glycolaldehyde-imine as the more reactive precursor, even though an additional oxidative step is required. As a result, a novel and very effective alternative mechanism was unraveled.

Selenopentathionic and Telluropentathionic Acids as Precursors for Formation of Semiconducting Layers on the Surface of Polyamide

Directory of Open Access Journals (Sweden)

Skirma Zalenkiene

2007-01-01

Full Text Available The layers of copper chalcogenides, which were formed on the surface of semihydrophilic polymer—polyamide 6 (PA using monoselenopentathionic H2SeS4O6 and monotelluropentathionic H2TeS4O6 acids as precursors of chalcogens, were characterized. Fourier transform infrared (FT-IR and UV spectroscopy were used to monitor the effect of chalcogens on the changes in structure of PA corresponding to the concentration of the precursor's solution and an exposure time. The IR spectra of modified PA were completely different from that of the initial PA. Further interaction of chalcogenized PA with copper (II/I salt solution leads to the formation of CuxS, CuxSe, CuxTe, and mixed –CuxS–CuySe and CuxS–CuyTe layers which have different electric transport properties. The surface properties of PA after treatment are studied using AFM and XRD. The electrical resistances of layers with various composition formed over a wide concentration range 0.01–0.5 mol⋅dm−3 of precursor's solution were measured. Variation in the conductivity of layers of Cu–Se–S and Cu–Te–S on the surface of PA shows an evident increase with the increasing of the mass fraction of selenium or tellurium.

Investigation of Chemical Kinetics on Soot Formation Event of n-Heptane Spray Combustion

DEFF Research Database (Denmark)

Pang, Kar Mun; Jangi, Mehdi; Bai, Xue-Song

2014-01-01

. Numerical computation is performed using OpenFOAM and chemistry coordinate mapping (CCM) approach is used to expedite the calculation. Three n-heptane kinetic mechanisms with different chemistry sizes and comprehensiveness in oxidation pathways and soot precursor formation are adopted. The three examined...

Tentative characterization of precursor compounds and co-factors of pigment formation in production of 'wu mi' from Vaccinium bracteatum Thunb. Leaves.

Science.gov (United States)

Fan, Mingcong; Fan, Yihui; Huang, Weiping; Wang, Li; Li, Yan; Qian, Haifeng; Zhang, Hui; Qi, Xiguang

2018-10-01

Vaccinium bracteatum leaves (VBTL) are traditionally used in China to dye rice grains, which assume a deep blue color, named 'Wu mi'. Information on the mechanism of pigment formation is limited. In this study, CIELAB color space parameters were used to represent the color of 'Wu mi'. Precursor compounds of pigments formed during the dyeing process were identified by UPLC Q-TOF MS analysis. The changes in co-factors for pigment formation in VBTL were measured at different growth stages. The L ∗ and b ∗ values of dyed rice increased as the leaves aged, whereas a ∗ values showed irregular changes. Six compounds were tentatively identified as pigment precursors by UPLC Q-TOF MS analysis. The pH and β-glucosidase activity at different growth stages of VBTL were indicated to be crucial co-factors for pigment formation. A tentative hypothesis is presented that iridoid glycosides are hydrolyzed by acids and β-glucosidases to form a dialdehyde structure that binds covalently with amino residues of lysine side chains in rice protein molecules. Copyright © 2018 Elsevier Ltd. All rights reserved.

Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

Directory of Open Access Journals (Sweden)

J. Lee-Taylor

2012-08-01

Full Text Available The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere. Gas phase oxidation schemes are generated for the C8–C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA formation for various preexisting organic aerosol concentration (COA. As expected, simulation results show that (i SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii SOA yield decreases with decreasing COA, (iii SOA production rates increase with increasing COA and (iv the number of oxidation steps (i.e. generations needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA, suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA with large yields. The limitations of the model are discussed.

Rapid synthesis of macrocycles from diol precursors

DEFF Research Database (Denmark)

Wingstrand, Magnus; Madsen, Charlotte Marie; Clausen, Mads Hartvig

2009-01-01

A method for the formation of synthetic macrocycles with different ring sizes from diols is presented. Reacting a simple diol precursor with electrophilic reagents leads to a cyclic carbonate, sulfite or phosphate in a single step in 25-60% yield. Converting the cyclization precursor to a bis-ele...

Precursors for use in vapour and solution phase thermolysis routes to II-VI thin films and nanodispersed oxide materials

International Nuclear Information System (INIS)

Chunggaze, M.

1999-12-01

-7 are formed in the vapour phase from (3) and (4). Compounds (3), (4) and (7) also form significant quantities of diethyl diselenide (EtSe 2 Et), as detected by GC-MS; whereas (5) and (6) do not. A series of precursors with pendant amine functions have also been synthesised in an effort to reduce the degree of association seen in the simple parent diethyl-dithiocarbamates. The preparation of nanocrystalline titanium dioxide and cerium oxide powders, which are used in dye-sensitised photovoltaic cells (Graetzel cells) and as catalysts respectively were prepared by the thermolysis of a series of suitable single source precursor in a thermolysing/passivating solvent such as tri-octyl-phosphine oxide (TOPO). The nano-particulate oxides formed have the unique property of being coated with TOPO and hence are stable in the solid form without leading to aggregation and are re-dispersible in organic solvents. The oxides formed were generally amorphous in nature and required further annealing to induce crystallinity. Other routes to preparing nano-porous titanium dioxide such as aerosol assisted CVD were also used in an attempt to deposit nano-porous films of titanium dioxide. Cerium oxide particles were synthesised at relatively low thermolysis temperatures (200-300 deg C) and were characterised to exist in the fluorite phase (CeO 2 ). The interaction of TOPO with the precursor was found to aid in lowering the thermolysing temperatures as well as favour the growth of the CeO 2 particles. Lowering the thermolysis temperature to 100 deg C allowed for the preparation of the pyramidal Ce 2 O 3 particles. (author)

Solid state {sup 13}C NMR study on the synthesis of graphite oxide from different graphitic precursors; Estudo atravéS de RMN de {sup 13}C no estado sólido sobre a síntese de oxido de grafite utilizando diferentes precursores grafíticos

Energy Technology Data Exchange (ETDEWEB)

Vieira, Mariana A.; Frasson, Carolina Maria R.; Costa, Tainara Luiza G.; Cipriano, Daniel F.; Schettino Junior, Miguel A.; Cunha, Alfredo G.; Freitas, Jair C.C., E-mail: marianaarpini@hotmail.com [Universidade Federal do Espírito Santo (UFES), Vitória, ES (Brazil). Lab. de Materiais Carbonosos e Cerâmicos

2017-10-15

The influence of the structural and microstructural characteristics of graphitic precursors on the production of graphite oxide (GO) is investigated in the present work. Six different graphitic precursors were used to produce GO following a modified Hummers method, namely: natural graphite, commercial lubricant graphite, milled graphite, graphite flakes, high-purity graphite and graphite recycled from Li-ion batteries. The products were characterized by X-ray diffraction (XRD), thermogravimetry, solid-state {sup 13}C nuclear magnetic resonance (NMR) and scanning electron microscopy (SEM). {sup 13}C NMR spectra revealed the presence of epoxy, hydroxyl, carbonyl and lactol groups in the synthesized GOs. However, the oxidation degree of each product was found to be dependent on the average crystallite size (Lc) and particle size of the graphitic precursors, with the best GO samples being produced from the milled graphite and the graphite recycled from ion-Li batteries. These results were rationalized in terms of the structural and microstructural differences among the graphitic precursors, as revealed by the XRD patterns and SEM images, evidencing the importance of the correct choice of the precursor aiming the achievement of a well-developed structure for the GO product. (author)

chemical kinetic study of nitrogen oxides formation in methane flameless combustion

International Nuclear Information System (INIS)

Alvarado T, Pedro N; Cadavid S, Francisco; Mondragon, P Fanor; Ruiz, Wilson

2009-01-01

The present paper deals with the nitrogen oxides formation in a flameless combustion process characterized for using air highly diluted and preheated at high temperatures. The combustion model used in this study was the one dimensional counterflow methane air diffusion flame. The NOx production rate analysis showed that the thermal and prompt mechanisms are the most important for the formation and consumption of NO under dilution conditions for the oxidant in N 2 and combustion products. These mechanisms are related since the starting reaction for NO formation (N2 molecular dissociation) belongs to the prompt mechanism while the NO formation is reported mainly for the thermal mechanism reactions. On the other hand, the NO - NO 2 equilibrium showed that the reaction rates are comparable to that obtained by the thermal and prompt mechanisms, but its global contribution to NO formation are almost insignificant due to the oxidation reaction with radicals HO 2 .

A mechanistic study on templated electrodeposition of one-dimensional TiO2 nanorods and nanotubes using TiOSO4 as a precursor

KAUST Repository

Teo, Gladys Y.

2014-10-01

One-dimensional (1D) TiO2 nanorods and nanotubes have been successfully synthesized by templated electrodeposition within an anodic aluminium oxide membrane (AAM) using an aqueous precursor containing TiOSO 4. The deposition voltages were found to influence the resultant nanostructure of TiO2. Using a precursor of aqueous TiOSO4 at pH 3 maintained at 10 °C, TiO2 nanorods were electrodeposited in the AAM between applied voltages of - 1.4 V to - 1.0 V (vs. Ag/AgCl), while TiO2 nanotubes were obtained at less negative voltages of - 1.0 V to - 0.3 V (vs. Ag/AgCl). Cyclic voltammetry (CV) revealed that nitrate reduction in the voltage range of - 0.3 V to - 1.4 V played an essential role in the formation of TiO2. The mechanism for TiO2 nanotube formation has been elucidated, paving the way for the future tailoring of metal oxide nanostructures by templated electrodeposition. © 2014 Elsevier B.V.

A mechanistic study on templated electrodeposition of one-dimensional TiO2 nanorods and nanotubes using TiOSO4 as a precursor

KAUST Repository

Teo, Gladys Y.; Ryan, Mary P.; Riley, D. Jason

2014-01-01

One-dimensional (1D) TiO2 nanorods and nanotubes have been successfully synthesized by templated electrodeposition within an anodic aluminium oxide membrane (AAM) using an aqueous precursor containing TiOSO 4. The deposition voltages were found to influence the resultant nanostructure of TiO2. Using a precursor of aqueous TiOSO4 at pH 3 maintained at 10 °C, TiO2 nanorods were electrodeposited in the AAM between applied voltages of - 1.4 V to - 1.0 V (vs. Ag/AgCl), while TiO2 nanotubes were obtained at less negative voltages of - 1.0 V to - 0.3 V (vs. Ag/AgCl). Cyclic voltammetry (CV) revealed that nitrate reduction in the voltage range of - 0.3 V to - 1.4 V played an essential role in the formation of TiO2. The mechanism for TiO2 nanotube formation has been elucidated, paving the way for the future tailoring of metal oxide nanostructures by templated electrodeposition. © 2014 Elsevier B.V.

Formation of crystalline InGaO₃(ZnO)n nanowires via the solid-phase diffusion process using a solution-based precursor.

Science.gov (United States)

Guo, Yujie; Van Bilzen, Bart; Locquet, Jean Pierre; Seo, Jin Won

2015-12-11

One-dimensional single crystalline InGaO3(ZnO)n (IGZO) nanostructures have great potential for various electrical and optical applications. This paper demonstrates for the first time, to our knowledge, a non-vacuum route for the synthesis of IGZO nanowires by annealing ZnO nanowires covered with solution-based IGZO precursor. This method results in nanowires with highly periodic IGZO superlattice structure. The phase transition of IGZO precursor during thermal treatment was systematically studied. Transmission electron microscopy studies reveal that the formation of the IGZO structure is driven by anisotropic inter-diffusion of In, Ga, and Zn atoms, and also by the crystallization of the IGZO precursor. Optical measurements using cathodoluminescence and UV-vis spectroscopy confirm that the nanowires consist of the IGZO compound with wide optical band gap and suppressed luminescence.

Single step radiolytic synthesis of iridium nanoparticles onto graphene oxide

International Nuclear Information System (INIS)

Rojas, J.V.; Molina Higgins, M.C.; Toro Gonzalez, M.; Castano, C.E.

2015-01-01

Graphical abstract: - Highlights: • Ir nanoparticles were synthesized through a single step gamma irradiation process. • Homogeneously distributed Ir nanoparticles on graphene oxide are ∼2.3 nm in size. • Ir−O bonds evidenced the interaction of the nanoparticles with the support. - Abstract: In this work a new approach to synthesize iridium nanoparticles on reduced graphene oxide is presented. The nanoparticles were directly deposited and grown on the surface of the carbon-based support using a single step reduction method through gamma irradiation. In this process, an aqueous isopropanol solution containing the iridium precursor, graphene oxide, and sodium dodecyl sulfate was initially prepared and sonicated thoroughly to obtain a homogeneous dispersion. The samples were irradiated with gamma rays with energies of 1.17 and 1.33 MeV emitted from the spontaneous decay of the 60 Co irradiator. The interaction of gamma rays with water in the presence of isopropanol generates highly reducing species homogeneously distributed in the solution that can reduce the Ir precursor down to a zero valence state. An absorbed dose of 60 kGy was used, which according to the yield of reducing species is sufficient to reduce the total amount of precursor present in the solution. This novel approach leads to the formation of 2.3 ± 0.5 nm Ir nanoparticles distributed along the surface of the support. The oxygenated functionalities of graphene oxide served as nucleation sites for the formation of Ir nuclei and their subsequent growth. XPS results revealed that the interaction of Ir with the support occurs through Ir−O bonds.

Elemental composition and oxidation of chamber organic aerosol

Directory of Open Access Journals (Sweden)

P. S. Chhabra

2011-09-01

Full Text Available Recently, graphical representations of aerosol mass spectrometer (AMS spectra and elemental composition have been developed to explain the oxidative and aging processes of secondary organic aerosol (SOA. It has been shown previously that oxygenated organic aerosol (OOA components from ambient and laboratory data fall within a triangular region in the f₄₄ vs. f₄₃ space, where f₄₄ and f₄₃ are the ratios of the organic signal at m/z 44 and 43 to the total organic signal in AMS spectra, respectively; we refer to this graphical representation as the "triangle plot." Alternatively, the Van Krevelen diagram has been used to describe the evolution of functional groups in SOA. In this study we investigate the variability of SOA formed in chamber experiments from twelve different precursors in both "triangle plot" and Van Krevelen domains. Spectral and elemental data from the high-resolution Aerodyne aerosol mass spectrometer are compared to offline species identification analysis and FTIR filter analysis to better understand the changes in functional and elemental composition inherent in SOA formation and aging. We find that SOA formed under high- and low-NO_x conditions occupy similar areas in the "triangle plot" and Van Krevelen diagram and that SOA generated from already oxidized precursors allows for the exploration of areas higher on the "triangle plot" not easily accessible with non-oxidized precursors. As SOA ages, it migrates toward the top of the triangle along a path largely dependent on the precursor identity, which suggests increasing organic acid content and decreasing mass spectral variability. The most oxidized SOA come from the photooxidation of methoxyphenol precursors which yielded SOA O/C ratios near unity. α-pinene ozonolysis and naphthalene photooxidation SOA systems have had the highest degree of mass closure in previous chemical characterization studies and also show the

Effect of diluents on soot precursor formation and temperature in ethylene laminar diffusion flames

KAUST Repository

Abhinavam Kailasanathan, Ranjith Kumar

2013-03-01

Soot precursor species concentrations and flame temperature were measured in a diluted laminar co-flow jet diffusion flame at pressures up to eight atmospheres while varying diluent type. The objective of this study was to gain a better understanding of soot production and oxidation mechanisms, which could potentially lead to a reduction in soot emissions from practical combustion devices. Gaseous samples were extracted from the centerline of an ethylene-air laminar diffusion flame, which was diluted individually with four diluents (argon, helium, nitrogen, and carbon dioxide) to manipulate flame temperature and transport properties. The diluted fuel and co-flow exit velocities (top-hat profiles) were matched at all pressures to minimize shear-layer effects, and the mass fluxes were fixed over the pressure range to maintain constant Reynolds number. The flame temperature was measured using a fine gauge R-type thermocouple at pressures up to four atmospheres. Centerline concentration profiles of major non-fuel hydrocarbons collected via extractive sampling with a quartz microprobe and quantification using GC/MS+FID are reported within. The measured hydrocarbon species concentrations are vary dramatically with pressure and diluent, with the helium and carbon dioxide diluted flames yielding the largest and smallest concentrations of soot precursors, respectively. In the case of C2H2 and C6H6, two key soot precursors, helium diluted flames had concentrations more than three times higher compared with the carbon dioxide diluted flame. The peak flame temperature vary with diluents tested, as expected, with carbon dioxide diluted flame being the coolest, with a peak temperature of 1760K at 1atm, and the helium diluted flame being the hottest, with a peak temperature of 2140K. At four atmospheres, the helium diluted flame increased to 2240K, but the CO2 flame temperature increased more, decreasing the difference to approximately 250K. © 2012 The Combustion Institute.

Biological Superoxide In Manganese Oxide Formation

Science.gov (United States)

Hansel, C.; Learman, D.; Zeiner, C.; Santelli, C. M.

2011-12-01

Manganese (Mn) oxides are among the strongest sorbents and oxidants within the environment, controlling the fate and transport of numerous elements and the degradation of recalcitrant carbon. Both bacteria and fungi mediate the oxidation of Mn(II) to Mn(III/IV) oxides but the genetic and biochemical mechanisms responsible remain poorly understood. Furthermore, the physiological basis for microbial Mn(II) oxidation remains an enigma. We have recently reported that a common marine bacterium (Roseobacter sp. AzwK-3b) oxidizes Mn(II) via reaction with extracellular superoxide (O2-) produced during exponential growth. Here we expand this superoxide-mediated Mn(II) oxidation pathway to fungi, introducing a surprising homology between prokaryotic and eukaryotic metal redox processes. For instance, Stibella aciculosa, a common soil Ascomycete filamentous fungus, precipitates Mn oxides at the base of asexual reproductive structures (synnemata) used to support conidia (Figure 1). This distribution is a consequence of localized production of superoxide (and it's dismutation product hydrogen peroxide, H2O2), leading to abiotic oxidation of Mn(II) by superoxide. Disruption of NADPH oxidase activity using the oxidoreductase inhibitor DPI leads to diminished cell differentiation and subsequent Mn(II) oxidation inhibition. Addition of Cu(II) (an effective superoxide scavenger) leads to a concentration dependent decrease in Mn oxide formation. We predict that due to the widespread production of extracellular superoxide within the fungal and likely bacterial kingdoms, biological superoxide may be an important contributor to the cycling of Mn, as well as other metals (e.g., Hg, Fe). Current and future explorations of the genes and proteins involved in superoxide production and Mn(II) oxidation will ideally lend insight into the physiological and biochemical basis for these processes.

Removal of both N-nitrosodimethylamine and trihalomethanes precursors in a single treatment using ion exchange resins.

Science.gov (United States)

Beita-Sandí, Wilson; Karanfil, Tanju

2017-11-01

Drinking water utilities are relying more than ever on water sources impacted by wastewater effluents. Disinfection/oxidation of these waters during water treatment may lead to the formation of several disinfection by-products, including the probable human carcinogen N-nitrosodimethylamine (NDMA) and the regulated trihalomethanes (THMs). In this study, the potential of ion exchange resins to control both NDMA and THMs precursors in a single treatment is presented. Two ion exchange resins were examined, a cation exchange resin (Plus) to target NDMA precursors and an anion exchange resin (MIEX) for THMs precursors control. We applied the resins, individually and combined, in the treatment of surface and wastewater effluent samples. The treatment with both resins removed simultaneously NDMA (43-85%) and THMs (39-65%) precursors. However, no removal of NDMA precursors was observed in the surface water with low initial NDMA FP (14 ng/L). The removals of NDMA FP and THMs FP with Plus and MIEX resins applied alone were (49-90%) and (41-69%), respectively. These results suggest no interaction between the resins, and thus the feasibility of effectively controlling NDMA and THMs precursors concomitantly. Additionally, the effects of the wastewater impact and the natural attenuation of precursors were studied. The results showed that neither the wastewater content nor the attenuation of the precursor affected the removals of NDMA and THMs precursors. Finally, experiments using a wastewater effluent sample showed that an increase in the calcium concentration resulted in a reduction in the removal of NDMA precursors of about 50%. Copyright © 2017 Elsevier Ltd. All rights reserved.

Silicone Resin Applications for Ceramic Precursors and Composites

Directory of Open Access Journals (Sweden)

Masaki Narisawa

2010-06-01

Full Text Available This article reviews the applications of silicone resins as ceramic precursors. The historical background of silicone synthesis chemistry is introduced to explain the production costs and supply availability of various silicones. Thermal degradation processes of silicones are classified in terms of the main chain structure and cyclic oligomer expulsion process, which determine the resulting ceramic yield and the chemical composition. The high temperature decomposition of Si-O-C beyond 1,400 °C in an inert atmosphere and formation of a protective silica layer on material surfaces beyond 1,200 °C in an oxidative atmosphere are discussed from the viewpoints of the wide chemical composition of the Si-O-C materials. Applications of the resins for binding agents, as starting materials for porous ceramics, matrix sources with impregnation, fiber spinning and ceramic adhesions are introduced. The recent development of the process of filler or cross-linking agent additions to resin compounds is also introduced. Such resin compounds are useful for obtaining thick coatings, MEMS parts and bulk ceramics, which are difficult to obtain by pyrolysis of simple organometallic precursors without additives.

Influence of Pd-precursor on the acetoxylation activity of Pd-Sb/TiO{sub 2} catalysts

Energy Technology Data Exchange (ETDEWEB)

Ben-homeid, A. [Benghazi Univ. (Libyan Arab Jamahiriya). Chemistry Dept.; Kalevaru, V.N.; Radnik, J.; Luecke, B.; Martin, A. [Leibniz-Institut fuer Katalyse e.V. an der Universitaet Rostock (Germany)

2013-11-01

The impact of palladium precursors (e.g. chloride-PdCl{sub 2}; acetate-Pd(OAc){sub 2}; nitrate-Pd(NO{sub 3}){sub 2}) on the catalytic properties of Pd-Sb/TiO{sub 2} catalysts used for acetoxylation of toluene has been investigated. The catalysts were characterized by different techniques such as N{sub 2}-adsorption (BET-surface area and pore volume), XRD, TEM, CO-Chemisorption and XPS for better understanding of the catalytic properties of the catalysts. The acetate and nitrate-type precursors exhibited higher surface areas, pore volumes and higher dispersion of Pd, but displayed poor performance compared to chloride precursor. TEM analysis indicated that the size of Pd particles depended upon the nature of Pd-precursor. Among the three, chloride precursor exhibited bigger Pd particles. XPS results revealed that all the fresh catalysts irrespective of Pd-precursor contained Pd in oxidized state (i.e. Pd{sup +2}), while in the spent catalysts such oxidized Pd species were reduced. The catalytic performance was found to depend strongly on the nature of precursor used. Among the three, the catalysts prepared from chloride-type precursor showed much higher overall catalytic activity (68%) than those of nitrate and/or acetate type precursors. Moreover, these two precursors (acetate and nitrate) gave higher total oxidation products due to oxidative decomposition of mainly acetic acid. Furthermore, the catalyst prepared from Cl-precursor revealed easy deactivation due to coke deposition and also due to loss of Pd in the near-surface-region. (orig.)

Formation of Micro and Mesoporous Amorphous Silica-Based Materials from Single Source Precursors

Directory of Open Access Journals (Sweden)

Mohd Nazri Mohd Sokri

2016-03-01

Full Text Available Polysilazanes functionalized with alkoxy groups were designed and synthesized as single source precursors for fabrication of micro and mesoporous amorphous silica-based materials. The pyrolytic behaviors during the polymer to ceramic conversion were studied by the simultaneous thermogravimetry-mass spectrometry (TG-MS analysis. The porosity of the resulting ceramics was characterized by the N2 adsorption/desorption isotherm measurements. The Fourier transform infrared spectroscopy (FT-IR and Raman spectroscopic analyses as well as elemental composition analysis were performed on the polymer-derived amorphous silica-based materials, and the role of the alkoxy group as a sacrificial template for the micro and mesopore formations was discussed from a viewpoint to establish novel micro and mesoporous structure controlling technologies through the polymer-derived ceramics (PDCs route.

Goat red blood cells as precursor for iron oxide nanocrystal synthesis to develop nuclear targeted lung cancer therapy

Energy Technology Data Exchange (ETDEWEB)

Sreevani, Vellingiri; Shanthi, Krishnamurthy; Kannan, Soundarapandian, E-mail: sk_protein@buc.edu.in

2013-09-01

Graphical abstract: - Highlights: • Molecular approach of synthesis of Fe{sub 2}O{sub 3}-NC using goat blood as a bio-precursor. • The method is simple, efficient and environment friendly. • Synthesized nanocrystals were characterized by UV–vis spectroscopy, XRD, SEM, TEM, DLS and EDS. • Nanocrystals exhibited potent cytotoxicity against A549 cancer cell. • Nuclear targeting with expression of caspase-3, caspase-7 and Bcl-2 in A549 cancer cells. - Abstract: In this study, we synthesised iron oxide nanocrystals (Fe{sub 2}O{sub 3}-NC) from goat blood (bio-precursor) using red blood cells (RBC) lysis method (a molecular level approach) for the first time. The formation of Fe{sub 2}O{sub 3}-NC was achieved through a single-phase chemical reduction method. The size distribution of Fe{sub 2}O{sub 3}-NC falls between 20–30 nm for pellet and 100–200 nm for lysate and were found to be crystalline. Fe{sub 2}O{sub 3}-NC demonstrated significant cytotoxicity on A549. We report the direct visualization of interactions between Fe{sub 2}O{sub 3}-NC and the cancer cell nucleus. The active transport of Fe{sub 2}O{sub 3}-NC to the nucleus induces major changes to nuclear phenotype via nuclear envelope invaginations. We further examined the root cause for the involvement of Fe{sub 2}O{sub 3}-NC on the expression of caspase-3, caspase-7 and Bcl-2 in A549 cancer cells. This functional proteomic analysis clearly implies that the lung cancer cell proliferation is perfectly targeted by the biosynthesised Fe{sub 2}O{sub 3}-NC which could provide new insight for nuclear-targeted cancer therapy.

Research progress in formation mechanism of anodizing aluminum oxide

Science.gov (United States)

Lv, Yudong

2017-12-01

The self-ordering porous anodizing aluminum oxide (AAO) has attracted much attention because of its potential value of application. Valve metals (Al, Ti, Zr etc.) anodic studies have been conducted for more than 80 years, but the mechanism of the formation of hexagonal prismatic cell structure has so far been different. In this paper, the research results of AAO film formation mechanism are reviewed, and the growth models of several AAO films are summarized, including the field-assisted dissolution (FAD), the viscous flow model, the critical current density effect model, the bulk expansion stress model and the steady-state pore growth model and so on. It analyzed the principle of each model and its rationality. This paper will be of great help to reveal the nature of pore formation and self-ordering, and with the hope that through the study of AAO film formation mechanism, the specific effects of various oxidation parameters on AAO film morphology can be obtained.

Precursors of nitrogenous disinfection by-products in drinking water--A critical review and analysis

Energy Technology Data Exchange (ETDEWEB)

Bond, Tom [Department of Civil and Environmental Engineering, Imperial College London, London SW7 2AZ (United Kingdom); Templeton, Michael R.; Graham, Nigel [Department of Civil and Environmental Engineering, Imperial College London, London SW7 2AZ (United Kingdom)

2012-10-15

Highlights: Black-Right-Pointing-Pointer The proportion of N-DBP formation attributable to specific precursors was calculated. Black-Right-Pointing-Pointer Precursor concentrations are typically insufficient to account for observed N-DBP formation, except CNX and NDMA. Black-Right-Pointing-Pointer Amino acid precursors are easier to remove during water treatment than suggested by laboratory studies. - Abstract: In recent years research into the formation of nitrogenous disinfection by-products (N-DBPs) in drinking water - including N-nitrosodimethylamine (NDMA), the haloacetonitriles (HANs), haloacetamides (HAcAms), cyanogen halides (CNX) and halonitromethanes (HNMs) - has proliferated. This is partly due to their high reported toxicity of N-DBPs. In this review paper information about the formation yields of N-DBPs from model precursors, and about environmental precursor occurrence, has been employed to assess the amount of N-DBP formation that is attributable to known precursors. It was calculated that for HANs and HAcAms, the concentrations of known precursors - mainly free amino acids are insufficient to account for the observed concentrations of these N-DBP groups. However, at least in some waters, a significant proportion of CNX and NDMA formation can be explained by known precursors. Identified N-DBP precursors tend to be of low molecular weight and low electrostatic charge relative to bulk natural organic matter (NOM). This makes them recalcitrant to removal by water treatment processes, notably coagulation, as confirmed by a number of bench-scale studies. However, amino acids have been found to be easier to remove during water treatment than would be suggested by the known molecular properties of the individual free amino acids.

Morphology and formation mechanism of ceria nanoparticles by spray pyrolysis

International Nuclear Information System (INIS)

Shih, Shao-Ju; Wu, Ying-Ying; Chen, Chin-Yi; Yu, Chin-Yang

2012-01-01

Ceria-based materials are used in industrial applications such as catalyst supports, carbon monoxide reduction catalysts, and solid oxide fuel cell electrolytes. Various applications require different morphological particles. The ceria particles with various morphologies from the precursors of cerium(III) acetate hydrate, cerium(IV) nitrate hydrate, and cerium(IV) ammonium nitrate were prepared by spray pyrolysis (SP) because SP has the potential for simple and continuous process. The precursor behaviors and the particle morphologies were characterized by thermogravimetric analysis and by transmission electron microscopy. Four main morphologies of solid spherical, hollow spherical with a single pore, hollow concave, and hollow spherical with multiple pores were observed. The experimental results suggest that the morphological formation mechanism is highly correlated with the factors of precursor solubilities, solvent evaporation rates (droplet diameters), and precursor melting temperatures. In addition, total concentrations of cerium(III) in the ceria particles from various precursors were examined using X-ray photoelectron spectroscopy.

Surface Mn(II) oxidation actuated by a multicopper oxidase in a soil bacterium leads to the formation of manganese oxide minerals.

Science.gov (United States)

Zhang, Zhen; Zhang, Zhongming; Chen, Hong; Liu, Jin; Liu, Chang; Ni, Hong; Zhao, Changsong; Ali, Muhammad; Liu, Fan; Li, Lin

2015-06-03

In this manuscript, we report that a bacterial multicopper oxidase (MCO266) catalyzes Mn(II) oxidation on the cell surface, resulting in the surface deposition of Mn(III) and Mn(IV) oxides and the gradual formation of bulky oxide aggregates. These aggregates serve as nucleation centers for the formation of Mn oxide micronodules and Mn-rich sediments. A soil-borne Escherichia coli with high Mn(II)-oxidizing activity formed Mn(III)/Mn(IV) oxide deposit layers and aggregates under laboratory culture conditions. We engineered MCO266 onto the cell surfaces of both an activity-negative recipient and wild-type strains. The results confirmed that MCO266 governs Mn(II) oxidation and initiates the formation of deposits and aggregates. By contrast, a cell-free substrate, heat-killed strains, and intracellularly expressed or purified MCO266 failed to catalyze Mn(II) oxidation. However, purified MCO266 exhibited Mn(II)-oxidizing activity when combined with cell outer membrane component (COMC) fractions in vitro. We demonstrated that Mn(II) oxidation and aggregate formation occurred through an oxygen-dependent biotic transformation process that requires a certain minimum Mn(II) concentration. We propose an approximate electron transfer pathway in which MCO266 transfers only one electron to convert Mn(II) to Mn(III) and then cooperates with other COMC electron transporters to transfer the other electron required to oxidize Mn(III) to Mn(IV).

Analysis of oxide formation induced by UV laser coloration of stainless steel

Energy Technology Data Exchange (ETDEWEB)

Li, Z.L., E-mail: zlli@SIMTech.a-star.edu.sg [Singapore Institute of Manufacturing Technology, 71 Nanyang Drive, 638075 (Singapore); Zheng, H.Y.; Teh, K.M.; Liu, Y.C.; Lim, G.C. [Singapore Institute of Manufacturing Technology, 71 Nanyang Drive, 638075 (Singapore); Seng, H.L.; Yakovlev, N.L. [Institute of Materials Research and Engineering, 3 Research Link, 117602 (Singapore)

2009-12-15

Laser-induced coloration on metal surfaces has important applications in product identification, enhancing styles and aesthetics. The color generation is the result of controlled surface oxidation during laser beam interaction with the metal surfaces. In this study, we aim to obtain in-depth understanding of the oxide formation process when an UV laser beam interacts with stainless steel in air. The oxide layer is analysed by means of optical microscopy, scanning electron microscopy (SEM) and time-of-flight secondary ion mass spectrometer (TOF-SIMS). TOF-SIMS results clearly show the formation of duplex oxide structures. The duplex structure includes an inner layer of Cr oxide solution and an outer layer of Fe oxide solution. The oxide layer thickness increased as the results of Fe diffusion to surface during multiple laser scanning passes.

Analysis of oxide formation induced by UV laser coloration of stainless steel

International Nuclear Information System (INIS)

Li, Z.L.; Zheng, H.Y.; Teh, K.M.; Liu, Y.C.; Lim, G.C.; Seng, H.L.; Yakovlev, N.L.

2009-01-01

Laser-induced coloration on metal surfaces has important applications in product identification, enhancing styles and aesthetics. The color generation is the result of controlled surface oxidation during laser beam interaction with the metal surfaces. In this study, we aim to obtain in-depth understanding of the oxide formation process when an UV laser beam interacts with stainless steel in air. The oxide layer is analysed by means of optical microscopy, scanning electron microscopy (SEM) and time-of-flight secondary ion mass spectrometer (TOF-SIMS). TOF-SIMS results clearly show the formation of duplex oxide structures. The duplex structure includes an inner layer of Cr oxide solution and an outer layer of Fe oxide solution. The oxide layer thickness increased as the results of Fe diffusion to surface during multiple laser scanning passes.

Formation of iron oxides from acid mine drainage and magnetic separation of the heavy metals adsorbed iron oxides

Energy Technology Data Exchange (ETDEWEB)

Kwon, Hee Won; Kim, Jeong Jin; Kim, Young Hun [Andong National University, Andong (Korea, Republic of); Ha, Dong Woo [Korea Electrotechnology Research Institute, Changwon (Korea, Republic of)

2016-03-15

There are a few thousand abandoned metal mines in South Korea. The abandoned mines cause several environmental problems including releasing acid mine drainage (AMD), which contain a very high acidity and heavy metal ions such as Fe, Cu, Cd, Pb, and As. Iron oxides can be formed from the AMD by increasing the solution pH and inducing precipitation. Current study focused on the formation of iron oxide in an AMD and used the oxide for adsorption of heavy metals. The heavy metal adsorbed iron oxide was separated with a superconducting magnet. The duration of iron oxide formation affected on the type of mineral and the degree of magnetization. The removal rate of heavy metal by the adsorption process with the formed iron oxide was highly dependent on the type of iron oxide and the solution pH. A high gradient magnetic separation (HGMS) system successfully separated the iron oxide and harmful heavy metals.

Formation of crystalline InGaO_3(ZnO)_n nanowires via the solid-phase diffusion process using a solution-based precursor

International Nuclear Information System (INIS)

Guo, Yujie; Seo, Jin Won; Bilzen, Bart Van; Locquet, Jean Pierre

2015-01-01

One-dimensional single crystalline InGaO_3(ZnO)_n (IGZO) nanostructures have great potential for various electrical and optical applications. This paper demonstrates for the first time, to our knowledge, a non-vacuum route for the synthesis of IGZO nanowires by annealing ZnO nanowires covered with solution-based IGZO precursor. This method results in nanowires with highly periodic IGZO superlattice structure. The phase transition of IGZO precursor during thermal treatment was systematically studied. Transmission electron microscopy studies reveal that the formation of the IGZO structure is driven by anisotropic inter-diffusion of In, Ga, and Zn atoms, and also by the crystallization of the IGZO precursor. Optical measurements using cathodoluminescence and UV-vis spectroscopy confirm that the nanowires consist of the IGZO compound with wide optical band gap and suppressed luminescence. (paper)

Continuous lengths of oxide superconductors

Science.gov (United States)

Kroeger, Donald M.; List, III, Frederick A.

2000-01-01

A layered oxide superconductor prepared by depositing a superconductor precursor powder on a continuous length of a first substrate ribbon. A continuous length of a second substrate ribbon is overlaid on the first substrate ribbon. Sufficient pressure is applied to form a bound layered superconductor precursor powder between the first substrate ribbon and the second substrate ribbon. The layered superconductor precursor is then heat treated to establish the oxide superconducting phase. The layered oxide superconductor has a smooth interface between the substrate and the oxide superconductor.

Precursors of nitrogenous disinfection by-products in drinking water––A critical review and analysis

International Nuclear Information System (INIS)

Bond, Tom; Templeton, Michael R.; Graham, Nigel

2012-01-01

Highlights: ► The proportion of N-DBP formation attributable to specific precursors was calculated. ► Precursor concentrations are typically insufficient to account for observed N-DBP formation, except CNX and NDMA. ► Amino acid precursors are easier to remove during water treatment than suggested by laboratory studies. - Abstract: In recent years research into the formation of nitrogenous disinfection by-products (N-DBPs) in drinking water – including N-nitrosodimethylamine (NDMA), the haloacetonitriles (HANs), haloacetamides (HAcAms), cyanogen halides (CNX) and halonitromethanes (HNMs) – has proliferated. This is partly due to their high reported toxicity of N-DBPs. In this review paper information about the formation yields of N-DBPs from model precursors, and about environmental precursor occurrence, has been employed to assess the amount of N-DBP formation that is attributable to known precursors. It was calculated that for HANs and HAcAms, the concentrations of known precursors – mainly free amino acids are insufficient to account for the observed concentrations of these N-DBP groups. However, at least in some waters, a significant proportion of CNX and NDMA formation can be explained by known precursors. Identified N-DBP precursors tend to be of low molecular weight and low electrostatic charge relative to bulk natural organic matter (NOM). This makes them recalcitrant to removal by water treatment processes, notably coagulation, as confirmed by a number of bench-scale studies. However, amino acids have been found to be easier to remove during water treatment than would be suggested by the known molecular properties of the individual free amino acids.

Effect of friction on oxidative graphite intercalation and high-quality graphene formation.

Science.gov (United States)

Seiler, Steffen; Halbig, Christian E; Grote, Fabian; Rietsch, Philipp; Börrnert, Felix; Kaiser, Ute; Meyer, Bernd; Eigler, Siegfried

2018-02-26

Oxidative wet-chemical delamination of graphene from graphite is expected to become a scalable production method. However, the formation process of the intermediate stage-1 graphite sulfate by sulfuric acid intercalation and its subsequent oxidation are poorly understood and lattice defect formation must be avoided. Here, we demonstrate film formation of micrometer-sized graphene flakes with lattice defects down to 0.02% and visualize the carbon lattice by transmission electron microscopy at atomic resolution. Interestingly, we find that only well-ordered, highly crystalline graphite delaminates into oxo-functionalized graphene, whereas other graphite grades do not form a proper stage-1 intercalate and revert back to graphite upon hydrolysis. Ab initio molecular dynamics simulations show that ideal stacking and electronic oxidation of the graphite layers significantly reduce the friction of the moving sulfuric acid molecules, thereby facilitating intercalation. Furthermore, the evaluation of the stability of oxo-species in graphite sulfate supports an oxidation mechanism that obviates intercalation of the oxidant.

Strong impacts on aerosol indirect effects from historical oxidant changes

Science.gov (United States)

Hafsahl Karset, Inger Helene; Koren Berntsen, Terje; Storelvmo, Trude; Alterskjær, Kari; Grini, Alf; Olivié, Dirk; Kirkevåg, Alf; Seland, Øyvind; Iversen, Trond; Schulz, Michael

2018-06-01

Uncertainties in effective radiative forcings through aerosol-cloud interactions (ERFaci, also called aerosol indirect effects) contribute strongly to the uncertainty in the total preindustrial-to-present-day anthropogenic forcing. Some forcing estimates of the total aerosol indirect effect are so negative that they even offset the greenhouse gas forcing. This study highlights the role of oxidants in modeling of preindustrial-to-present-day aerosol indirect effects. We argue that the aerosol precursor gases should be exposed to oxidants of its era to get a more correct representation of secondary aerosol formation. Our model simulations show that the total aerosol indirect effect changes from -1.32 to -1.07 W m-2 when the precursor gases in the preindustrial simulation are exposed to preindustrial instead of present-day oxidants. This happens because of a brightening of the clouds in the preindustrial simulation, mainly due to large changes in the nitrate radical (NO3). The weaker oxidative power of the preindustrial atmosphere extends the lifetime of the precursor gases, enabling them to be transported higher up in the atmosphere and towards more remote areas where the susceptibility of the cloud albedo to aerosol changes is high. The oxidation changes also shift the importance of different chemical reactions and produce more condensate, thus increasing the size of the aerosols and making it easier for them to activate as cloud condensation nuclei.

Directed synthesis of bio-inorganic vanadium oxide composites using genetically modified filamentous phage

Energy Technology Data Exchange (ETDEWEB)

Mueller, Michael; Baik, Seungyun [Environmental Safety Group, Korea Institute of Science and Technology Europe (KIST-Europe) Forschungsgesellschaft mbH, Campus E 7 1, Saarbruecken (Germany); Jeon, Hojeong; Kim, Yuchan [Center for Biomaterials, Biomedical Research Institute Korea Institute of Science and Technology (KIST), Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Kim, Jungtae [Environmental Safety Group, Korea Institute of Science and Technology Europe (KIST-Europe) Forschungsgesellschaft mbH, Campus E 7 1, Saarbruecken (Germany); Kim, Young Jun, E-mail: youngjunkim@kist-europe.de [Environmental Safety Group, Korea Institute of Science and Technology Europe (KIST-Europe) Forschungsgesellschaft mbH, Campus E 7 1, Saarbruecken (Germany)

2015-05-15

Highlights: • Phage is an excellent seeding for bio-templates for environmentally benign vanadium oxide nanocomposite synthesis. • The synthesized bio-inorganic vanadium oxide showed photodegradation activities. • The fabricated wt phage/vanadium oxide composite exhibited bundle-like structure. • The fabricated RSTB-phage/vanadium oxide composite exhibited a ball with a fiber-like nanostructure. • The virus/vanadium oxide composite could be applied in photocatalysts, sensors and nanoelectronic applications. - Abstract: The growth of crystalline vanadium oxide using a filamentous bacteriophage template was investigated using sequential incubation in a V{sub 2}O{sub 5} precursor. Using the genetic modification of the bacteriophage, we displayed two cysteines that constrained the RSTB-1 peptide on the major coat protein P8, resulting in vanadium oxide crystallization. The phage-driven vanadium oxide crystals with different topologies, microstructures, photodegradation and vanadium oxide composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), quartz microbalance and dissipation (QCM-D) and X-ray photoelectron spectroscopy (XPS). Non-specific electrostatic attraction between a wild-type phage (wt-phage) and vanadium cations in the V{sub 2}O{sub 5} precursor caused phage agglomeration and fiber formation along the length of the viral scaffold. As a result, the addition of recombinant phage (re-phage) in V{sub 2}O{sub 5} precursors formed heterogeneous structures, which led to efficient condensation of vanadium oxide crystal formation in lines, shown by QCM-D analysis. Furthermore, re-phage/V{sub x}O{sub x} composites showed significantly enhanced photodegradation activities compared with the synthesized wt-phage-V{sub 2}O{sub 5} composite under illumination. This study demonstrates that peptide-mediated vanadium oxide mineralization is governed by a complicated interplay of peptide sequence, local structure

Thin HTSC films produced by a polymer metal precursor technique

Science.gov (United States)

Lampe, L. v.; Zygalsky, F.; Hinrichsen, G.

In precursors the metal ions are combined with acid groups of polymethacrylic acid (PMAA), polyacrylic acid (PAA) or novolac. Compared to thermal degradation temperature of pure polymers those of precursors are low. Precursors films were patterned by UV lithography. Diffractometric investigations showed that the c-axis oriented epitaxial films of YBa 2Cu 3O x and Bi 2Sr 2CaCu 2O x originated from amorphous metal oxide films, which were received after thermal degradation of the precursor. Transition temperatures and current densities were determined by electric resistivity measurements.

Atomic layer deposition precursor step repetition and surface plasma pretreatment influence on semiconductor–insulator–semiconductor heterojunction solar cell

Energy Technology Data Exchange (ETDEWEB)

Talkenberg, Florian, E-mail: florian.talkenberg@ipht-jena.de; Illhardt, Stefan; Schmidl, Gabriele; Schleusener, Alexander; Sivakov, Vladimir [Leibniz Institute of Photonic Technology, Albert-Einstein-Str. 9, D-07745 Jena (Germany); Radnóczi, György Zoltán; Pécz, Béla [Centre for Energy Research, Institute of Technical Physics and Materials Science, Konkoly-Thege Miklós u. 29-33, H-1121 Budapest (Hungary); Dikhanbayev, Kadyrjan; Mussabek, Gauhar [Department of Physics and Engineering, al-Farabi Kazakh National University, 71 al-Farabi Ave., 050040 Almaty (Kazakhstan); Gudovskikh, Alexander [Nanotechnology Research and Education Centre, St. Petersburg Academic University, Russian Academy of Sciences, Hlopina Str. 8/3, 194021 St. Petersburg (Russian Federation)

2015-07-15

Semiconductor–insulator–semiconductor heterojunction solar cells were prepared using atomic layer deposition (ALD) technique. The silicon surface was treated with oxygen and hydrogen plasma in different orders before dielectric layer deposition. A plasma-enhanced ALD process was applied to deposit dielectric Al{sub 2}O{sub 3} on the plasma pretreated n-type Si(100) substrate. Aluminum doped zinc oxide (Al:ZnO or AZO) was deposited by thermal ALD and serves as transparent conductive oxide. Based on transmission electron microscopy studies the presence of thin silicon oxide (SiO{sub x}) layer was detected at the Si/Al{sub 2}O{sub 3} interface. The SiO{sub x} formation depends on the initial growth behavior of Al{sub 2}O{sub 3} and has significant influence on solar cell parameters. The authors demonstrate that a hydrogen plasma pretreatment and a precursor dose step repetition of a single precursor improve the initial growth behavior of Al{sub 2}O{sub 3} and avoid the SiO{sub x} generation. Furthermore, it improves the solar cell performance, which indicates a change of the Si/Al{sub 2}O{sub 3} interface states.

Generalized trends in the formation energies of perovskite oxides

DEFF Research Database (Denmark)

Zeng, Zhenhua; Calle-Vallejo, Federico; Mogensen, Mogens Bjerg

2013-01-01

Generalized trends in the formation energies of several families of perovskite oxides (ABO3) and plausible explanations to their existence are provided in this study through a combination of DFT calculations, solid-state physics analyses and simple physical/chemical descriptors. The studied...... elements at the A site of perovskites comprise rare-earth, alkaline-earth and alkaline metals, whereas 3d and 5d metals were studied at the B site. We also include ReO3-type compounds, which have the same crystal structure of cubic ABO3 perovskites except without A-site elements. From the observations we...... extract the following four conclusions for the perovskites studied in the present paper: for a given cation at the B site, (I) perovskites with cations of identical oxidation state at the A site possess close formation energies; and (II) perovskites with cations of different oxidation states at the A site...

Gas phase precursors to anthropogenic secondary organic aerosol: detailed observations of 1,3,5-trimethylbenzene photooxidation

Directory of Open Access Journals (Sweden)

K. P. Wyche

2009-01-01

Full Text Available A series of photooxidation experiments were conducted in an atmospheric simulation chamber in order to investigate the oxidation mechanism and secondary organic aerosol (SOA formation potential of the model anthropogenic gas phase precursor, 1,3,5-trimethylbenzene. Alongside specific aerosol measurements, comprehensive gas phase measurements, primarily by Chemical Ionisation Reaction Time-of-Flight Mass Spectrometry (CIR-TOF-MS, were carried out to provide detailed insight into the composition and behaviour of the organic components of the gas phase matrix during SOA formation. An array of gas phase organic compounds was measured during the oxidation process, including several previously unmeasured primary bicyclic compounds possessing various functional groups. Analysis of results obtained during this study implies that these peroxide bicyclic species along with a series of ring opening products and organic acids contribute to SOA growth. The effect of varying the VOC/NO_x ratio on SOA formation was explored, as was the effect of acid seeding. It was found that low NO_x conditions favour more rapid aerosol formation and a higher aerosol yield, a result that implies a role for organic peroxides in the nucleation process and SOA growth.

Synthesis and Characterization of Some Alkaline-Earth-Oxide Nanoparticles

Science.gov (United States)

Singh, Jitendra Pal; Lim, Weon Cheol; Won, Sung Ok; Song, Jonghan; Chae, Keun Hwa

2018-04-01

The present work reports the synthesis of MgO and CaO nanoparticles by using the sol-gel autocombustion method. The annealing of the precursor at 1200 °C was observed to lead the formation of MgO nanoparticles having average crystallite size of 31 nm. Annealing the precursor at same temperature produced materials having a CaO phase with a minor impure phase of calcium carbonate ( 3%). The crystallite size corresponding to the CaO phase was 38 nm. A change of thermal history in the precursor was observed not to result in an improvement of the CaO phase. The change of thermal history in the precursor gave rise to mixed phases of CaCO3 and Ca(OH)2 rather than the phase of CaO. Further, annealing at 1200 °C for 12 h resulted in the formation of the CaO phase along with almost 1 - 5% of calcium hydroxide as an impurity phase. X-ray absorption spectroscopic measurements carried out on these materials revealed that the local electronic/atomic structure of these oxides was not only affected by the impurity phases but also influenced by the carbaneous impurities attached to the crystallites.

Preparation of superconductor precursor powders

Science.gov (United States)

Bhattacharya, Raghunath

1998-01-01

A process for the preparation of a precursor metallic powder composition for use in the subsequent formation of a superconductor. The process comprises the steps of providing an electrodeposition bath comprising an electrolyte medium and a cathode substrate electrode, and providing to the bath one or more soluble salts of one or more respective metals which are capable of exhibiting superconductor properties upon subsequent appropriate treatment. The bath is continually energized to cause the metallic and/or reduced particles formed at the electrode to drop as a powder from the electrode into the bath, and this powder, which is a precursor powder for superconductor production, is recovered from the bath for subsequent treatment. The process permits direct inclusion of all metals in the preparation of the precursor powder, and yields an amorphous product mixed on an atomic scale to thereby impart inherent high reactivity. Superconductors which can be formed from the precursor powder include pellet and powder-in-tube products.

Identification of an indigo precursor from leaves of Isatis tinctoria (Woad).

Science.gov (United States)

Maugard, T; Enaud, E; Choisy, P; Legoy, M D

2001-11-01

Indole is presumably a product of indole-3-glycerol phosphate catabolism in Isatis tinctoria. It is oxidized into indoxyl and stored in young leaves as indigo precursor. Further oxidation and dimerization of indoxyl produces indigoid pigments. In this work, we describe an HPLC method dedicated to the identification and quantification of indigoid pigments (indigo, indirubin, isoindigo and isoindirubin) and indigo precursors produced in I. tinctoria (Woad). This work, carried out with two cultivars of I. tinctoria, has confirmed that the quantity of indigo precursors is dependent on the species and the harvest period. In addition we have shown for the first time that young leaves of I. tinctoria, harvested in June contained a new indigo precursor in addition to isatan B (indoxyl-5-ketogluconate) and indican (indoxyl-beta-D-glucoside). We suggest the name "isatan C" for this new indigo precursor in I. tinctoria. Its chemical characteristics point to an dioxindole ester with PM of 395. We have shown that isatan C reacts with isatan B increasing the red pigment production.

Biochemical Removal of HAP Precursors From Coal

Energy Technology Data Exchange (ETDEWEB)

Olson, G.; Tucker, L.; Richards, J.

1997-07-01

This project addresses DOE`s interest in advanced concepts for controlling emissions of air toxics from coal-fired utility boilers. We are determining the feasibility of developing a biochemical process for the precombustion removal of substantial percentages of 13 inorganic hazardous air pollutant (HAP) precursors from coal. These HAP precursors are Sb, As, Be, Cd, Cr, Cl, Co, F, Pb, Hg, Mn, Ni, and Se. Although rapid physical coal cleaning is done routinely in preparation plants, biochemical processes for removal of HAP precursors from coal potentially offer advantages of deeper cleaning, more specificity, and less coal loss. Compared to chemical processes for coal cleaning, biochemical processes potentially offer lower costs and milder process conditions. Pyrite oxidizing bacteria, most notably Thiobacillusferrooxidans, are being evaluated in this project for their ability to remove HAP precursors from U.S. coals.

Biochemical Removal of HAP Precursors From Coal

International Nuclear Information System (INIS)

Olson, G.; Tucker, L.; Richards, J.

1997-07-01

This project addresses DOE's interest in advanced concepts for controlling emissions of air toxics from coal-fired utility boilers. We are determining the feasibility of developing a biochemical process for the precombustion removal of substantial percentages of 13 inorganic hazardous air pollutant (HAP) precursors from coal. These HAP precursors are Sb, As, Be, Cd, Cr, Cl, Co, F, Pb, Hg, Mn, Ni, and Se. Although rapid physical coal cleaning is done routinely in preparation plants, biochemical processes for removal of HAP precursors from coal potentially offer advantages of deeper cleaning, more specificity, and less coal loss. Compared to chemical processes for coal cleaning, biochemical processes potentially offer lower costs and milder process conditions. Pyrite oxidizing bacteria, most notably Thiobacillusferrooxidans, are being evaluated in this project for their ability to remove HAP precursors from U.S. coals

Aluminum doped nickel oxide thin film with improved electrochromic performance from layered double hydroxides precursor in situ pyrolytic route

International Nuclear Information System (INIS)

Shi, Jingjing; Lai, Lincong; Zhang, Ping; Li, Hailong; Qin, Yumei; Gao, Yuanchunxue; Luo, Lei; Lu, Jun

2016-01-01

Electrochromic materials with unique performance arouse great interest on account of potential application values in smart window, low-power display, automobile anti-glare rearview mirror, and e-papers. In this paper, high-performing Al-doped NiO porous electrochromic film grown on ITO substrate has been prepared via a layered double hydroxides(LDHs) precursor in situ pyrolytic route. The Al 3+ ions distributed homogenously within the NiO matrix can significantly influence the crystallinity of Ni-Al LDH and NiO:Al 3+ films. The electrochromic performance of the films were evaluated by means of UV–vis absorption spectroscopy, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronoamperometry(CA) measurements. In addition, the ratio of Ni 3+ /Ni 2+ also varies with Al content which can lead to different electrochemical performances. Among the as-prepared films, NiO film prepared from Ni-Al (19:1) LDH show the best electrochromic performance with a high transparency of 96%, large optical modulation range (58.4%), fast switching speed (bleaching/coloration times are 1.8/4.2 s, respectively) and excellent durability (30% decrease after 2000 cycles). The improved performance was owed to the synergy of large NiO film specific surface area and porous morphology, as well as Al doping stifled the formation of Ni 3+ making bleached state more pure. This LDHs precursor pyrolytic method is simple, low-cost and environmental benign and is feasible for the preparation of NiO:Al and other Al-doped oxide thin film. - Graphical abstract: The ratio of Ni 3+ /Ni 2+ varies with Al content which can lead to different electrochemical performances. Among the as-prepared films, NiO film prepared from Ni-Al (19:1) LDH show the best electrochromic performance with a high transparency of 96%, large optical modulation range, fast switching speed and excellent durability. Display Omitted

Precursor directed synthesis--"molecular" mechanisms in the Soft Chemistry approaches and their use for template-free synthesis of metal, metal oxide and metal chalcogenide nanoparticles and nanostructures.

Science.gov (United States)

Seisenbaeva, Gulaim A; Kessler, Vadim G

2014-06-21

This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials.

Limonene protects osteoblasts against methylglyoxal-derived adduct formation by regulating glyoxalase, oxidative stress, and mitochondrial function.

Science.gov (United States)

Suh, Kwang Sik; Chon, Suk; Choi, Eun Mi

2017-12-25

Methylglyoxal (MG) is a potent protein glycating agent and an important precursor of advanced glycation end products, which are involved in the pathogenesis of diabetic osteopathy. In this study, we investigated the effects of limonene on MG-induced damage in osteoblastic MC3T3-E1 cells. Pretreating cells with limonene prevented MG-induced protein adduct formation, tumor necrosis factor alpha and interleukin-6 release, mitochondrial superoxide production, and cardiolipin peroxidation. In addition, limonene increased glyoxalase I activity, and glutathione and heme oxygenase-1 levels in the presence of MG. Pretreatment with limonene prior to MG exposure reduced MG-induced mitochondrial dysfunction by preventing mitochondrial membrane potential dissipation and adenosine triphosphate loss, and reduced the levels of adenosine monophosphate-activated protein kinase, peroxisome proliferator activated receptor γ coactivator 1α, and nitric oxide. These results demonstrate that limonene may prevent the development of diabetic osteopathy. Copyright © 2017 Elsevier B.V. All rights reserved.

Chemical kinetic models for combustion of hydrocarbons and formation of nitric oxide

Science.gov (United States)

Jachimowski, C. J.; Wilson, C. H.

1980-01-01

The formation of nitrogen oxides NOx during combustion of methane, propane, and a jet fuel, JP-4, was investigated in a jet stirred combustor. The results of the experiments were interpreted using reaction models in which the nitric oxide (NO) forming reactions were coupled to the appropriate hydrocarbon combustion reaction mechanisms. Comparison between the experimental data and the model predictions reveals that the CH + N2 reaction process has a significant effect on NO formation especially in stoichiometric and fuel rich mixtures. Reaction models were assembled that predicted nitric oxide levels that were in reasonable agreement with the jet stirred combustor data and with data obtained from a high pressure (5.9 atm (0.6 MPa)), prevaporized, premixed, flame tube type combustor. The results also suggested that the behavior of hydrocarbon mixtures, like JP-4, may not be significantly different from that of pure hydrocarbons. Application of the propane combustion and nitric oxide formation model to the analysis of NOx emission data reported for various aircraft gas turbines showed the contribution of the various nitric oxide forming processes to the total NOx formed.

Features of the theories of the formation of oxide films on aluminum alloys piston diesel engines with micro-arc oxidation

OpenAIRE

Skryabin M.L.; Smekhova I. N.

2017-01-01

The article considers one of the promising methods of surface hardening of piston aluminum alloy – microarc oxidation. Described fundamental differences from the micro-arc oxidation anodizing and similar electrochemical processes. The schemes of formation of the barrier and outer layers surface treatment in aqueous electrolytes. Shows the mechanism of formation of the interface. Considers the formation of layers with high porosity and method of exposure. Also describes the exponential depende...

Effect of the Milling Time of the Precursors on the Physical Properties of Sprayed Aluminum-Doped Zinc Oxide (ZnO:Al Thin Films

Directory of Open Access Journals (Sweden)

María De La Luz Olvera

2012-08-01

Full Text Available Aluminum doped zinc oxide (ZnO:Al thin films were deposited on soda-lime glass substrates by the chemical spray technique. The atomization of the solution was carried out by ultrasonic excitation. Six different starting solutions from both unmilled and milled Zn and Al precursors, dissolved in a mix of methanol and acetic acid, were prepared. The milling process was carried out using a planetary ball mill at a speed of 300 rpm, and different milling times, namely, 15, 25, 35, 45, and 60 min. Molar concentration, [Al]/[Zn] atomic ratio, deposition temperature and time, were kept at constant values; 0.2 M, 3 at.%, 475 °C, and 10 min, respectively. Results show that, under the same deposition conditions, electrical resistivities of ZnO:Al thin films deposited from milled precursors are lower than those obtained for films deposited from unmilled precursors. X-ray diffraction analysis revealed that all films display a polycrystalline structure, fitting well with the hexagonal wurtzite structure. Changes in surface morphology were observed by scanning electron microscopy (SEM as well, since films deposited from unmilled precursors show triangular shaped grains, in contrast to films deposited from 15 and 35 min milled precursors that display thin slices with hexagonal shapes. The use of milled precursors to prepare starting solutions for depositing ZnO:Al thin films by ultrasonic pyrolysis influences their physical properties.

Iron Oxide Doped Alumina-Zirconia Nanoparticle Synthesis by Liquid Flame Spray from Metal Organic Precursors

Directory of Open Access Journals (Sweden)

Juha-Pekka Nikkanen

2008-01-01

Full Text Available The liquid flame spray (LFS method was used to make iron oxide doped alumina-zirconia nanoparticles. Nanoparticles were generated using a turbulent, high-temperature (Tmax⁡∼3000 K H2-O2 flame. The precursors were aluminium-isopropoxide, zirconium-n-propoxide, and ferrocene in xylene solution. The solution was atomized into micron-sized droplets by high velocity H2 flow and introduced into the flame where nanoparticles were formed. The particle morphology, size, phase, and chemical composition were determined by TEM, XRD, XPS, and N2-adsorption measurements. The collected particulate material consists of micron-sized aggregates with nanosized primary particles. In both doped and undoped samples, tetragonal phase of zirconia was detected in room temperature while alumina was found to be noncrystalline. In the doped powder, Fe was oxidized to Fe2O3. The primary particle size of collected sample was approximately from 6 nm to 40 nm. Doping was observed to increase the specific surface area of the powder from 39 m2/g to 47 m2/g.

Oxidation Products of Biogenic Emissions Contribute to Nucleation of Atmospheric Particles

CERN Document Server

Riccobono, Francesco; Baltensperger, Urs; Worsnop, Douglas R; Curtius, Joachim; Carslaw, Kenneth S; Wimmer, Daniela; Wex, Heike; Weingartner, Ernest; Wagner, Paul E; Vrtala, Aron; Viisanen, Yrjö; Vaattovaara, Petri; Tsagkogeorgas, Georgios; Tomé, Antonio; Stratmann, Frank; Stozhkov, Yuri; Spracklen, Dominick V; Sipilä, Mikko; Praplan, Arnaud P; Petäjä, Tuukka; Onnela, Antti; Nieminen, Tuomo; Mathot, Serge; Makhmutov, Vladimir; Lehtipalo, Katrianne; Laaksonen, Ari; Kvashin, Alexander N.; Kürten, Andreas; Kupc, Agnieszka; Keskinen, Helmi; Kajos, Maija; Junninen, Heikki; Hansel, Armin; Franchin, Alessandro; Flagan, Richard C; Ehrhart, Sebastian; Duplissy, Jonathan; Dunne, Eimear M; Downard, Andrew; David, André; Breitenlechner, Martin; Bianchi, Federico; Amorim, Antonio; Almeida, João; Rondo, Linda; Ortega, Ismael K; Dommen, Josef; Scott, Catherine E; Vrtala, Aron; Santos, Filipe D; Schallhart, Simon; Seinfeld, John H; Sipila, Mikko; Donahue, Neil M; Kirkby, Jasper; Kulmala, Markku

2014-01-01

Atmospheric new-particle formation affects climate and is one of the least understood atmospheric aerosol processes. The complexity and variability of the atmosphere has hindered elucidation of the fundamental mechanism of new-particle formation from gaseous precursors. We show, in experiments performed with the CLOUD (Cosmics Leaving Outdoor Droplets) chamber at CERN, that sulfuric acid and oxidized organic vapors at atmospheric concentrations reproduce particle nucleation rates observed in the lower atmosphere. The experiments reveal a nucleation mechanism involving the formation of clusters containing sulfuric acid and oxidized organic molecules from the very first step. Inclusion of this mechanism in a global aerosol model yields a photochemically and biologically driven seasonal cycle of particle concentrations in the continental boundary layer, in good agreement with observations.

Fatty acid cosubstrates provide β-oxidation precursors for rhamnolipid biosynthesis in Pseudomonas aeruginosa, as evidenced by isotope tracing and gene expression assays.

Science.gov (United States)

Zhang, Lin; Veres-Schalnat, Tracey A; Somogyi, Arpad; Pemberton, Jeanne E; Maier, Raina M

2012-12-01

Rhamnolipids have multiple potential applications as "green" surfactants for industry, remediation, and medicine. As a result, they have been intensively investigated to add to our understanding of their biosynthesis and improve yields. Several studies have noted that the addition of a fatty acid cosubstrate increases rhamnolipid yields, but a metabolic explanation has not been offered, partly because biosynthesis studies to date have used sugar or sugar derivatives as the carbon source. The objective of this study was to investigate the role of fatty acid cosubstrates in improving rhamnolipid biosynthesis. A combination of stable isotope tracing and gene expression assays was used to identify lipid precursors and potential lipid metabolic pathways used in rhamnolipid synthesis when fatty acid cosubstrates are present. To this end, we compared the rhamnolipids produced and their yields using either glucose alone or glucose and octadecanoic acid-d(35) as cosubstrates. Using a combination of sugar and fatty acids, the rhamnolipid yield was significantly higher (i.e., doubled) than when glucose was used alone. Two patterns of deuterium incorporation (either 1 or 15 deuterium atoms) in a single Rha-C(10) lipid chain were observed for octadecanoic acid-d(35) treatment, indicating that in the presence of a fatty acid cosubstrate, both de novo fatty acid synthesis and β-oxidation are used to provide lipid precursors for rhamnolipids. Gene expression assays showed a 200- to 600-fold increase in the expression of rhlA and rhlB rhamnolipid biosynthesis genes and a more modest increase of 3- to 4-fold of the fadA β-oxidation pathway gene when octadecanoic acid was present. Taken together, these results suggest that the simultaneous use of de novo fatty acid synthesis and β-oxidation pathways allows for higher production of lipid precursors, resulting in increased rhamnolipid yields.

From iron(III) precursor to magnetite and vice versa

International Nuclear Information System (INIS)

Gotic, M.; Jurkin, T.; Music, S.

2009-01-01

The syntheses of nanosize magnetite particles by wet-chemical oxidation of Fe 2+ have been extensively investigated. In the present investigation the nanosize magnetite particles were synthesised without using the Fe(II) precursor. This was achieved by γ-irradiation of water-in-oil microemulsion containing only the Fe(III) precursor. The corresponding phase transformations were monitored. Microemulsions (pH ∼ 12.5) were γ-irradiated at a relatively high dose rate of ∼22 kGy/h. Upon 1 h of γ-irradiation the XRD pattern of the precipitate showed goethite and unidentified low-intensity peaks. Upon 6 h of γ-irradiation, reductive conditions were achieved and substoichiometric magnetite (∼Fe 2.71 O 4 ) particles with insignificant amount of goethite particles found in the precipitate. Hydrated electrons (e aq - ), organic radicals and hydrogen gas as radiolytic products were responsible for the reductive dissolution of iron oxide in the microemulsion and the reduction Fe 3+ → Fe 2+ . Upon 18 h of γ-irradiation the precipitate exhibited dual behaviour, it was a more oxidised product than the precipitate obtained after 6 h of γ-irradiation, but it contained magnetite particles in a more reduced form (∼Fe 2.93 O 4 ). It was presumed that the reduction and oxidation processes existed as concurrent competitive processes in the microemulsion. After 18 h of γ-irradiation the pH of the medium shifted from the alkaline to the acidic range. The high dose rate of ∼22 kGy/h was directly responsible for this shift to the acidic range. At a slightly acidic pH a further reduction of Fe 3+ → Fe 2+ resulted in the formation of more stoichiometric magnetite particles, whereas the oxidation conditions in the acidic medium permitted the oxidation Fe 2+ → Fe 3+ . The Fe 3+ was much less soluble in the acidic medium and it hydrolysed and recrystallised as goethite. The γ-irradiation of the microemulsion for 25 h at a lower dose rate of 16 kGy/h produced pure

Iron Oxide Deposition from Aqueous Solution and Iron Formations on Mars

Science.gov (United States)

Catling, David; Moore, Jeff

2000-01-01

Iron formations are ancient, laminated chemical sediments containing at least 15 wt% Fe. We discuss possible mechanisms for their formation in aqueous environments on early Mars. Such iron oxide deposits may be detectable today.

Low temperature formation of CuIn{sub 1−x}Ga{sub x}Se{sub 2} solar cell absorbers by all printed multiple species nanoparticulate Se + Cu-In + Cu-Ga precursors

Energy Technology Data Exchange (ETDEWEB)

Möckel, Stefan A., E-mail: Stefan.A.Moeckel@FAU.de [Department of Materials Science, Chair of Materials for Electronics and Energy Technology, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Martensstr, 7, 91058 Erlangen (Germany); Wernicke, Tobias; Arzig, Matthias; Köder, Philipp [Department of Materials Science, Chair of Materials for Electronics and Energy Technology, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Martensstr, 7, 91058 Erlangen (Germany); Brandl, Marco [Chair for Crystallography and Structural Physics, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Staudtstr. 3, 91058 Erlangen (Germany); Ahmad, Rameez; Distaso, Monica; Peukert, Wolfgang [Institute of Particle Technology, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Cauerstr. 4, 91058 Erlangen (Germany); Hock, Rainer [Chair for Crystallography and Structural Physics, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Staudtstr. 3, 91058 Erlangen (Germany); Wellmann, Peter J. [Department of Materials Science, Chair of Materials for Electronics and Energy Technology, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Martensstr, 7, 91058 Erlangen (Germany)

2015-05-01

In this work an all nanoparticulate precursor for application in Cu(In{sub 1−x}Ga{sub x})Se{sub 2} solar cell absorbers is presented. Binary Cu-In nanoparticles, Cu-Ga powder and elemental Se nanoparticles were mixed in dispersion and deposited on Mo-coated substrates. Research was focused on Cu(In{sub 1−x}Ga{sub x})Se{sub 2} layer formation kinetics, phase composition characterised by differential scanning calorimetry and in-situ X-ray diffraction (XRD). Furthermore phase composition and morphology were studied by ex-situ XRD, Raman spectroscopy and scanning electron microscopy. The results revealed a fast consumption of the precursor and the formation of CuInSe{sub 2} below 340 °C. Binary secondary phases were not observed at any temperature. - Highlights: • All printable precursor for CIGSe • Formation of Ga droplets • Complete consumption below 340 °C.

The effect of inorganic precursors on disinfection byproduct formation during UV-chlorine/chloramine drinking water treatment.

Science.gov (United States)

Lyon, Bonnie A; Dotson, Aaron D; Linden, Karl G; Weinberg, Howard S

2012-10-01

Ultraviolet (UV) disinfection is being increasingly used in drinking water treatment. It is important to understand how its application to different types of water may influence finished water quality, particularly as anthropogenic activity continues to impact the quality of source waters. The objective of this study was to evaluate the effect of inorganic precursors on the formation of regulated and unregulated disinfection byproducts (DBPs) during UV irradiation of surface waters when combined with chlorination or chloramination. Samples were collected from three drinking water utilities supplied by source waters with varying organic and inorganic precursor content. The filtered samples were treated in the laboratory with a range of UV doses delivered from low pressure (LP, UV output at 253.7 nm) and medium pressure (MP, polychromatic UV output 200-400 nm) mercury lamps followed by chlorination or chloramination, in the presence and absence of additional bromide and nitrate. The regulated trihalomethanes and haloacetic acids were not affected by UV pretreatment at disinfection doses (40-186 mJ/cm²). With higher doses (1000 mJ/cm²), trihalomethane formation was increased 30-40%. While most effects on DBPs were only observed with doses much higher than typically used for UV disinfection, there were some effects on unregulated DBPs at lower doses. In nitrate-spiked samples (1-10 mg N/L), chloropicrin formation doubled and increased three- to six-fold with 40 mJ/cm² MP UV followed by chloramination and chlorination, respectively. Bromopicrin formation was increased in samples containing bromide (0.5-1 mg/L) and nitrate (1-10 mg N/L) when pretreated with LP or MP UV (30-60% with 40 mJ/cm² LP UV and four- to ten-fold increase with 40 mJ/cm² MP UV, after subsequent chlorination). The formation of cyanogen chloride doubled and increased three-fold with MP UV doses of 186 and 1000 mJ/cm², respectively, when followed by chloramination in nitrate-spiked samples but

Crystal-free Formation of Non-Oxide Optical Fiber

Science.gov (United States)

Nabors, Sammy A.

2015-01-01

Researchers at NASA Marshall Space Flight Center have devised a method for the creation of crystal-free nonoxide optical fiber preforms. Non-oxide fiber optics are extensively used in infrared transmitting applications such as communication systems, chemical sensors, and laser fiber guides for cutting, welding and medical surgery. However, some of these glasses are very susceptible to crystallization. Even small crystals can lead to light scatter and a high attenuation coefficient, limiting their usefulness. NASA has developed a new method of non-oxide fiber formation that uses axial magnetic fields to suppress crystallization. The resulting non-oxide fibers are crystal free and have lower signal attenuation rates than silica based optical fibers.

PREPARATION OF TANTALUM CARBIDE FROM AN ORGANOMETALLIC PRECURSOR

Directory of Open Access Journals (Sweden)

C. P. SOUZA

1999-03-01

Full Text Available In this work we have synthesized an organometallic oxalic precursor from tantalum oxide. This oxide was solubilized by heating with potassium hydrogen sulfate. In order to precipitate Ta2O5.nH2O, the fused mass obtained was dissolved in a sulfuric acid solution and neutralized with ammonia. The hydrated tantalum oxide precipitated was dissolved in an equimolar solution of oxalic acid/ammonium oxalate. The synthesis and the characterization of the tantalum oxalic precursor are described. Pyrolysis of the complex in a mixture of hydrogen and methane at atmospheric pressure was studied. The gas-solid reaction made it possible to obtain tantalum carbide, TaC, in the powder form at 1000oC. The natural sintering of TaC powder in an inert atmosphere at 1400°C during 10 hours, under inert atmosphere made it possible to densify the carbide to 96% of the theoretical value.

Solution mining and heating by oxidation for treating hydrocarbon containing formations

Science.gov (United States)

Vinegar, Harold J.; Stegemeier, George Leo

2009-06-23

A method for treating an oil shale formation comprising nahcolite includes providing a first fluid to a portion of the formation. A second fluid is produced from the portion. The second fluid includes at least some nahcolite dissolved in the first fluid. A controlled amount of oxidant is provided to the portion of the formation. Hydrocarbon fluids are produced from the formation.

Secondary organic aerosol production from pinanediol, a semi-volatile surrogate for first-generation oxidation products of monoterpenes

Science.gov (United States)

Ye, Penglin; Zhao, Yunliang; Chuang, Wayne K.; Robinson, Allen L.; Donahue, Neil M.

2018-05-01

We have investigated the production of secondary organic aerosol (SOA) from pinanediol (PD), a precursor chosen as a semi-volatile surrogate for first-generation oxidation products of monoterpenes. Observations at the CLOUD facility at CERN have shown that oxidation of organic compounds such as PD can be an important contributor to new-particle formation. Here we focus on SOA mass yields and chemical composition from PD photo-oxidation in the CMU smog chamber. To determine the SOA mass yields from this semi-volatile precursor, we had to address partitioning of both the PD and its oxidation products to the chamber walls. After correcting for these losses, we found OA loading dependent SOA mass yields from PD oxidation that ranged between 0.1 and 0.9 for SOA concentrations between 0.02 and 20 µg m-3, these mass yields are 2-3 times larger than typical of much more volatile monoterpenes. The average carbon oxidation state measured with an aerosol mass spectrometer was around -0.7. We modeled the chamber data using a dynamical two-dimensional volatility basis set and found that a significant fraction of the SOA comprises low-volatility organic compounds that could drive new-particle formation and growth, which is consistent with the CLOUD observations.

Methods of making copper selenium precursor compositions with a targeted copper selenide content and precursor compositions and thin films resulting therefrom

Science.gov (United States)

Curtis, Calvin J [Lakewood, CO; Miedaner, Alexander [Boulder, CO; van Hest, Marinus Franciscus Antonius Maria; Ginley, David S [Evergreen, CO; Leisch, Jennifer [Denver, CO; Taylor, Matthew [West Simsbury, CT; Stanbery, Billy J [Austin, TX

2011-09-20

Precursor compositions containing copper and selenium suitable for deposition on a substrate to form thin films suitable for semi-conductor applications. Methods of forming the precursor compositions using primary amine solvents and methods of forming the thin films wherein the selection of temperature and duration of heating controls the formation of a targeted species of copper selenide.

Strong impacts on aerosol indirect effects from historical oxidant changes

Directory of Open Access Journals (Sweden)

I. H. H. Karset

2018-06-01

Full Text Available Uncertainties in effective radiative forcings through aerosol–cloud interactions (ERFaci, also called aerosol indirect effects contribute strongly to the uncertainty in the total preindustrial-to-present-day anthropogenic forcing. Some forcing estimates of the total aerosol indirect effect are so negative that they even offset the greenhouse gas forcing. This study highlights the role of oxidants in modeling of preindustrial-to-present-day aerosol indirect effects. We argue that the aerosol precursor gases should be exposed to oxidants of its era to get a more correct representation of secondary aerosol formation. Our model simulations show that the total aerosol indirect effect changes from −1.32 to −1.07 W m−2 when the precursor gases in the preindustrial simulation are exposed to preindustrial instead of present-day oxidants. This happens because of a brightening of the clouds in the preindustrial simulation, mainly due to large changes in the nitrate radical (NO3. The weaker oxidative power of the preindustrial atmosphere extends the lifetime of the precursor gases, enabling them to be transported higher up in the atmosphere and towards more remote areas where the susceptibility of the cloud albedo to aerosol changes is high. The oxidation changes also shift the importance of different chemical reactions and produce more condensate, thus increasing the size of the aerosols and making it easier for them to activate as cloud condensation nuclei.

Formation of Amino Acid Precursors by Bombardment of Interstellar Ice Analogs with High Energy Heavy Ions

Science.gov (United States)

Kobayashi, Kensei; Mita, Hajime; Yoshida, Satoshi; Shibata, Hiromi; Enomoto, Shingo; Matsuda, Tomoyuki; Fukuda, Hitoshi; Kondo, Kotaro; Oguri, Yoshiyuki; Kebukawa, Yoko

2016-07-01

A wide variety of organic compounds have been detected in extraterrestrial bodies. It has been recognized that carbonaceous chondrites contain pristine amino acids [1]. There are several scenarios of the formation of such extraterrestrial amino acids or their precursors. Greenberg proposed a scenario that complex organic compounds were formed in interstellar ices in dense clouds, which were brought into solar system small bodies when the solar system was formed [2]. The ice mantles of interstellar dust particles (ISDs) in dense clouds are composed of H2O, CO, CH3OH, CH4, CO2, NH3, etc. In order to verify the scenario, a number of laboratory experiments have been conducted where interstellar ice analogs were irradiated with high-energy particles [3,4] or UV [5,6], and formation of complex organic compounds including amino acid precursors were detected in the products. Though ion-molecular reactions in gaseous phase and surface reactions on the ice mantles have been studied intensively, much less works on cosmic rays-induced reaction have been reported. In order to study possible formation of complex molecules in interstellar ices, frozen mixtures of water, methanol and ammonia with various mixing ratios were irradiated with high-energy heavy ions such as carbon ions (290 MeV/u) and neon ions (400 MeV/u) from HIMAC, NIRS, Japan. For comparison, gaseous mixtures of water, ammonia, carbon monoxide, carbon dioxide, and/or methane were irradiated with protons (2.5 MeV) from a Tandem accelerator, Tokyo Tech, Japan. Amino acids in the products were determined by cation exchange HPLC after acid hydrolysis. Products, both before and after acid hydrolysis, were also characterized by FT-IR and other techniques. Amino acids were detected in the hydrolyzed products after mixture of CH3OH, NH3 and H2O with various mixing ratios were irradiated with heavy ions, including when their mixing ratio was set close to the reported value of the interstellar ices (10:1:37). In the HIMAC

Mesoporous metal oxides and processes for preparation thereof

Energy Technology Data Exchange (ETDEWEB)

Suib, Steven L.; Poyraz, Altug Suleyman

2018-03-06

A process for preparing a mesoporous metal oxide, i.e., transition metal oxide. Lanthanide metal oxide, a post-transition metal oxide and metalloid oxide. The process comprises providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to form the mesoporous metal oxide. A mesoporous metal oxide prepared by the above process. A method of controlling nano-sized wall crystallinity and mesoporosity in mesoporous metal oxides. The method comprises providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to control nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxides. Mesoporous metal oxides and a method of tuning structural properties of mesoporous metal oxides.

Hydrokinetic simulations of nanoscopic precursor films in rough channels

International Nuclear Information System (INIS)

Chibbaro, S; Biferale, L; Binder, K; Milchev, A; Dimitrov, D; Diotallevi, F; Succi, S

2009-01-01

We report on simulations of capillary filling of highly wetting fluids in nanochannels with and without obstacles. We use atomistic (molecular dynamics) and hydrokinetic (lattice Boltzmann; LB) approaches which indicate clear evidence of the formation of thin precursor films, moving ahead of the main capillary front. The dynamics of the precursor films is found to obey a square-root law like that obeyed by the main capillary front, z 2 (t)∝t, although with a larger prefactor, which we find to take the same value for the different geometries (2D–3D) under inspection. The two methods show a quantitative agreement which indicates that the formation and propagation of thin precursors can be handled at a mesoscopic/hydrokinetic level. This can be considered as a validation of the LB method and opens the possibility of using hydrokinetic methods to explore space–time scales and complex geometries of direct experimental relevance. Then, the LB approach is used to study the fluid behaviour in a nanochannel when the precursor film encounters a square obstacle. A complete parametric analysis is performed which suggests that thin-film precursors may have an important influence on the efficiency of nanochannel-coating strategies

CuO reduction induced formation of CuO/Cu2O hybrid oxides

Science.gov (United States)

Yuan, Lu; Yin, Qiyue; Wang, Yiqian; Zhou, Guangwen

2013-12-01

Reduction of CuO nanowires results in the formation of a unique hierarchical hybrid nanostructure, in which the parent oxide phase (CuO) works as the skeleton while the lower oxide (Cu2O) resulting from the reduction reaction forms as partially embedded nanoparticles that decorate the skeleton of the parent oxide. Using in situ transmission electron microscopy observations of the reduction process of CuO nanowires, we demonstrate that the formation of such a hierarchical hybrid oxide structure is induced by topotactic nucleation and growth of Cu2O islands on the parent CuO nanowires.

Small angle X-ray scattering by TiO2/ZrO2 mixed oxide particles and a Synroc precursor

International Nuclear Information System (INIS)

Gazeau, D.; Zemb, T.; Amal, R.; Bartlett, J.

1992-09-01

This high resolution small angle X-ray scattering study of a concentrated oxide sol, precursor of the SYNROC matrix for the storage of the high level radioactive waste, evidences a locally cylindrical microstructure. Locally, nanometric cylinders show disordered axis with some concentration dependent connections. This microstructure explains the paradoxal stability of this oxide dispersions upon the addition of concentrated acidic solutions. This stability has a steric origin and electrostatic repulsions are not needed. The addition of aluminium to the initial titanium-zirconium mixture enhances branching on the locally cylindrical microstructure. Finally, we show that the solid powder obtained after calcination (drying) of the sol has the same specific area (∼ 1000 m 2 /g) than the sol. (Author). 23 refs., 7 figs., 1 tab

Titanium di-oxide films using a less hygroscopic colloidal precursor

Energy Technology Data Exchange (ETDEWEB)

Vandana,, E-mail: vandana1@nplindia.org; Batra, Neha; Kumar, Praveen; Sharma, Pooja; Singh, P.K., E-mail: pksingh@nplindia.org

2014-04-01

We report the study of titanium dioxide films (TiO{sub 2}) using titanium di-isopropoxyl di-2ethyl hexanoate Ti(OC{sub 3}H{sub 7}){sub 2} (C{sub 7}H{sub 15}COO){sub 2} colloidal precursor. This compound is less hygroscopic in nature and easy to use with processes like spin or dip coating. Thin films of TiO{sub 2} are made on silicon substrates and their structural and optical properties are studied. The effect of Ti content in the precursor, sintering temperature and its duration on film thickness and refractive index are investigated. Refractive index shows an increasing trend with the rise in the sintering temperature but remains unchanged with the time. The film thickness decreases with both sintering temperature and time and increases with Ti content in the precursor. Reflectivity measurements show marked reduction in the reflection losses compared to bare silicon surface wherein the film thickness is altered by spin speed. XRD results show anatase phase in the samples sintered at lower temperature (<680 °C), however, a mix of anatase, brookite and rutile phases is seen above this temperature. In the samples sintered above 1100 °C, rutile phase is dominant. These results are supported by the X-ray photoelectron spectroscopy. Atomic force microscopy reveals larger grain size at higher sintering temperature. The titanium dioxide films of desirable thickness and refractive index could be used as an antireflection coating on solar cells. - Highlights: • TiO{sub 2} films are made using titanium di-isopropoxyl di-2ethyl hexanoate precursor. • Effect of Ti content in the precursor, sintering temperature and time is studied. • Refractive index (μ) increases with sintering temperature but is independent of time. • Films of desired thickness and μ could be used as an antireflection coating. • XRD results show that rutile phase dominates in samples sintered above 1100 °C.

Biochemical Removal of HAP Precursors from Coal

Energy Technology Data Exchange (ETDEWEB)

Olson, Gregory J

1997-05-12

Column biooxidation tests with Kentucky coal confirmed results of earlier shake flask tests showing significant removal from the coal of arsenic, selenium, cobalt, manganese, nickel and cadmium. Rates of pyrite biooxidation in Kentucky coal were only slightly more than half the rates found previously for Indiana and Pittsburgh coals. Removal of pyrite from Pittsburgh coal by ferric ion oxidation slows markedly as ferrous ions accumulate in solution, requiring maintenance of high redox potentials in processes designed for removal of pyrite and hazardous air pollutant (HAP) precursors by circulation of ferric solutions through coal. The pyrite oxidation rates obtained in these tests were used by Unifield Engineering to support the conceptual designs for alternative pyrite and HAP precursor bioleaching processes for the phase 2 pilot plant. Thermophilic microorganisms were tested to determine if mercury could be mobilized from coal under elevated growth temperatures. There was no evidence for mercury removal from coal under these conditions. However, the activity of the organisms may have liberated mercury physically. It is also possible that the organisms dissolved mercury and it readsorbed to the clay preferentially. Both of these possibilities are undergoing further testing. The Idaho National Engineering and Environmental Laboratory's (INEEL) slurry column reactor was operated and several batches of feed coal, product coal, waste solids and leach solutions were submitted to LBL for HAP precursor analysis. Results to date indicate significant removal of mercury, arsenic and other HAP precursors in the combined physical-biological process.

Preparation and characterization of sub-20 nm Cu{sub X}@Ag{sub 1} core-shell nanoparticles by changing concentration of silver precursor

Energy Technology Data Exchange (ETDEWEB)

Chee, Sang-Soo; Lee, Jong-Hyun, E-mail: pljh@snut.ac.kr

2017-01-01

Ultrafine Ag-coated Cu (Cu@Ag) nanoparticles (NPs) less than 20 nm in diameter were prepared. After synthesizing ultrafine Cu NPs using a solvothermal method to serve as the core particles, Cu@Ag NPs were fabricated with different initial Ag precursor concentrations, resulting in different thicknesses, densities, and uniformities of Ag shells. The average thickness and density of the Ag shell increased with increasing initial Ag precursor concentration in a Cu:Ag atomic ratio from 6:1 to 1:1. However, excessive Ag precursor concentrations induced homogeneous nucleation and growth of surplus fine pure NPs. Ag dewetting behavior and Cu oxidation in the Cu{sub 4}@Ag{sub 1} NPs were observed, they occurred during heating at 200 and 250 °C, respectively. The electrical resistivities of sintered Cu{sub 4}@Ag{sub 1} films decreased with increasing temperature from 200 to 240 °C. The resistivity after washing the OA and sintering for 60 min at 240 °C in air was measured to be 4.96 × 10{sup −3} Ω cm. The film was sintered in nitrogen using the ink containing non-washed Cu{sub 4}@Ag{sub 1} NPs indicated the lower resistivity of 2.70 × 10{sup −3} Ω cm owing to the non-oxidation atmosphere, although the chemically capped oleylamine in the core-shell NPs hindered the sintering behavior. - Highlights: • Ultrafine Ag-coated Cu nanoparticles less than 20 nm in diameter were fabricated. • Different Ag precursor concentrations influenced thickness and density of Ag shell. • Excessive Ag precursor concentrations induced formation of surplus fine pure NPs. • Ag dewetting behavior and Cu oxidation in Cu{sub 4}@Ag{sub 1} nanoparticles were observed. • Electrical resistivities of sintered Cu{sub 4}@Ag{sub 1} films were 2.70–4.96 × 10{sup −3} Ω cm.

Study of Oxide Formation on Alloy 800 by Potentiostatic Polarization

Energy Technology Data Exchange (ETDEWEB)

Jung, Chong Hun [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Momenib, M.; Wren, C. J. [University of Western Ontario, London (Canada)

2015-10-15

The objectives of study are to investigate the effect of potential on oxide formation and conversion on alloy 800 under potentiostatic conditions. For this study we have focused primarily on corrosion at pH{sub 25.}deg. C8.4. The results presented in Figures 1 show that in the range from -0.8 V{sub SCE} to +0.2 V{sub SCE} there are four potential regions having distinctly different short- and long-term characteristics in the log |i| vs. log t and Q vs. t plots. At a potential below -0.8 V{sub SCE}, the current becomes cathodic immediately (< 10 s) upon polarization, indicating negligible metal oxidation and hence is not of interest. In nuclear power plants, it is used for steam generator tubing in pressurized water reactors (PWRs), including Canadian Deuterium Uranium (CANDU) reactors. However, failures resulting from localized corrosion such as pitting, crevice and stress corrosion cracking (SCC) have been observed in the service environments. There exists still considerable controversy over the type of oxide that can be formed and the mechanism of oxide formation on Alloy 800.

Synthesis of boron nitride nanotubes by an oxide-assisted chemical method

International Nuclear Information System (INIS)

Singhal, S. K.; Srivastava, A. K.; Gupta, Anil K.; Chen, Z. G.

2010-01-01

We report a new method for the synthesis of boron nitride (BN) nanotubes employing a two-step process in which some oxides have found to catalyze the growth of BN nanotubes. In the first step, a precursor containing B-N-O-Fe/Mg was prepared by ball milling a mixture of B, B 2 O 3 , Fe 2 O 3 and MgO (1:7:2:1 mass ratio) in NH 3 for 3 h. BN nanotubes (diameter: 20-100 nm) were grown in the second step from this precursor by isothermal annealing at 1,350 o C in NH 3 for about 4 h. XRD, SEM and HR-TEM studies elucidated the spindle-like morphology of these nanotubes of hexagonal crystal structure. The Raman spectrum showed the peak broadening and shifts to higher frequency. The present method showed that some oxides assisted the growth of BN nanotubes. A possible reaction mechanism on the formation of BN nanotubes in the presence of these oxides is discussed.

Formation and fates of nitrosamines and their formation potentials from a surface water source to drinking water treatment plants in Southern Taiwan.

Science.gov (United States)

Chen, Wei-Hsiang; Wang, Chung-Ya; Huang, Tsung-Hsien

2016-10-01

Nitrosamines are toxic and emerging disinfection byproducts. In this study, three drinking water treatment plants (DWTPs) in southern Taiwan treating the same source water in Gaoping River with comparable technologies were selected. The objective was to evaluate the formation and fates of six nitrosamines and their formation potentials (FPs) from a surface water source to drinking water. Albeit decreased further downstream in the river, four nitrosamine-FPs were observed in the source water due to anthropogenic pollution in the upstream areas. In the DWTPs, nitrosamines were formed and NDMA was the main species. While high organic carbon concentrations indicated elevated nitrosamine-FPs in the source water, NDMA formation in the DWTPs was more positively associated with reductions of water parameters that quantify organic matters with double bonded ring structures. Although precursor removal via pre-oxidation is a viable approach to limit nitrosamine formation during post-disinfection, this study clearly indicates that a great portion of NDMA in treated water has been formed in the 1st oxidation step of drinking water treatment. The pre-oxidation simulations in the lab demonstrated the impact of pre-chlorination on nitrosamine formation. Given the limited removal in conventional treatment processes, avoiding nitrosamine-FPs in sources and/or nitrosamine formation during pre-oxidation become important issues to control the threats of nitrosamines in drinking water. Under current circumstance in which pre-oxidation is widely used to optimize the treatment effectiveness in many DWTPs, its adverse effect by forming nitrosamines needs to be carefully minimized and using technologies other than pre-chlorination (e.g., pre-ozonation) may be considered. Copyright © 2016 Elsevier Ltd. All rights reserved.

A novel route for synthesis and growth formation of metal oxides microspheres: Insights from V_2O_3 microspheres

International Nuclear Information System (INIS)

Zhang, Yifu; Huang, Chi; Meng, Changgong; Hu, Tao

2016-01-01

Highly polydisperse V_2O_3 solid microspheres with large specific surface area were successfully synthesized via a facile hydrothermal decomposition of VOC_2O_4 solution. The morphology and composition were characterized by scanning electron microscopy (SEM), Energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). V_2O_3 microspheres display an obvious Mott phase transition at −128.5 °C (cooling curve) and −114.5 °C (heating curve). Some parameters including the reaction temperature, concentration of VOC_2O_4, reaction time, surfactant, H_2C_2O_4 and precursor were briefly discussed to reveal the formation of V_2O_3 microspheres. It was found that the precursor is crucial for the fabrication of microsphere. A self-assembly growth mechanism was suggested to explain the growth process of microspheres and the autogenic CO and CO_2 gas served as the soft templates. Furthermore, this route was developed to synthesize different metal oxides microspheres, and it was found that AlO(OH), Fe_3O_4, Fe_2O_3, Co_3O_4, Cr_2O_3, MoO_2 and WO_3 microspheres were obtained. All the results showed this process was successfully explored as a methodology to synthesize different metal oxides microspheres using the gas as the templates by this facile hydrothermal route. - Highlights: • Highly uniform V_2O_3 solid microspheres were synthesized. • V_2O_3 microspheres display an obvious Mott phase transition. • The autogenic CO and CO_2 gas served as the soft templates for designed synthesis. • AlO(OH), Fe_3O_4, Fe_2O_3, Co_3O_4, Cr_2O_3, MoO_2 and WO_3 microspheres were obtained. • A methodology to synthesize different metal oxides microspheres was developed.

Contribution of sulfuric acid and oxidized organic compounds to particle formation and growth

Directory of Open Access Journals (Sweden)

F. Riccobono

2012-10-01

Full Text Available Lack of knowledge about the mechanisms underlying new particle formation and their subsequent growth is one of the main causes for the large uncertainty in estimating the radiative forcing of atmospheric aerosols in global models. We performed chamber experiments designed to study the contributions of sulfuric acid and organic vapors to the formation and early growth of nucleated particles. Distinct experiments in the presence of two different organic precursors (1,3,5-trimethylbenzene and α-pinene showed the ability of these compounds to reproduce the formation rates observed in the low troposphere. These results were obtained measuring the sulfuric acid concentrations with two chemical ionization mass spectrometers confirming the results of a previous study which modeled the sulfuric acid concentrations in presence of 1,3,5-trimethylbenzene.

New analysis methods were applied to the data collected with a condensation particle counter battery and a scanning mobility particle sizer, allowing the assessment of the size resolved growth rates of freshly nucleated particles. The effect of organic vapors on particle growth was investigated by means of the growth rate enhancement factor (Γ, defined as the ratio between the measured growth rate in the presence of α-pinene and the kinetically limited growth rate of the sulfuric acid and water system. The observed Γ values indicate that the growth is already dominated by organic compounds at particle diameters of 2 nm. Both the absolute growth rates and Γ showed a strong dependence on particle size, supporting the nano-Köhler theory. Moreover, the separation of the contributions from sulfuric acid and organic compounds to particle growth reveals that the organic contribution seems to be enhanced by the sulfuric acid concentration. Finally, the size resolved growth analysis indicates that both condensation of oxidized organic compounds and reactive uptake contribute to particle growth.

Oxide scale formation of modified FeCrAl coatings exposed to liquid lead

Energy Technology Data Exchange (ETDEWEB)

Fetzer, Renate, E-mail: renate.fetzer@kit.edu [Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe (Germany); Weisenburger, Alfons; Jianu, Adrian; Mueller, Georg [Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe (Germany)

2012-02-15

Highlights: Black-Right-Pointing-Pointer Modified FeCrAl coatings show oxide scale formation when exposed to liquid lead. Black-Right-Pointing-Pointer Formation of thin Al-rich oxide scales is promoted by the presence of Y. Black-Right-Pointing-Pointer FeCrAlY with at least 8 wt.% Al forms thin Al-rich oxide scales. Black-Right-Pointing-Pointer For low Al content, thick multilayer Fe-based oxide scales are found. - Abstract: Modified FeCrAl coatings were studied with respect to their capability to form a thin protective oxide scale in liquid lead environment. They were manufactured by low pressure plasma spraying and GESA surface melting, thereby tuning the Al content. The specimens were exposed for 900 h to liquid lead containing 10{sup -6} and 10{sup -8} wt.% oxygen, respectively, at various temperatures from 400 to 550 Degree-Sign C. Threshold values for an Al content that guarantees the formation of thin protective Al-rich oxide scales are determined, dependent on the respective chromium content, on the presence of yttrium in the modified coating, and on the exposure conditions.

N-nitrosodimethylamine (NDMA) formation at an indirect potable reuse facility.

Science.gov (United States)

Sgroi, Massimiliano; Roccaro, Paolo; Oelker, Gregg L; Snyder, Shane A

2015-03-01

Full-scale experiments to evaluate N-nitrosodimethylamine (NDMA) formation and attenuation were performed within an advanced indirect potable reuse (IPR) treatment system, which includes, sequentially: chloramination for membrane fouling control, microfiltration (MF), reverse osmosis (RO), ultraviolet irradiation with hydrogen peroxide (UV/H₂O₂), final chloramination, and pH stabilization. Results of the study demonstrate that while RO does effectively remove the vast majority of NDMA precursors, RO permeate can still contain significant concentrations of NDMA precursors resulting in additional NDMA formation during chloramination. Thus, it is possible for this advanced treatment system to produce water with NDMA levels higher than regional requirements for potable applications (10 ng/L). The presence of H2O2 during UV oxidation reduced NDMA photolysis efficiency and increased NDMA formation (∼22 ng/L) during the secondary chloramination and lime stabilization. This is likely due to formation of UV/H₂O₂ degradation by-products with higher NDMA formation rate than the parent compounds. However, this effect was diminished with higher UV doses. Bench-scale experiments confirmed an enhanced NDMA formation during chloramination after UV/H2O2 treatment of dimethylformamide, a compound detected in RO permeate and used as model precursor in this study. The effect of pre-ozonation for membrane fouling control on NDMA formation was also evaluated at pilot- (ozone-MF-RO) and bench-scale. Relatively large NDMA formation (117-227 ng/L) occurred through ozone application that was dose dependent, whereas chloramination under typical dosages and contact times of IPR systems resulted in only a relatively small increase of NDMA (∼20 ng/L). Thus, this research shows that NDMA formation within a potable water reuse facility can be challenging and must be carefully evaluated and controlled. Copyright © 2014 Elsevier Ltd. All rights reserved.

NOx emissions trading: Precursor to future growth

International Nuclear Information System (INIS)

Colella, A.

1993-01-01

Title I of the Clean Air Act Amendments (CAAA) of 1990 specified the framework for enhanced regulation in ozone non-attainment areas with increasingly stringent requirements dependent on the area classification - marginal, moderate, serious, severe or extreme. Before the CAAA were passed, only volatile organic compounds (VOCs) were regulated as precursors to ozone formation, Now, by statute, emissions of nitrogen oxides (NO x ) are also regulated as ozone precursor. Under the CAAA, new sources and modifications of existing sources are subject to Title I permitting requirements in ozone non-attainment areas if emissions of NO x and/or VOCs exceed certain triggering levels. For many new or facility expansion projects, especially power generation, the NO x thresholds are easily exceeded thus triggering Title I non-attainment new source review which requires application of control technology to new equipment which results in the Lowest Achievable Emission Rate (LAER), and securing emission reductions either internally or from other major sources to offset the increased emission from the new or modified source. The selection of a LAER technology is generally within an applicant's control. An applicant can determine up-front the engineering and cost considerations associated with LAER technology is assessing a project's viability. However, without a clear source of emission offsets of a means to secure them, assessing project viability could be difficult if not impossible. No available emission offsets means no industrial growth. For sources of NO x undergoing Title I new source review, a regional or state banking system that facilitates NO x emissions trading is needed as a precursor to future growth. This paper presents an overview of EPA's Emissions Trading Policy and Title I new source review offset provisions. Industry's concerns about emissions trading and recommendations for future trading programs are presented

Formation of Oxides in the Interior of Friction Stir Welds

Science.gov (United States)

Schneider, Judy; Chen, Po; Nunes, Arthur C., Jr.

2016-01-01

In friction stir welding (FSWing) the actual solid state joining takes place between the faying surfaces which form the weld seam. Thus the seam trace is often investigated for clues when the strength of the weld is reduced. Aluminum and its alloys are known to form a native, protective oxide on the surface. If these native surface oxides are not sufficiently broken up during the FSW process, they are reported to remain in the FSW interior and weaken the bond strength. This type of weld defect has been referred to as a lazy "S", lazy "Z", joint line defect, kissing bond, or residual oxide defect. Usually these defects are mitigated by modification of the process parameters, such as increased tool rotation rate, which causes a finer breakup of the native oxide particles. This study proposes that there may be an alternative mechanism for formation of oxides found within the weld nugget. As the oxidation rate increases at elevated temperatures above 400ºC, it may be possible for enhanced oxidation to occur on the interior surfaces during the FSW process from entrained air entering the seam gap. Normally, FSWs of aluminum alloys are made without a purge gas and it is unknown how process parameters and initial fit up could affect a potential air path into the interior during the processing. In addition, variations in FSW parameters, such as the tool rotation, are known to have a strong influence on the FSW temperature which may affect the oxidation rate if internal surfaces are exposed to entrained air. A series of FSWs were made in 3 different thickness panels of AA2219 (0.95, 1.27 and 1.56 cm) at 2 different weld pitches. As the thickness of the panels increased, there was an increased tendency for a gap to form in advance of the weld tool. If sufficient air is able to enter the workpiece gap prior to consolidation, the weld temperature can increase the oxidation rate on the interior surfaces. These oxidation rates would also be accelerated in areas of localized

A single source precursor route to group 13 homo- and heterometallic oxides as highly active supports for gold-catalyzed aerobic epoxidation of trans-stilbene

KAUST Repository

Mishra, Shashank K.; Mendez, Violaine; Jeanneau, Erwann; Caps, Valerie; Daniè le, Sté phane

2012-01-01

A new Mitsubishi-type of star-shaped homoleptic derivative of indium(III), In4(mdea)6 (2, mdeaH2 = N-methyldiethanolamine) , was synthesized by the chloro-aminoalkoxo exchange reaction of a heteroleptic complex In6Cl6(mdea)6 (1) and used as a facile single source molecular precursor for the sol-gel preparation of high surface area indium oxide. Successful deposition of gold nanoparticles (1 wt.-%) of average size 3.3 nm on the above metal oxide by using HAuCl4· 3H2O afforded a highly efficient Au/In2O3 catalyst for the aerobic epoxidation of trans-stilbene at low temperature. The above single source precursor approach was further extended to obtain other group 13 homo- and heterometallic oxides, namely, α-Ga2O 3, β-Ga2O3 and Al4Ga 2O9, as highly active supports for gold catalysts. The obtained Au/M2O3 (M = Ga, In) and Au/Al4Ga 2O9 catalysts were thoroughly characterized by using several physicochemical techniques such as XRD, high resolution transmission electron microscopy (HR-TEM), energy-dispersive X-ray (EDX) spectroscopy, and X-ray photoelectron spectroscopy (XPS). A comparative study of the above catalysts for the model aerobic oxidation of stilbene in methylcyclohexane was undertaken. Highly efficient catalysts for aerobic oxidation reactions were obtained by depositing gold nanoparticles on group 13 mono- or mixed metal oxides prepared from the hydrolysis of well-characterized homo- and heterometallic N-methyldiethanolaminate derivatives. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A single source precursor route to group 13 homo- and heterometallic oxides as highly active supports for gold-catalyzed aerobic epoxidation of trans-stilbene

KAUST Repository

Mishra, Shashank K.

2012-12-14

A new Mitsubishi-type of star-shaped homoleptic derivative of indium(III), In4(mdea)6 (2, mdeaH2 = N-methyldiethanolamine) , was synthesized by the chloro-aminoalkoxo exchange reaction of a heteroleptic complex In6Cl6(mdea)6 (1) and used as a facile single source molecular precursor for the sol-gel preparation of high surface area indium oxide. Successful deposition of gold nanoparticles (1 wt.-%) of average size 3.3 nm on the above metal oxide by using HAuCl4· 3H2O afforded a highly efficient Au/In2O3 catalyst for the aerobic epoxidation of trans-stilbene at low temperature. The above single source precursor approach was further extended to obtain other group 13 homo- and heterometallic oxides, namely, α-Ga2O 3, β-Ga2O3 and Al4Ga 2O9, as highly active supports for gold catalysts. The obtained Au/M2O3 (M = Ga, In) and Au/Al4Ga 2O9 catalysts were thoroughly characterized by using several physicochemical techniques such as XRD, high resolution transmission electron microscopy (HR-TEM), energy-dispersive X-ray (EDX) spectroscopy, and X-ray photoelectron spectroscopy (XPS). A comparative study of the above catalysts for the model aerobic oxidation of stilbene in methylcyclohexane was undertaken. Highly efficient catalysts for aerobic oxidation reactions were obtained by depositing gold nanoparticles on group 13 mono- or mixed metal oxides prepared from the hydrolysis of well-characterized homo- and heterometallic N-methyldiethanolaminate derivatives. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

NO ICE HYDROGENATION: A SOLID PATHWAY TO NH2OH FORMATION IN SPACE

International Nuclear Information System (INIS)

Congiu, Emanuele; Dulieu, François; Chaabouni, Henda; Baouche, Saoud; Lemaire, Jean Louis; Fedoseev, Gleb; Ioppolo, Sergio; Lamberts, Thanja; Linnartz, Harold; Laffon, Carine; Parent, Philippe; Cuppen, Herma M.

2012-01-01

Icy dust grains in space act as catalytic surfaces onto which complex molecules form. These molecules are synthesized through exothermic reactions from precursor radicals and, mostly, hydrogen atom additions. Among the resulting products are species of biological relevance, such as hydroxylamine—NH 2 OH—a precursor molecule in the formation of amino acids. In this Letter, laboratory experiments are described that demonstrate NH 2 OH formation in interstellar ice analogs for astronomically relevant temperatures via successive hydrogenation reactions of solid nitric oxide (NO). Inclusion of the experimental results in an astrochemical gas-grain model proves the importance of a solid-state NO+H reaction channel as a starting point for prebiotic species in dark interstellar clouds and adds a new perspective to the way molecules of biological importance may form in space.

Oxidation products of biogenic emissions contribute to nucleation of atmospheric particles.

Science.gov (United States)

Riccobono, Francesco; Schobesberger, Siegfried; Scott, Catherine E; Dommen, Josef; Ortega, Ismael K; Rondo, Linda; Almeida, João; Amorim, Antonio; Bianchi, Federico; Breitenlechner, Martin; David, André; Downard, Andrew; Dunne, Eimear M; Duplissy, Jonathan; Ehrhart, Sebastian; Flagan, Richard C; Franchin, Alessandro; Hansel, Armin; Junninen, Heikki; Kajos, Maija; Keskinen, Helmi; Kupc, Agnieszka; Kürten, Andreas; Kvashin, Alexander N; Laaksonen, Ari; Lehtipalo, Katrianne; Makhmutov, Vladimir; Mathot, Serge; Nieminen, Tuomo; Onnela, Antti; Petäjä, Tuukka; Praplan, Arnaud P; Santos, Filipe D; Schallhart, Simon; Seinfeld, John H; Sipilä, Mikko; Spracklen, Dominick V; Stozhkov, Yuri; Stratmann, Frank; Tomé, Antonio; Tsagkogeorgas, Georgios; Vaattovaara, Petri; Viisanen, Yrjö; Vrtala, Aron; Wagner, Paul E; Weingartner, Ernest; Wex, Heike; Wimmer, Daniela; Carslaw, Kenneth S; Curtius, Joachim; Donahue, Neil M; Kirkby, Jasper; Kulmala, Markku; Worsnop, Douglas R; Baltensperger, Urs

2014-05-16

Atmospheric new-particle formation affects climate and is one of the least understood atmospheric aerosol processes. The complexity and variability of the atmosphere has hindered elucidation of the fundamental mechanism of new-particle formation from gaseous precursors. We show, in experiments performed with the CLOUD (Cosmics Leaving Outdoor Droplets) chamber at CERN, that sulfuric acid and oxidized organic vapors at atmospheric concentrations reproduce particle nucleation rates observed in the lower atmosphere. The experiments reveal a nucleation mechanism involving the formation of clusters containing sulfuric acid and oxidized organic molecules from the very first step. Inclusion of this mechanism in a global aerosol model yields a photochemically and biologically driven seasonal cycle of particle concentrations in the continental boundary layer, in good agreement with observations. Copyright © 2014, American Association for the Advancement of Science.

Formation of jarosite during Fe{sup 2+} oxidation by Acidithiobacillus ferrooxidans

Energy Technology Data Exchange (ETDEWEB)

Daoud, J.; Karamanev, D. [University of Western Ontario, London, ON (Canada). Dept. of Chemical & Biochemical Engineering

2006-07-15

Jarosite precipitation is a very important phenomenon that is observed in many bacterial cultures. In many applications involving Acidithiobacillus ferrooxidans, like coal desulphurization and bioleaching, it is crucial to minimize jarosite formation in order to increase efficiency. The formation of jarosite during the oxidation of ferrous iron by free suspended cells of A. ferrooxidans was studied. The process was studied as a function of time, pH and temperature. The main parameter affecting the jarosite formation was pH. Several experiments yielded results showing oxidation rates as high as 0.181-0.194 g/L h, with low jarosite precipitation of 0.0125-0.0209 g at conditions of pH 1.6-1.7 with an operating temperature of 35{sup o} C.

Nanogravimetric studies of tungsten oxide thin films obtained by the polymeric precursor method

International Nuclear Information System (INIS)

Fernandes, V.C.; Santos, M.C.; Bulhoes, L.O.S.

2007-01-01

In this work, the intercalation/de-intercalation process of Li + ions in the tungsten oxide matrix was investigated. The reaction mechanism involved was also investigated. The WO 3 films, prepared by the polymeric precursor method, were deposited on a Pt covered quartz crystal using the dip-coating technique. The electrolyte was 0.1 mol L -1 LiClO 4 in acetonitrile. The morphology and structure of the deposit was accomplished by scanning electron microscopy and X-ray diffraction, respectively. In the electrochemical quartz crystal nanobalance results, it was observed that the mass transport as well as the kinetic processes involved are facilitated in the films cycled at lower potential sweep-rates. The mass variation data as a function of the charge variations in the anodic and cathodic regions indicate the participation of solvent molecules (acetonitrile) during the Li + ion intercalation/de-intercalation process. This was confirmed by the development of a model of the species flux as a function of the potential

Hydrous Ferric Oxides in Sediment Catalyze Formation of Reactive Oxygen Species during Sulfide Oxidation

Directory of Open Access Journals (Sweden)

Sarah A. Murphy

2016-11-01

Full Text Available Abstract: This article describes the formation of reactive oxygen species as a result of the oxidation of dissolved sulfide by Fe(III-containing sediments suspended in oxygenated seawater over the pH range 7.00 and 8.25. Sediment samples were obtained from across the coastal littoral zone in South Carolina, US, at locations from the beach edge to the forested edge of a Spartina dominated estuarine salt marsh and suspended in aerated seawater. Reactive oxygen species (superoxide and hydrogen peroxide production was initiated in sediment suspensions by the addition of sodium bisulfide. The subsequent loss of HS-, formation of Fe(II (as indicated by Ferrozine, and superoxide and hydrogen peroxide were monitored over time. The concentration of superoxide rose from the baseline and then persisted at an apparent steady state concentration of approximately 500 nanomolar at pH 8.25 and 200 nanomolar at pH 7.00 respectively until >97% hydrogen sulfide was consumed. Measured superoxide was used to predict hydrogen peroxide yield based on superoxide dismutation. Dismutation alone quantitatively predicted hydrogen peroxide formation at pH 8.25 but over predicted hydrogen peroxide formation at pH 7 by a factor of approximately 102. Experiments conducted with episodic spikes of added hydrogen peroxide indicated rapid hydrogen peroxide consumption could account for its apparent low instantaneous yield, presumably the result of its reaction with Fe(II species, polysulfides or bisulfite. All sediment samples were characterized for total Fe, Cu, Mn, Ni, Co and hydrous ferric oxide by acid extraction followed by mass spectrometric or spectroscopic characterization. Sediments with the highest loadings of hydrous ferric oxide were the only sediments that produced significant dissolved Fe(II species or ROS as a result of sulfide exposure.

Crystal size effect on the electrochemical oxidation of formate on carbon-supported palladium nanoparticles

International Nuclear Information System (INIS)

Santos, Rayana Marcela Izidoro da Silva; Nakazato, Roberto Zenhei; Ciapina, Eduardo Goncalves

2016-01-01

Full text: The electrochemical oxidation of formate in alkaline electrolytes has emerged an a promising anodic reaction in the Direct Formate Fuel Cells[1]. Although palladium is considered to be one of the best electro catalyst for the oxidation of formate, important structure-activity relationships are still not understood. In the present work, we investigated the effect of the size of the palladium crystals in the electrochemical oxidation of formate in 0.1 mol L -1 KOH. Carbon-supported palladium nanoparticles (Pd/C) were prepared by chemical reduction of palladium (II) chloride in aqueous media by sodium borohydride in the presence of varying quantities of sodium citrate in the reaction media to obtain metallic crystals with distinct sizes. Analysis of the X-ray diffraction profile revealed the presence of palladium crystals in the range of 6 to 19 nm. Potentiostatic oxidation of formate on the distinct Pd/C samples revealed a volcano-like dependence of the specific activity with the size of the palladium crystals, presenting the highest activity for crystals around 7.5 nm. Reference: [1] A.M. Bartrom, J.L. Haan, The direct formate fuel cell with an alkaline anion exchange membrane, J. Power Sources. 214 (2012) 68-74. (author)

Weld oxide formation on lean duplex stainless steel

Energy Technology Data Exchange (ETDEWEB)

Westin, E.M. [Outokumpu Stainless, Avesta Research Centre, P.O. Box 74, SE-774 22 Avesta (Sweden)], E-mail: elin.westin@outokumpu.com; Olsson, C.-O.A. [Outokumpu Stainless, Avesta Research Centre, P.O. Box 74, SE-774 22 Avesta (Sweden); Hertzman, S. [Outokumpu Stainless Research Foundation, Brinellvaegen 23, SE-100 44 Stockholm (Sweden)

2008-09-15

Weld oxides have a strong influence on corrosion resistance, but have hitherto only been studied to a limited extent for duplex stainless steels. X-ray photoelectron spectroscopy (XPS) has here been used to study heat tint formed on gas tungsten arc (GTA) welds on the commercial duplex grades LDX 2101 (EN 1.4162/UNS S32101) and 2304 (EN 1.4362/UNS S32304) welded with and without nitrogen additions to the shielding gas. The process of heat tint formation is discussed in terms of transport phenomena to explain the effect of atmosphere, temperature and composition. The oxides formed were found to be enriched in manganese and corrosion testing shows that nitrogen has a strong influence on the weld oxide. A mechanism is proposed including evaporation from the weld pool and subsequent redeposition.

Weld oxide formation on lean duplex stainless steel

International Nuclear Information System (INIS)

Westin, E.M.; Olsson, C.-O.A.; Hertzman, S.

2008-01-01

Weld oxides have a strong influence on corrosion resistance, but have hitherto only been studied to a limited extent for duplex stainless steels. X-ray photoelectron spectroscopy (XPS) has here been used to study heat tint formed on gas tungsten arc (GTA) welds on the commercial duplex grades LDX 2101 (EN 1.4162/UNS S32101) and 2304 (EN 1.4362/UNS S32304) welded with and without nitrogen additions to the shielding gas. The process of heat tint formation is discussed in terms of transport phenomena to explain the effect of atmosphere, temperature and composition. The oxides formed were found to be enriched in manganese and corrosion testing shows that nitrogen has a strong influence on the weld oxide. A mechanism is proposed including evaporation from the weld pool and subsequent redeposition

Flame Synthesis of Composite Oxides for Catalytic Applications

DEFF Research Database (Denmark)

Jensen, Joakim Reimer

2002-01-01

gas (CO/CO2/H2) and an excellent thermal stability. Addition of alumina as a structural promoter is necessary in order to obtain a high activity for methanol formation. The binary systems, i.e., CuO/ZnO, ZnO/Al2O3 and CuO/Al2O3 are investigated as a prelude to the preparation of the ternary catalyst...... the flame temperature, the high temperature residence time and the precursor concentration. The Cu/ZnO/Al2O3 methanol catalyst is used as a model system for the preparation of catalytic materials. The flame synthesized catalyst exhibits a high and reproducible activity for methanol formation from synthesis...... crystallites is oxidized. A number of complications may arise using the N2O-titration. It may be difficult to obtain full oxidation of the copper surface without having some oxidation of the bulk. Secondly, some sintering of the nano-sized copper crystallites may occur due to the exothermic nature...

Crystal structure of human lysyl oxidase-like 2 (hLOXL2) in a precursor state.

Science.gov (United States)

Zhang, Xi; Wang, Qifan; Wu, Jianping; Wang, Jiawei; Shi, Yigong; Liu, Minhao

2018-04-10

Lysyl oxidases (LOXs), a type of copper- and lysyl tyrosylquinone (LTQ) -dependent amine oxidase, catalyze the oxidative deamination of lysine residues of extracellular matrix (ECM) proteins such as elastins and collagens and generate aldehyde groups. The oxidative deamination of lysine represents the foundational step for the cross-linking of elastin and collagen and thus is crucial for ECM modeling. Despite their physiological significance, the structure of this important family of enzymes remains elusive. Here we report the crystal structure of human lysyl oxidase-like 2 (hLOXL2) at 2.4-Å resolution. Unexpectedly, the copper-binding site of hLOXL2 is occupied by zinc, which blocks LTQ generation and the enzymatic activity of hLOXL2 in our in vitro assay. Biochemical analysis confirms that copper loading robustly activates hLOXL2 and supports LTQ formation. Furthermore, the LTQ precursor residues in the structure are distanced by 16.6 Å, corroborating the notion that the present structure may represent a precursor state and that pronounced conformational rearrangements would be required for protein activation. The structure presented here establishes an important foundation for understanding the structure-function relationship of LOX proteins and will facilitate LOX-targeting drug discovery. Copyright © 2018 the Author(s). Published by PNAS.

Facile solid-state synthesis of oxidation-resistant metal nanoparticles at ambient conditions

Science.gov (United States)

Lee, Kyu Hyung; Jung, Hyuk Joon; Lee, Ju Hee; Kim, Kyungtae; Lee, Byeongno; Nam, Dohyun; Kim, Chung Man; Jung, Myung-Hwa; Hur, Nam Hwi

2018-05-01

A simple and scalable method for the synthesis of metal nanoparticles in the solid-state was developed, which can produce nanoparticles in the absence of solvents. Nanoparticles of coinage metals were synthesized by grinding solid hydrazine and the metal precursors in their acetates and oxides at 25 °C. The silver and gold acetates converted completely within 6 min into Ag and Au nanoparticles, respectively, while complete conversion of the copper acetate to the Cu sub-micrometer particles took about 2 h. Metal oxide precursors were also converted into metal nanoparticles by grinding alone. The resulting particles exhibit distinctive crystalline lattice fringes, indicating the formation of highly crystalline phases. The Cu sub-micrometer particles are better resistant to oxidation and exhibit higher conductivity compared to conventional Cu nanoparticles. This solid-state method was also applied for the synthesis of platinum group metals and intermetallic Cu3Au, which can be further extended to synthesize other metal nanoparticles.

Generation and confinement of mobile charges in buried oxide of SOI substrates

International Nuclear Information System (INIS)

Gruber, O.; Krawiec, S.; Musseau, O.; Paillet, Ph.; Courtot-Descharles, A.

1999-01-01

We analyze the mechanisms of generation and confinement of mobile protons resulting from hydrogen annealing of SOI buried oxides. This study of the mechanisms of generation and confinement of mobile protons in the buried oxide of SOI wafers emphasizes the importance of H+ diffusion in the oxide in the formation of a mobile charge. Under specific electric field conditions the irradiation of these devices results in a pinning of this mobile charge at the bottom Si-SiO 2 interface. Ab initio calculations are in progress to investigate the possible precursor defects in the oxide and detail the mechanism for mobile proton generation and confinement. (authors)

Formation of oxide-trapped charges in 6H-SiC MOS structures

Energy Technology Data Exchange (ETDEWEB)

Yoshikawa, Masahito; Ohshima, Takeshi; Itoh, Hisayoshi; Nashiyama, Isamu [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan). Takasaki Radiation Chemistry Research Establishment; Okumura, Hajime; Yoshida, Sadafumi

1997-03-01

The silicon and the carbon faces of hexagonal silicon carbide (6H-SiC) substrates were oxidized pyrogenically at 1100degC, and the metal-oxide-semiconductor structures were formed on these faces. The MOS capacitors developed using the silicon and the carbon faces were irradiated with {sup 60}Co gamma-rays under argon atmosphere at room temperature. The bias voltages with the different polarity were applied to the gate electrode during irradiation to examine the formation mechanisms of the trapped charges in the oxides of these MOS capacitors. The amount of the trapped charges in the oxide were obtained from capacitance pulse voltage characteristics. The generation of the trapped charges are affects with not only the absorbed dose but also the bias polarity applied to the gate electrodes during irradiation. The formation mechanisms of the trapped charges in the oxides were estimated in conjunction with the surface orientation of 6H-SiC substrates. (author)

Comparison of N-nitrosodimethylamine formation mechanisms from dimethylamine during chloramination and ozonation: A computational study

Energy Technology Data Exchange (ETDEWEB)

Liu, Yong Dong, E-mail: ydliu@bjut.edu.cn; Zhong, Rugang

2017-01-05

Highlights: • NDMA formation mechanisms from dimethylamine in chloramination/ozonation were reinvestigated by G4 method. • The reactivity order of halo-/hydroxyl-amines reacting with dimethylamine is NHCl{sub 2} ∼ NHBrCl > NH{sub 2}Cl >> NH{sub 2}OH. • Nitrene compound is an important intermediate to form NDMA in oxidation reaction. • Oxidation of unsymmetrical dimethylhydrazine by O{sub 2} is significantly less feasible compared to that by O{sub 3}. • The amines containing the second nitrogen source are potential NDMA precursors in ozonation. - Abstract: N-nitrosodimethylamine (NDMA) as a disinfection by-product has recently become the focus of considerable research interest due to its unusually high carcinogenicity. In this study, the formation mechanisms of NDMA from dimethylamine (DMA) during chloramination and ozonation were investigated by using the quantum chemical G4 method. The reactivity of haloamines and hydroxylamine reacting with DMA was found in the order: NHCl{sub 2} ∼ NHBrCl (Br{sup -}leaving) > NHBr{sub 2} > NH{sub 2}Cl ∼ NH{sub 2}Br >> NH{sub 2}OH. This offers a theoretical support for the experimentally proposed mechanism that dimethylamine reacts with NHCl{sub 2} rather than NH{sub 2}Cl to form chlorinated unsymmetrical dimethylhydrazine intermediate and the existence of bromochloramine in the presence of bromide during chloramination, and explains the observation that NDMA yield during ozonation is much lower than that during chloramination. Importantly, an N,N-dimethylaminonitrene was found to be a significant intermediate to form NDMA in oxidation reactions by molecular oxygen and ozone. Additionally, results suggest that the amines containing the second nitrogen source directly connecting or close to the N-(CH{sub 3}){sub 2} moiety are potential significant NDMA precursors upon ozonation. The findings of this study are helpful for expanding the knowledge of NDMA formation mechanism, and predicting potential NDMA precursors

Development of a simple unified volatility-based scheme (SUVS for secondary organic aerosol formation using genetic algorithms

Directory of Open Access Journals (Sweden)

A. G. Xia

2011-07-01

Full Text Available A new method is proposed to simplify complex atmospheric chemistry reaction schemes, while preserving SOA formation properties, using genetic algorithms. The method is first applied in this study to the gas-phase α-pinene oxidation scheme. The simple unified volatility-based scheme (SUVS reflects the multi-generation evolution of chemical species from a near-explicit master chemical mechanism (MCM and, at the same time, uses the volatility-basis set speciation for condensable products. The SUVS also unifies reactions between SOA precursors with different oxidants under different atmospheric conditions. A total of 412 unknown parameters (product yields of parameterized products, reaction rates, etc. from the SUVS are estimated by using genetic algorithms operating on the detailed mechanism. The number of organic species was reduced from 310 in the detailed mechanism to 31 in the SUVS. Output species profiles, obtained from the original subset of the MCM reaction scheme for α-pinene oxidation, are reproduced with maximum fractional error at 0.10 for scenarios under a wide range of ambient HC/NO_x conditions. Ultimately, the same SUVS with updated parameters could be used to describe the SOA formation from different precursors.

Technical Note: Methionine, a precursor of methane in living plants

Science.gov (United States)

Lenhart, K.; Althoff, F.; Greule, M.; Keppler, F.

2015-03-01

When terrestrial plants were identified as producers of the greenhouse gas methane, much discussion and debate ensued not only about their contribution to the global methane budget but also with regard to the validity of the observation itself. Although the phenomenon has now become more accepted for both living and dead plants, the mechanism of methane formation in living plants remains to be elucidated and its precursor compounds to be identified. We made use of stable isotope techniques to verify the in vivo formation of methane, and, in order to identify the carbon precursor, 13C positionally labeled organic compounds were employed. Here we show that the amino acid L-methionine acts as a methane precursor in living plants. Employing 13C-labeled methionine clearly identified the sulfur-bound methyl group of methionine as a carbon precursor of methane released from lavender (Lavandula angustifolia). Furthermore, when lavender plants were stressed physically, methane release rates and the stable carbon isotope values of the emitted methane greatly increased. Our results provide additional support that plants possess a mechanism for methane production and suggest that methionine might play an important role in the formation of methane in living plants, particularly under stress conditions.

Formation of TiC/Al{sub 2}O{sub 3} composites from metal-polymer-precursors

Energy Technology Data Exchange (ETDEWEB)

Jost, H.; Braun, M.; Staedler, C. [Technische Univ. Berlin (Germany). Inst. fuer Nichtmetallische Werkstoffe

2002-07-01

A new synthesis route for TiC/Al{sub 2}O{sub 3} materials was developed starting from a mixed metal-polymer precursor. The Precursor was prepared from aluminium nitrate, titantetrachloride and polymethacrylic acid dissolved in a solvent in order to achieve a high homogeneity of the precursor reactants. (orig.)

NO ICE HYDROGENATION: A SOLID PATHWAY TO NH{sub 2}OH FORMATION IN SPACE

Energy Technology Data Exchange (ETDEWEB)

Congiu, Emanuele; Dulieu, Francois; Chaabouni, Henda; Baouche, Saoud; Lemaire, Jean Louis [LERMA-LAMAp, Universite de Cergy-Pontoise, Observatoire de Paris, ENS, UPMC, UMR 8112 du CNRS, 5 Mail Gay Lussac, 95000 Cergy Pontoise Cedex (France); Fedoseev, Gleb; Ioppolo, Sergio; Lamberts, Thanja; Linnartz, Harold [Raymond and Beverly Sackler Laboratory for Astrophysics, Leiden Observatory, University of Leiden, P.O. Box 9513, 2300 RA Leiden (Netherlands); Laffon, Carine; Parent, Philippe [Laboratoire de Chimie-Physique, Matiere et Rayonnement, Universite Pierre-et-Marie Curie (Paris 06) and CNRS (UMR 7614), 11 rue Pierre-et-Marie-Curie, 75231 Paris (France); Cuppen, Herma M., E-mail: emanuele.congiu@u-cergy.fr [Faculty of Science, Radboud University Nijmegen, IMM, P.O. Box 9010, NL 6500 GL Nijmegen (Netherlands)

2012-05-01

Icy dust grains in space act as catalytic surfaces onto which complex molecules form. These molecules are synthesized through exothermic reactions from precursor radicals and, mostly, hydrogen atom additions. Among the resulting products are species of biological relevance, such as hydroxylamine-NH{sub 2}OH-a precursor molecule in the formation of amino acids. In this Letter, laboratory experiments are described that demonstrate NH{sub 2}OH formation in interstellar ice analogs for astronomically relevant temperatures via successive hydrogenation reactions of solid nitric oxide (NO). Inclusion of the experimental results in an astrochemical gas-grain model proves the importance of a solid-state NO+H reaction channel as a starting point for prebiotic species in dark interstellar clouds and adds a new perspective to the way molecules of biological importance may form in space.

Cu(InGa)Se{sub 2} absorber formation by in-situ, low-temperature annealing of co-evaporated bilayer (InGa){sub 2}Se{sub 3}/CuSe precursors

Energy Technology Data Exchange (ETDEWEB)

Moon, Kyeongchan; Kim, Woo Kyoung, E-mail: wkim@ynu.ac.kr

2015-12-01

Chalcopyrite Cu(InGa)Se{sub 2} (CIGS) absorbers were fabricated by the formation of bilayer stacked glass/Mo/(InGa){sub 2}Se{sub 3}/CuSe precursors followed by in-situ thermal annealing at 450 °C for approximately 10 min in a vacuum evaporator. The material properties (e.g., crystal orientation, compositional depth profile, and overall composition) and device performance of the resulting CIGS absorbers were compared with those of the CIGS absorbers formed by conventional 1-stage and 3-stage CIGS formation processes at a similar temperature. X-ray diffraction confirmed that the 1-stage co-evaporation and in-situ annealing of the bilayer precursor produced a polycrystalline CIGS absorber without a specific texture, whereas the CIGS absorber formed by the 3-stage process showed a highly (220) preferred orientation. Secondary ion mass spectrometry revealed Ga accumulation at the bottom of CIGS formed by in-situ annealing of the bilayer precursors. The cell efficiency of the device with the CIGS absorber formed by the in-situ, low-temperature (450 °C) annealing of bilayer stacked glass/Mo/(InGa){sub 2}Se{sub 3}/CuSe precursors was comparable to that produced by the conventional 3-stage process at a similar temperature. - Highlights: • Annealing of (InGa){sub 2}Se{sub 3}/CuSe precursors was compared with coevaporation process. • In-situ annealing of (InGa){sub 2}Se{sub 3}/CuSe precursors at 450 °C produced about 9% solar cell. • Ga profile within Cu(InGa)Se{sub 2} depended on process profile during co-evaporation.

Multiphase composition changes and reactive oxygen species formation during limonene oxidation in the new Cambridge Atmospheric Simulation Chamber (CASC)

Science.gov (United States)

Gallimore, Peter J.; Mahon, Brendan M.; Wragg, Francis P. H.; Fuller, Stephen J.; Giorio, Chiara; Kourtchev, Ivan; Kalberer, Markus

2017-08-01

The chemical composition of organic aerosols influences their impacts on human health and the climate system. Aerosol formation from gas-to-particle conversion and in-particle reaction was studied for the oxidation of limonene in a new facility, the Cambridge Atmospheric Simulation Chamber (CASC). Health-relevant oxidising organic species produced during secondary organic aerosol (SOA) formation were quantified in real time using an Online Particle-bound Reactive Oxygen Species Instrument (OPROSI). Two categories of reactive oxygen species (ROS) were identified based on time series analysis: a short-lived component produced during precursor ozonolysis with a lifetime of the order of minutes, and a stable component that was long-lived on the experiment timescale (˜ 4 h). Individual organic species were monitored continuously over this time using Extractive Electrospray Ionisation (EESI) Mass Spectrometry (MS) for the particle phase and Proton Transfer Reaction (PTR) MS for the gas phase. Many first-generation oxidation products are unsaturated, and we observed multiphase aging via further ozonolysis reactions. Volatile products such as C9H14O (limonaketone) and C10H16O2 (limonaldehyde) were observed in the gas phase early in the experiment, before reacting again with ozone. Loss of C10H16O4 (7-hydroxy limononic acid) from the particle phase was surprisingly slow. A combination of reduced C = C reactivity and viscous particle formation (relative to other SOA systems) may explain this, and both scenarios were tested in the Pretty Good Aerosol Model (PG-AM). A range of characterisation measurements were also carried out to benchmark the chamber against existing facilities. This work demonstrates the utility of CASC, particularly for understanding the reactivity and health-relevant properties of organic aerosols using novel, highly time-resolved techniques.

Particle size effect on formation and stability of β-La2Mo2O9 ionic conductor

International Nuclear Information System (INIS)

Rocha, R.A.; Muccillo, E.N.S.

2007-01-01

The La 2 Mo 2 O 9 compound was prepared by thermal crystallization from a mixed nitrate solution to obtain a precursor material with different particle size than that obtained by the conventional mixing of starting oxides. This precursor material was characterized by several techniques before and after thermal decomposition into the final compound. X-ray diffraction and electron microscopy results evidence the formation of the high-temperature β-La 2 Mo 2 O 9 phase after calcination at 550 deg. C . The well-known α-to-β phase transition was detected at temperatures lower than that for powders prepared from mixing of starting oxides. Electrical conductivity measurements at several oxygen partial pressures show that specimens prepared from nitrates have a different behavior when compared to those specimens obtained by the conventional route. The overall results reveal the role of particle size of the precursor material on phase transition and stability of sintered La 2 Mo 2 O 9

High-performance zno transistors processed via an aqueous carbon-free metal oxide precursor route at temperatures between 80-180 °c

KAUST Repository

Lin, Yenhung

2013-06-25

An aqueous and carbon-free metal-oxide precursor route is used in combination with a UV irradiation-assisted low-temperature conversion method to fabricate low-voltage ZnO transistors with electron mobilities exceeding 10 cm2/Vs at temperatures <180°C. Because of its low temperature requirements the method allows processing of high-performance transistors onto temperature sensitive substrates such as plastic. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

International Nuclear Information System (INIS)

Kubatko, K.; Helean, K.; Navrotsky, A.; Burns, P.C.

2005-01-01

The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO 2 ) 4 O(OH) 6 ](H 2 O) 5 , metaschoepite; β-UO 2 (OH) 2 ; CaUO 4 ; Ca(UO 2 ) 6 O 4 (OH) 6 (H 2 O) 8 , becquerelite; Ca(UO 2 ) 4 O 3 (OH) 4 (H 2 O) 2 ; Na(UO 2 )O(OH), clarkeite; Na 2 (UO 2 ) 6 O 4 (OH) 6 (H 2 O) 7 , the sodium analogue of compreignacite and Pb 3 (UO 2 ) 8 O 8 (OH) 6 (H 2 O) 2 , curite. The enthalpy of formation from the binary oxides, ΔH f-ox , at 298 K was calculated for each compound from the respective drop solution enthalpy, ΔH ds . The standard enthalpies of formation from the elements, ΔH f o , at 298 K are -1791.0 ± 3.2, -1536.2 ± 2.8, -2002.0 ± 3.2, -11389.2 ± 13.5, -6653.1 ± 13.8, -1724.7 ± 5.1, -10936.4 ± 14.5 and -13163.2 ± 34.4 kJ mol -1 , respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments

Aluminum doped nickel oxide thin film with improved electrochromic performance from layered double hydroxides precursor in situ pyrolytic route

Energy Technology Data Exchange (ETDEWEB)

Shi, Jingjing; Lai, Lincong; Zhang, Ping; Li, Hailong; Qin, Yumei; Gao, Yuanchunxue; Luo, Lei; Lu, Jun, E-mail: lujun@mail.buct.edu.cn

2016-09-15

Electrochromic materials with unique performance arouse great interest on account of potential application values in smart window, low-power display, automobile anti-glare rearview mirror, and e-papers. In this paper, high-performing Al-doped NiO porous electrochromic film grown on ITO substrate has been prepared via a layered double hydroxides(LDHs) precursor in situ pyrolytic route. The Al{sup 3+} ions distributed homogenously within the NiO matrix can significantly influence the crystallinity of Ni-Al LDH and NiO:Al{sup 3+} films. The electrochromic performance of the films were evaluated by means of UV–vis absorption spectroscopy, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronoamperometry(CA) measurements. In addition, the ratio of Ni{sup 3+}/Ni{sup 2+} also varies with Al content which can lead to different electrochemical performances. Among the as-prepared films, NiO film prepared from Ni-Al (19:1) LDH show the best electrochromic performance with a high transparency of 96%, large optical modulation range (58.4%), fast switching speed (bleaching/coloration times are 1.8/4.2 s, respectively) and excellent durability (30% decrease after 2000 cycles). The improved performance was owed to the synergy of large NiO film specific surface area and porous morphology, as well as Al doping stifled the formation of Ni{sup 3+} making bleached state more pure. This LDHs precursor pyrolytic method is simple, low-cost and environmental benign and is feasible for the preparation of NiO:Al and other Al-doped oxide thin film. - Graphical abstract: The ratio of Ni{sup 3+}/Ni{sup 2+} varies with Al content which can lead to different electrochemical performances. Among the as-prepared films, NiO film prepared from Ni-Al (19:1) LDH show the best electrochromic performance with a high transparency of 96%, large optical modulation range, fast switching speed and excellent durability. Display Omitted.

Formation and dissolution of the anodic oxide film on zirconium in alcoholic aqueous solutions

International Nuclear Information System (INIS)

Mogoda, A.S.

1995-01-01

The dissolution behavior of the anodic oxide film formed in alcoholic aqueous solutions was studied. Results indicated the dissolution mechanism of the duplex oxide film followed a zero-order rate equation. The increase in methanol concentration in the formation medium (phosphoric acid [H 3 PO 4 ]) resulted in formation of an oxide film that incorporated little phosphate ion and that dissolved at a low rate. The dissolution rate of the oxide film decreased with increasing methanol concentration in the dissolution medium. This was attributed to the increase in the viscosity of the medium, which led to a decrease in the diffusion coefficient of the dissolution product of the zirconium oxide film. Dissolution of the anodic oxide film also was investigated as a function of the chain length of alcohols

Synthesis of carbide fuels from nano-structured precursors: impact on carbo-reduction and physico-chemical properties

International Nuclear Information System (INIS)

Saravia, Alvaro

2015-01-01

The classical way classically used for manufacturing carbide fuels consists of carbo-reducing at high temperature (1600 C) and under primary vacuum a mixture of AnO 2 and graphite powders. These conditions are disadvantageous for the synthesis of mixed (U,Pu)C carbides on account of plutonium volatilization. Therefore, one of the main aims of these studies is to decrease the carbo-reduction temperature. The experiments focused mainly on the lowering of the uranium oxide temperature. This result has been obtained with the use of uranium oxide and carbon nano-structured precursors. To achieve this goal colloidal suspensions of uranium oxide have been prepared and stabilized by cellulosic ethers. Cellulosic ethers are both stabiliser for uranium oxide nanoparticles and carbon source for carbo-reduction. It has been shown that these precursors are more efficient for carbo-reduction than the standard precursors: a reduction of 300 C of carbo-reduction temperature has been obtained. The impact of these precursors on carbo-reduction and on physico-chemical properties as well as the structural and microstructural characterizations of the obtained carbides have been carried out. (author) [fr

Formation of nano iridium oxide: material properties and neural cell culture

International Nuclear Information System (INIS)

Lee, In-Seop; Whang, Chung-Nam; Lee, Young-Hee; Hwan Lee, Gun; Park, Bong-Joo; Park, Jong-Chul; Seo, Won-Seon; Cui Fuzhai

2005-01-01

Iridium film with the thickness of 30 and 60 nm were formed on both Si wafer and commercially pure (CP) Ti by electron beam evaporation. The thin iridium film showed the identical charge injection capability with the bulk Ir. However, the charge injection value of iridium film was decreased with continuous potential cycling when the deposited iridium became depleted due to the formation of oxide. The number of cycles at which the charge injection value decreased was 800 and 1600 cycles for the 30- and 60-nm-thick Ir film, respectively. FE-SEM observations on the cross section of Ir film clearly showed the thicker iridium oxide was formed with the more potential cycling. Ar ion beam etching to substrates before deposition certainly improved the adhesion strength of Ir film enough to resist to the strain induced by the larger volume occupation of iridium oxide. Swiss 3T3 fibroblasts culture on Ir and Ir oxide showed no cytotoxicity. Also, embryonic cortical neural cell culture on electrode indicated neurons adhered and survived by the formation of neurofilament

Real-time measurements of secondary organic aerosol formation and aging from ambient air in an oxidation flow reactor in the Los Angeles area

Science.gov (United States)

Ortega, Amber M.; Hayes, Patrick L.; Peng, Zhe; Palm, Brett B.; Hu, Weiwei; Day, Douglas A.; Li, Rui; Cubison, Michael J.; Brune, William H.; Graus, Martin; Warneke, Carsten; Gilman, Jessica B.; Kuster, William C.; de Gouw, Joost; Gutiérrez-Montes, Cándido; Jimenez, Jose L.

2016-06-01

Field studies in polluted areas over the last decade have observed large formation of secondary organic aerosol (SOA) that is often poorly captured by models. The study of SOA formation using ambient data is often confounded by the effects of advection, vertical mixing, emissions, and variable degrees of photochemical aging. An oxidation flow reactor (OFR) was deployed to study SOA formation in real-time during the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign in Pasadena, CA, in 2010. A high-resolution aerosol mass spectrometer (AMS) and a scanning mobility particle sizer (SMPS) alternated sampling ambient and reactor-aged air. The reactor produced OH concentrations up to 4 orders of magnitude higher than in ambient air. OH radical concentration was continuously stepped, achieving equivalent atmospheric aging of 0.8 days-6.4 weeks in 3 min of processing every 2 h. Enhancement of organic aerosol (OA) from aging showed a maximum net SOA production between 0.8-6 days of aging with net OA mass loss beyond 2 weeks. Reactor SOA mass peaked at night, in the absence of ambient photochemistry and correlated with trimethylbenzene concentrations. Reactor SOA formation was inversely correlated with ambient SOA and Ox, which along with the short-lived volatile organic compound correlation, indicates the importance of very reactive (τOH ˜ 0.3 day) SOA precursors (most likely semivolatile and intermediate volatility species, S/IVOCs) in the Greater Los Angeles Area. Evolution of the elemental composition in the reactor was similar to trends observed in the atmosphere (O : C vs. H : C slope ˜ -0.65). Oxidation state of carbon (OSc) in reactor SOA increased steeply with age and remained elevated (OSC ˜ 2) at the highest photochemical ages probed. The ratio of OA in the reactor output to excess CO (ΔCO, ambient CO above regional background) vs. photochemical age is similar to previous studies at low to moderate ages and also extends to

Real-time measurements of secondary organic aerosol formation and aging from ambient air in an oxidation flow reactor in the Los Angeles area

Directory of Open Access Journals (Sweden)

A. M. Ortega

2016-06-01

Full Text Available Field studies in polluted areas over the last decade have observed large formation of secondary organic aerosol (SOA that is often poorly captured by models. The study of SOA formation using ambient data is often confounded by the effects of advection, vertical mixing, emissions, and variable degrees of photochemical aging. An oxidation flow reactor (OFR was deployed to study SOA formation in real-time during the California Research at the Nexus of Air Quality and Climate Change (CalNex campaign in Pasadena, CA, in 2010. A high-resolution aerosol mass spectrometer (AMS and a scanning mobility particle sizer (SMPS alternated sampling ambient and reactor-aged air. The reactor produced OH concentrations up to 4 orders of magnitude higher than in ambient air. OH radical concentration was continuously stepped, achieving equivalent atmospheric aging of 0.8 days–6.4 weeks in 3 min of processing every 2 h. Enhancement of organic aerosol (OA from aging showed a maximum net SOA production between 0.8–6 days of aging with net OA mass loss beyond 2 weeks. Reactor SOA mass peaked at night, in the absence of ambient photochemistry and correlated with trimethylbenzene concentrations. Reactor SOA formation was inversely correlated with ambient SOA and Ox, which along with the short-lived volatile organic compound correlation, indicates the importance of very reactive (τOH  ∼  0.3 day SOA precursors (most likely semivolatile and intermediate volatility species, S/IVOCs in the Greater Los Angeles Area. Evolution of the elemental composition in the reactor was similar to trends observed in the atmosphere (O : C vs. H : C slope  ∼  −0.65. Oxidation state of carbon (OSc in reactor SOA increased steeply with age and remained elevated (OSC  ∼  2 at the highest photochemical ages probed. The ratio of OA in the reactor output to excess CO (ΔCO, ambient CO above regional background vs. photochemical age is similar to

Position Assignment and Oxidation State Recognition of Fe and Co Centers in Heterometallic Mixed-Valent Molecular Precursors for the Low-Temperature Preparation of Target Spinel Oxide Materials

Energy Technology Data Exchange (ETDEWEB)

Lieberman, Craig M. [Department of Chemistry, University at Albany, Albany, New York 12222, United States; Barry, Matthew C. [Department of Chemistry, University at Albany, Albany, New York 12222, United States; Wei, Zheng [Department of Chemistry, University at Albany, Albany, New York 12222, United States; Rogachev, Andrey Yu. [Department; Wang, Xiaoping [Chemical and Engineering Materials Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States; Liu, Jun-Liang [CNRS, CRPP, UPR 8641, F-33600 Pessac, France; Univ. Bordeaux, UPR 8641, F-33600 Pessac, France; MOE Key Lab of Bioinorganic and Synthetic Chemistry,; Clérac, Rodolphe [CNRS, CRPP, UPR 8641, F-33600 Pessac, France; Univ. Bordeaux, UPR 8641, F-33600 Pessac, France; Chen, Yu-Sheng [ChemMatCARS, Center for Advanced Radiation; Filatov, Alexander S. [Department; Dikarev, Evgeny V. [Department of Chemistry, University at Albany, Albany, New York 12222, United States

2017-07-31

A series of mixed-valent, heterometallic (mixed-transition metal) diketonates that can be utilized as prospective volatile single-source precursors for the low-temperature preparation of M_xM'_3–xO₄ spinel oxide materials is reported. Three iron–cobalt complexes with Fe/Co ratios of 1:1, 1:2, and 2:1 were synthesized by several methods using both solid-state and solution reactions. On the basis of nearly quantitative reaction yields, elemental analyses, and comparison of metal–oxygen bonds with those in homometallic analogues, heterometallic compounds were formulated as [Fe^III(acac)₃][Co^II(hfac)₂] (1), [Co^II(hfac)₂][Fe^III(acac)₃][Co^II(hfac)₂] (2), and [Fe^II(hfac)₂][Fe^III(acac)₃][Co^II(hfac)₂] (3). In the above heteroleptic complexes, the Lewis acidic, coordinatively unsaturated CoII/FeII centers chelated by two hexafluoroacetylacetonate (hfac) ligands maintain bridging interactions with oxygen atoms of acetylacetonate (acac) groups that chelate the neighboring Fe^III metal ion. Preliminary assignment of Fe and Co positions/oxidation states in 1–3 drawn from X-ray structural investigation was corroborated by a number of complementary techniques. Single-crystal resonant synchrotron diffraction and neutron diffraction experiments unambiguously confirmed the location of Fe and Co sites in the molecules of dinuclear (1) and trinuclear (2) complexes, respectively. Direct analysis in real time mass spectrometry revealed the presence of Fe^III- and Co^II-based fragments in the gas phase upon evaporation of precursors 1 and 2 as well as of Fe^III, Fe^II, and Co^II species for complex 3. Theoretical investigation of two possible “valent isomers”, [Fe^III(acac)₃

Seasonal cycles of secondary organic aerosol tracers in rural Guangzhou, Southern China: The importance of atmospheric oxidants.

Science.gov (United States)

Yuan, Qi; Lai, Senchao; Song, Junwei; Ding, Xiang; Zheng, Lishan; Wang, Xinming; Zhao, Yan; Zheng, Junyu; Yue, Dingli; Zhong, Liuju; Niu, Xiaojun; Zhang, Yingyi

2018-05-21

Thirteen secondary organic aerosol (SOA) tracers of isoprene (SOA I ), monoterpenes (SOA M ), sesquiterpenes (SOA S ) and aromatics (SOA A ) in fine particulate matter (PM 2.5 ) were measured at a Pearl River Delta (PRD) regional site for one year. The characteristics including their seasonal cycles and the factors influencing their formation in this region were studied. The seasonal patterns of SOA I , SOA M and SOA S tracers were characterized over three enhancement periods in summer (I), autumn (II) and winter (III), while the elevations of SOA A tracer (i.e., 2,3-dihydroxy-4-oxopentanoic acid, DHOPA) were observed in Periods II and III. We found that SOA formed from different biogenic precursors could be driven by several factors during a one-year seasonal cycle. Isoprene emission controlled SOA I formation throughout the year, while monoterpene and sesquiterpene emissions facilitated SOA M and SOA S formation in summer rather than in other seasons. The influence of atmospheric oxidants (O x ) was found to be an important factor of the formation of SOA M tracers during the enhancement periods in autumn and winter. The formation of SOA S tracer was influenced by the precursor emissions in summer, atmospheric oxidation in autumn and probably also by biomass burning in both summer and winter. In this study, we could not see the strong contribution of biomass burning to DHOPA as suggested by previous studies in this region. Instead, good correlations between observed DHOPA and O x as well as [NO 2 ][O 3 ] suggest the involvement of both ozone (O 3 ) and nitrogen dioxide (NO 2 ) in the formation of DHOPA. The results showed that regional air pollution may not only increase the emissions of aromatic precursors but also can greatly promote the formation processes. Copyright © 2018 Elsevier Ltd. All rights reserved.

Thermal decomposition behavior of the co-precipitated carbonate precursor for La0.84Sr0.16MnO3

International Nuclear Information System (INIS)

Sankaranarayanan, A.; Kalekar, B.B.; Ramanathan, S.

2004-01-01

A carbonate precursor for lanthanum strontium manganite powder (La 0.84 Sr 0.16 MnO 3 - LSM) was obtained by addition of an aqueous solution of nitrates of lanthanum, strontium and manganese into a bath of ammonium carbonate solution. The precipitate was filtered, washed, dried and dry ground for homogenization. The thermal decomposition behavior of the precursor was studied by simultaneous TG-DTA-EGA technique while the precursor and intermediates formed at different temperatures were characterized by FTIR and XRD techniques for decomposition of carbonate and compound formation. It exhibited a loss in weight and endotherms in stages in the temperature ranges of 20 to 260 deg C, 260 deg to 500 deg C, 500 deg to 600 deg C, 600 deg to 900 deg C. The loss of carbon dioxide was exhibited in the EGA data and FTIR spectra while phase formation was confirmed by XRD. A comparative study of all these results showed that the processes occurring at various temperature ranges (20 deg to 260 deg C, 260 deg to 500 deg C, 500 deg to 600 deg C, 600 deg to 900 deg C) are dehydration of adsorbed moisture and water of crystallization, decomposition of manganese hydroxycarbonate to manganese dioxide, lanthanum carbonate to lanthanum oxy-carbonate and interaction between lanthanum oxy-carbonate, manganese dioxide and strontium carbonate to form finally LSM. Even though decomposition of carbonates into oxides was complete at 900 deg C, phase pure compound formation occurred at 1100 deg C, under the conditions used. (author)

A Novel Investigation of the Formation of Titanium Oxide Nanotubes on Thermally Formed Oxide of Ti-6Al-4V.

Science.gov (United States)

Butt, Arman; Hamlekhan, Azhang; Patel, Sweetu; Royhman, Dmitry; Sukotjo, Cortino; Mathew, Mathew T; Shokuhfar, Tolou; Takoudis, Christos

2015-10-01

Traditionally, titanium oxide (TiO2) nanotubes (TNTs) are anodized on Ti-6Al-4V alloy (Ti-V) surfaces with native TiO2 (amorphous TiO2); subsequent heat treatment of anodized surfaces has been observed to enhance cellular response. As-is bulk Ti-V, however, is often subjected to heat treatment, such as thermal oxidation (TO), to improve its mechanical properties. Thermal oxidation treatment of Ti-V at temperatures greater than 200°C and 400°C initiates the formation of anatase and rutile TiO2, respectively, which can affect TNT formation. This study aims at understanding the TNT formation mechanism on Ti-V surfaces with TO-formed TiO2 compared with that on as-is Ti-V surfaces with native oxide. Thermal oxidation-formed TiO2 can affect TNT formation and surface wettability because TO-formed TiO2 is expected to be part of the TNT structure. Surface characterization was carried out with field emission scanning electron microscopy, energy dispersive x-ray spectroscopy, water contact angle measurements, and white light interferometry. The TNTs were formed on control and 300°C and 600°C TO-treated Ti-V samples, and significant differences in TNT lengths and surface morphology were observed. No difference in elemental composition was found. Thermal oxidation and TO/anodization treatments produced hydrophilic surfaces, while hydrophobic behavior was observed over time (aging) for all samples. Reduced hydrophobic behavior was observed for TO/anodized samples when compared with control, control/anodized, and TO-treated samples. A method for improved surface wettability and TNT morphology is therefore discussed for possible applications in effective osseointegration of dental and orthopedic implants.

Preparation of photoelectrodes with spectral response in the visible without applied bias based on photochemically deposited copper oxide inside a porous titanium dioxide film

Energy Technology Data Exchange (ETDEWEB)

Vigil, Elena [Institute of Materials-Physics Faculty, University of Havana, Colina Universitaria, C. Habana 10 400 (Cuba); Gonzalez, Bernardo [Institute of Materials-Physics Faculty, University of Havana, Colina Universitaria, C. Habana 10 400 (Cuba); Zumeta, Inti [Institute of Materials-Physics Faculty, University of Havana, Colina Universitaria, C. Habana 10 400 (Cuba); Domingo, Concepcion [Institut de Ciencia de Materials de Barcelona (ICMAB), CSIC, 08290 Cerdanyola del Valles (Spain); Domenech, Xavier [Department of Chemistry, Universitat Autonoma de Barcelona, 08290 Cerdanyola del Valles (Spain); Ayllon, Jose A. [Department of Chemistry, Universitat Autonoma de Barcelona, 08290 Cerdanyola del Valles (Spain)]. E-mail: JoseAntonio.Ayllon@uab.es

2005-10-01

A soft and simple photochemical technique is proposed for the incorporation of copper oxide to nanoporous TiO{sub 2} with the purpose of sensitizing the TiO{sub 2} to wavelengths in the visible range. An aqueous solution of copper formate is employed as precursor. The light intensity value needed for the process, as well as its spectral range, is readily attainable with solar light. Because of the importance of heterojunctions of porous semiconductors in solar energy application, like extremely thin absorber solar cells, experimental conditions have been studied in order to obtain a thin absorption layer of copper oxide covering the TiO{sub 2}. Selection of copper formate solution concentration, irradiation time and previous immersion time in the precursor solution has been studied using X-ray diffraction, scanning electron microscopy and optical spectral transmission. Direction and wavelength dependence of photocurrent show that photons are absorbed by the copper oxide and electrons injected to the TiO{sub 2}.

Nitrogen chemistry on dust grains: the formation of hydroxylamine, precursor to glycine

Science.gov (United States)

Vidali, Gianfranco; Lemaire, Jean Louis; Shi, Jianming; Hopkins, Tyler; Garrod, Rob; He, Jiao

2015-08-01

In ices coating dust grains in molecular clouds, nitrogen-containing molecules - mostly NH3 - are present in sizable quantity, up to 15-20% with respect to water ice, the largest component. We studied the oxidation of ammonia in a series of experiments using beams of oxygen and ammonia in various configurations (co-deposition and sequential deposition with various NH3:O ratios). We detected the formation of hydroxylamine (NH2OH) and other products, depending on the degree of oxidation. A simulation of a dense cloud with input from experimental data shows that on and in ices at 14 K and with modest activation energy for reaction, NH2OH is easily formed and its abundance never falls below a tenth of the NH3 abundance. Strategies for detection of hydroxylamine in the ISM will be presented.This work is supported by the NSF Astronomy and Astrophysics Division (grant No.1311958 to G.V.). R.T.G. acknowledges the support of the NASA Astrophysics Theory Program (grant No. NNX11AC38G).

On the potential of positron lifetime spectroscopy for the study of early stages of zeolites formation from their amorphous precursors

International Nuclear Information System (INIS)

Bosnar, S.; Kosanovic, C.; Subotic, B.; Bosnar, D.; Kajcsos, Zs.; Liszkay, L.; Lohonyai, L.; Molnar, B.; Lazar, K.

2007-01-01

The applicability of positron lifetime (LT) spectroscopy to the study of progress of formation of Secondary Building Units (SBU) in gels yielding in FAU and LTA type zeolites was investigated. Samples were prepared from aluminosilicate gels with various degrees of local structural order. LT measurements were performed at room temperature in air and in vacuum. Coexistence of annihilation modi with long lifetime components was shown; a correlation with precursors of nucleation and type of exchanged ions was also indicated

Influence of oxidation process on the adsorption capacity of activated carbons from lignocellulosic precursors

Energy Technology Data Exchange (ETDEWEB)

Mourao, P.A.M.; Laginhas, C.; Custodio, F.; Nabais, J.M.V.; Carrott, P.J.M.; Carrott, M.M.L. Ribeiro [Evora Univ. (Portugal). Centro de Quimica de Evora

2011-02-15

A set of activated carbon materials non-oxidised and oxidised, were successfully prepared from two different lignocellulosic precursors, almond shell and vine shoot, by physical activation with carbon dioxide and posterior oxidation with nitric acid. All samples were characterised in relation to their structural properties and chemical composition, by different techniques, namely nitrogen adsorption at 77 K, elemental analysis (C, H, N, O and S), point of zero charge (PZC) and FTIR. A judicious choice was made to obtain carbon materials with similar structural properties (apparent BET surface area {proportional_to} 850-950 m{sup 2}g{sup -1}, micropore volume {proportional_to} 0.4 cm{sup 3}g{sup -1}, mean pore width {proportional_to} 1.2 nm and external surface area {proportional_to} 14-26 m{sup 2}g{sup -1}). After their characterisation, these microporous activated carbons were also tested for the adsorption of phenolic compounds (p-nitrophenol and phenol) in the liquid phase at room temperature. The performance in liquid phase was correlated with their structural and chemical properties. The oxidation had a major impact at a chemical level but only a moderate modification of the porous structure of the samples. The Langmuir and Freundlich equations were applied to the experimental adsorption isotherms of phenolic compounds with good agreement for the different estimated parameters. (author)

Comparison of Polythionates as Precursors for the Formation of Thallium Sulfide Layers

Directory of Open Access Journals (Sweden)

Vitalijus JANICKIS

2011-11-01

Full Text Available The processes of obtaining layers of thallium, sulfides, TlxSy, by the sorption-diffusion method on polyamide 6 using solutions of lower polythionates - sodium trithionate and tetrathionate, Na2S3O6, Na2S4O6, potassium pentathionate, K2S5O6, and of dodecathionic acid, H2S12O6, as precursors of sulfur are compared. The concentration of sorbed sulfur increases with increasing the duration of treatment, the concentration and temperature of precursor solution. It rather significantly also depends on the nature - sulfurity of polythionate, i. e. on the number of sulfur atoms in the polythionate anion: effectiveness of sulfurization using solutions of dodecathionic acid is significantly higher than that of lower polythionates. Thallium sulfide layers are formed on the surface of polyamide after the treatment of sulfurized polymer with Tl(I salt solution. The concentration of thallium in the layer increases with the increase of initial sulfurization duration and in case of H2S12O6 solution used - on the temperature of this process. The results of X-ray diffraction analysis confirmed the formation of thallium sulfide layers in the surface of polyamide 6. The phase composition of layer changes depending on the conditions of initial treatment in a H2S12O6 solution. Five thallium sulfide phases, two forms of TlS, Tl2S2, Tl4S3 and Tl2S5 were identified in the composition of the layers treated for different time with a solution of dodecathionic acid at the temperature of 20 °C and 30 °C and then with Tl(I salt solution by X-ray diffraction but the maxima of TlS and Tl2S5 phases predominate in the diffractograms.http://dx.doi.org/10.5755/j01.ms.17.4.774

Whole-cell fungal transformation of precursors into dyes

Directory of Open Access Journals (Sweden)

Jarosz-Wilkołazka Anna

2010-07-01

Full Text Available Abstract Background Chemical methods of producing dyes involve extreme temperatures and unsafe toxic compounds. Application of oxidizing enzymes obtained from fungal species, for example laccase, is an alternative to chemical synthesis of dyes. Laccase can be replaced by fungal biomass acting as a whole-cell biocatalyst with properties comparable to the isolated form of the enzyme. The application of the whole-cell system simplifies the transformation process and reduces the time required for its completion. In the present work, four fungal strains with a well-known ability to produce laccase were tested for oxidation of 17 phenolic and non-phenolic precursors into stable and non-toxic dyes. Results An agar-plate screening test of the organic precursors was carried out using four fungal strains: Trametes versicolor, Fomes fomentarius, Abortiporus biennis, and Cerrena unicolor. Out of 17 precursors, nine were transformed into coloured substances in the presence of actively growing fungal mycelium. The immobilized fungal biomass catalyzed the transformation of 1 mM benzene and naphthalene derivatives in liquid cultures yielding stable and non-toxic products with good dyeing properties. The type of fungal strain had a large influence on the absorbance of the coloured products obtained after 48-hour transformation of the selected precursors, and the most effective was Fomes fomentarius (FF25. Whole-cell transformation of AHBS (3-amino-4-hydroxybenzenesulfonic acid into a phenoxazinone dye was carried out in four different systems: in aqueous media comprising low amounts of carbon and nitrogen source, in buffer, and in distilled water. Conclusions This study demonstrated the ability of four fungal strains belonging to the ecological type of white rot fungi to transform precursors into dyes. This paper highlights the potential of fungal biomass for replacing isolated enzymes as a cheaper industrial-grade biocatalyst for the synthesis of dyes and other

NO oxidation on Zeolite Supported Cu Catalysts: Formation and Reactivity of Surface Nitrates

Energy Technology Data Exchange (ETDEWEB)

Chen, Hai-Ying; Wei, Zhehao; Kollar, Marton; Gao, Feng; Wang, Yilin; Szanyi, Janos; Peden, Charles HF

2016-04-18

The comparative activities of a small-pore Cu-CHA and a large-pore Cu-BEA catalyst for the selective catalytic reduction (SCR) of NOx with NH3, and for the oxidation of NO to NO2 and the subsequent formation of surface nitrates were investigated. Although both catalysts are highly active in SCR reactions, they exhibit very low NO oxidation activity. Furthermore, Cu-CHA is even less active than Cu-BEA in catalyzing NO oxidation but is clearly more active for SCR reactions. Temperature-programed desorption (TPD) experiments following the adsorption of (NO2 + NO + O2) with different NO2:NO ratios reveal that the poor NO oxidation activity of the two catalysts is not due to the formation of stable surface nitrates. On the contrary, NO is found to reduce and decompose the surface nitrates on both catalysts. To monitor the reaction pathways, isotope exchange experiments were conducted by using 15NO to react with 14N-nitrate covered catalyst surfaces. The evolution of FTIR spectra during the isotope exchange process demonstrates that 14N-nitrates are simply displaced with no formation of 15N-nitrates on the Cu-CHA sample, which is clearly different from that observed on the Cu-BEA sample where formation of 15N-nitrates is apparent. The results suggest that the formal oxidation state of N during the NO oxidation on Cu-CHA mainly proceeds from its original +2 to a +3 oxidation state, whereas reaching a higher oxidation state for N, such as +4 or +5, is possible on Cu-BEA. The authors at PNNL gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

Novel transparent conducting oxide technology for solar cells

Energy Technology Data Exchange (ETDEWEB)

Bishop, P.T.; Sutton, P.A.; Gardener, M.; Wakefield, G.

2005-07-01

This report outlines the development of both n- and p-type transparent Conducting Oxide (TCO) materials and the demonstrated feasibility of economic production of TCO films by deposition techniques. Descriptions are given of the four main tasks of the project with Task A concentrating on material design and synthesis covering the new precursor to zinc oxide thin films and selection of polymers for formulation; Task B dealing with film formation involving film deposition by spin coating, screen printing, inkjet printing, dip coating and chemical vapour deposition; Task C concerning performance evaluation; and Task D examining manufacturing process development. The prospects for commercialisation are explored and recommendation for future work are considered.

Formation of conductive polymers using nitrosyl ion as an oxidizing agent

Energy Technology Data Exchange (ETDEWEB)

Choi, Kyoung-Shin; Jung, Yongju; Singh, Nikhilendra

2016-06-07

A method of forming a conductive polymer deposit on a substrate is disclosed. The method may include the steps of preparing a composition comprising monomers of the conductive polymer and a nitrosyl precursor, contacting the substrate with the composition so as to allow formation of nitrosyl ion on the exterior surface of the substrate, and allowing the monomer to polymerize into the conductive polymer, wherein the polymerization is initiated by the nitrosyl ion and the conductive polymer is deposited on the exterior surface of the substrate. The conductive polymer may be polypyrrole.

Platinized titanium dioxide electrodes for methanol oxidation and photo-oxidation

Directory of Open Access Journals (Sweden)

IOANNIS POULIOS

2012-11-01

Full Text Available Platinized deposits have been formed on TiO2 particulate films supported on Ti substrates, by means of galvanic replacement of pre-deposited metallic Cu and subsequent immersion of the Cu/TiO2 coatings into a chloroplatinic acid solution. The spontaneous replacement of Cu by Pt results in Pt(Cu/TiO2/Ti electrodes. Both the platinized and the precursor TiO2/Ti electrodes have been characterized by SEM micro­scopy/EDS spectroscopy, their surface electrochemistry has been assessed by cyclic voltammetry in the dark and their photoelectrochemical properties by photovolta­m­metry under UV illumination. It has been found that, although platinized rutile-rich electrodes exhibit typical Pt surface electrochemistry, the anatase-rich electrodes show only traces of oxide formation and stripping. The latter has been translated to a suppression of methanol oxidation at anatase-rich electrodes. On the contrary, methanol oxidation at platinized rutile-rich electrodes occurs at significant rates and can be further enhanced upon UV illumination, as a result of Pt and TiO2 synergism in the photoelectrochemical oxidation of methanol.

Synthesis and characterization of ceramic pigments based on oxides of chromium and iron, on TiO2

International Nuclear Information System (INIS)

Silva, E.M. da; Galvao, S.B.; Paskocimas, C.A.

2011-01-01

This work used oxides of chromium and iron, as precursors of the synthesis of ceramic pigments. The synthesis is based on the dissolution of citric acid as a complexing agent, addition of metal oxides, such as ion chromophores; polymerization with ethylene glycol and doping with titanium oxide. Passing through pre-calcination, breakdown, calcination at different temperatures (900 and 1100 ° C), resulting in pigments: green for pigment chrome deposited on TiO 2 and orange for iron on TiO 2 . Noticing an increase in the opacity with increasing temperature. The thermal analysis (TG and DTA), evaluated their thermal behavior, the XRD revealed the formation of crystalline phases as Iron Titanate and Chrome Titanate; SEM showed the formation of hexagonal particles for both oxides. Thus, the synthesized oxides were within the requirements for application as ceramic pigments. (author)

Bulk and Surface Structures of Palladium-Modified Copper-Zinc Oxides ex Hydroxycarbonate Precursors

NARCIS (Netherlands)

López Granados, M.; Melián-Cabrera, I.; Fierro, J.L.G.

2002-01-01

(Pd)-Cu-Zn ex hydroxycarbonate precursors were prepared and characterized by several bulk and surface techniques. A palladium-free Cu-Zn precursor (CZ) was prepared by coprecipitation. Two Pd-Cu-Zn samples were prepared by coprecipitation (PCZ-CP) and sequential precipitation (PCZ-SP). It is shown

Using superoxide dismutase/catalase mimetics to manipulate the redox environment of neural precursor cells

International Nuclear Information System (INIS)

Limoli, C. L.; Giedzinski, E.; Baure, J.; Doctrow, S. R.; Rola, R.; Fike, J. R.

2006-01-01

Past work has shown that neural precursor cells are predisposed to redox sensitive changes, and that oxidative stress plays a critical role in the acute and persistent changes that occur within the irradiated CNS. Irradiation leads to a marked rise in reactive oxygen species (ROS) that correlates with oxidative endpoints in vivo and reductions in neuro-genesis. To better understand the impact of oxidative stress on neural precursor cells, and to determine if radiation-induced oxidative damage and precursor cell loss after irradiation could be reduced, a series of antioxidant compounds (EUK-134, EUK-163, EUK-172, EUK-189) were tested, three of which possess both superoxide dismutase (SOD) and catalase activities and one (EUK-163) whose only significant activity is SOD. Our results show that these SOD/catalase mimetics apparently increase the oxidation of a ROS-sensitive fluorescent indicator dye, particularly after short (12 h) treatments, but that longer treatments (24 h) decrease oxidation attributable to radiation-induced ROS. Similarly, other studies found that cells incubated with CuZnSOD showed some increase in intracellular ROS levels. Subsequent data suggested that the dye-oxidising capabilities of the EUK compounds were linked to differences in their catalase activity and, most likely, their ability to catalyse per-oxidative pathways. In unirradiated mice, the EUK-134 analogue induced some decrease of proliferating precursor cells and immature neurons 48 h after radiation, an effect that may be attributable to cytotoxicity and/or inhibition of precursor proliferation. In irradiated mice, a single injection of EUK-134 was not found to be an effective radioprotector at acute times (48 h). The present results support continued development of our in vitro model as a tool for predicting certain in vivo responses, and suggest that in some biological systems the capability to scavenge superoxide but produce excess H 2 O 2 , as is known for CuZnSOD, may be

Aluminum Oxide Formation On Fecral Catalyst Support By Electro-Chemical Coating

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Yang H.S.

2015-06-01

Full Text Available FeCrAl is comprised essentially of Fe, Cr, Al and generally considered as metallic substrates for catalyst support because of its advantage in the high-temperature corrosion resistance, high mechanical strength, and ductility. Oxidation film and its adhesion on FeCrAl surface with aluminum are important for catalyst life. Therefore various appropriate surface treatments such as thermal oxidation, Sol, PVD, CVD has studied. In this research, PEO (plasma electrolytic oxidation process was applied to form the aluminum oxide on FeCrAl surface, and the formed oxide particle according to process conditions such as electric energy and oxidation time were investigated. Microstructure and aluminum oxide particle on FeCrAl surface after PEO process was observed by FE-SEM and EDS with element mapping analysis. The study presents possibility of aluminum oxide formation by electro-chemical coating process without any pretreatment of FeCrAl.

Tailored synthesis of nanostructures by laser irradiation of a precursor microdroplet stream in open-air

Science.gov (United States)

Palanco, S.; Marino, S.; Gabás, M.; Ayala, L.; Ramos-Barrado, J. R.

2014-12-01

A method to synthesize multicomponent nanostructures in open-air is presented. A microdroplet precursor target is irradiated with a nanosecond laser pulse to induce plasma. At low droplet dispensing rates, the precursor and solvent are fully atomized without debris to produce nanoparticles and nanofilaments during plasma cooling. More complex structures like nanolayers or nanofoams can be synthetised at kilohertz droplet dispensing rates as additional droplets in the vicinity of the target droplet are subjected to the laser-induced plasma and its associated shockwave. Examples of both low- and fast-rate mechanisms are presented for Mn-Fe bi-metal oxide nanoparticles and zinc oxide nanoparticles, nanofilaments and nanofoams. Real-time diagnostics were carried out with time-resolved imaging, atomic emission spectroscopy, light scattering and shadowgraphy. In addition to overcoming some of the difficulties associated with pulsed-laser deposition (PLD), the use of a liquid precursor whose composition can be tailored on a droplet-to-droplet basis opens a number of possibilities.A method to synthesize multicomponent nanostructures in open-air is presented. A microdroplet precursor target is irradiated with a nanosecond laser pulse to induce plasma. At low droplet dispensing rates, the precursor and solvent are fully atomized without debris to produce nanoparticles and nanofilaments during plasma cooling. More complex structures like nanolayers or nanofoams can be synthetised at kilohertz droplet dispensing rates as additional droplets in the vicinity of the target droplet are subjected to the laser-induced plasma and its associated shockwave. Examples of both low- and fast-rate mechanisms are presented for Mn-Fe bi-metal oxide nanoparticles and zinc oxide nanoparticles, nanofilaments and nanofoams. Real-time diagnostics were carried out with time-resolved imaging, atomic emission spectroscopy, light scattering and shadowgraphy. In addition to overcoming some of the

Inhibition of trihalomethane formation in city water by radiation-ozone treatment and rapid composting of radiation disinfected sewage sludge

International Nuclear Information System (INIS)

Takehisa, M.; Arai, H.; Arai, M.

1985-01-01

Humic acid and Fulvic acid in natural water are precursors of carcinogenic THM which is formed during chlorine disinfection in city water processing. The radiation-oxidation process in the presence of ozone is effective to remove the precursors. The THM formation was reduced more than the decrease in TOC by the combination treatment. This is mainly due to a change in the chemical structure of the oxidation products. A composting of radiation disinfected sludge cake for agricultural reuse could be achieved within 3 days primary fermentation in a sewage plant. The rapid fermentation with use of radiation is effective to scale down of a fermentor of composting plant and the process reduces a health risk from the workers as well as final users. (author)

Inhibition of trihalomethane formation in city water by radiation-ozone treatment and rapid composting of radiation disinfected sewage sludge

Energy Technology Data Exchange (ETDEWEB)

Takehisa, M; Arai, H; Arai, M

1985-01-01

Humic acid and Fulvic acid in natural water are precursors of carcinogenic THM which is formed during chlorine disinfection in city water processing. The radiation-oxidation process in the presence of ozone is effective to remove the precursors. The THM formation was reduced more than the decrease in TOC by the combination treatment. This is mainly due to a change in the chemical structure of the oxidation products. A composting of radiation disinfected sludge cake for agricultural reuse could be achieved within 3 days primary fermentation in a sewage plant. The rapid fermentation with use of radiation is effective to scale down a fermentor of a composting plant and the process reduces health risk for the workers as well as final users.

Reaction Mechanism for the Formation of Nitrogen Oxides (NO x ) During Coke Oxidation in Fluidized Catalytic Cracking Units

KAUST Repository

Chaparala, Sree Vidya

2015-06-11

Fluidized catalytic cracking (FCC) units in refineries process heavy feedstock obtained from crude oil distillation. While cracking feed, catalysts get deactivated due to coke deposition. During catalyst regeneration by burning coke in air, nitrogen oxides (NOx) are formed. The increase in nitrogen content in feed over time has resulted in increased NOx emissions. To predict NOx concentration in flue gas, a reliable model for FCC regenerators is needed that requires comprehensive understanding and accurate kinetics for NOx formation. Based on the nitrogen-containing functional groups on coke, model molecules are selected to study reactions between coke-bound nitrogen and O2 to form NO and NO2 using density functional theory. The reaction kinetics for the proposed pathways are evaluated using transition state theory. It is observed that the addition of O2 on coke is favored only when the free radical is present on the carbon atom instead of nitrogen atom. Thus, NOx formation during coke oxidation does not result from the direct attack by O2 on N atoms of coke, but from the transfer of an O atom to N from a neighboring site. The low activation energies required for NO formation indicate that it is more likely to form than NO2 during coke oxidation. The favorable pathways for NOx formation that can be used in FCC models are identified. Copyright © 2015 Taylor & Francis Group, LLC.

Formation of highly oxygenated organic molecules from aromatic compounds

Science.gov (United States)

Molteni, Ugo; Bianchi, Federico; Klein, Felix; El Haddad, Imad; Frege, Carla; Rossi, Michel J.; Dommen, Josef; Baltensperger, Urs

2018-02-01

Anthropogenic volatile organic compounds (AVOCs) often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs), such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs) with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene) and ethylbenzene), as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl). We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AVOCs may contribute substantially to new particle formation events that have been detected in urban areas.

Formation of highly oxygenated organic molecules from aromatic compounds

Directory of Open Access Journals (Sweden)

U. Molteni

2018-02-01

Full Text Available Anthropogenic volatile organic compounds (AVOCs often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs, such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene and ethylbenzene, as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl. We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AVOCs may contribute substantially to new particle formation events that have been detected in urban areas.

Determination of Insulator-to-Semiconductor Transition in Sol-Gel Oxide Semiconductors Using Derivative Spectroscopy.

Science.gov (United States)

Lee, Woobin; Choi, Seungbeom; Kim, Kyung Tae; Kang, Jingu; Park, Sung Kyu; Kim, Yong-Hoon

2015-12-23

We report a derivative spectroscopic method for determining insulator-to-semiconductor transition during sol-gel metal-oxide semiconductor formation. When an as-spun sol-gel precursor film is photochemically activated and changes to semiconducting state, the light absorption characteristics of the metal-oxide film is considerable changed particularly in the ultraviolet region. As a result, a peak is generated in the first-order derivatives of light absorption ( A' ) vs. wavelength (λ) plots, and by tracing the peak center shift and peak intensity, transition from insulating-to-semiconducting state of the film can be monitored. The peak generation and peak center shift are described based on photon-energy-dependent absorption coefficient of metal-oxide films. We discuss detailed analysis method for metal-oxide semiconductor films and its application in thin-film transistor fabrication. We believe this derivative spectroscopy based determination can be beneficial for a non-destructive and a rapid monitoring of the insulator-to-semiconductor transition in sol-gel oxide semiconductor formation.

Characterization of N-nitrosodimethylamine formation from the ozonation of ranitidine.

Science.gov (United States)

Lv, Juan; Wang, Lin; Li, Yongmei

2017-08-01

N-nitrosodimethylamine (NDMA) is an emerging disinfection by-product which is formed during water disinfection in the presence of amine-based precursors. Ranitidine, as one kind of amine-based pharmaceuticals, has been identified as NDMA precursor with high NDMA molar conversion during chloramination. This study focused on the characterization of NDMA formation during ozonation of ranitidine. Influences of operational variables (ozone dose, pH value) and water matrix on NDMA generation as well as ranitidine degradation were evaluated. The results indicate high reactivity of ranitidine with ozone. Dimethylamine (DMA) and NDMA were generated due to ranitidine oxidation. High pH value caused more NDMA accumulation. NDMA formation was inhibited under acid conditions (pH≤5) mainly due to the protonation of amines. Water matrix such as HCO 3 - and humic acid impacted NDMA generation due to OH scavenging. Compared with OH, ozone molecules dominated the productions of DMA and NDMA. However, OH was a critical factor in NDMA degradation. Transformation products of ranitidine during ozonation were identified using gas chromatography-mass spectrometry. Among these products, just DMA and N,N-dimethylformamide could contribute to NDMA formation due to the DMA group in the molecular structures. The NDMA formation pathway from ranitidine ozonation was also proposed. Copyright © 2017. Published by Elsevier B.V.

Iodine oxides in large-scale THAI tests

International Nuclear Information System (INIS)

Funke, F.; Langrock, G.; Kanzleiter, T.; Poss, G.; Fischer, K.; Kühnel, A.; Weber, G.; Allelein, H.-J.

2012-01-01

Highlights: ► Iodine oxide particles were produced from gaseous iodine and ozone. ► Ozone replaced the effect of ionizing radiation in the large-scale THAI facility. ► The mean diameter of the iodine oxide particles was about 0.35 μm. ► Particle formation was faster than the chemical reaction between iodine and ozone. ► Deposition of iodine oxide particles was slow in the absence of other aerosols. - Abstract: The conversion of gaseous molecular iodine into iodine oxide aerosols has significant relevance in the understanding of the fission product iodine volatility in a LWR containment during severe accidents. In containment, the high radiation field caused by fission products released from the reactor core induces radiolytic oxidation into iodine oxides. To study the characteristics and the behaviour of iodine oxides in large scale, two THAI tests Iod-13 and Iod-14 were performed, simulating radiolytic oxidation of molecular iodine by reaction of iodine with ozone, with ozone injected from an ozone generator. The observed iodine oxides form submicron particles with mean volume-related diameters of about 0.35 μm and show low deposition rates in the THAI tests performed in the absence of other nuclear aerosols. Formation of iodine aerosols from gaseous precursors iodine and ozone is fast as compared to their chemical interaction. The current approach in empirical iodine containment behaviour models in severe accidents, including the radiolytic production of I 2 -oxidizing agents followed by the I 2 oxidation itself, is confirmed by these THAI tests.

Precursor Dependent Structural Properties and Antibacterial Activity ...

Indian Academy of Sciences (India)

71

10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30 ... absorption spectroscopy, Scanning electron microscopy (SEM) and Zeta ... The antibacterial activity of the synthesized CuO were studied against human .... Sample d : Copper oxide synthesized with cupric sulphate as precursor ...... Chem.4 86.

Cobalamin Deficiency Results in Increased Production of Formate Secondary to Decreased Mitochondrial Oxidation of One-Carbon Units in Rats.

Science.gov (United States)

MacMillan, Luke; Tingley, Garrett; Young, Sara K; Clow, Kathy A; Randell, Edward W; Brosnan, Margaret E; Brosnan, John T

2018-03-01

Formate is produced in mitochondria via the catabolism of serine, glycine, dimethylglycine, and sarcosine. Formate produced by mitochondria may be incorporated into the cytosolic folate pool where it can be used for important biosynthetic reactions. Previous studies from our lab have shown that cobalamin deficiency results in increased plasma formate concentrations. Our goal was to determine the basis for elevated formate in vitamin B-12 deficiency. Male Sprague Dawley rats were randomly assigned to consume either a cobalamin-replete (50 μg cobalamin/kg diet) or -deficient (no added cobalamin) diet for 6 wk. Formate production was measured in vivo and in isolated liver mitochondria from a variety of one-carbon precursors. We also measured the oxidation of [3-14C]-l-serine to 14CO2 in isolated rat liver mitochondria and the expression of hepatic genes involved in one-carbon unit and formate metabolism. Cobalamin-deficient rats produce formate at a rate 55% higher than that of replete rats. Formate production from serine was increased by 60% and from dimethylglycine and sarcosine by ∼200% in liver mitochondria isolated from cobalamin-deficient rats compared with cobalamin-replete rats. There was a 26% decrease in the 14CO2 produced by mitochondria from cobalamin-deficient rats. Gene expression analysis showed that 10-formyltetrahydrofolate dehydrogenase-cytosolic (Aldh1l1) and mitochondrial (Aldh1l2) expression were decreased by 40% and 60%, respectively, compared to control, while 10-formyltetrahydrofolate synthetase, mitochondrial, monofunctional (Mthfd1l) expression was unchanged. We propose that a bifurcation in mitochondrial one-carbon metabolism is a key control mechanism in determining the fate of one-carbon units, to formate or CO2. During cobalamin deficiency in rats the disposition of 10-formyl-tetrahydrofolate carbon is shifted in favor of formate production. This may represent a mechanism to generate more one-carbon units for the replenishment of the S

Preparation of highly dispersed Ru-Sn bimetallic supported catalysts from the single source precursors Cp(PPh32Ru-SnX3 (X = Cl or Br

Directory of Open Access Journals (Sweden)

Ana Cláudia Bernardes Silva

2003-06-01

Full Text Available In this work highly dispersed Ru-Sn bimetallic catalysts have been prepared from organobimetallic Cp(PPh32Ru-SnX3 (X = Cl or Br complexes. These single source precursors can be easily impregnated in high surface area supports, such as activated carbon and sol-gel SiO2, and upon controlled thermal treatment the ligands are released as volatile products resulting in the formation of the bimetallic system Ru-Sn. Catalytic reactions, such as hydrodechlorination of CCl4 and chlorobenzene and TPR (Temperature Programmed Reduction experiments carried out with these RuSn catalysts suggested a strong interaction between Ruthenium and Tin. Mössbauer measurements showed that these materials when exposed to air are immediately oxidized to form Sn (IV. It was shown that upon controlled reduction conditions with H2 it is possible to reduce selectively Sn to different oxidation states and different phases. The Sn oxidation state showed significant effect on the catalytic hydrogenation of 1,5-cyclooctadiene. The use of these single source precursors with a controlled decomposition/reduction procedure allows the preparation of unique catalysts with an intimate interaction between the components ruthenium and tin and the possibility of varying the Sn oxidation state around the Ru metal.

Layered double hydroxide supported gold nanoclusters by glutathione-capped Au nanoclusters precursor method for highly efficient aerobic oxidation of alcohols

Science.gov (United States)

Li, Lun; Dou, Liguang; Zhang, Hui

2014-03-01

M3Al-layered double hydroxide (LDH, M = Mg, Ni, Co) supported Au nanoclusters (AuNCs) catalysts have been prepared for the first time by using water-soluble glutathione-capped Au nanoclusters as precursor. Detailed characterizations show that the ultrafine Au nanoclusters (ca. 1.5 +/- 0.6 nm) were well dispersed on the surface of LDH with a loading of Au below ~0.23 wt% upon synergetic interaction between AuNCs and M3Al-LDH. AuNCs/Mg3Al-LDH-0.23 exhibits much higher catalytic performance for the oxidation of 1-phenylethanol in toluene than Au/Mg3Al-LDH(DP) by the conventional deposition precipitation method and can be applied for a wide range of alcohols without basic additives. This catalyst can also be reused without loss of activity or selectivity. The AuNCs/M(= Ni, Co)3Al-LDH catalysts present even higher alcohol oxidation activity than AuNCs/Mg3Al-LDH. Particularly, AuNCs/Ni3Al-LDH-0.22 exhibits the highest activity (46 500 h-1) for the aerobic oxidation of 1-phenylethanol under solvent-free conditions attributed to its strongest Au-support synergy. The excellent activity and stability of AuNCs/M3Al-LDH catalysts render these materials promising candidates for green base-free selective oxidation of alcohols by molecular oxygen.M3Al-layered double hydroxide (LDH, M = Mg, Ni, Co) supported Au nanoclusters (AuNCs) catalysts have been prepared for the first time by using water-soluble glutathione-capped Au nanoclusters as precursor. Detailed characterizations show that the ultrafine Au nanoclusters (ca. 1.5 +/- 0.6 nm) were well dispersed on the surface of LDH with a loading of Au below ~0.23 wt% upon synergetic interaction between AuNCs and M3Al-LDH. AuNCs/Mg3Al-LDH-0.23 exhibits much higher catalytic performance for the oxidation of 1-phenylethanol in toluene than Au/Mg3Al-LDH(DP) by the conventional deposition precipitation method and can be applied for a wide range of alcohols without basic additives. This catalyst can also be reused without loss of activity

Formation and transformation of a short range ordered iron carbonate precursor

DEFF Research Database (Denmark)

Dideriksen, Knud; Frandsen, Cathrine; Bovet, Nicolas

2015-01-01

(II) with varying pH produced broad peaks in X-ray diffraction and contained dominantly Fe and CO3 when probed with X-ray photoelectron spectroscopy. Reduced pair distribution function (PDF) analysis shows only peaks corresponding to interatomic distances below 15Å, reflecting a material with no long range...... structural order. Moreover, PDF peak positions differ from those for known iron carbonates and hydroxides. Mössbauer spectra also deviate from those expected for known iron carbonates and suggest a less crystalline structure. These data show that a previously unidentified iron carbonate precursor phase...... formed. Its coherent scattering domains determined from PDF analysis are slightly larger than for amorphous calcium carbonate, suggesting that the precursor could be nanocrystalline. Replica exchange molecular dynamics simulations of Fe-carbonate polynuclear complexes yield PDF peak positions that agree...

Suppression of new particle formation from monoterpene oxidation by NOx

Science.gov (United States)

Wildt, J.; Mentel, T. F.; Kiendler-Scharr, A.; Hoffmann, T.; Andres, S.; Ehn, M.; Kleist, E.; Müsgen, P.; Rohrer, F.; Rudich, Y.; Springer, M.; Tillmann, R.; Wahner, A.

2014-03-01

The impact of nitrogen oxides (NOx = NO + NO2) on new particle formation (NPF) and on photochemical ozone production from real plant volatile organic compound (BVOC) emissions was studied in a laboratory setup. At high NOx conditions ([BVOC] / [NOx] 23 ppb) new particle formation was suppressed. Instead, photochemical ozone formation was observed resulting in higher hydroxyl radical (OH) and lower nitrogen monoxide (NO) concentrations. When [NO] was reduced back to levels below 1 ppb by OH reactions, NPF was observed. Adding high amounts of NOx caused NPF to be slowed by orders of magnitude compared to analogous experiments at low NOx conditions ([NOx] ~300 ppt), although OH concentrations were higher. Varying NO2 photolysis enabled showing that NO was responsible for suppression of NPF. This suggests that peroxy radicals are involved in NPF. The rates of NPF and photochemical ozone production were related by power law dependence with an exponent approaching -2. This exponent indicated that the overall peroxy radical concentration must have been similar when NPF occurred. Thus, permutation reactions of first-generation peroxy radicals cannot be the rate limiting step in NPF from monoterpene oxidation. It was concluded that permutation reactions of higher generation peroxy-radical-like intermediates limit the rate of new particle formation. In contrast to the strong effects on the particle numbers, the formation of particle mass was substantially less sensitive to NOx concentrations. If at all, yields were reduced by about an order of magnitude only at very high NOx concentrations.

Surface structural evolvement in the conversion of polyacrylonitrile precursors to carbon fibers

International Nuclear Information System (INIS)

Qian, Xin; Zou, Ruifen; OuYang, Qin; Wang, Xuefei; Zhang, Yonggang

2015-01-01

Highlights: • The characteristic striated topography of PAN precursors resulted from the wet spinning process could pass down to carbon fibers. • The ridges and grooves monitored became much more well-defined after the thermo-oxidation. • Both the depth and the width of longitudinal grooves decreased after the carbonization. • Carbon, nitrogen, oxygen and silicon were the governing elements on the fiber surface. - Abstract: Surface structural evolvement in the conversion of polyacrylonitrile (PAN) precursors to carbon fibers was investigated through scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). SEM results showed that the characteristic striated topography of PAN precursors resulted from the wet spinning process could pass down to carbon fibers. The fiber diameter gradually decreased from 11.3 μm to 5.5 μm and the corresponding density increased from 1.18 g/cm 3 to 1.80 g/cm 3 in the conversion of PAN precursors to carbon fibers. The ridges and grooves monitored by AFM became much more well-defined after the thermo-oxidation. However, the original longitudinal grooves were destroyed and both the depth and the width of longitudinal grooves decreased after the carbonization. XPS results revealed that carbon, nitrogen, oxygen and silicon were the governing elements on the fiber surface. The −C−C functional groups was the dominant groups and the relative contents of −C=O and −COO groups gradually increased in the process of thermo-oxidation and carbonization

Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

Energy Technology Data Exchange (ETDEWEB)

K. Kubatko; K. Helean; A. Navrotsky; P.C. Burns

2005-05-11

The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO{sub 2}){sub 4}O(OH){sub 6}](H{sub 2}O){sub 5}, metaschoepite; {beta}-UO{sub 2}(OH){sub 2}; CaUO{sub 4}; Ca(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 8}, becquerelite; Ca(UO{sub 2}){sub 4}O{sub 3}(OH){sub 4}(H{sub 2}O){sub 2}; Na(UO{sub 2})O(OH), clarkeite; Na{sub 2}(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 7}, the sodium analogue of compreignacite and Pb{sub 3}(UO{sub 2}){sub 8}O{sub 8}(OH){sub 6}(H{sub 2}O){sub 2}, curite. The enthalpy of formation from the binary oxides, {Delta}H{sub f-ox}, at 298 K was calculated for each compound from the respective drop solution enthalpy, {Delta}H{sub ds}. The standard enthalpies of formation from the elements, {Delta}H{sub f}{sup o}, at 298 K are -1791.0 {+-} 3.2, -1536.2 {+-} 2.8, -2002.0 {+-} 3.2, -11389.2 {+-} 13.5, -6653.1 {+-} 13.8, -1724.7 {+-} 5.1, -10936.4 {+-} 14.5 and -13163.2 {+-} 34.4 kJ mol{sup -1}, respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments.

A photochemical proposal for the preparation of ZnAl{sub 2}O{sub 4} and MgAl{sub 2}O{sub 4} thin films from β-diketonate complex precursors

Energy Technology Data Exchange (ETDEWEB)

Cabello, G., E-mail: gerardocabelloguzman@hotmail.com [Departamento de Ciencias Básicas, Facultad de Ciencias, Universidad del Bío-Bío, Chillán (Chile); Lillo, L.; Caro, C.; Seguel, M.; Sandoval, C. [Departamento de Ciencias Básicas, Facultad de Ciencias, Universidad del Bío-Bío, Chillán (Chile); Buono-Core, G.E. [Instituto de Química, Pontificia Universidad Católica de Valparaíso, Valparaíso (Chile); Chornik, B.; Flores, M. [Deparamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Santiago 8370415 (Chile)

2016-05-15

Highlights: • ZnAl{sub 2}O{sub 4} and MgAl{sub 2}O{sub 4} thin films were prepared by photo-chemical method. • The Zn(II), Mg(II) and Al(III) β-diketonate complexes were used as precursors. • The photochemical reaction was monitored by UV–vis and FT-IR spectroscopy. • The results reveal spinel oxide formation and the generation of intermediate products. - Abstract: ZnAl{sub 2}O{sub 4} and MgAl{sub 2}O{sub 4} thin films were grown on Si(100) and quartz plate substrates using a photochemical method in the solid phase with thin films of β-diketonate complexes as the precursors. The films were deposited by spin-coating and subsequently photolyzed at room temperature using 254 nm UV light. The photolysis of these films results in the deposition of metal oxide thin films and fragmentation of the ligands from the coordination sphere of the complexes. The obtained samples were post-annealed at different temperatures (350–1100 °C) for 2 h and characterized by FT-Infrared spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force miscroscopy (AFM), and UV–vis spectroscopy. The results indicate the formation of spinel-type structures and other phases. These characteristics determined the quality of the films, which were obtained from the photodeposition of ternary metal oxides.

Formation of nitrogen-containing compounds during slow pyrolysis and oxidation of petroleum coke

Energy Technology Data Exchange (ETDEWEB)

Furimsky, E.; Ohtsuka, Y. [IMAF Group, Ottawa, ON (Canada)

1997-09-01

The petroleum coke from a fluid coking process was pyrolyzed in helium and oxidized in 1% and 4% O{sub 2} and in air, with the aim to determine N-containing compounds such as HCN, NH{sub 3}, NO, and N{sub 2}O. The experiments were performed with and without limestone. NO was the major product during all oxidation runs. N{sub 2}O was formed only in air. In this case, N{sub 2}O formation was delayed when compared with that of NO. The addition of limestone decreased formation of HCN and increased that of NH{sub 3}, whereas NO formation was least affected. 36 refs., 8 figs., 6 tabs.

Bicarbonate-induced activation of H₂O₂ for metal-free oxidative desulfurization.

Science.gov (United States)

Bokare, Alok D; Choi, Wonyong

2016-03-05

Efficient oxidative desulfurization (ODS) of model oil containing dibenzothiophene (DBT) and aromatic thiophenic derivatives has been achieved at room temperature using hydrogen peroxide activation by inorganic bicarbonate (HCO3(-)). Using in-situ formation of peroxymonocarbonate as oxidant, the transformation of main model substrate DBT to corresponding DBT-sulfone was easily accomplished in biphasic reaction conditions. In the presence of water-acetonitrile polar phase, increasing the water content upto 50% decreased the extraction capacity more than 3 times, but ∼ 90% DBT oxidation was still achieved. The oxidizing capacity of bicarbonate catalyst was maintained during repeated ODS cycles, but DBT removal efficiency was critically dependent on the extraction capacity of the polar phase. Under heterogeneous reaction conditions, bicarbonate-modified ion-exchange resin achieved similar ODS activity compared to the homogeneous catalytic system. Additionally, the efficient formation of peroxymonocarbonate using gaseous CO2 precursor in alkaline conditions was also utilized for DBT oxidation. The present study proposes the NaHCO3/H2O2 catalytic system as an efficient and cheap metal-free alternative for the oxidative removal of aromatic sulfur compounds from fuel oil. Copyright © 2015 Elsevier B.V. All rights reserved.

Detailed Visualization of Phase Evolution during Rapid Formation of Cu(InGa)Se2 Photovoltaic Absorber from Mo/CuGa/In/Se Precursors.

Science.gov (United States)

Koo, Jaseok; Kim, Sammi; Cheon, Taehoon; Kim, Soo-Hyun; Kim, Woo Kyoung

2018-03-02

Amongst several processes which have been developed for the production of reliable chalcopyrite Cu(InGa)Se 2 photovoltaic absorbers, the 2-step metallization-selenization process is widely accepted as being suitable for industrial-scale application. Here we visualize the detailed thermal behavior and reaction pathways of constituent elements during commercially attractive rapid thermal processing of glass/Mo/CuGa/In/Se precursors on the basis of the results of systematic characterization of samples obtained from a series of quenching experiments with set-temperatures between 25 and 550 °C. It was confirmed that the Se layer crystallized and then melted between 250 and 350 °C, completely disappearing at 500 °C. The formation of CuInSe 2 and Cu(InGa)Se 2 was initiated at around 450 °C and 550 °C, respectively. It is suggested that pre-heat treatment to control crystallization of Se layer should be designed at 250-350 °C and Cu(InGa)Se 2 formation from CuGa/In/Se precursors can be completed within a timeframe of 6 min.

Hydrogen production by ethanol partial oxidation over nano-iron oxide catalysts produced by chemical vapour synthesis

Energy Technology Data Exchange (ETDEWEB)

Ahmed, Wael Ahmed Abou Taleb Sayed

2011-01-13

This work presents the experimental results of the synthesis of unsupported and supported SiC iron oxide nanoparticles and their catalytic activity towards ethanol partial oxidation. For comparison, further unsupported iron oxide phases were investigated towards the ethanol partial oxidation. These {gamma}-Fe{sub 2}O{sub 3} and {alpha}/{gamma}-Fe{sub 2}O{sub 3} phase catalysts were prepared by the CVS method using Fe(CO){sub 5} as precursor, supplied by another author. The {alpha}-Fe{sub 2}O{sub 3} and SiC nanoparticles were prepared by the CVS method using a home made hot wall reactor technique at atmospheric pressure. Ferrocene and tetramethylsilane were used as precursor for the production process. Process parameters of precursor evaporation temperature, precursor concentration, gas mixture velocity and gas mixture dilution were investigated and optimised to produce particle sizes in a range of 10 nm. For Fe{sub 2}O{sub 3}/SiC catalyst series production, a new hot wall reactor setup was used. The particles were produced by simultaneous thermal decomposition of ferrocene and tetramethylsilane in one reactor from both sides. The production parameters of inlet tube distance inside the reactor, precursor evaporation temperature and carrier gas flow were investigated to produce a series of samples with different iron oxide content. The prepared catalysts composition, physical and chemical properties were characterized by XRD, EDX, SEM, BET surface area, FTIR, XPS and dynamic light scattering (DLS) techniques. The catalytic activity for the ethanol gas-phase oxidation was investigated in a temperature range from 260 C to 290 C. The product distributions obtained over all catalysts were analysed with mass spectrometry analysis tool. The activity of bulk Fe{sub 2}O{sub 3} and SiC nanoparticles was compared with prepared nano-iron oxide phase catalysts. The reaction parameters, such as reaction temperature and O{sub 2}/ethanol ratio were investigated. The catalysts

Structural, optical investigations of graphene from graphene oxide using green method

International Nuclear Information System (INIS)

Kumar, Dinesh; Shukla, Shobha; Saxena, Sumit

2015-01-01

Graphene nano sheets (GNS) are synthesized from Graphene Oxide (GO) using commercial sugar as a reducing agent. A green and facile approach is followed to synthesize chemically converted GNS using exfoliated GO as precursor. The merit of this method is that both the reducing agents themselves and the oxidized products are environmentally friendly. The prepared materials are characterized with X-ray diffraction (XRD), UV-Visible absorption spectroscopy, High resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED). The results of XRD, UV-vis analysis provide a clear indication of removal of oxygen-containing groups from GO and the formation of GNS

New investigations in the USA into formation of nitrogen oxides

Energy Technology Data Exchange (ETDEWEB)

Kotler, V.R.

1983-06-01

This paper discusses laboratory investigations in the USA on air pollution by nitrogen oxides during coal combustion. Laboratory combustors used for combustion of black coal, anthracite and brown coal are described. Measuring systems and measuring instruments used for flue gas analyses and determining nitrogen oxide, hydrocyanic acid and ammonia content in flue gas are evaluated. Effects of excess air on nitrogen oxide formation are analyzed. Analyses show that excess air influences relation between nitrogen oxides, hydrocyanic acid and ammonia. Recommendations on the optimum excess air rate are made. In the case of all coal typs, with the exception of anthracite, the optimum excess air rate is 0.7 which guarantees the highest transformation rate of nitrogen in fuel into molecular nitrogen. Effects of excess air on oxidation of hydrocyanic acid and ammonia are described. The analyses consider effects of excess air on chemical reactions during coal combustion under laboratory conditions. (4 refs.) (In Russian)

Effect of pores formation process and oxygen plasma treatment to hydroxyapatite formation on bioactive PEEK prepared by incorporation of precursor of apatite.

Science.gov (United States)

Yabutsuka, Takeshi; Fukushima, Keito; Hiruta, Tomoko; Takai, Shigeomi; Yao, Takeshi

2017-12-01

When bioinert substrates with fine-sized pores are immersed in a simulated body fluid (SBF) and the pH value or the temperature is increased, fine particles of calcium phosphate, which the authors denoted as 'precursor of apatite' (PrA), are formed in the pores. By this method, hydroxyapatite formation ability can be provided to various kinds of bioinert materials. In this study, the authors studied fabrication methods of bioactive PEEK by using the above-mentioned process. First, the fine-sized pores were formed on the surface of the PEEK substrate by H 2 SO 4 treatment. Next, to provide hydrophilic property to the PEEK, the surfaces of the PEEK were treated with O 2 plasma. Finally, PrA were formed in the pores by the above-mentioned process, which is denoted as 'Alkaline SBF' treatment, and the bioactive PEEK was obtained. By immersing in SBF with the physiological condition, hydroxyapatite formation was induced on the whole surface of the substrate within 1day. The formation of PrA directly contributed to hydroxyapatite formation ability. By applying the O 2 plasma treatment, hydroxyapatite formation was uniformly performed on the whole surface of the substrate. The H 2 SO 4 treatment contributed to a considerable enhancement of adhesive strength of the formed hydroxyapatite layer formed in SBF because of the increase of surface areas of the substrate. As a comparative study, the sandblasting method was applied as the pores formation process instead of the H 2 SO 4 treatment. Although hydroxyapatite formation was provided also in this case, however, the adhesion of the formed hydroxyapatite layer to the substrate was not sufficient even if the O 2 plasma treatment was conducted. This result indicates that the fine-sized pores should be formed on the whole surface of the substrate uniformly to achieve high adhesive strength of the hydroxyapatite layer. Therefore, it is considered that the H 2 SO 4 treatment before the O 2 plasma and the 'Alkaline SBF' treatment

Silicon oxynitride films deposited by reactive high power impulse magnetron sputtering using nitrous oxide as a single-source precursor

Energy Technology Data Exchange (ETDEWEB)

Hänninen, Tuomas, E-mail: tuoha@ifm.liu.se; Schmidt, Susann; Jensen, Jens; Hultman, Lars; Högberg, Hans [Thin Film Physics Division, Department of Physics, Chemistry, and Biology (IFM), Linköping University, Linköping SE-581 83 (Sweden)

2015-09-15

Silicon oxynitride thin films were synthesized by reactive high power impulse magnetron sputtering of silicon in argon/nitrous oxide plasmas. Nitrous oxide was employed as a single-source precursor supplying oxygen and nitrogen for the film growth. The films were characterized by elastic recoil detection analysis, x-ray photoelectron spectroscopy, x-ray diffraction, x-ray reflectivity, scanning electron microscopy, and spectroscopic ellipsometry. Results show that the films are silicon rich, amorphous, and exhibit a random chemical bonding structure. The optical properties with the refractive index and the extinction coefficient correlate with the film elemental composition, showing decreasing values with increasing film oxygen and nitrogen content. The total percentage of oxygen and nitrogen in the films is controlled by adjusting the gas flow ratio in the deposition processes. Furthermore, it is shown that the film oxygen-to-nitrogen ratio can be tailored by the high power impulse magnetron sputtering-specific parameters pulse frequency and energy per pulse.

Roles of texture in controlling oxidation, hydrogen ingress and hydride formation in Zr alloys

International Nuclear Information System (INIS)

Szpunar, Jerzy A.; Qin, Wen; Li, Hualong; Kumar, Kiran

2011-01-01

Experimental observations shows that the oxide formed on Zr alloys are strongly textured. The texture and grain-boundary characteristics of oxide are dependent on the texture of metal substrate. Computer simulation and thermodynamic modeling clarify the effect of metal substrate on structure of oxide film, and intrinsic factors affecting the microstructure. Models of diffusion process of hydrogen atoms and oxygen diffusion through oxide are presented. Both intra-granular and inter-granular hydrides were found following (0001) α-Zr //(111) δ-ZrH1.5 relationship. The through-thickness texture inhomogeneity in cladding tubes, the effects of hoop stress on the hydride orientation and the formation of interlinked hydride structure were studied. A thermodynamic model was developed to analyze the nucleation and the stress-induced reorientation of intergranular hydrides. These works provide a framework for understanding the oxidation, the hydrogen ingress and the hydride formation in Zr alloys. (author)

Exploring the Role of Persulfate in the Activation Process: Radical Precursor Versus Electron Acceptor.

Science.gov (United States)

Yun, Eun-Tae; Yoo, Ha-Young; Bae, Hyokwan; Kim, Hyoung-Il; Lee, Jaesang

2017-09-05

This study elucidates the mechanism behind persulfate activation by exploring the role of various oxyanions (e.g., peroxymonosulfate, periodate, and peracetate) in two activation systems utilizing iron nanoparticle (nFe 0 ) as the reducing agent and single-wall carbon nanotubes (CNTs) as electron transfer mediators. Since the tested oxyanions serve as both electron acceptors and radical precursors in most cases, oxidative degradation of organics was achievable through one-electron reduction of oxyanions on nFe 0 (leading to radical-induced oxidation) and electron transfer mediation from organics to oxyanions on CNTs (leading to oxidative decomposition involving no radical formation). A distinction between degradative reaction mechanisms of the nFe 0 /oxyanion and CNT/oxyanion systems was made in terms of the oxyanion consumption efficacy, radical scavenging effect, and EPR spectral analysis. Statistical study of substrate-specificity and product distribution implied that the reaction route induced on nFe 0 varies depending on the oxyanion (i.e., oxyanion-derived radical), whereas the similar reaction pathway initiates organic oxidation in the CNT/oxyanion system irrespective of the oxyanion type. Chronoamperometric measurements further confirmed electron transfer from organics to oxyanions in the presence of CNTs, which was not observed when applying nFe 0 instead.

Applications of direct analysis in real time-mass spectrometry (DART-MS) in Allium chemistry. (Z)-butanethial S-oxide and 1-butenyl thiosulfinates and their S-(E)-1-butenylcysteine S-oxide precursor from Allium siculum.

Science.gov (United States)

Kubec, Roman; Cody, Robert B; Dane, A John; Musah, Rabi A; Schraml, Jan; Vattekkatte, Abith; Block, Eric

2010-01-27

Lachrymatory (Z)-butanethial S-oxide along with several 1-butenyl thiosulfinates was detected by DART mass spectrometry upon cutting Allium siculum , a popular ornamental Allium species used in some cultures as a spice. (Z)-Butanethial S-oxide isolated from the plant was shown to be identical to a synthetic sample. Its likely precursor, (R(S),R(C),E)-S-(1-butenyl)cysteine S-oxide (homoisoalliin), was isolated from homogenates of A. siculum, and a closely related species Allium tripedale , and fully characterized. Through use of LC-MS, a series of related gamma-glutamyl derivatives were tentatively identified in A. siculum and A. tripedale homogenates, including gamma-glutamyl-(E)-S-(1-butenyl)cysteine and its S-oxide, gamma-glutamyl-S-butylcysteine and its S-oxide, and gamma-glutamyl-S-methylcysteine and its S-oxide. Because compounds containing the 1-butenyl group have not been previously identified in genus Allium species, this work extends the range of known Allium sulfur compounds. The general applicability of DART mass spectrometry in identifying naturally occurring, thermally fragile thial S-oxides and thiosulfinates is illustrated with onion, Allium cepa , as well as a plant from a different genus, Petiveria alliacea .

Synthesis of zinc sulfide by chemical vapor deposition using an organometallic precursor: Di-tertiary-butyl-disulfide

International Nuclear Information System (INIS)

Vasekar, Parag; Dhakal, Tara; Ganta, Lakshmikanth; Vanhart, Daniel; Desu, Seshu

2012-01-01

Zinc sulfide has gained popularity in the last few years as a cadmium-free heterojunction partner for thin film solar cells and is seen as a good replacement for cadmium sulfide due to better blue photon response and non-toxicity. In this work, zinc sulfide films are prepared using an organic sulfur source. We report a simple and repeatable process for development of zinc sulfide using a cost-effective and less hazardous organic sulfur source. The development of zinc sulfide has been studied on zinc oxide-coated glass where the zinc oxide is converted into zinc sulfide. Zinc oxide grown by atomic layer deposition as well as commercially available zinc oxide-coated glass was used. The zinc sulfide synthesis has been studied and the films are characterized using scanning electron microscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and a UV–VIS spectrophotometer. XRD, XPS and optical characterization confirm the zinc sulfide phase formation. - Highlights: ► Synthesis of ZnS using a less-hazardous precursor, di-tertiary-butyl-disulfide. ► ZnS process optimized for two types of ZnO films. ► Preliminary results for a solar cell show an efficiency of 1.09%.

Building Composite Fe-Mn Oxide Flower-Like Nanostructures: A Detailed Magnetic Study

KAUST Repository

Zuddas, Efisio; Lentijo Mozo, Sergio; Casu, Alberto; Deiana, Davide; Falqui, Andrea

2017-01-01

Here we show that it’s possible to produce different magnetic core-multiple shells heterostructures from monodispersed iron oxide spherical magnetic seeds by finely controlling the amount of a manganese precursor and using in a smart and simple way a cation exchange synthetic approach. In particular, by increasing the amount of precursor we were able to produce nanostructures ranging from Fe3O4/Mn-ferrite core/single shell nanospheres to larger, flower-like Fe3O4/Mn-ferrite/Mn3O4 core-double shell nanoparticles. We first demonstrate how the formation of the initial thin manganese-ferrite shell determines a dramatic reduction of the superficial disorder in the starting iron oxide, bringing to nanomagnets with lower hardness. Then, the growth of the second and most external manganese oxide shell causes the magnetical hardening of the heterostructures, while its magnetic exchange coupling with the rest of the heterostructure can be antiferromagentic or ferromagnetic, depending on the strength of the applied external magnetic field. This response is similar to that of an iron oxide-manganese oxide core-shell system but differs from what observed in multiple-shell heterostructures. Finally, we report as the most external shell becomes magnetically irrelevant above the ferrimagnetic-paramagnetic transition of the manganese oxide and the resulting magnetic behavior of the flower-like structures is then studied in-depth.

Building Composite Fe-Mn Oxide Flower-Like Nanostructures: A Detailed Magnetic Study

KAUST Repository

Zuddas, Efisio

2017-07-21

Here we show that it’s possible to produce different magnetic core-multiple shells heterostructures from monodispersed iron oxide spherical magnetic seeds by finely controlling the amount of a manganese precursor and using in a smart and simple way a cation exchange synthetic approach. In particular, by increasing the amount of precursor we were able to produce nanostructures ranging from Fe3O4/Mn-ferrite core/single shell nanospheres to larger, flower-like Fe3O4/Mn-ferrite/Mn3O4 core-double shell nanoparticles. We first demonstrate how the formation of the initial thin manganese-ferrite shell determines a dramatic reduction of the superficial disorder in the starting iron oxide, bringing to nanomagnets with lower hardness. Then, the growth of the second and most external manganese oxide shell causes the magnetical hardening of the heterostructures, while its magnetic exchange coupling with the rest of the heterostructure can be antiferromagentic or ferromagnetic, depending on the strength of the applied external magnetic field. This response is similar to that of an iron oxide-manganese oxide core-shell system but differs from what observed in multiple-shell heterostructures. Finally, we report as the most external shell becomes magnetically irrelevant above the ferrimagnetic-paramagnetic transition of the manganese oxide and the resulting magnetic behavior of the flower-like structures is then studied in-depth.

Formation of complex precursors of amino acids by irradiation of simulated interstellar media with heavy ions

Science.gov (United States)

Kobayashi, K.; Suzuki, N.; Taniuchi, T.; Kaneko, T.; Yoshida, S.

A wide variety of organic compounds have been detected in such extraterrestrial bodies as meteorites and comets Amino acids were identified in the extracts from Murchison meteorite and other carbonaceous chondrites It is hypothesized that these compounds are originally formed in ice mantles of interstellar dusts ISDs in molecular clouds by cosmic rays and ultraviolet light UV Formation of amino acid precursors by high energy protons or UV irradiation of simulated ISDs was reported by several groups The amino acid precursors were however not well-characterized We irradiated a frozen mixture of methanol ammonia and water with heavy ions to study possible organic compounds abiotically formed in molecular clouds by cosmic rays A mixture of methanol ammonia and water was irradiated with carbon beams 290 MeV u from a heavy ion accelerator HIMAC of National Institute of Radiological Sciences Japan Irradiation was performed either at room temperature liquid phase or at 77 K solid phase The products were characterized by gel filtration chromatography GFC FT-IR pyrolysis PY -GC MS etc Amino acids were analyzed by HPLC and GC MS after acid hydrolysis or the products Amino acids such as glycine and alanine were identified in the products in both the cases of liquid phase and solid phase irradiation Energy yields G-values of glycine were 0 014 liquid phase and 0 007 solid phase respectively Average molecular weights of the products were estimated as to 2300 in both the case Aromatic hydrocarbons N-containing heterocyclic

Synthesis of Sol-Gel Precursors for Ceramics from Lunar and Martian Soil Simulars

Science.gov (United States)

Sibille, L.; Gavira-Gallardo, J. A.; Hourlier-Bahloul, D.

2004-01-01

Recent NASA mission plans for the human exploration of our Solar System has set new priorities for research and development of technologies necessary to enable a long-term human presence on the Moon and Mars. The recovery and processing of metals and oxides from mineral sources on other planets is under study to enable use of ceramics, glasses and metals by explorer outposts. We report initial results on the production of sol-gel precursors for ceramic products using mineral resources available in martian or lunar soil. The presence of SO2, TiO2, and Al2O3 in both martian (44 wt.% SiO2, 1 wt.% TiO2, 7 wt.% Al2O3) and lunar (48 wt.% SiO2, 1.5 wt.% TiO2, 16 wt.% Al2O3) soils and the recent developments in chemical processes to solubilize silicates using organic reagents and relatively little energy indicate that such an endeavor is possible. In order to eliminate the risks involved in the use of hydrofluoric acid to dissolve silicates, two distinct chemical routes are investigated to obtain soluble silicon oxide precursors from lunar and martian soil simulars. Clear solutions of sol-gel precursors have been obtained by dissolution of silica from lunar soil similar JSC-1 in basic ethylene glycol (C2H4(OH)2) solutions to form silicon glycolates. Similarly, sol-gel solutions produced from martian soil simulars reveal higher contents of iron oxides. Characterization of the precursor molecules and efforts to further concentrate and hydrolyze the products to obtain gel materials will be presented for evaluation as ceramic precursors.

Synthesis of Sol-Gel Precursors for Ceramics from Lunar and Martian Soil Simulars

Science.gov (United States)

Sibille, L.; Gavira-Gallardo, J. A.; Hourlier-Bahloul, D.

2003-01-01

Recent NASA mission plans for the human exploration of our Solar System has set new priorities for research and development of technologies necessary to enable a long-term human presence on the Moon and Mars. The recovery and processing of metals and oxides from mineral sources on other planets is under study to enable use of ceramics, glasses and metals by explorer outposts. We report initial results on the production of sol-gel precursors for ceramic products using mineral resources available in martian or lunar soil. The presence of SiO2, TiO2, and Al2O3 in both martian (44 wt.% SiO2, 1 wt.% TiO2,7 wt.% Al2O3) and lunar (48 wt.% SiO2, 1.5 wt.% TiO2, 16 wt.% Al2O3) soils and the recent developments in chemical processes to solubilize silicates using organic reagents and relatively little energy indicate that such an endeavor is possible. In order to eliminate the risks involved in the use of hydrofluoric acid to dissolve silicates, two distinct chemical routes are investigated to obtain soluble silicon oxide precursors from lunar and martian soil simulars. Clear solutions of sol-gel precursors have been obtained by dissolution of silica from lunar soil simular in basic ethylene glycol (C2H4(OH)2) solutions to form silicon glycolates. Similarly, sol-gel solutions produced from martian soil simulars reveal higher contents of iron oxides. The elemental composition and structure of the precursor molecules were characterized. Further concentration and hydrolysis of the products was performed to obtain gel materials for evaluation as ceramic precursors.

Atmospheric pressure plasma enhanced chemical vapor deposition of zinc oxide and aluminum zinc oxide

International Nuclear Information System (INIS)

Johnson, Kyle W.; Guruvenket, Srinivasan; Sailer, Robert A.; Ahrenkiel, S. Phillip; Schulz, Douglas L.

2013-01-01

Zinc oxide (ZnO) and aluminum-doped zinc oxide (AZO) thin films were deposited via atmospheric pressure plasma enhanced chemical vapor deposition. A second-generation precursor, bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)(N,N′-diethylethylenediamine) zinc, exhibited significant vapor pressure and good stability at one atmosphere where a vaporization temperature of 110 °C gave flux ∼ 7 μmol/min. Auger electron spectroscopy confirmed that addition of H 2 O to the carrier gas stream mitigated F contamination giving nearly 1:1 metal:oxide stoichiometries for both ZnO and AZO with little precursor-derived C contamination. ZnO and AZO thin film resistivities ranged from 14 to 28 Ω·cm for the former and 1.1 to 2.7 Ω·cm for the latter. - Highlights: • A second generation precursor was utilized for atmospheric pressure film growth. • Addition of water vapor to the carrier gas stream led to a marked reduction of ZnF 2 . • Carbonaceous contamination from the precursor was minimal

Heterometallic molecular precursors for a lithium-iron oxide material: synthesis, solid state structure, solution and gas-phase behaviour, and thermal decomposition.

Science.gov (United States)

Han, Haixiang; Wei, Zheng; Barry, Matthew C; Filatov, Alexander S; Dikarev, Evgeny V

2017-05-02

Three heterometallic single-source precursors with a Li : Fe = 1 : 1 ratio for a LiFeO 2 oxide material are reported. Heterometallic compounds LiFeL 3 (L = tbaoac (1), ptac (2), and acac(3)) have been obtained on a large scale, in nearly quantitative yields by one-step reactions that employ readily available reagents. The heterometallic precursor LiFe(acac) 3 (3) with small, symmetric substituents on the ligand (acac = pentane-2,4-dionate), maintains a 1D polymeric structure in the solid state that limits its volatility and prevents solubility in non-coordinating solvents. The application of the unsymmetrical ligands, tbaoac (tert-butyl acetoacetate) and ptac (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate), that exhibit different bridging properties at the two ends of the ligand, allowed us to change the connectivity pattern within the heterometallic assembly. The latter was demonstrated by structural characterization of heterometallic complexes LiFe(tbaoac) 3 (1) and LiFe(ptac) 3 (2) that consist of discrete heterocyclic tetranuclear molecules Li 2 Fe 2 L 6 . The compounds are highly volatile and exhibit a congruent sublimation character. DART mass spectrometric investigation revealed the presence of heterometallic molecules in the gas phase. The positive mode spectra are dominated by the presence of [M - L] + peaks (M = Li 2 Fe 2 L 6 ). In accord with their discrete molecular structure, complexes 1 and 2 are highly soluble in nearly all common solvents. In order to test the retention of the heterometallic structure in solution, the diamagnetic analog of 1, LiMg(tbaoac) 3 (4), has been isolated. Its tetranuclear molecular structure was found to be isomorphous to that of the iron counterpart. 1 H and 7 Li NMR spectroscopy unambiguously confirmed the presence of heterometallic molecules in solutions of non-coordinating solvents. The heterometallic precursor 1 was shown to exhibit clean thermal decomposition in air that results in phase-pure �

Interaction of amines with native aluminium oxide layers in non-aqueous environment: Application to the understanding of the formation of epoxy-amine/metal interphases

International Nuclear Information System (INIS)

Mercier, D.; Rouchaud, J.-C.; Barthes-Labrousse, M.-G.

2008-01-01

Interaction of propylamine (PA), 1,2-diaminoethane (DAE) or 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophorone diamine, IPDA) with native aluminium oxide layers in non-aqueous environment has been studied using time-resolved inductively coupled plasma optical emission spectroscopy (ICP-OES) and X-ray photoelectron spectroscopy (XPS). The formation of several surface complexes has been evidenced. Monodentate and bidentate metal-bond surface complexes (MBSC) result from interactions between the amine terminations of the molecule and aluminium cations by donation of the N lone electron pair to the metal ion (Lewis-like mechanism leading to O-Al...N bonds). Monodentate and bidentate hydrogen-bond surface complexes (HBSC) are due to interaction of the amino group with surface hydroxyl groups by protonation of the amine termination (Bronsted-like mechanism leading to the formation of Al-OH...N bonds) or interaction with carbonaceous contamination (C x O y H z ...N bonds). Diamines can also form mixed complexes with one amino group forming an O-Al...N bond and the other group forming an Al-OH...N or C x O y H z ...N bond. Al-OH...N and C x O y H z ...N bonds are less stable under vacuum than O-Al...N bonds, leading to partial desorption of the DAE molecules in vacuum and modification of the interaction modes. Only DAE and IPDA can lead to partial dissolution of the aluminium native (hydr)oxide films. A detailed mechanism of dissolution has been proposed based on the formation of mononuclear bidentate (chelate) MBSC by ligand exchange between the terminal η 1 -OH and bridged μ 2 -OH surface sites and the amino terminations of the molecule. The detachment of this complex from the surface is likely to be the precursor step to the formation of the interphase in epoxy-amine/metal systems

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

Science.gov (United States)

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

2015-01-01

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

Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

CERN Document Server

Schobesberger, Siegfried; Bianchi, Federico; Lönn, Gustaf; Ehn, Mikael; Lehtipalo, Katrianne; Dommen, Josef; Ehrhart, Sebastian; Ortega, Ismael K; Franchin, Alessandro; Nieminen, Tuomo; Riccobono, Francesco; Hutterli, Manuel; Duplissy, Jonathan; Almeida, João; Amorim, Antonio; Breitenlechner, Martin; Downard, Andrew J; Dunne, Eimear M; Flagan, Richard C; Kajos, Maija; Keskinen, Helmi; Kirkby, Jasper; Kupc, Agnieszka; Kürten, Andreas; Kurtén, Theo; Laaksonen, Ari; Mathot, Serge; Onnela, Antti; Praplan, Arnaud P; Rondo, Linda; Santos, Filipe D; Schallhart, Simon; Schnitzhofer, Ralf; Sipilä, Mikko; Tomé, António; Tsagkogeorgas, Georgios; Vehkamäki, Hanna; Wimmer, Daniela; Baltensperger, Urs; Carslaw, Kenneth S; Curtius, Joachim; Hansel, Armin; Petäjä, Tuukka; Kulmala, Markku; Donahue, Neil M; Worsnop, Douglas R

2013-01-01

Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molec...

Boron nitride ceramics from molecular precursors: synthesis, properties and applications.

Science.gov (United States)

Bernard, Samuel; Salameh, Chrystelle; Miele, Philippe

2016-01-21

Hexagonal boron nitride (h-BN) attracts considerable interest because its structure is similar to that of carbon graphite while it displays different properties which are of interest for environmental and green technologies. The polar nature of the B-N bond in sp(2)-bonded BN makes it a wide band gap insulator with different chemistry on its surface and particular physical and chemical properties such as a high thermal conductivity, a high temperature stability, a high resistance to corrosion and oxidation and a strong UV emission. It is chemically inert and nontoxic and has good environmental compatibility. h-BN also has enhanced physisorption properties due to the dipolar fields near its surface. Such properties are closely dependent on the processing method. Bottom-up approaches consist of transforming molecular precursors into non-oxide ceramics with retention of the structural units inherent to the precursor molecule. The purpose of the present review is to give an up-to-date overview on the most recent achievements in the preparation of h-BN from borazine-based molecular single-source precursors including borazine and 2,4,6-trichloroborazine through both vapor phase syntheses and methods in the liquid/solid state involving polymeric intermediates, called the Polymer-Derived Ceramics (PDCs) route. In particular, the effect of the chemistry, composition and architecture of the borazine-based precursors and derived polymers on the shaping ability as well as the properties of h-BN is particularly highlighted.

Advanced Precursor Reaction Processing for Cu(InGa)(SeS)2 Solar Cells

Energy Technology Data Exchange (ETDEWEB)

Shafarman, William N. [Univ. of Delaware, Newark, DE (United States)

2015-10-12

This project “Advanced Precursor Reaction Processing for Cu(InGa)(SeS)2 Solar Cells”, completed by the Institute of Energy Conversion (IEC) at the University of Delaware in collaboration with the Department of Chemical Engineering at the University of Florida, developed the fundamental understanding and technology to increase module efficiency and improve the manufacturability of Cu(InGa)(SeS)2 films using the precursor reaction approach currently being developed by a number of companies. Key results included: (1) development of a three-step H2Se/Ar/H2S reaction process to control Ga distribution through the film and minimizes back contact MoSe2 formation; (2) Ag-alloying to improve precursor homogeneity by avoiding In phase agglomeration, faster reaction and improved adhesion to allow wider reaction process window; (3) addition of Sb, Bi, and Te interlayers at the Mo/precursor junction to produce more uniform precursor morphology and improve adhesion with reduced void formation in reacted films; (4) a precursor structure containing Se and a reaction process to reduce processing time to 5 minutes and eliminate H2Se usage, thereby increasing throughput and reducing costs. All these results were supported by detailed characterization of the film growth, reaction pathways, thermodynamic assessment and device behavior.

Photochemical Formation of C1-C5 Alkyl Nitrates in Suburban Hong Kong and over the South China Sea.

Science.gov (United States)

Zeng, Lewei; Lyu, Xiaopu; Guo, Hai; Zou, Shichun; Ling, Zhenhao

2018-04-24

Alkyl nitrates (RONO 2 ) are important reservoirs of atmospheric nitrogen, regulating nitrogen cycling and ozone (O 3 ) formation. In this study, we found that propane and n-butane were significantly lower at the offshore site (WSI) in Hong Kong ( p 0.05). Stronger oxidative capacity at WSI led to more efficient RONO 2 formation. Relative incremental reactivity (RIR) was for the first time used to evaluate RONO 2 -precursor relationships. In contrast to a consistently volatile organic compounds (VOC)-limited regime at TC, RONO 2 formation at WSI switched from VOC-limited regime during O 3 episodes to VOC and nitrogen oxides (NO x ) colimited regime during nonepisodes. Furthermore, unlike the predominant contributions of parent hydrocarbons to C 4 -C 5 RONO 2 , the production of C 1 -C 3 RONO 2 was more sensitive to other VOCs like aromatics and carbonyls, which accounted for ∼40-90% of the productions of C 1 -C 3 alkylperoxy (RO 2 ) and alkoxy radicals (RO) at both sites. This resulted from the decomposition of larger RO 2 /RO and the change of OH abundance under the photochemistry of other VOCs. This study advanced our understanding of the photochemical formation of RONO 2 , particularly the relationships between RONO 2 and their precursors, which were not confined to the parent hydrocarbons.

MOCVD and ALD of rare earth containing multifunctional materials. From precursor chemistry to thin film deposition and applications

International Nuclear Information System (INIS)

Milanov, Andrian Petrov

2010-01-01

The present thesis deals with the development of metal-organic complexes of rare elements. They should be used as novel precursors for the production of rare earth thin films by metal-organic chemical vapor deposition (MOCVD) and Atomic Layer Deposition (ALD). Within the work two precursor classes were examined, the tris-Malonato-complexes as well as the tris-Guanidinato-complexes of a series of rare earth metals. The latter showed excellent properties regarding to their volatility, their thermal stability, the defined decomposition and high reactivity towards water. They have been successfully used as precursors for the MOCVD of rare earth oxide layers. By using of a gadolinium guanidinate it could also be shown that the rare earth guanidinates are promising precursors for ALD of rare earth oxide and MOCVD of rare earth nitride layers. [de

Formation of brominated phenolic contaminants from natural manganese oxides-catalyzed oxidation of phenol in the presence of Br(.).

Science.gov (United States)

Lin, Kunde; Song, Lianghui; Zhou, Shiyang; Chen, Da; Gan, Jay

2016-07-01

Brominated phenolic compounds (BPCs) are a class of persistent and potentially toxic compounds ubiquitously present in the aquatic environment. However, the origin of BPCs is not clearly understood. In this study, we investigated the formation of BPCs from natural manganese oxides (MnOx)-catalyzed oxidation of phenol in the presence of Br(-). Experiments at ambient temperature clearly demonstrated that BPCs were readily produced via the oxidation of phenol by MnOx in the presence of Br(-). In the reaction of MnOx sand with 0.213 μmol/L phenol and 0.34 mmol/L Br(-) for 10 min, more than 60% of phenol and 56% of Br(-) were consumed to form BPCs. The yield of BPCs increased with increasing concentrations of phenol and Br(-). Overall, a total of 14 BPCs including simple bromophenols (4-bromophenol, 2,4-dibromophenol, and 2,4,6-tribromophenol), hydroxylated polybrominated diphenyl ethers (OH-PBDEs), and hydroxylated polybrominated biphenyls (OH-PBBs) were identified. The production of BPCs increased with increasing concentrations of Br(-) or phenol. It was deduced that Br(-) was first oxidized to form active bromine, leading to the subsequent bromination of phenol to form bromophenols. The further oxidation of bromophenols by MnOx resulted in the formation of OH-PBDEs and OH-PBBs. In view of the ubiquity of phenol, Br(-), and MnOx in the environment, MnOx-mediated oxidation may play a role on the natural production of BPCs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Polycrystalline oxides formation during transient oxidation of (001) Cu-Ni binary alloys studied by in situ TEM and XRD

International Nuclear Information System (INIS)

Yang, J.C.; Li, Z.Q.; Sun, L.; Zhou, G.W.; Eastman, J.A.; Fong, D.D.; Fuoss, P.H.; Baldo, P.M.; Rehn, L.E.; Thompson, L.J.

2009-01-01

The nucleation and growth of Cu 2 O and NiO islands due to oxidation of Cu x Ni 1-x (001) films were monitored, at various temperatures, by in situ ultra-high vacuum (UHV) transmission electron microscopy (TEM) and in situ synchrotron X-ray diffraction (XRD). In remarkable contrast to our previous observations of Cu and Cu-Au oxidation, irregular-shaped polycrystalline oxide islands formed with respect to the Cu-Ni alloy film, and an unusual second oxide nucleation stage was noted. In situ XRD experiments revealed that NiO formed first epitaxially, then other orientations appeared, and finally polycrystalline Cu 2 O developed as the oxidation pressure was increased. The segregation of Ni and Cu towards or away, respectively, from the alloy surface during oxidation could disrupt the surface and cause polycrystalline oxide formation.

Acrylamide formation in almonds (Prunus dulcis): influences of roasting time and temperature, precursors, varietal selection, and storage.

Science.gov (United States)

Zhang, Gong; Huang, Guangwei; Xiao, Lu; Seiber, James; Mitchell, Alyson E

2011-08-10

Acrylamide is a probable human carcinogen that is found in many roasted and baked foods. This paper describes two sensitive and reliable LC-(ESI)MS/MS methods for the analysis of (1) acrylamide and (2) common acrylamide precursors (i.e., glucose, fructose, asparagine, and glutamine) in raw and roasted almonds. These methods were used to evaluate the impact of roasting temperatures (between 129 and 182 °C) and times on acrylamide formation. Controlling the roasting temperature at or below 146 °C resulted in acrylamide levels below 200 ppb at all roasting times evaluated. Six varieties of almonds collected in various regions of California over two harvest years and roasted at 138 °C for 22 min had acrylamide levels ranging from 117 ± 5 μg/kg (Sonora) to 221 ± 95 μg/kg (Butte) with an average of 187 ± 71 μg/kg. A weak correlation between asparagine content in raw almonds and acrylamide formation was observed (R(2) = 0.6787). No statistical relationship was found between acrylamide formation and almond variety, orchard region, or harvest year. Stability studies on roasted almonds indicated that acrylamide levels decreased by 12.9-68.5% (average of 50.2%) after 3 days of storage at 60 °C. Short-term elevated temperature storage may be another approach for mitigating acrylamide levels in roasted almonds.

Accumulation of the Vitamin D Precursor Cholecalciferol Antagonizes Hedgehog Signaling to Impair Hemogenic Endothelium Formation

Directory of Open Access Journals (Sweden)

Mauricio Cortes

2015-10-01

Full Text Available Hematopoietic stem and progenitor cells (HSPCs are born from hemogenic endothelium in the dorsal aorta. Specification of this hematopoietic niche is regulated by a signaling axis using Hedgehog (Hh and Notch, which culminates in expression of Runx1 in the ventral wall of the artery. Here, we demonstrate that the vitamin D precursor cholecalciferol (D3 modulates HSPC production by impairing hemogenic vascular niche formation. Accumulation of D3 through exogenous treatment or inhibition of Cyp2r1, the enzyme required for D3 25-hydroxylation, results in Hh pathway antagonism marked by loss of Gli-reporter activation, defects in vascular niche identity, and reduced HSPCs. Mechanistic studies indicated the effect was specific to D3, and not active 1,25-dihydroxy vitamin D3, acting on the extracellular sterol-binding domain of Smoothened. These findings highlight a direct impact of inefficient vitamin D synthesis on cell fate commitment and maturation in Hh-regulated tissues, which may have implications beyond hemogenic endothelium specification.

Aging promotes todorokite formation from layered manganese oxide at near-surface conditions

Energy Technology Data Exchange (ETDEWEB)

Cui, Haojie [Chinese Academy of Sciences, Xiamen (China). Key Lab. of Urban Environment and Health; Huazhong Agricultural Univ., Ministry of Agriculture, Wuhan (China). Key Lab. of Subtropical Agricultural Resources and Environment; Liu, Fan; Feng, Xionghan; Tan, Wenfeng [Huazhong Agricultural Univ., Ministry of Agriculture, Wuhan (China). Key Lab. of Subtropical Agricultural Resources and Environment; Wang, Ming Kuang [National Taiwan Univ., Taipei (China). Dept. of Agricultural Chemistry

2010-12-15

Todorokite is one common manganese oxide in soils and sediments and is commonly formed from layered Na-buserite. Aging processes can alter the physicochemical properties of freshly formed Na-buserite in natural environments. However, it is not clear whether and how aging affects the formation of todorokites. In the present paper, Na-buserite with aging treatment was employed to prepare todorokite at atmospheric pressure to investigate the effects of aging treatment of Na-buserite on the formation of todorokite. Four aged Na-buserite samples, which are produced through oxidation of Mn{sup 2+} in concentrated NaOH medium by O{sub 2} with aging for 3, 6, 9, and 12 months, were employed to investigate the effects of aging processes on the transformation from Na-buserite to todorokite by Mg{sup 2+}-templating reaction at atmospheric pressure. The manganese oxides were examined using X-ray diffraction (XRD), elemental analysis, determinations of the average manganese oxidation number, infrared spectroscopy (IR), and transmission electron microscopy (TEM). The XRD, IR, and elemental analyses indicate that aging treatment can alter the substructure of the freshly synthesized Na-buserite. During the aging process, some of the Mn(III) may migrate into the interlayer region or disproportionate to form Mn{sup 2+} and Mn{sup 4+} from the layer of Na-buserite and the concomitant formation of layer vacancies. The interlayer Mn{sup 3+} or Mn{sup 2+} occupied above or below the layer vacancy sites and become corner-sharing octahedral. XRD analyses and TEM clearly show that the transformation from Na-buserite to todorokite was promoted by aging treatments. The alterations of substructure of aged Na-buserites can promote the rearrangement of manganese to construct a tunnel structure during the transformation from layered manganese oxides to tunnel-structure todorokite at atmospheric pressure. The transformation from Na-buserite to todorokite was promoted by aging treatments at

Formation of porous silicon oxide from substrate-bound silicon rich silicon oxide layers by continuous-wave laser irradiation

Science.gov (United States)

Wang, Nan; Fricke-Begemann, Th.; Peretzki, P.; Ihlemann, J.; Seibt, M.

2018-03-01

Silicon nanocrystals embedded in silicon oxide that show room temperature photoluminescence (PL) have great potential in silicon light emission applications. Nanocrystalline silicon particle formation by laser irradiation has the unique advantage of spatially controlled heating, which is compatible with modern silicon micro-fabrication technology. In this paper, we employ continuous wave laser irradiation to decompose substrate-bound silicon-rich silicon oxide films into crystalline silicon particles and silicon dioxide. The resulting microstructure is studied using transmission electron microscopy techniques with considerable emphasis on the formation and properties of laser damaged regions which typically quench room temperature PL from the nanoparticles. It is shown that such regions consist of an amorphous matrix with a composition similar to silicon dioxide which contains some nanometric silicon particles in addition to pores. A mechanism referred to as "selective silicon ablation" is proposed which consistently explains the experimental observations. Implications for the damage-free laser decomposition of silicon-rich silicon oxides and also for controlled production of porous silicon dioxide films are discussed.

Ozone Promotes Chloropicrin Formation by Oxidizing Amines to Nitro Compounds.

Science.gov (United States)

McCurry, Daniel L; Quay, Amanda N; Mitch, William A

2016-02-02

Chloropicrin formation has been associated with ozonation followed by chlorination, but the reaction pathway and precursors have been poorly characterized. Experiments with methylamine demonstrated that ozonation converts methylamine to nitromethane at ∼100% yield. Subsequent chlorination converts nitromethane to chloropicrin at ∼50% yield under the conditions evaluated. Similarly high yields from other primary amines were limited to those with functional groups on the β-carbon (e.g., the carboxylic acid in glycine) that facilitate carbon-carbon bond cleavage to release nitromethyl anion. Secondary amines featuring these reactive primary amines as functional groups (e.g., secondary N-methylamines) formed chloropicrin at high yields, likely by facile dealkylation to release the primary nitro compound. Chloropicrin yields from tertiary amines were low. Natural water experiments, including derivatization to transform primary and secondary amines to less reactive carbamate functional groups, indicated that primary and secondary amines were the dominant chloropicrin precursors during ozonation/chlorination. Ozonation followed by chlorination of the primary amine side chain of lysine demonstrated low yields (∼0.2%) of chloropicrin, but high yields (∼17%) of dichloronitrolysine, a halonitroalkane structural analogue to chloropicrin. However, chloropicrin yields increased and dichloronitrolysine yields decreased in the absence of hydroxyl radical scavengers, suggesting that future research should characterize the potential occurrence of such halonitroalkane analogues relative to natural radical scavenger (e.g., carbonate) concentrations.

Spray deposited gallium doped tin oxide thinfilm for acetone sensor application

Science.gov (United States)

Preethi, M. S.; Bharath, S. P.; Bangera, Kasturi V.

2018-04-01

Undoped and gallium doped (1 at.%, 2 at.% and 3 at.%) tin oxide thin films were prepared using spray pyrolysis technique by optimising the deposition conditions such as precursor concentration, substrate temperature and spraying rate. X-ray diffraction analysis revealed formation of tetragonally structured polycrystalline films. The SEM micrographs of Ga doped films showed microstructures. The electrical resistivity of the doped films was found to be more than that of the undoped films. The Ga-doped tin oxide thin films were characterised for gas sensors. 1 at.% Ga doped thin films were found to be better acetone gas sensor, showed 68% sensitivity at 350°C temperature.

Empirical soot formation and oxidation model

Directory of Open Access Journals (Sweden)

Boussouara Karima

2009-01-01

Full Text Available Modelling internal combustion engines can be made following different approaches, depending on the type of problem to be simulated. A diesel combustion model has been developed and implemented in a full cycle simulation of a combustion, model accounts for transient fuel spray evolution, fuel-air mixing, ignition, combustion, and soot pollutant formation. The models of turbulent combustion of diffusion flame, apply to diffusion flames, which one meets in industry, typically in the diesel engines particulate emission represents one of the most deleterious pollutants generated during diesel combustion. Stringent standards on particulate emission along with specific emphasis on size of emitted particulates have resulted in increased interest in fundamental understanding of the mechanisms of soot particulate formation and oxidation in internal combustion engines. A phenomenological numerical model which can predict the particle size distribution of the soot emitted will be very useful in explaining the above observed results and will also be of use to develop better particulate control techniques. A diesel engine chosen for simulation is a version of the Caterpillar 3406. We are interested in employing a standard finite-volume computational fluid dynamics code, KIVA3V-RELEASE2.

Using Dopants to Tune Oxygen Vacancy Formation in Transition Metal Oxide Resistive Memory.

Science.gov (United States)

Jiang, Hao; Stewart, Derek A

2017-05-17

Introducing dopants is an important way to tailor and improve electronic properties of transition metal oxides used as high-k dielectric thin films and resistance switching layers in leading memory technologies, such as dynamic and resistive random access memory (ReRAM). Ta 2 O 5 has recently received increasing interest because Ta 2 O 5 -based ReRAM demonstrates high switching speed, long endurance, and low operating voltage. However, advances in optimizing device characteristics with dopants have been hindered by limited and contradictory experiments in this field. We report on a systematic study on how various metal dopants affect oxygen vacancy formation in crystalline and amorphous Ta 2 O 5 from first principles. We find that isoelectronic dopants and weak n-type dopants have little impact on neutral vacancy formation energy and that p-type dopants can lower the formation energy significantly by introducing holes into the system. In contrast, n-type dopants have a deleterious effect and actually increase the formation energy for charged oxygen vacancies. Given the similar doping trend reported for other binary transition metal oxides, this doping trend should be universally valid for typical binary transition metal oxides. Based on this guideline, we propose that p-type dopants (Al, Hf, Zr, and Ti) can lower the forming/set voltage and improve retention properties of Ta 2 O 5 ReRAM.

A conceptual and calculational model for gas formation from impure calcined plutonium oxides

International Nuclear Information System (INIS)

Lyman, John L.; Eller, P. Gary

2000-01-01

Safe transport and storage of pure and impure plutonium oxides requires an understanding of processes that may generate or consume gases in a confined storage vessel. We have formulated conceptual and calculational models for gas formation from calcined materials. The conceptual model for impure calcined plutonium oxides is based on the data collected to date

Formation of Lamellar Structured Oxide Dispersion Strengthening Layers in Zircaloy-4

Energy Technology Data Exchange (ETDEWEB)

Jung, Yang-Il; Park, Jung-Hwan; Park, Dong-Jun; Kim, Hyun-Gil; Yang, Jae-Ho; Koo, Yang-Hyun [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Lim, Yoon-Soo [Hanbat National University, Daejeon (Korea, Republic of)

2016-10-15

Korea Atomic Energy Research Institute (KAERI) is one of the leading organizations for developing ATF claddings. One concept is to form an oxidation-resistant layer on Zr cladding surface. The other is to increase high-temperature mechanical strength of Zr tube. The oxide dispersion strengthened (ODS) zirconium was proposed to increase the strength of the Zr-based alloy up to high temperatures. According to our previous investigations, the tensile strength of Zircaloy-4 was increased by up to 20% with the formation of a thin dispersed oxide layer with a thickness less than 10% of that of the Zircaloy-4 substrate. However, the tensile elongation of the samples decreased drastically. The brittle fracture was a major concern in development of the ODS Zircaloy-4. In this study, a lamellar structure of ODS layer was formed to increase ductility of the ODS Zircaloy-4. The mechanical properties were varied depending on the structure of ODS layer. For example, the partial formation of ODS layer with the thickness of 10% to the substrate thickness induced the increase in tensile strength up to about 20% than fresh Zircaloy-4.

Carboxyhemoglobin formation secondary to nitric oxide therapy in the setting of interstitial lung disease and pulmonary hypertension.

Science.gov (United States)

Ruisi, Phillip; Ruisi, Michael

2011-01-01

Carbon monoxide (CO) has been widely recognized as an exogenous poison, although endogenous mechanisms for its formation involve heme-oxygenase (HO) isoforms, more specifically HO-1, in the setting of oxidative stress such as acute respiratory distress syndrome, sepsis, trauma, and nitric oxide use have been studied. In patients with refractory hypoxemia, inhaled nitric oxide (iNO) therapy is used to selectively vasodilate the pulmonary vasculature and improve ventilation-perfusion match. Inhaled nitric oxide is rapidly inactivated on binding to hemoglobin in the formation of nitrosyl- and methemoglobin in the pulmonary vasculature. Hence, inhaled nitric oxide has minimal systemic dissemination. Several experimental design studies involving lab rats have demonstrated increased levels of carboxyhemoglobin and exhaled CO as a result of nitric oxide HO-1 induction.

Hygroscopicity of secondary organic aerosols formed by oxidation of cycloalkenes, monoterpenes, sesquiterpenes, and related compounds

Directory of Open Access Journals (Sweden)

V. Varutbangkul

2006-01-01

Full Text Available A series of experiments has been conducted in the Caltech indoor smog chamber facility to investigate the water uptake properties of aerosol formed by oxidation of various organic precursors. Secondary organic aerosol (SOA from simple and substituted cycloalkenes (C5-C8 is produced in dark ozonolysis experiments in a dry chamber (RH~5%. Biogenic SOA from monoterpenes, sesquiterpenes, and oxygenated terpenes is formed by photooxidation in a humid chamber (~50% RH. Using the hygroscopicity tandem differential mobility analyzer (HTDMA, we measure the diameter-based hygroscopic growth factor (GF of the SOA as a function of time and relative humidity. All SOA studied is found to be slightly hygroscopic, with smaller water uptake than that of typical inorganic aerosol substances. The aerosol water uptake increases with time early in the experiments for the cycloalkene SOA, but decreases with time for the sesquiterpene SOA. This behavior could indicate competing effects between the formation of more highly oxidized polar compounds (more hygroscopic, and formation of longer-chained oligomers (less hygroscopic. All SOA also exhibit a smooth water uptake with RH with no deliquescence or efflorescence. The water uptake curves are found to be fitted well with an empirical three-parameter functional form. The measured pure organic GF values at 85% RH are between 1.09–1.16 for SOA from ozonolysis of cycloalkenes, 1.01–1.04 for sesquiterpene photooxidation SOA, and 1.06–1.10 for the monoterpene and oxygenated terpene SOA. The GF of pure SOA (GForg in experiments in which inorganic seed aerosol is used is determined by assuming volume-weighted water uptake (Zdanovskii-Stokes-Robinson or 'ZSR' approach and using the size-resolved organic mass fraction measured by the Aerodyne Aerosol Mass Spectrometer. Knowing the water content associated with the inorganic fraction yields GForg values. However, for each precursor, the GForg values computed from different

Catalytic oxidation of n-hexane promoted by Ce1−xCuxO2 catalysts prepared by one-step polymeric precursor method

International Nuclear Information System (INIS)

Araújo, Vinícius D.; Lima, Maurício M. de; Cantarero, Andrés; Bernardi, Maria I.B.; Bellido, Jorge D.A.; Assaf, Elisabete M.; Balzer, Rosana; Probst, Luiz F.D.; Fajardo, Humberto V.

2013-01-01

Ceria-supported copper catalysts (Ce 1−x Cu x O 2 , with x (mol) = 0, 0.01, 0.03, 0.05 and 0.10) were prepared in one step through the polymeric precursor method. The textural properties of the catalysts were investigated by X-ray diffraction (XRD), Rietveld refinement, N 2 -physisorption (BET surface area), electron paramagnetic resonance (EPR), UV–visible diffuse reflectance and photoluminescence spectroscopies and temperature-programmed reduction (TPR). In a previous study ceria-supported copper catalysts were found to be efficient in the preferential oxidation of CO. In this study, we extended the catalytic application of Ce 1−x Cu x O 2 systems to n-hexane oxidation and it was verified that the catalysts were highly efficient in the proposed reaction. The best performance (up to 95% conversion) was observed for the catalysts with low copper loads (Ce 0.97 Cu 0.03 O 2 and Ce 0.99 Cu 0.01 O 2 , respectively). The physicochemical characterizations revealed that these behaviors could be attributed to the copper species present in the catalysts and the interaction between CuO and CeO 2 , which vary according to the copper content. - Highlights: • Synthesis of CuO/CeO2 catalysts by the one-step polymeric precursor method. • 95% n-hexane conversion on Ce0.97Cu0.03O2 catalyst. • Redox properties play a key role in the catalytic performance

Influence of Process Parameters on Nitrogen Oxide Formation in

DEFF Research Database (Denmark)

Lans, Robert Pieter Van Der; Glarborg, Peter; Dam-Johansen, Kim

1997-01-01

This paper describes the influence of burner operating conditions, burner geometry and fuel parameters on the formation of nitrogen oxide during combustion of pulverized coal. Main attention has been paid to combustion test facilities with self-sustaining flames, while extensions have been made...... to full scale boilers and furnace modeling. Since coal combustion and flame aerodynamics have been reviewed earlier, these phenomena are only treated briefly....

Ion-molecule reactions in the binary mixture of ethylene oxide and trioxane, 1

International Nuclear Information System (INIS)

Kumakura, Minoru; Sugiura, Toshio.

1977-01-01

The formation mechanism of protonated molecular ions by cross-reactions in ethylene oxide-trioxane mixtures has been studied with use of a modified time-of-flight mass spectrometer. The precursors of the product ions were determined by analysis of the fine structure of their ionization efficiency curves using deuterated ethylene oxide. Protonated ethylene oxide is formed by the hydrogen atom transfer reaction of ethylene oxide molecular ion with trioxane, and protonated trioxane by the proton transfer reaction of CHO + (from ethylene oxide) with trioxane. In the ion-molecule reactions of ethylene-d 4 oxide-trioxane mixtures, appreciable isotope effect was observed. The CHO + from ethylene oxide is an important reactant ion as compared with that from trioxane in the proton transfer reaction, and CHO + from ethylene oxide was suggested as a thermal reactive ion. The order of proton affinity could be estimated from the proton transfer reactions involving CHO + . It was found that the proton affinity of trioxane is smaller than that of ethylene oxide. (auth.)

Formation and Transformation of Iron Oxide-Kaolinite Associations in the Presence of Iron(II)

NARCIS (Netherlands)

Wei, S.Y.; Liu, F.; Feng, X.H.; Tan, W.F.; Koopal, L.K.

2011-01-01

Iron oxide-kaolinite associations are important components of tropical and subtropical soils and have significant influence on the physical and chemical properties of soils. In this study, the formation and transformation of Fe oxide-kaolinite associations as a function of pH, temperature, and time

Nickel Oxide (NiO nanoparticles prepared by solid-state thermal decomposition of Nickel (II schiff base precursor

Directory of Open Access Journals (Sweden)

Aliakbar Dehno Khalaji

2015-06-01

Full Text Available In this paper, plate-like NiO nanoparticles were prepared by one-pot solid-state thermal decomposition of nickel (II Schiff base complex as new precursor. First, the nickel (II Schiff base precursor was prepared by solid-state grinding using nickel (II nitrate hexahydrate, Ni(NO32∙6H2O, and the Schiff base ligand N,N′-bis-(salicylidene benzene-1,4-diamine for 30 min without using any solvent, catalyst, template or surfactant. It was characterized by Fourier Transform Infrared spectroscopy (FT-IR and elemental analysis (CHN. The resultant solid was subsequently annealed in the electrical furnace at 450 °C for 3 h in air atmosphere. Nanoparticles of NiO were produced and characterized by X-ray powder diffraction (XRD at 2θ degree 0-140°, FT-IR spectroscopy, scanning electron microscopy (SEM and transmission electron microscopy (TEM. The XRD and FT-IR results showed that the product is pure and has good crystallinity with cubic structure because no characteristic peaks of impurity were observed, while the SEM and TEM results showed that the obtained product is tiny, aggregated with plate-like shape, narrow size distribution with an average size between 10-40 nm. Results show that the solid state thermal decomposition method is simple, environmentally friendly, safe and suitable for preparation of NiO nanoparticles. This method can also be used to synthesize nanoparticles of other metal oxides.

Fluorination of Boron-Doped Diamond Film Electrodes for Minimization of Perchlorate Formation.

Science.gov (United States)

Gayen, Pralay; Chaplin, Brian P

2017-08-23

This research investigated the effects of surface fluorination on both rates of organic compound oxidation (phenol and terephthalic acid (TA)) and ClO 4 - formation at boron-doped diamond (BDD) film anodes at 22 °C. Different fluorination methods (i.e., electrochemical oxidation with perfluorooctanoic acid (PFOA), radio frequency plasma, and silanization) were used to incorporate fluorinated moieties on the BDD surface, which was confirmed by X-ray photoelectron spectroscopy (XPS). The silanization method was found to be the most effective fluorination method using a 1H,1H,2H,2H-perfluorodecyltrichlorosilane precursor to form a self-assembled monolayer (SAM) on the oxygenated BDD surface. The ClO 4 - formation decreased from rates of 0.45 ± 0.03 mmol m -2 min -1 during 1 mM NaClO 3 oxidation and 0.28 ± 0.01 mmol m -2 min -1 during 10 mM NaCl oxidation on the BDD electrode to below detectable levels (layer on the BDD surface that inhibited charge transfer via steric hindrance and hydrophobic effects. The surface coverages and thicknesses of the fluorinated films controlled the charge transfer rates, which was confirmed by estimates of film thicknesses using XPS and density functional theory simulations. The aliphatic silanized electrode also showed very high stability during OH • production. Perchlorate formation rates were below the detection limit (<0.12 μmoles m -2 min -1 ) for up to 10 consecutive NaClO 3 oxidation experiments.

Reduced graphene oxide-wrapped MoO3 composites prepared by using metal-organic frameworks as precursor for all-solid-state flexible supercapacitors.

Science.gov (United States)

Cao, Xiehong; Zheng, Bing; Shi, Wenhui; Yang, Jian; Fan, Zhanxi; Luo, Zhimin; Rui, Xianhong; Chen, Bo; Yan, Qingyu; Zhang, Hua

2015-08-26

Reduced graphene oxide-wrapped MoO3M (rGO/MoO3 ) is prepared by a novel and simple method that is developed by using a metal-organic framework as the precursor. After a two-step annealing process, the obtained rGO/MoO3 composite is used for a high-performance supercapacitor electrode. Moreover, an all-solid-state flexible supercapacitor is fabricated based on the rGO/MoO3 composite, which shows stable performance under different bending states. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

PARTITIONING TUNGSTEN BETWEEN MATRIX PRECURSORS AND CHONDRULE PRECURSORS THROUGH RELATIVE SETTLING

Energy Technology Data Exchange (ETDEWEB)

Hubbard, Alexander, E-mail: ahubbard@amnh.org [American Museum of Natural History, New York, NY (United States)

2016-08-01

Recent studies of chondrites have found a tungsten isotopic anomaly between chondrules and matrix. Given the refractory nature of tungsten, this implies that W was carried into the solar nebula by at least two distinct families of pre-solar grains. The observed chondrule/matrix split requires that the distinct families were kept separate during the dust coagulation process, and that the two families of grain interacted with the chondrule formation mechanism differently. We take the co-existence of different families of solids in the same general orbital region at the chondrule-precursor size as given, and explore the requirements for them to have interacted with the chondrule formation process at significantly different rates. We show that this sorting of families of solids into chondrule- and matrix-destined dust had to have been at least as powerful a sorting mechanism as the relative settling of aerodynamically distinct grains at least two scale heights above the midplane. The requirement that the chondrule formation mechanism was correlated in some fashion with a dust-grain sorting mechanism argues strongly for spatially localized chondrule formation mechanisms such as turbulent dissipation in non-thermally ionized disk surface layers, and argues against volume-filling mechanisms such as planetesimal bow shocks.

PARTITIONING TUNGSTEN BETWEEN MATRIX PRECURSORS AND CHONDRULE PRECURSORS THROUGH RELATIVE SETTLING

International Nuclear Information System (INIS)

Hubbard, Alexander

2016-01-01

Recent studies of chondrites have found a tungsten isotopic anomaly between chondrules and matrix. Given the refractory nature of tungsten, this implies that W was carried into the solar nebula by at least two distinct families of pre-solar grains. The observed chondrule/matrix split requires that the distinct families were kept separate during the dust coagulation process, and that the two families of grain interacted with the chondrule formation mechanism differently. We take the co-existence of different families of solids in the same general orbital region at the chondrule-precursor size as given, and explore the requirements for them to have interacted with the chondrule formation process at significantly different rates. We show that this sorting of families of solids into chondrule- and matrix-destined dust had to have been at least as powerful a sorting mechanism as the relative settling of aerodynamically distinct grains at least two scale heights above the midplane. The requirement that the chondrule formation mechanism was correlated in some fashion with a dust-grain sorting mechanism argues strongly for spatially localized chondrule formation mechanisms such as turbulent dissipation in non-thermally ionized disk surface layers, and argues against volume-filling mechanisms such as planetesimal bow shocks.

Formation of assimilable organic carbon during oxidation of natural waters with ozone, chlorine dioxide, chlorine, permanganate, and ferrate.

Science.gov (United States)

Ramseier, Maaike K; Peter, Andreas; Traber, Jacqueline; von Gunten, Urs

2011-02-01

Five oxidants, ozone, chlorine dioxide, chlorine, permanganate, and ferrate were studied with regard to the formation of assimilable organic carbon (AOC) and oxalate in absence and presence of cyanobacteria in lake water matrices. Ozone and ferrate formed significant amounts of AOC, i.e. more than 100 μg/L AOC were formed with 4.6 mg/L ozone and ferrate in water with 3.8 mg/L dissolved organic carbon. In the same water samples chlorine dioxide, chlorine, and permanganate produced no or only limited AOC. When cyanobacterial cells (Aphanizomenon gracile) were added to the water, an AOC increase was detected with ozone, permanganate, and ferrate, probably due to cell lysis. This was confirmed by the increase of extracellular geosmin, a substance found in the selected cyanobacterial cells. AOC formation by chlorine and chlorine dioxide was not affected by the presence of the cells. The formation of oxalate upon oxidation was found to be a linear function of the oxidant consumption for all five oxidants. The following molar yields were measured in three different water matrices based on oxidant consumed: 2.4-4.4% for ozone, 1.0-2.8% for chlorine dioxide and chlorine, 1.1-1.2% for ferrate, and 11-16% for permanganate. Furthermore, oxalate was formed in similar concentrations as trihalomethanes during chlorination (yield ∼ 1% based on chlorine consumed). Oxalate formation kinetics and stoichiometry did not correspond to the AOC formation. Therefore, oxalate cannot be used as a surrogate for AOC formation during oxidative water treatment. Copyright © 2010 Elsevier Ltd. All rights reserved.

Synthesis of aluminum oxide by the polymer precursor method (Pechini) in 4: 1 ratio of citric acid: metal cation: calcination temperature effect

International Nuclear Information System (INIS)

Silva, M.C.; Lira, H.L.; Ribeiro, P.C.; Freitas, N.L.

2014-01-01

The technology field is nanopowders prominent in science since these materials fall in various sectors regarding their applications. This work aims at the synthesis of aluminum oxide by polymeric precursors in 4:1 ratio of citric acid:metal cation and evaluate the influence of calcination temperature on their structural and morphological characteristics. The samples after reaction were characterized by XRD and thermal analysis. After calcination 500-1200°C the samples were characterized by XRD, SEM and particle size distribution. The results showed that the variation of the calcination temperature is sufficient to achieve a same material with different structural and morphological characteristics. The most stable phase aluminum oxide arose only after calcination at 1100°C, below 900°C, the amorphous material appeared. As regards the morphology, the change was not as significant as compared to the structure. (author)

Molecular structure impacts on secondary organic aerosol formation from glycol ethers

Science.gov (United States)

Li, Lijie; Cocker, David R.

2018-05-01

Glycol ethers, a class of widely used solvents in consumer products, are often considered exempt as volatile organic compounds based on their vapor pressure or boiling points by regulatory agencies. However, recent studies found that glycol ethers volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents indicating the potential of glycol ethers to form secondary organic aerosol (SOA). This is the first work on SOA formation from glycol ethers. The impact of molecular structure, specifically -OH, on SOA formation from glycol ethers and related ethers are investigated in the work. Ethers with and without -OH, with methyl group hindrance on -OH and with -OH at different location are studied in the presence of NOX and under "NOX free" conditions. Photooxidation experiments under different oxidation conditions confirm that the processing of ethers is a combination of carbonyl formation, cyclization and fragmentation. Bulk SOA chemical composition analysis and oxidation products identified in both gas and particle phase suggests that the presence and location of -OH in the carbon bond of ethers determine the occurrence of cyclization mechanism during ether oxidation. The cyclization is proposed as a critical SOA formation mechanism to prevent the formation of volatile compounds from fragmentation during the oxidation of ethers. Glycol ethers with -CH2-O-CH2CH2OH structure is found to readily form cyclization products, especially with the presence of NOx, which is more relevant to urban atmospheric conditions than without NOx. Glycol ethers are evaluated as dominating SOA precursors among all ethers studied. It is estimated that the contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources. The contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources and will play a more important role in future anthropogenic SOA

SOA formation from photooxidation of naphthalene and methylnaphthalenes with m-xylene and surrogate mixtures

Science.gov (United States)

Chen, Chia-Li; Li, Lijie; Tang, Ping; Cocker, David R.

2018-05-01

SOA formation is not well predicted in current models in urban area. The interaction among multiple anthropogenic volatile organic compounds is essential for the SOA formation in the complex urban atmosphere. Secondary organic aerosol (SOA) from the photooxidation of naphthalene, 1-methylnaphthalene, and 2-methylnaphthalene as well as individual polycyclic aromatic hydrocarbons (PAHs) mixed with m-xylene or an atmospheric surrogate mixture was explored in the UCR CE-CERT environmental chamber under urban relevant low NOx and extremely low NOx (H2O2) conditions. Addition of m-xylene suppressed SOA formation from the individual PAH precursor. A similar suppression effect on SOA formation was observed during the surrogate mixture photooxidation suggesting the importance of gas-phase chemical reactivity to SOA formation. The SOA growth rate for different PAH-m-xylene mixtures was strongly correlated with initial [HO2]/[RO2] ratio but negatively correlated with initial m-xylene/NO ratio. Decreasing SOA formation was observed for increasing m-xylene/PAHs ratios and increasing initial m-xylene/NO ratio. The SOA chemical composition characteristics such as f44 versus f43, H/C ratio, O/C ratio, and the oxidation state of the carbon OSbarc were consistent with a continuously aging with the SOA exhibiting characteristics of both individual precursors. SOA formation from PAHs was also suppressed within an atmospheric surrogate mixture compared to the SOA formed from individual PAHs, indicating that atmospheric reactivity directly influences SOA formation from PAHs.

Essential elucidation for preparation of supported nickel phosphide upon nickel phosphate precursor

International Nuclear Information System (INIS)

Liu, Xuguang; Xu, Lei; Zhang, Baoquan

2014-01-01

Preparation of supported nickel phosphide (Ni 2 P) depends on nickel phosphate precursor, generally related to its chemical composition and supports. Study of this dependence is essential and meaningful for the preparation of supported Ni 2 P with excellent catalytic activity. The chemical nature of nickel phosphate precursor is revealed by Raman and UV–vis spectra. It is found that initial P/Ni mole ratio ≥0.8 prohibits the Ni-O-Ni bridge bonding (i.e., nickel oxide). This chemical bonding will not result in Ni 2 P structure, verified by XRD characterization results. The alumina (namely, γ-Al 2 O 3 , θ-Al 2 O 3 , or α-Al 2 O 3 ) with distinct physiochemical properties also results in diverse chemical nature of nickel phosphate, and then different nickel phosphides. The influence of alumina support on producing Ni 2 P was explained by the theory of surface energy heterogeneity, calculated by the NLDFT method based on N 2 -sorption isotherm. The uniform surface energy of α-Al 2 O 3 results only in the nickel phosphosate precursor and thus the Ni 2 P phase. - Graphical abstract: Surface energy heterogeneity in alumina (namely α-Al 2 O 3 , θ-Al 2 O 3 , and γ-Al 2 O 3 ) supported multi-oxidic precursors with different reducibilities and thus diverse nickel phosphides (i.e., Ni 3 P, Ni 12 P 5 , Ni 2 P). - Highlights: • Preparing pure Ni 2 P. • Elucidating nickel phosphate precursor. • Associating with surface energy

Polymethacrylic acid as a new precursor of CuO nanoparticles

Science.gov (United States)

Hosny, Nasser Mohammed; Zoromba, Mohamed Shafick

2012-11-01

Polymethacrylic acid and its copper complexes have been synthesized and characterized. These complexes have been used as precursors to produce CuO nanoparticles by thermal decomposition in air. The stages of decompositions and the calcination temperature of the precursors have been determined from thermal analyses (TGA). The obtained CuO nanoparticles have been characterized by X-ray diffraction (XRD), scanning tunneling microscopy (STM) and transmission electron microscopy (TEM). XRD showed a monoclinic structure with particle size 8-20 nm for the synthesized copper oxide nanoparticles. These nanoparticles are catalytically active in decomposing hydrogen peroxide and a mechanism of decomposition has been suggested.

UVA Light-excited Kynurenines Oxidize Ascorbate and Modify Lens Proteins through the Formation of Advanced Glycation End Products

Science.gov (United States)

Linetsky, Mikhail; Raghavan, Cibin T.; Johar, Kaid; Fan, Xingjun; Monnier, Vincent M.; Vasavada, Abhay R.; Nagaraj, Ram H.

2014-01-01

Advanced glycation end products (AGEs) contribute to lens protein pigmentation and cross-linking during aging and cataract formation. In vitro experiments have shown that ascorbate (ASC) oxidation products can form AGEs in proteins. However, the mechanisms of ASC oxidation and AGE formation in the human lens are poorly understood. Kynurenines are tryptophan oxidation products produced from the indoleamine 2,3-dioxygenase (IDO)-mediated kynurenine pathway and are present in the human lens. This study investigated the ability of UVA light-excited kynurenines to photooxidize ASC and to form AGEs in lens proteins. UVA light-excited kynurenines in both free and protein-bound forms rapidly oxidized ASC, and such oxidation occurred even in the absence of oxygen. High levels of GSH inhibited but did not completely block ASC oxidation. Upon UVA irradiation, pigmented proteins from human cataractous lenses also oxidized ASC. When exposed to UVA light (320–400 nm, 100 milliwatts/cm2, 45 min to 2 h), young human lenses (20–36 years), which contain high levels of free kynurenines, lost a significant portion of their ASC content and accumulated AGEs. A similar formation of AGEs was observed in UVA-irradiated lenses from human IDO/human sodium-dependent vitamin C transporter-2 mice, which contain high levels of kynurenines and ASC. Our data suggest that kynurenine-mediated ASC oxidation followed by AGE formation may be an important mechanism for lens aging and the development of senile cataracts in humans. PMID:24798334

New Insights into the Diels-Alder Reaction of Graphene Oxide.

Science.gov (United States)

Brisebois, Patrick P; Kuss, Christian; Schougaard, Steen B; Izquierdo, Ricardo; Siaj, Mohamed

2016-04-18

Graphene oxide is regarded as a major precursor for graphene-based materials. The development of graphene oxide based derivatives with new functionalities requires a thorough understanding of its chemical reactivity, especially for canonical synthetic methods such as the Diels-Alder cycloaddition. The Diels-Alder reaction has been successfully extended with graphene oxide as a source of diene by using maleic anhydride as a dienophile, thereby outlining the presence of the cis diene present in the graphene oxide framework. This reaction provides fundamental information for understanding the exact structure and chemical nature of graphene oxide. On the basis of high-resolution (13) C-SS NMR spectra, we show evidence for the formation of new sp(3) carbon centers covalently bonded to graphene oxide following hydrolysis of the reaction product. DFT calculations are also used to show that the presence of a cis dihydroxyl and C vacancy on the surface of graphene oxide are promoting the reaction with significant negative reaction enthalpies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A single cysteine post-translational oxidation suffices to compromise globular proteins kinetic stability and promote amyloid formation

Directory of Open Access Journals (Sweden)

Patrizia Marinelli

2018-04-01

Full Text Available Oxidatively modified forms of proteins accumulate during aging. Oxidized protein conformers might act as intermediates in the formation of amyloids in age-related disorders. However, it is not known whether this amyloidogenic conversion requires an extensive protein oxidative damage or it can be promoted just by a discrete, localized post-translational modification of certain residues. Here, we demonstrate that the irreversible oxidation of a single free Cys suffices to severely perturb the folding energy landscape of a stable globular protein, compromise its kinetic stability, and lead to the formation of amyloids under physiological conditions. Experiments and simulations converge to indicate that this specific oxidation-promoted protein aggregation requires only local unfolding. Indeed, a large scale analysis indicates that many cellular proteins are at risk of undergoing this kind of deleterious transition; explaining how oxidative stress can impact cell proteostasis and subsequently lead to the onset of pathological states. Keywords: Protein oxidation, Protein misfolding, Protein aggregation, Oxidative stress, Post-translational modification

Bi-template assisted synthesis of mesoporous manganese oxide nanostructures: Tuning properties for efficient CO oxidation.

Science.gov (United States)

Roy, Mouni; Basak, Somjyoti; Naskar, Milan Kanti

2016-02-21

A simple soft bi-templating process was used for the synthesis of mesoporous manganese oxide nanostructures using KMnO4 as a precursor and polyethylene glycol and cetyltrimethylammonium bromide as templates in the presence of benzaldehyde as an organic additive in alkaline media, followed by calcination at 400 °C. X-ray diffraction and Raman spectroscopic analysis of the calcined products confirmed the existence of stoichiometric (MnO2 and Mn5O8) and non-stoichiometric mixed phases (MnO2 + Mn5O8) of Mn oxides obtained by tuning the concentration of the additive and the synthesis time. The surface properties of the prepared Mn oxides were determined by X-ray photoelectron spectroscopy. The mesoporosity of the samples was confirmed by N2 adsorption-desorption. Different synthetic conditions resulted in the formation of different morphologies of the Mn oxides (α-MnO2, Mn5O8, and α-MnO2 + Mn5O8), such as nanoparticles, nanorods, and nanowires. The synthesized mesoporous Mn oxide nanostructures were used for the catalytic oxidation of the harmful air pollutant carbon monoxide. The Mn5O8 nanoparticles with the highest Brunauer-Emmett-Teller surface area and the non-stoichiometric manganese oxide (α-MnO2 + Mn5O8) nanorods with a higher Mn(3+) concentration had the best catalytic efficiency.

Adsorption of N-nitrosodimethylamine precursors by powdered and granular activated carbon.

Science.gov (United States)

Hanigan, David; Zhang, Jinwei; Herckes, Pierre; Krasner, Stuart W; Chen, Chao; Westerhoff, Paul

2012-11-20

Activated carbon (AC) has been shown to remove precursors of halogenated disinfection byproducts. Granular and powdered activated carbon (GAC, PAC) were investigated for their potential to adsorb N-nitrosodimethylamine (NDMA) precursors from blends of river water and effluent from a wastewater treatment plant (WWTP). At bench scale, waters were exposed to lignite or bituminous AC, either as PAC in bottle point experiments or as GAC in rapid small-scale column tests (RSSCTs). NDMA formation potential (FP) was used as a surrogate for precursor removal. NDMA FP was reduced by 37, 59, and 91% with 3, 8, and 75 mg/L of one PAC, respectively, with a 4-h contact time. In RSSCTs and in full-scale GAC contactors, NDMA FP removal always exceeded that of the bulk dissolved organic carbon (DOC) and UV absorbance at 254 nm. For example, whereas DOC breakthrough exceeded 90% of its influent concentration after 10,000 bed volumes of operation in an RSSCT, NDMA FP was less than 40% of influent concentration after the same bed life of the GAC. At full or pilot scale, high NDMA FP reduction ranging from >60 to >90% was achieved across GAC contactors, dependent upon the GAC bed life and/or use of a preoxidant (chlorine or ozone). In all experiments, NDMA formation was not reduced to zero, which suggests that although some precursors are strongly sorbed, others are not. This is among the first studies to show that AC is capable of adsorbing NDMA precursors, but further research is needed to better understand NDMA precursor chemical properties (e.g., hydrophobicity, molecular size) and evaluate how best to incorporate this finding into full-scale designs and practice.

Cisplatin upregulates mitochondrial nitric oxide synthase and peroxynitrite formation to promote renal injury

International Nuclear Information System (INIS)

Jung, Michaela; Hotter, Georgina; Vinas, Jose Luis; Sola, Anna

2009-01-01

The mitochondria are a critical target for cisplatin-associated nephrotoxicity. Though nitric oxide formation has been implicated in the toxicity of cisplatin, this formation has not so far been related to a possible activation of mitochondrial nitric oxide synthase (mNOS). We show here that the upregulation of oxide mNOS and peroxynitrite formation in cisplatin treatment are key events that influence the development of the harmful parameters described in cisplatin-associated kidney failure. We confirm this by isolating the mitochondrial fraction of the kidney and across different access routes such as the use of a specific inhibitor of neuronal NOS, L-NPA, a peroxynitrite scavenger, FeTMPyP, and a peroxynitrite donor, SIN-1. The in vitro studies corroborated the information obtained in the in vivo experiments. The administration of cisplatin reveals a clear upregulation in the transcription of neuronal NOS and an increase in the levels of nitrites in the mitochondrial fractions of the kidneys. The upregulated transcription directly affects the cytoskeleton structure and the apoptosis. The inhibition of neuronal NOS reduces the levels of nitrites, cell death, and cytoskeleton derangement. Peroxynitrite is involved in the mechanism promoting the NOS transcription. In addition, in controls SIN-1 imitates the effects of cisplatin. In summary, we demonstrate that upregulation of mNOS in cisplatin treatment is a key component in both the initiation and the spread of cisplatin-associated damage in the kidney. Furthermore, peroxynitrite formation is directly involved in this process

Effect of nitrogen precursors on the electrochemical performance of nitrogen-doped reduced graphene oxide towards oxygen reduction reaction

International Nuclear Information System (INIS)

Soo, Li Ting; Loh, Kee Shyuan; Mohamad, Abu Bakar; Daud, Wan Ramli Wan; Wong, Wai Yin

2016-01-01

A series of nitrogen-doped reduced graphene oxides (NGs) with different ratios are synthesized by thermal annealing of graphene oxide with melamine or urea. The total nitrogen content in NG is high, with values of up to 5.88 at.%. The NG samples prepared by melamine exhibited thin transparent graphene sheets structure, with consist of higher nitrogen doping level and quaternary N content compared to those NG samples prepared from urea. Electrochemical characterizations show that NG is a promising metal-free electrocatalyst for an oxygen reduction reaction (ORR). Incorporation of nitrogen atoms into graphene basal plane can enhances its electrocatalytic activity toward ORR in alkaline media. The onset potential and mean number of electron transfers on NG 1 are −0.10 V and 3.80 respectively, which is higher than that of reduced graphene oxide (−0.15 V, 3.52). This study suggests that quaternary-N of the NG samples is the active site which determines the ORR activity Moreover, the NG samples with the transparent layer of graphene-like structure have better ORR performances than that of bulk graphite-like NG samples. - Highlights: • Synthesis of nitrogen-doped graphene (NG) via thermal annealing. • The effects of the nitrogen precursors on the synthesized NG are discussed. • Electrochemical performances of the NG are correlated to N doping and EASA. • Graphitic-N is proposed to be the active site for ORR.

Effect of nitrogen precursors on the electrochemical performance of nitrogen-doped reduced graphene oxide towards oxygen reduction reaction

Energy Technology Data Exchange (ETDEWEB)

Soo, Li Ting, E-mail: nicolesoo90@gmail.com [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Loh, Kee Shyuan, E-mail: ksloh@ukm.edu.my [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Mohamad, Abu Bakar, E-mail: drab@ukm.edu.my [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Daud, Wan Ramli Wan, E-mail: wramli@ukm.edu.my [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Wong, Wai Yin, E-mail: waiyin.wwy@gmail.com [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); School of Engineering, Taylor' s University' s Lakeside Campus, No. 1, Jalan Taylor' s, 46500 Subang Jaya, Selangor (Malaysia)

2016-08-25

A series of nitrogen-doped reduced graphene oxides (NGs) with different ratios are synthesized by thermal annealing of graphene oxide with melamine or urea. The total nitrogen content in NG is high, with values of up to 5.88 at.%. The NG samples prepared by melamine exhibited thin transparent graphene sheets structure, with consist of higher nitrogen doping level and quaternary N content compared to those NG samples prepared from urea. Electrochemical characterizations show that NG is a promising metal-free electrocatalyst for an oxygen reduction reaction (ORR). Incorporation of nitrogen atoms into graphene basal plane can enhances its electrocatalytic activity toward ORR in alkaline media. The onset potential and mean number of electron transfers on NG 1 are −0.10 V and 3.80 respectively, which is higher than that of reduced graphene oxide (−0.15 V, 3.52). This study suggests that quaternary-N of the NG samples is the active site which determines the ORR activity Moreover, the NG samples with the transparent layer of graphene-like structure have better ORR performances than that of bulk graphite-like NG samples. - Highlights: • Synthesis of nitrogen-doped graphene (NG) via thermal annealing. • The effects of the nitrogen precursors on the synthesized NG are discussed. • Electrochemical performances of the NG are correlated to N doping and EASA. • Graphitic-N is proposed to be the active site for ORR.

Aroma Precursors in Grapes and Wine: Flavor Release during Wine Production and Consumption.

Science.gov (United States)

Parker, Mango; Capone, Dimitra L; Francis, I Leigh; Herderich, Markus J

2018-03-14

Pioneering investigations into precursors of fruity and floral flavors established the importance of terpenoid and C 13 -norisoprenoid glycosides to the flavor of aromatic wines. Nowadays flavor precursors in grapes and wine are known to be structurally diverse, encompassing glycosides, amino acid conjugates, odorless volatiles, hydroxycinnamic acids, and many others. Flavor precursors mainly originate in the grape berry but also from oak or other materials involved in winemaking. Flavors are released from precursors during crushing and subsequent production steps by enzymatic and nonenzymatic transformations, via microbial glycosidases, esterases, C-S lyases, and decarboxylases, and through acid-catalyzed hydrolysis and chemical rearrangements. Flavors can also be liberated from glycosides and amino acid conjugates by oral microbiota. Hence, it is increasingly likely that flavor precursors contribute to retronasal aroma formation through in-mouth release during consumption, prompting a shift in focus from identifying aroma precursors in grapes to understanding aroma precursors present in bottled wine.

Silicon dioxide obtained by Polymeric Precursor Method; Obtencao de dioxido de silicio pelo Metodo dos Precursores Polimericos

Energy Technology Data Exchange (ETDEWEB)

Oliveira, C.T.; Granado, S.R.; Lopes, S.A.; Cavalheiro, A.A., E-mail: cinthia_quimica@hotmail.com [Universidade Estadual de Mato Grosso do Sul (CPTREN/UEMS), Navirai, MS (Brazil). Centro de Pesquisas Tecnologicas em Recursos Naturais

2011-07-01

The Polymeric Precursor Method is able for obtaining several oxide material types with high surface area even obtained in particle form. Several MO{sub 2} oxide types such as titanium, silicon and zirconium ones can be obtained by this methodology. In this work, the synthesis of silicon oxide was monitored by thermal analysis, XRD and surface area analysis in order to demonstrate the influence of the several synthesis and calcining parameters. Surface area values as higher as 370m2/g and increasing in the micropore volume nm were obtained when the material was synthesized by using ethylene glycol as polymerizing agent. XRD analysis showed that the material is amorphous when calcinated at 600°C in despite of the time of calcining, but the material morphology is strongly influenced by the polymeric resin composition. Using Glycerol as polymerizing agent, the pore size increase and the surface area goes down with the increasing in decomposition time, when compared to ethylene glycol. (author)

Porosity formation in Al-Si casting alloys: role of Sr oxide