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Sample records for nh3 temperature-programmed desorption

  1. Temperature programmed desorption of weakly bound adsorbates on Au(111)

    NASA Astrophysics Data System (ADS)

    Engelhart, Daniel P.; Wagner, Roman J. V.; Meling, Artur; Wodtke, Alec M.; Schäfer, Tim

    2016-08-01

    We have performed temperature programmed desorption (TPD) experiments to analyze the desorption kinetics of Ar, Kr, Xe, C2H2, SF6, N2, NO and CO on Au(111). We report desorption activation energies (Edes), which are an excellent proxy for the binding energies. The derived binding energies scale with the polarizability of the molecules, consistent with the conclusion that the surface-adsorbate bonds arise due to dispersion forces. The reported results serve as a benchmark for theories of dispersion force interactions of molecules at metal surfaces.

  2. Reduction Kinetics of Graphene Oxide Determined by Temperature Programmed Desorption

    NASA Astrophysics Data System (ADS)

    Ventrice, Carl; Clark, Nicholas; Field, Daniel; Geisler, Heike; Jung, Inhwa; Yang, Dongxing; Piner, Richard; Ruoff, Rodney

    2009-10-01

    Graphene oxide, which is an electrical insulator, shows promise for use in several technological applications such as dielectric layers in nanoscale electronic devices or as the active region of chemical sensors. In principle, graphene oxide films could also be used as a precursor for the formation of large-scale graphene films by either thermal or chemical reduction of the graphene oxide. In order to determine the thermal stability and reduction kinetics of graphene oxide, temperature program desorption (TPD) measurements have been performed on multilayer films of graphene oxide deposited on SiO2/Si(100) substrates. The graphene oxide was exfoliated from the graphite oxide source material by slow-stirring in aqueous solution, which produces single-layer platelets with an average lateral size of ˜10 μm. From the TPD measurements, it was determined that the decomposition process begins at ˜80 ^oC. The primary desorption products of the graphene oxide films for temperatures up to 300 ^oC are H2O, CO2, and CO, with only trace amounts of O2 being detected. An activation energy of 1.4 eV/molecule was determined by assuming an Arrhenius dependence for the decomposition process.

  3. An investigation of the desorption of hydrogen from lithium oxide using temperature programmed desorption and diffuse reflectance infrared spectroscopy

    SciTech Connect

    Kopasz, J.P.; Johnson, C.E.; Ortiz-Villafuerte, J.

    1994-09-01

    The addition of hydrogen to the purge stream has been shown to enhance tritium release from ceramic breeder materials. In an attempt to determine the mechanism for this enhancement the authors have investigated the adsorption and desorption of hydrogen and water from lithium oxide (a leading candidate for the breeder material) by temperature programmed desorption and diffuse reflectance infrared spectroscopy. The results from these studies indicate that several different types of hydroxide groups are formed on the lithium oxide surface. They also suggest that under certain conditions hydride species form on the surface. The role of these species in tritium release from lithium oxide is discussed.

  4. Temperature programmed desorption studies of water interactions with Apollo lunar samples 12001 and 72501

    NASA Astrophysics Data System (ADS)

    Poston, Michael J.; Grieves, Gregory A.; Aleksandrov, Alexandr B.; Hibbitts, Charles A.; Dyar, M. Darby; Orlando, Thomas M.

    2015-07-01

    The desorption activation energies for water molecules chemisorbed on Apollo lunar samples 72501 (highlands soil) and 12001 (mare soil) were determined by temperature programmed desorption experiments in ultra-high vacuum. A significant difference in both the energies and abundance of chemisorption sites was observed, with 72501 retaining up to 40 times more water (by mass) and with much stronger adsorption interactions, possibly approaching 1.5 eV. The dramatic difference between the samples may be due to differences in mineralogy and surface exposure age. The distribution function of water desorption activation energies for sample 72501 was used as an initial condition to simulate water persistence through a temperature profile matching the lunar day.

  5. Monte Carlo simulations of temperature-programmed and isothermal desorption from single-crystal surfaces

    SciTech Connect

    Lombardo, S.J. . Dept. of Chemical Engineering Lawrence Berkeley Lab., CA )

    1990-08-01

    The kinetics of temperature-programmed and isothermal desorption have been simulated with a Monte Carlo model. Included in the model are the elementary steps of adsorption, surface diffusion, and desorption. Interactions between adsorbates and the metal as well as interactions between the adsorbates are taken into account with the Bond-Order-Conservation-Morse-Potential method. The shape, number, and location of the TPD peaks predicted by the simulations is shown to be sensitive to the binding energy, coverage, and coordination of the adsorbates. In addition, the occurrence of lateral interactions between adsorbates is seen to strongly effect the distribution of adsorbates is seen to strongly effect the distribution of adsorbates on the surface. Temperature-programmed desorption spectra of a single type of adsorbate have been simulated for the following adsorbate-metal systems: CO on Pd(100); H{sub 2} on Mo(100); and H{sub 2} on Ni(111). The model predictions are in good agreement with experimental observation. TPD spectra have also been simulated for two species coadsorbed on a surface; the model predictions are in qualitative agreement with the experimental results for H{sub 2} coadsorbed with strongly bound atomic species on Mo(100) and Fe(100) surfaces as well as for CO and H{sub 2} coadsorbed on Ni(100) and Rh(100) surfaces. Finally, the desorption kinetics of CO from Pd(100) and Ni(100) in the presence of gas-phase CO have been examined. The effect of pressure is seen to lead to an increase in the rate of desorption relative to the rate observed in the absence of gas-phase CO. This increase arises as a consequence of higher coverages and therefore stronger lateral interactions between the adsorbed CO molecules.

  6. Note: A versatile mass spectrometer chamber for molecular beam and temperature programmed desorption experiments

    NASA Astrophysics Data System (ADS)

    Tonks, James P.; Galloway, Ewan C.; King, Martin O.; Kerherve, Gwilherm; Watts, John F.

    2016-08-01

    A dual purpose mass spectrometer chamber capable of performing molecular beam scattering (MBS) and temperature programmed desorption (TPD) is detailed. Two simple features of this design allow it to perform these techniques. First, the diameter of entrance aperture to the mass spectrometer can be varied to maximize signal for TPD or to maximize angular resolution for MBS. Second, the mass spectrometer chamber can be radially translated so that it can be positioned close to the sample to maximize signal or far from the sample to maximize angular resolution. The performance of this system is described and compares well with systems designed for only one of these techniques.

  7. Note: A versatile mass spectrometer chamber for molecular beam and temperature programmed desorption experiments.

    PubMed

    Tonks, James P; Galloway, Ewan C; King, Martin O; Kerherve, Gwilherm; Watts, John F

    2016-08-01

    A dual purpose mass spectrometer chamber capable of performing molecular beam scattering (MBS) and temperature programmed desorption (TPD) is detailed. Two simple features of this design allow it to perform these techniques. First, the diameter of entrance aperture to the mass spectrometer can be varied to maximize signal for TPD or to maximize angular resolution for MBS. Second, the mass spectrometer chamber can be radially translated so that it can be positioned close to the sample to maximize signal or far from the sample to maximize angular resolution. The performance of this system is described and compares well with systems designed for only one of these techniques. PMID:27587173

  8. Simulation Analysis of the NH3-H2O Two-Stage Desorption Type Absorption Refrigerator Driven by Low Grade Waste Heat

    NASA Astrophysics Data System (ADS)

    Takei, Toshitaka; Kimijima, Shinji; Saito, Kiyoshi; Kawai, Sunao

    Recently, from a view point of the environmental protection, NH3-H2O absorption refrigerator attracts attention in the field of the refrigeration and the air conditioning. Since NH3-H2O absorption refrigerators can produce below zero degree products, this type of refrigerators have many usages in the refrigeration. This paper describes the two-stage desorption type absorption refrigerator driven by waste heat of co-generation system. There are two absorption cycles which are operated under the condition of the different pressure and the solution concentration in this absorption refrigerator. It becomes essential to clarify the characteristics of this absorption refrigerator since the operating conditions are changed through out the year in the co-generation system. Particularly, in this paper, we investigate the effects of evaporating temperature of ammonia and cooling water temperature for the performance of this absorption refrigerator by simulation analysis. Through out the research, it is shown that COP can be improved when evaporating temperature is higher or cooling water temperature is lower. In addition to this, it is obtained that the necessary temperature of hot water becomes lower in such condition. As a result, the effectiveness of using this absorption refrigerator under the operating condition of which hot watertemperatureis90∼100[°C] and evaporating temperature is -10∼- 20 [°C] is clarified

  9. TEMPERATURE-PROGRAMMED DESORPTION: PRINCIPLES, INSTRUMENT DESIGN, AND DEMONSTRATION WITH NAALH4

    SciTech Connect

    Stowe, A; Ragaiy Zidan, R

    2006-11-07

    This article is a brief introduction to temperature-programmed desorption (TPD), an analytical technique devised to analyze, in this case, materials for their potential as hydrogen storage materials. The principles and requirements of TPD are explained and the different components of a generic TPD apparatus are described. The construction of a modified TPD instrument from commercially available components is reported together with the control and acquisition technique used to create a TPD spectrum. The chemical and instrumental parameters to be considered in a typical TPD experiment and the analytical utility of the technique are demonstrated by the dehydrogenation of titanium-doped NaAlH{sub 4} by means of thermally programmed desorption.

  10. Effects of surface coordination on the temperature-programmed desorption of oxalate from goethite

    SciTech Connect

    Boily, Jean F.; Szanyi, Janos; Felmy, Andrew R.

    2007-11-15

    The temperature-programmed desorption (TPD) of weakly-bound, hydrogen-bonded and metal-bonded oxalate complexes at the goethite surface was investigated in the 300-900 K range with concerted Fourier Transform Infrared (FTIR) measurements (TPD-FTIR). These reactions took place with the concomitant dehydroxylation reaction of goethite to hematite and decarbonation of bulk-occluded carbonate. The measurements revealed three important stages of desorption. Stage I (300-440 K) corresponds to the desorption of weakly-and/or un-bound oxalate molecules in the goethite powder with a thermal decomposition reaction pathway characteristic of oxalic acid. Stage II (440-520 K) corresponds to a thermally-driven dehydration of hydrogen-bonded surface complexes, leading to a partial desorption via oxalic acid thermal decomposition pathways and to a partial conversion to metal-bonded surface complexes. This latter mechanism led to the increase in FTIR bands characteristic of these complexes. Finally, Stage III (520-660 K) corresponds to the thermal decomposition of the metal-bonded oxalate complex, proceeding through a 2 electron reduction pathway.

  11. Characterization of carbon surface chemistry by combined temperature programmed desorption with in situ X-ray photoelectron spectrometry and temperature programmed desorption with mass spectrometry analysis.

    PubMed

    Brender, Patrice; Gadiou, Roger; Rietsch, Jean-Christophe; Fioux, Philippe; Dentzer, Joseph; Ponche, Arnaud; Vix-Guterl, Cathie

    2012-03-01

    The analysis of the surface chemistry of carbon materials is of prime importance in numerous applications, but it is still a challenge to identify and quantify the surface functional groups which are present on a given carbon. Temperature programmed desorption with mass spectrometry analysis (TPD-MS) and X-ray photoelectron spectroscopy with an in situ heating device (TPD-XPS) were combined in order to improve the characterization of carbon surface chemistry. TPD-MS analysis allowed the quantitative analysis of the released gases as a function of temperature, while the use of a TPD device inside the XPS setup enabled the determination of the functional groups that remain on the surface at the same temperatures. TPD-MS results were then used to add constraints on the deconvolution of the O1s envelope of the XPS spectra. Furthermore, a better knowledge of the evolution of oxygen functional groups with temperature during a thermal treatment could be obtained. Hence, we show here that the combination of these two methods allows to increase the reliability of the analysis of the surface chemistry of carbon materials. PMID:22242697

  12. Catalytic reduction of CO with hydrogen sulfide. 4. Temperature-programmed desorption of methanethiol on anatase, rutile, and sulfided rutile

    SciTech Connect

    Beck, D.D.; White, J.M.; Ratcliffe, C.T.

    1986-07-03

    The interaction of methanethiol with anatase, rutile, and sulfided rutile was studied by temperature-programmed desorption. Dissociative adsorption occurs on rutile but is insignificant on anatase. Decomposition products are dominated by H/sub 2/ on rutile and by CH/sub 4/ on sulfided rutile. In both cases desorption occurs between 500 and 775 K. The 5- and 4-coordinate sites on the (110) face of rutile are proposed as the active sites for decomposition. The dominance of methane on a sulfided surface is attributed to the relatively large supply of highly mobile surface hydrogen atoms.

  13. The dissociation kinetics of NO on Rh(111) as studied by temperature programmed static secondary ion mass spectrometry and desorption

    NASA Astrophysics Data System (ADS)

    Borg, H. J.; Reijerse, J. F. C.-J. M.; van Santen, R. A.; Niemantsverdriet, J. W.

    1994-12-01

    Temperature programmed static secondary ion mass spectrometry (TPSSIMS) and temperature programmed desorption (TPD) have been used to study the kinetics of adsorption, dissociation, and desorption of NO on Rh(111). At 100 K, NO adsorption is molecular and proceeds via mobile precursor state kinetics with a high initial sticking probability. SSIMS indicates the presence of two distinct NO adsorption states, indicative of threefold adsorption at low coverage, and occupation of bridge sites at higher coverages. Three characteristic coverage regimes appear with respect to NO dissociation. At low coverages θNO<0.25 ML, NO dissociates completely at temperatures between 275 and 340 K. If we neglect lateral interactions and assume pure first order dissociation kinetics, we find effective values for the activation barrier and preexponential factor of 40±6 kJ/mol and 106±1 s-1 for the dissociation of 0.15-0.20 ML NO. However, if we assume that a NO molecule needs an ensemble of three to four vacant sites in order to dissociate, the preexponential factor and activation energy are ˜1011 s-1 and 65 kJ/mol, in better agreement with transition state theory expectations. The Nads and Oads dissociation products desorb as N2 and O2, respectively, with desorption parameters Edes=118±10 kJ/mol and νdes=1010.1±1.0 s-1 for N2 in the zero coverage limit. At higher coverages, the desorption kinetics of N2 is strongly influenced by the presence of coadsorbed oxygen. In the medium coverage range 0.25<θNO<0.50 ML, part of the NO desorbs molecularly, with an estimated desorption barrier of 113±10 kJ/mol and a preexponential of 1013.5±1.0 s-1. Dissociation of NO becomes progressively inhibited due to site blocking, the onset shifting from 275 K at 0.25 ML to 400 K, coinciding with the NO desorption temperature, at a coverage of 0.50 ML. The accumulation of nitrogen and oxygen atoms on the highly covered surface causes a destabilization of the nitrogen atoms, which results in an

  14. Interaction of D2 with H2O amorphous ice studied by temperature-programmed desorption experiments.

    PubMed

    Amiaud, L; Fillion, J H; Baouche, S; Dulieu, F; Momeni, A; Lemaire, J L

    2006-03-01

    The gas-surface interaction of molecular hydrogen D2 with a thin film of porous amorphous solid water (ASW) grown at 10 K by slow vapor deposition has been studied by temperature-programmed-desorption (TPD) experiments. Molecular hydrogen diffuses rapidly into the porous network of the ice. The D2 desorption occurring between 10 and 30 K is considered here as a good probe of the effective surface of ASW interacting with the gas. The desorption kinetics have been systematically measured at various coverages. A careful analysis based on the Arrhenius plot method has provided the D2 binding energies as a function of the coverage. Asymmetric and broad distributions of binding energies were found, with a maximum population peaking at low energy. We propose a model for the desorption kinetics that assumes a complete thermal equilibrium of the molecules with the ice film. The sample is characterized by a distribution of adsorption sites that are filled according to a Fermi-Dirac statistic law. The TPD curves can be simulated and fitted to provide the parameters describing the distribution of the molecules as a function of their binding energy. This approach contributes to a correct description of the interaction of molecular hydrogen with the surface of possibly porous grain mantles in the interstellar medium. PMID:16526867

  15. Improving of understanding of beta-hexachlorocyclohexane (HCH) adsorption on activated carbons by temperature-programmed desorption studies.

    PubMed

    Passé-Coutrin, Nady; Maisonneuve, Laetitia; Durimel, Axelle; Dentzer, Joseph; Gadiou, Roger; Gaspard, Sarra

    2016-01-01

    In order to understand the interactions between beta-hexachlorocyclohexane (HCH) and chemical groups at activated carbon (AC) surface, the solid samples were hydrogenated aiming to decrease the amounts of oxygenated groups. Two AC samples designated by BagH2O and BagP1.5 were prepared by water vapor activation and phosphoric acid activation, respectively, of sugarcane bagasse used as an AC precursor. A more simple molecule 1,2,3-trichloropropane (TCP) is used as a model of chlorinated compound. The AC were characterized by infrared, X-ray photoelectron spectroscopy (XPS), Raman resonance spectroscopies, as well as temperature-programmed desorption coupled with mass spectrometry (TPD-MS). BagP1.5 and BagH2O AC surface contained oxygenated groups. Upon hydrogenation, a decrease of most of these group amxounts was observed for both samples, while hydroxyl groups increased. On the basis of temperature-programmed desorption data obtained for AC samples contaminated with TCP or HCH, it was possible to determine the type of hydrogen bond formed between each AC and HCH. PMID:26018287

  16. Temperature-programmed desorption study of NO reactions on rutile TiO2(110)-1 × 1

    NASA Astrophysics Data System (ADS)

    Kim, Boseong; Dohnálek, Zdenek; Szanyi, János; Kay, Bruce D.; Kim, Yu Kwon

    2016-10-01

    Systematic temperature-programmed desorption (TPD) studies of NO adsorption and reactions on rutile TiO2(110)-1 × 1 surface reveal several distinct reaction channels in a temperature range of 50-500 K. NO readily reacts on TiO2(110) to form N2O, which desorbs between 50 and 200 K (LT N2O channels), which leaves the TiO2 surface populated with adsorbed oxygen atoms (Oa) as a by-product of N2O formation. In addition, we observe simultaneous desorption peaks of NO and N2O at 270 K (HT1 N2O) and 400 K (HT2 N2O), respectively, both of which are attributed to reaction-limited processes. No N-derived reaction product desorbs from TiO2(110) surface above 500 K or higher, while the surface may be populated with Oa's and oxidized products such as NO2 and NO3. The adsorbate-free TiO2 surface with oxygen vacancies can be regenerated by prolonged annealing at 850 K or higher. Detailed analysis of the three N2O desorption yields reveals that the surface species for the HT channels are likely to be various forms of NO dimers.

  17. Temperature-programmed desorption study of NO reactions on rutile TiO2(110)-1×1

    DOE PAGESBeta

    Kim, Boseong; Dohnalek, Zdenek; Szanyi, Janos; Kay, Bruce D.; Kim, Yu Kwon

    2016-02-24

    In this study, systematic temperature-programmed desorption (TPD) studies of NO adsorption and reactions on rutile TiO2(110)-1 × 1 surface reveal several distinct reaction channels in a temperature range of 50–500 K. NO readily reacts on TiO2(110) to form N2O, which desorbs between 50 and 200 K (LT N2O channels), which leaves the TiO2 surface populated with adsorbed oxygen atoms (Oa) as a by-product of N2O formation. In addition, we observe simultaneous desorption peaks of NO and N2O at 270 K (HT1 N2O) and 400 K (HT2 N2O), respectively, both of which are attributed to reaction-limited processes. No N-derived reaction productmore » desorbs from TiO2(110) surface above 500 K or higher, while the surface may be populated with Oa's and oxidized products such as NO2 and NO3. The adsorbate-free TiO2 surface with oxygen vacancies can be regenerated by prolonged annealing at 850 K or higher. Detailed analysis of the three N2O desorption yields reveals that the surface species for the HT channels are likely to be various forms of NO dimers.« less

  18. Temperature Programmed Desorption of Quench-condensed Krypton and Acetone in Air; Selective Concentration of Ultra-trace Gas Components.

    PubMed

    Suzuki, Taku T; Sakaguchi, Isao

    2016-01-01

    Selective concentration of ultra-trace components in air-like gases has an important application in analyzing volatile organic compounds in the gas. In the present study, we examined quench-condensation of the sample gas on a ZnO substrate below 50 K followed by temperature programmed desorption (TPD) (low temperature TPD) as a selective gas concentration technique. We studied two specific gases in the normal air; krypton as an inert gas and acetone as a reactive gas. We evaluated the relationship between the operating condition of low temperature TPD and the lowest detection limit. In the case of krypton, we observed the selective concentration by exposing at 6 K followed by thermal desorption at about 60 K. On the other hand, no selectivity appeared for acetone although trace acetone was successfully concentrated. This is likely due to the solvent effect by a major component in the air, which is suggested to be water. We suggest that pre-condensation to remove the water component may improve the selectivity in the trace acetone analysis by low temperature TPD. PMID:27063719

  19. Interaction between water molecules and zinc sulfide nanoparticles studied by temperature-programmed desorption and molecular dynamics simulations.

    PubMed

    Zhang, Hengzhong; Rustad, James R; Banfield, Jillian F

    2007-06-14

    We have investigated the bonding of water molecules to the surfaces of ZnS nanoparticles (approximately 2-3 nm sphalerite) using temperature-programmed desorption (TPD). The activation energy for water desorption was derived as a function of the surface coverage through kinetic modeling of the experimental TPD curves. The binding energy of water equals the activation energy of desorption if it is assumed that the activation energy for adsorption is nearly zero. Molecular dynamics (MD) simulations of water adsorption on 3 and 5 nm sphalerite nanoparticles provided insights into the adsorption process and water binding at the atomic level. Water binds with the ZnS nanoparticle surface mainly via formation of Zn-O bonds. As compared with bulk ZnS crystals, ZnS nanoparticles can adsorb more water molecules per unit surface area due to the greatly increased curvature, which increases the distance between adjacent adsorbed molecules. Results from both TPD and MD show that the water binding energy increases with decreasing the water surface coverage. We attribute the increase in binding energy with decreasing surface water coverage to the increasing degree of surface under-coordination as removal of water molecules proceeds. MD also suggests that the water binding energy increases with decreasing particle size due to the further distance and hence lower interaction between adsorbed water molecules on highly curved smaller particle surfaces. Results also show that the binding energy, and thus the strength of interaction of water, is highest in isolated nanoparticles, lower in nanoparticle aggregates, and lowest in bulk crystals. Given that water binding is driven by surface energy reduction, we attribute the decreased binding energy for aggregated as compared to isolated particles to the decrease in surface energy that occurs as the result of inter-particle interactions. PMID:17518448

  20. The effect of oxygen vacancies on the binding interactions of NH3 with rutile TiO2(110) -1×1

    SciTech Connect

    Kim, Boseong; Li, Zhenjun; Kay, Bruce D.; Dohnalek, Zdenek; Kim, Yu Kwon

    2012-11-21

    A series of NH3 temperature-programmed desorption (TPD) spectra was taken after the NH3 dose at 70 K on rutile TiO2(110)-1×1 surfaces with the oxygen vacancy (VO) concentrations of ~0% (p-TiO2) and 5% (r-TiO2), respectively, to study the effect of VO’s on the desorption energy of NH3 as a function of the coverage, θ. Our results show that at zero coverage limit, the desorption energy of NH3 on r-TiO2 is 115 kJ/mol, which is 10 kJ/mol less than that on p-TiO2. The desorption energy from the Ti4+ sites decreases with increasing θ due to the repulsive NH3 - NH3 interactions and approaches ~ 55 kJ/mol upon the saturation of Ti4+ sites (θ = 1 monolayer, ML) on both p- and r-TiO2. The absolute saturation coverage is determined to be about 10% smaller on r-TiO2 than that on p-TiO2. Further, the trailing edges of the NH3 TPD spectra on the hydroxylated TiO2(110) (h-TiO2) appear to be the same as that on r-TiO2 while those on oxidized TiO2(110) (o-TiO2) shift to higher temperatures. We present the detailed analysis of the results and reconcile the observed differences based on the repulsive adsorbate-adsorbate interactions between neighboring NH3 molecules and the surface charge associated with the presence of VO’s. Besides NH3, no other reaction products are observed in the TPD spectra.

  1. Dosimeter-Type NOx Sensing Properties of KMnO4 and Its Electrical Conductivity during Temperature Programmed Desorption

    PubMed Central

    Groβ, Andrea; Kremling, Michael; Marr, Isabella; Kubinski, David J.; Visser, Jacobus H.; Tuller, Harry L.; Moos, Ralf

    2013-01-01

    An impedimetric NOx dosimeter based on the NOx sorption material KMnO4 is proposed. In addition to its application as a low level NOx dosimeter, KMnO4 shows potential as a precious metal free lean NOx trap material (LNT) for NOx storage catalysts (NSC) enabling electrical in-situ diagnostics. With this dosimeter, low levels of NO and NO2 exposure can be detected electrically as instantaneous values at 380 °C by progressive NOx accumulation in the KMnO4 based sensitive layer. The linear NOx sensing characteristics are recovered periodically by heating to 650 °C or switching to rich atmospheres. Further insight into the NOx sorption-dependent conductivity of the KMnO4-based material is obtained by the novel eTPD method that combines electrical characterization with classical temperature programmed desorption (TPD). The NOx loading amount increases proportionally to the NOx exposure time at sorption temperature. The cumulated NOx exposure, as well as the corresponding NOx loading state, can be detected linearly by electrical means in two modes: (1) time-continuously during the sorption interval including NOx concentration information from the signal derivative or (2) during the short-term thermal NOx release. PMID:23549366

  2. Dosimeter-type NOx sensing properties of KMnO4 and its electrical conductivity during temperature programmed desorption.

    PubMed

    Groß, Andrea; Kremling, Michael; Marr, Isabella; Kubinski, David J; Visser, Jacobus H; Tuller, Harry L; Moos, Ralf

    2013-01-01

    An impedimetric NOx dosimeter based on the NOx sorption material KMnO4 is proposed. In addition to its application as a low level NOx dosimeter, KMnO4 shows potential as a precious metal free lean NOx trap material (LNT) for NOx storage catalysts (NSC) enabling electrical in-situ diagnostics. With this dosimeter, low levels of NO and NO2 exposure can be detected electrically as instantaneous values at 380 °C by progressive NOx accumulation in the KMnO4 based sensitive layer. The linear NOx sensing characteristics are recovered periodically by heating to 650 °C or switching to rich atmospheres. Further insight into the NOx sorption-dependent conductivity of the KMnO4-based material is obtained by the novel eTPD method that combines electrical characterization with classical temperature programmed desorption (TPD). The NOx loading amount increases proportionally to the NOx exposure time at sorption temperature. The cumulated NOx exposure, as well as the corresponding NOx loading state, can be detected linearly by electrical means in two modes: (1) time-continuously during the sorption interval including NOx concentration information from the signal derivative or (2) during the short-term thermal NOx release. PMID:23549366

  3. Temperature-programmed desorption study of the selective oxidation of alcohols on silica-supported vanadium oxide.

    PubMed

    Feng, T; Vohs, J M

    2005-02-17

    The partial oxidation of methanol and ethanol on silica-supported vanadium oxide catalysts was studied using temperature-programmed desorption (TPD), Raman spectroscopy, and diffuse reflectance infrared spectroscopy (DRIFTS). Methanol TPD results for V2O5/SiO2 samples as a function of vanadia loading in conjunction with X-ray diffraction data and Raman spectra indicated that dispersed vanadia on silica agglomerates into vanadia crystallites during a CH3OH TPD experiment. For ethanol-dosed samples, agglomeration of the dispersed vanadia was less severe, and it was possible to measure the activation energy for the dehydrogenation of adsorbed ethoxides to produce CH3CHO. Assuming a preexponential factor of 10(13) s(-1), the activation energy for this reaction was estimated to be 132 kJ/mol. The results of this study further demonstrate that there is a relatively weak interaction between vanadia and silica and suggest that adsorbed methoxide species help facilitate agglomeration of dispersed vanadia. PMID:16851203

  4. UV-Raman spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption studies of model and bulk heterogeneous catalysts

    SciTech Connect

    Tewell, Craig R.

    2002-08-19

    X-ray photoelectron spectroscopy (XPS) and Temperature Programmed Desorption (TPD) have been used to investigate the surface structure of model heterogeneous catalysts in ultra-high vacuum (UHV). UV-Raman spectroscopy has been used to probe the structure of bulk model catalysts in ambient and reaction conditions. The structural information obtained through UV-Raman spectroscopy has been correlated with both the UHV surface analysis and reaction results. The present day propylene and ethylene polymerization catalysts (Ziegler-Natta catalysts) are prepared by deposition of TiCl{sub 4} and a Al(Et){sub 3} co-catalyst on a microporous Mg-ethoxide support that is prepared from MgCl{sub 2} and ethanol. A model thin film catalyst is prepared by depositing metallic Mg on a Au foil in a UHV chamber in a background of TiCl{sub 4} in the gas phase. XPS results indicate that the Mg is completely oxidized to MgCl{sub 2} by TiCl{sub 4} resulting in a thin film of MgCl{sub 2}/TiCl{sub x}, where x = 2, 3, and 4. To prepare an active catalyst, the thin film of MgCl{sub 2}/TiCl{sub x} on Au foil is enclosed in a high pressure cell contained within the UHV chamber and exposed to {approx}1 Torr of Al(Et){sub 3}.

  5. The deactivation mechanism of Cl on Ce/TiO2 catalyst for selective catalytic reduction of NO with NH3

    NASA Astrophysics Data System (ADS)

    Yang, Ning-zhi; Guo, Rui-tang; Pan, Wei-guo; Chen, Qi-lin; Wang, Qing-shan; Lu, Chen-zi; Wang, Shu-xian

    2016-08-01

    The poisoning mechanism of Cl on Ce/TiO2 catalyst was investigated based on temperature programmed desorption (TPD) and the in situ diffuse reflectance infrared transform spectroscopy (DRIFT) studies. The results of NH3-TPD and NO-TPD indicated that the addition of Cl on Ce/TiO2 catalyst would inhibit the adsorption of NH3 species and NOx species on it. As can be seen from the results of in situ DRIFT study, the NH3-SCR reaction over Ce/TiO2 and Ce/TiO2-Cl were all followed both the Eley-Rideal mechanism and the Langmuir-Hinshelwood mechanism. And the decreased adsorption ability of NH3 species and NOx species on the surface of Ce/TiO2-Cl should be mainly responsible for its low SCR activity.

  6. Optimizing the crystallinity and acidity of H-SAPO-34 by fluoride for synthesizing Cu/SAPO-34 NH3-SCR catalyst.

    PubMed

    Ma, Jing; Si, Zhichun; Wu, Xiaodong; Weng, Duan; Ma, Yue

    2016-03-01

    A series of H-SAPO-34 zeolites were synthesized by a hydrothermal method in fluoride media. The as-synthesized H-SAPO-34 zeolites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 physisorption, temperature-programmed desorption of NH3 (NH3-TPD) and nuclear magnetic resonance (NMR) measurements. The results showed that a certain concentration of F(-) anions promoted the nucleation and crystallization of H-SAPO-34. The H-SAPO-34 synthesized in the fluoride media showed high crystallinity, uniform particle size distribution, large specific surface area and pore volume, and enhanced acidity. Therefore, Cu/SAPO-34 based on the fluoride-assisted zeolite showed a broadened temperature window for the selective catalytic reduction of NO by NH3 (NH3-SCR) reaction due to the enhanced acidity of the zeolite and the improved dispersion of copper species. PMID:26969071

  7. Investigation of the distribution of acidity strength in zeolites by temperature-programmed desorption of probe molecules. 2. Dealuminated Y-type zeolites

    SciTech Connect

    Karge, H.G.; Dondur, V. ); Weitkamp, J. )

    1991-01-10

    The acidity of dealuminated hydrogen forms of Y-type zeolites (Si/Al = 2.4-8.6) is determined by temperature-programmed desorption of ammonia or pyridine, which is monitored through a mass spectrometer. Four types of acidic sites are indicated by ammonia, viz., weak Broensted and/or Lewis centers and medium and strong Broensted and strong Lewis sites. In contrast, pyridine, after sample activation at 675 K, probed only two types of sites, i.e., medium and strong Broensted sites. This difference is ascribed to different accessibility of sites for the two probe molecules. From the desorption spectra (i) the fractional coverage of the various sites, (ii) the most frequent energies of activation, {anti E}{sub d}, for desorption, and (iii) the probability functions of the activation energies are derived by using a previously described method of evaluation.

  8. Thermal transformation of bioactive caffeic acid on fumed silica seen by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry and quantum chemical methods.

    PubMed

    Kulik, Tetiana V; Lipkovska, Natalia O; Barvinchenko, Valentyna M; Palyanytsya, Borys B; Kazakova, Olga A; Dudik, Olesia O; Menyhárd, Alfréd; László, Krisztina

    2016-05-15

    Thermochemical studies of hydroxycinnamic acid derivatives and their surface complexes are important for the pharmaceutical industry, medicine and for the development of technologies of heterogeneous biomass pyrolysis. In this study, structural and thermal transformations of caffeic acid complexes on silica surfaces were studied by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry (TPD MS) and quantum chemical methods. Two types of caffeic acid surface complexes are found to form through phenolic or carboxyl groups. The kinetic parameters of the chemical reactions of caffeic acid on silica surface are calculated. The mechanisms of thermal transformations of the caffeic chemisorbed surface complexes are proposed. Thermal decomposition of caffeic acid complex chemisorbed through grafted ester group proceeds via three parallel reactions, producing ketene, vinyl and acetylene derivatives of 1,2-dihydroxybenzene. Immobilization of phenolic acids on the silica surface improves greatly their thermal stability. PMID:26939077

  9. The analysis of temperature programmed desorption experiments of systems with lateral interactions; implications of the compensation effect

    NASA Astrophysics Data System (ADS)

    Nieskens, D. L. S.; van Bavel, A. P.; Niemantsverdriet, J. W.

    2003-12-01

    In this paper we have investigated problems that arise when analyzing TPD spectra of desorption processes in which lateral interactions between adsorbed species are present. Dynamic Monte Carlo (DMC) simulations are used to simulate the effect of adsorbate interactions on TPD spectra and we applied the most common methods to derive the activation energy and the pre-exponential factor. The extraction of the kinetic parameters in the zero-coverage limit works well for all methods. The extraction of the coverage dependent values on the other hand is quite difficult since a 'forced' compensation effect can occur, leading to false values for the pre-exponential factor as well as false values for the activation energy. Finally, we suggest a new approach that can be used to estimate the activation energy over the entire coverage range.

  10. Chemistry of L-proline on Pd(1 1 1): Temperature-programmed desorption and X-ray photoelectron spectroscopic study

    NASA Astrophysics Data System (ADS)

    Gao, Feng; Wang, Yilin; Burkholder, Luke; Tysoe, W. T.

    2007-09-01

    The surface chemistry of proline is explored on Pd(1 1 1) using a combination of temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy. Proline adsorbs on Pd(1 1 1) at temperatures of 250 K and below into second and subsequent layers prior to the saturation of the first layer, where approximately 70% of the adsorbed proline is present in its zwitterionic form. Molecular proline desorbs between ˜315 K and ˜333 K depending on coverage. When adsorbed at ˜300 K, only the first monolayer is formed, and the proline is present as zwitterions, oriented such that all of the carbons are detected equally by XPS. Proline decomposes by scission of the C-COO bond, where the carboxylate moiety desorbs as carbon monoxide and carbon dioxide, while the nitrogen-containing moiety desorbs as to HCN, and evolves pyrrole at ˜390 K, pyrrolidine at ˜410 K, and final species that desorbs at ˜450 K that cannot be unequivocally assigned but may be 2-butenenitrile (CH 3-CH dbnd CH-CN), 3-butenenitrile (CH 2dbnd CH-CH 2-CN), 2-methyl-2-propenenitrile (CH 2dbnd C(CH 3)-CN) or cyclopropanecarbonitrile.

  11. Adsorption of acrolein, propanal, and allyl alcohol on Pd(111): a combined infrared reflection-absorption spectroscopy and temperature programmed desorption study.

    PubMed

    Dostert, Karl-Heinz; O'Brien, Casey P; Mirabella, Francesca; Ivars-Barceló, Francisco; Schauermann, Swetlana

    2016-05-18

    Atomistic-level understanding of the interaction of α,β-unsaturated aldehydes and their derivatives with late transition metals is of fundamental importance for the rational design of new catalytic materials with the desired selectivity towards C[double bond, length as m-dash]C vs. C[double bond, length as m-dash]O bond partial hydrogenation. In this study, we investigate the interaction of acrolein, and its partial hydrogenation products propanal and allyl alcohol, with Pd(111) as a prototypical system. A combination of infrared reflection-absorption spectroscopy (IRAS) and temperature programmed desorption (TPD) experiments was applied under well-defined ultrahigh vacuum (UHV) conditions to obtain detailed information on the adsorption geometries of acrolein, propanal, and allyl alcohol as a function of coverage. We compare the IR spectra obtained for multilayer coverages, reflecting the molecular structure of unperturbed molecules, with the spectra acquired for sub-monolayer coverages, at which the chemical bonds of the molecules are strongly distorted. Coverage-dependent IR spectra of acrolein on Pd(111) point to the strong changes in the adsorption geometry with increasing acrolein coverage. Acrolein adsorbs with the C[double bond, length as m-dash]C and C[double bond, length as m-dash]O bonds lying parallel to the surface in the low coverage regime and changes its geometry to a more upright orientation with increasing coverage. TPD studies indicate decomposition of the species adsorbed in the sub-monolayer regime upon heating. Similar strong coverage dependence of the IR spectra were found for propanal and allyl alcohol. For all investigated molecules a detailed assignment of vibrational bands is reported. PMID:27149902

  12. Regeneration of field-spent activated carbon catalysts for low-temperature selective catalytic reduction of NOx with NH3

    SciTech Connect

    Jeon, Jong Ki; Kim, Hyeonjoo; Park, Young-Kwon; Peden, Charles HF; Kim, Do Heui

    2011-10-15

    In the process of producing liquid crystal displays (LCD), the emitted NOx is removed over an activated carbon catalyst by using selective catalytic reduction (SCR) with NH3 at low temperature. However, the catalyst rapidly deactivates primarily due to the deposition of boron discharged from the process onto the catalyst. Therefore, this study is aimed at developing an optimal regeneration process to remove boron from field-spent carbon catalysts. The spent carbon catalysts were regenerated by washing with a surfactant followed by drying and calcination. The physicochemical properties before and after the regeneration were investigated by using elemental analysis, TG/DTG (thermogravimetric/differential thermogravimetric) analysis, N2 adsorption-desorption and NH3 TPD (temperature programmed desorption). Spent carbon catalysts demonstrated a drastic decrease in DeNOx activity mainly due to heavy deposition of boron. Boron was accumulated to depths of about 50 {mu}m inside the granule surface of the activated carbons, as evidenced by cross-sectional SEM-EDX analysis. However, catalyst activity and surface area were significantly recovered by removing boron in the regeneration process, and the highest NOx conversions were obtained after washing with a non-ionic surfactant in H2O at 70 C, followed by treatment with N2 at 550 C.

  13. Effects of Alkali and Alkaline Earth Cocations on the Activity and Hydrothermal Stability of Cu/SSZ-13 NH3-SCR Catalysts

    SciTech Connect

    Gao, Feng; Wang, Yilin; Washton, Nancy M.; Kollar, Marton; Szanyi, Janos; Peden, Charles HF

    2015-10-13

    Using a three-step aqueous solution ion-exchange method, cocation modified Cu/SSZ-13 SCR catalysts were synthesized. These catalysts, in both fresh and hydrothermally aged forms, were characterized with several methods including temperature-programmed reduction by H2 (H2-TPR), temperature-programmed desorption of NH3 (NH3-TPD), and 27Al solid-state nuclear magnetic resonance (NMR) and diffuse reflectance Infrared Fourier Transform (DRIFT) spectroscopies. Their catalytic performance was probed using steady-state standard NH3-SCR. Characterization results indicate that cocations weaken interactions between Cu-ions and the CHA framework making them more readily reducible. By removing a portion of Brønsted acid sites, cocations also help to mitigate hydrolysis of the zeolite catalysts during hydrothermal aging as evidenced from 27Al NMR. Reaction tests show that certain cocations, especially Li+ and Na+, promote low-temperature SCR rates while others show much less pronounced effects. In terms of applications, our results indicate that introducing cocations can be a viable strategy to improve both low- and high-temperature performance of Cu/SSZ-13 SCR catalysts.

  14. [Poisoning effect of Ca depositing over Mn-Ce/TiO2 catalyst for low-temperature selective catalytic reduction of NO by NH3].

    PubMed

    Zhou, Ai-Yi; Mao, Hua-Feng; Sheng, Zhong-Yi; Tan, Yue; Yang, Liu

    2014-12-01

    Calcium carbonate (CaCO3), calcium sulfate (CaSO4), and calcium chloride (CaCl2) were chosen as the precursors to prepare the Ca salts deposited Mn-Ce/TiO2 catalysts through an impregnation method. The influence of Ca on the performance of the Mn-Ce/TiO2 catalyst for low-temperature selective catalytic reduction of NO by NH3 was investigated. Experimental results showed that Ca salts had negative effects on the activity of Mn-Ce/TiO2 and the precursors of Ca salts also affected the catalytic activity. The precursor CaCl2 had a greater impact on the catalytic activity, while CaCO3 had minimal effect. The samples were characterized by Brunner-Emmet-Teller measurements (BET), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and NH3temperature programmed desorption (NH3 -TPD). The characterization results indicated that the significant changes in physical and chemical properties of Mn-Ce/TiO2 were observed after Ca was deposited on the catalysts. The significant decreases in surface areas and NH,3adsorption amounts were observed after Ca was deposited on the catalysts, which could be considered as the main reasons for the deactivation of Ca deposited Mn-Ce/TiO,2 PMID:25826949

  15. Temperature-programmed decomposition desorption of mercury species over activated carbon sorbents for mercury removal from coal-derived fuel gas

    SciTech Connect

    M. Azhar Uddin; Masaki Ozaki; Eiji Sasaoka; Shengji Wu

    2009-09-15

    The mercury (Hg{sup 0}) removal process for coal-derived fuel gas in the integrated gasification combined cycle (IGCC) process will be one of the important issues for the development of a clean and highly efficient coal power generation system. Recently, iron-based sorbents, such as iron oxide (Fe{sub 2}O{sub 3}), supported iron oxides on TiO{sub 2}, and iron sulfides, were proposed as active mercury sorbents. The H{sub 2}S is one of the main impurity compounds in coal-derived fuel gas; therefore, H{sub 2}S injection is not necessary in this system. HCl is also another impurity in coal-derived fuel gas. In this study, the contribution of HCl to the mercury removal from coal-derived fuel gas by a commercial activated carbon (AC) was studied using a temperature-programmed decomposition desorption (TPDD) technique. The TPDD technique was applied to understand the decomposition characteristics of the mercury species on the sorbents. The Hg{sup 0}-removal experiments were carried out in a laboratory-scale fixed-bed reactor at 80-300{sup o}C using simulated fuel gas and a commercial AC, and the TPDD experiments were carried out in a U-tube reactor in an inert carrier gas (He or N{sub 2}) after mercury removal. The following results were obtained from this study: (1) HCl contributed to the mercury removal from the coal-derived fuel gas by the AC. (2) The mercury species captured on the AC in the HCl{sup -} and H{sub 2}S-presence system was more stable than that of the H{sub 2}S-presence system. (3) The stability of the mercury surface species formed on the AC in the H{sub 2}S-absence and HCl-presence system was similar to that of mercury chloride (HgClx) species. 25 refs., 12 figs., 1 tab.

  16. Secondary ion emission induced by fission fragment impact in CO-NH(3) and CO-NH(3)-H(2)O ices: modification in the CO-NH(3) ice structure.

    PubMed

    Martinez, R; Farenzena, L S; Iza, P; Ponciano, C R; Homem, M G P; de Brito, A Naves; Wien, K; da Silveira, E F

    2007-10-01

    CO-NH(3) and CO-NH(3)-H(2)O ices at 25-130 K were bombarded by (252)Cf fission fragments ( approximately 65 MeV at the target surface) and the emitted secondary ions were analyzed by time-of-flight mass spectrometry (TOF-SIMS). It is observed that the mass spectra obtained from both ices have similar patterns. The production of hybrid ions (formed from CO and NH(3) molecules) emitted from CO-NH(3) ice has already been reported by R. Martinez et al., Int. J. Mass. Spectrom. 262 (2006) 195; here, the secondary ion emission and the modifications of the CO--NH(3) ice structure during the temperature increase of the ice are addressed. These studies are expected to throw light on the sputtering from planetary and interstellar ices and the possible formation of new organic molecules in CO-NH(3)-H(2)O ice by megaelectronvolt ion bombardment. The presence of water in the CO-NH(3) ice mixture generates molecular ion series such as (NH(3))(p-q)(H(2)O)(q)CO(+) and replaces the cluster series (NH(3))(n)NH(4) (+) emission by the hybrid series (NH(3))(I-i)(H(2)O)(i=1, 2...I)H(+). The distribution of NH(3) and H(2)O molecules within the cluster groups indicates that ammonia and water mix homogeneously in the icy condensate at T = 25 K. The desorption yield distribution of the cluster series (NH(3))(n)NH(4) (+) is described by the sum of two exponential functions: one, slow-decreasing, attributed to the fragmentation of the solid target into clusters; and another, fast-decreasing, due to a local sublimation followed by recombination of ammonia molecules. The analysis of the time-temperature dependence of these two yield components gives information on the formation process of molecular ions, the transient composition of the ice target and structural changes of the ice. Data suggest that the amorphous and porous structure of the NH(3) ice, formed by the condensation of the CO--NH(3) gas at T = 25 K, survives CO sublimation until the occurrence of a phase transition around 80 K

  17. Low Temperature Catalyst for NH3 Removal

    NASA Technical Reports Server (NTRS)

    Monje, Oscar; Melendez, Orlando

    2013-01-01

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

  18. Bonding of NH3 to Cu

    NASA Technical Reports Server (NTRS)

    Bauschlicher, C. W., Jr.

    1985-01-01

    Bagus et al. (1984) have studied the chemisorption of NH3 at the on-top site of Cu(100), using a cluster model, Cu5(1,4)NH3. On the basis of the value of the NH3 chemisorption energy obtained, it was concluded that NH3 chemisorbs directly above a Cu atom. In order to consider also other sites, Al(111) was substituted for Cu(100). Chemisorption on Al can be quite different from a transition metal, however, and questions arise regarding the suitability of the choice of the Al model. Thus, in this note, NH3 into hollows is considered for Cu(111). Attention is given to the conduction of self-consistent field calculations, problems of site determination, and the consideration of electrostatic interaction.

  19. Aquaporin 4 as a NH3 Channel.

    PubMed

    Assentoft, Mette; Kaptan, Shreyas; Schneider, Hans-Peter; Deitmer, Joachim W; de Groot, Bert L; MacAulay, Nanna

    2016-09-01

    Ammonia is a biologically potent molecule, and the regulation of ammonia levels in the mammalian body is, therefore, strictly controlled. The molecular paths of ammonia permeation across plasma membranes remain ill-defined, but the structural similarity of water and NH3 has pointed to the aquaporins as putative NH3-permeable pores. Accordingly, a range of aquaporins from mammals, plants, fungi, and protozoans demonstrates ammonia permeability. Aquaporin 4 (AQP4) is highly expressed at perivascular glia end-feet in the mammalian brain and may, with this prominent localization at the blood-brain-interface, participate in the exchange of ammonia, which is required to sustain the glutamate-glutamine cycle. Here we observe that AQP4-expressing Xenopus oocytes display a reflection coefficient <1 for NH4Cl at pH 8.0, at which pH an increased amount of the ammonia occurs in the form of NH3 Taken together with an NH4Cl-mediated intracellular alkalization (or lesser acidification) of AQP4-expressing oocytes, these data suggest that NH3 is able to permeate the pore of AQP4. Exposure to NH4Cl increased the membrane currents to a similar extent in uninjected oocytes and in oocytes expressing AQP4, indicating that the ionic NH4 (+) did not permeate AQP4. Molecular dynamics simulations revealed partial pore permeation events of NH3 but not of NH4 (+) and a reduced energy barrier for NH3 permeation through AQP4 compared with that of a cholesterol-containing lipid bilayer, suggesting AQP4 as a favored transmembrane route for NH3 Our data propose that AQP4 belongs to the growing list of NH3-permeable water channels. PMID:27435677

  20. Plasma-assisted CuO/CeO2/TiO2-γ-Al2O3 catalysts for NO + CH4 reaction and NO temperature programmed desorption studies

    NASA Astrophysics Data System (ADS)

    Li, Huijuan; Jiang, Xiaoyuan; Zheng, Xiaoming

    2013-09-01

    The removal of NO and CH4 has been studied with a hybrid system integrating plasma activation and four Cu-based catalysts. The best catalytic performance was observed for catalysts obtained from CuO/CeO2/TiO2/γ-Al2O3.The efficiency of NO removal decreased with the order: 12%CuO/10%CeO2/15%TiO2/γ-Al2O3 > 12%CuO/15%TiO2/γ-Al2O3 > 12%CuO/γ-Al2O3 > 12% CuO/TiO2. Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD) Temperature-programmed reduction (H2-TPR) and NO temperature-programmed desorption (NO-TPD) experiments were carried out to gain insight into the synergetic effects with the catalysts. The results revealed that copper species existed as bulk CuO crystalline for all the catalysts, H2-TPR suggested that the Cu2+ incorporated TiO2 or CeO2 lattice and crystalline CuO might be the most active component for NO removal, and NO-TPD studies indicated that 12%CuO/10%CeO2/15%TiO2/γ-Al2O3 catalyst had lower NO desorption temperature and larger peak area, which seemed to be responsible for the better catalytic activity over NO + CH4 reactions than other catalysts.

  1. TES/Aura L2 Ammonia (NH3) Nadir (TL2NH3NS)

    Atmospheric Science Data Center

    2015-01-30

    TES/Aura L2 Ammonia (NH3) Nadir (TL2NH3NS) News:  TES News ... Level:  L2 Platform:  TES/Aura L2 Ammonia Spatial Coverage:  5.3 x 8.5 km nadir ... Data: TES Order Tool Parameters:  Ammonia Order Data:  Reverb:   Order Data ...

  2. TES/Aura L2 Ammonia (NH3) Nadir (TL2NH3N)

    Atmospheric Science Data Center

    2015-01-30

    TES/Aura L2 Ammonia (NH3) Nadir (TL2NH3N) News:  TES News ... Level:  L2 Instrument:  TES/Aura L2 Ammonia Spatial Coverage:  5.3 x 8.5 km nadir ... Data: TES Order Tool Parameters:  Ammonia Order Data:  Reverb:   Order Data ...

  3. TES/Aura L3 Ammonia (NH3) Daily (TL3NH3D)

    Atmospheric Science Data Center

    2015-08-28

    TES/Aura L3 Ammonia (NH3) Daily (TL3NH3D) News:  TES News ... Level:  L3 Instrument:  TES/Aura L3 Ammonia Spatial Coverage:  5.3 x 8.5 km Spatial ... Data: TES Order Tool Parameters:  Ammonia Order Data:  Reverb:   Order Data ...

  4. NH{sub 3} adsorption and decomposition on Ir(110): A combined temperature programmed desorption and high resolution fast x-ray photoelectron spectroscopy study

    SciTech Connect

    Weststrate, C.J.; Bakker, J.W.; Rienks, E.D.L.; Lizzit, S.; Petaccia, L.; Baraldi, A.; Vinod, C.P.; Nieuwenhuys, B.E.

    2005-05-08

    The adsorption and decomposition of NH{sub 3} on Ir(110) has been studied in the temperature range from 80 K to 700 K. By using high-energy resolution x-ray photoelectron spectroscopy it is possible to distinguish chemically different surface species. At low temperature a NH{sub 3} multilayer, which desorbs at {approx}110 K, was observed. The second layer of NH{sub 3} molecules desorbs around 140 K, in a separate desorption peak. Chemisorbed NH{sub 3} desorbs in steps from the surface and several desorption peaks are observed between 200 and 400 K. A part of the NH{sub 3ad} decomposes into NH{sub ad} between 225 and 300 K. NH{sub ad} decomposes into N{sub ad} between 400 K and 500 K and the hydrogen released in this process immediately desorbs. N{sub 2} desorption takes place between 500 and 700 K via N{sub ad} combination. The steady state decomposition reaction of NH{sub 3} starts at 500 K. The maximum reaction rate is observed between 540 K and 610 K. A model is presented to explain the occurrence of a maximum in the reaction rate. Hydrogenation of N{sub ad} below 400 K results in NH{sub ad}. No NH{sub 2ad} or NH{sub 3ad}/NH{sub 3} were observed. The hydrogenation of NH{sub ad} only takes place above 400 K. On the basis of the experimental findings an energy scheme is presented to account for the observations.

  5. TES/Aura L2 Ammonia (NH3) Lite Nadir (TL2NH3LN)

    Atmospheric Science Data Center

    2015-08-26

    TES/Aura L2 Ammonia (NH3) Lite Nadir (TL2NH3LN) News:  TES News ... Level:  L2 Instrument:  TES/Aura L2 Ammonia Spatial Coverage:  5.3 km nadir Spatial ... OPeNDAP Access:  OPeNDAP Parameters:  Ammonia Order Data:  Reverb:   Order Data ...

  6. Hybrid molecular ions emitted from CO-NH3 ice bombarded by fission fragments

    NASA Astrophysics Data System (ADS)

    Martinez, R.; Ponciano, C. R.; Farenzena, L. S.; Iza, P.; Homem, M. G. Pe; Naves de Brito, A.; da Silveira, E. F.; Wien, K.

    2007-05-01

    CO-NH3 ice at 25 K is bombarded by 65 MeV fission fragments and the emitted secondary ions are analyzed by time-of-flight mass spectrometry. The yields of the specific ion species (those formed only from CO or from NH3 molecules) and of the hybrid ion species (formed from both CO and NH3 molecules) are determined as a function of the ice temperature. The time-temperature dependence of desorption yields has been used for secondary ion identification because its behavior characterizes the ion's origin around the sublimation temperature of CO ice (~30 K). The mass spectrum of positive ions measured before CO sublimation is decomposed into three spectra corresponding to CO specific ions, NH3 specific ions and hybrid molecular ions, respectively. The observed spectrum after CO sublimation is very similar to that of a pure NH3 specific spectrum. The total yield of all positive hybrid molecular ions over 600 u mass range is found to be about 2 ions/impact: 20% of this is attributed to N and NH3 containing ions and 80% are ions having the CnOmHl+ structure. The ions CnNH3OH+ and NH3CO+ were identified. At T = 25 K, the total yield of negative ions is about 20 times lower than that of positive ions, the most abundant species being the cyanide ion CN-. Observation of cluster ions based on (HCN)n indicates the formation of hydrogen cyanide.

  7. Promotion of redox and stability features of doped Ce-W-Ti for NH3-SCR reaction over a wide temperature range

    NASA Astrophysics Data System (ADS)

    Zhao, Kun; Han, Weiliang; Lu, Gongxuan; Lu, Jiangyin; Tang, Zhicheng; Zhen, Xinping

    2016-08-01

    In this study, transition metals Co, Mn, and Cu were introduced into a Ce-W-Ti catalyst to promote low-temperature catalytic activity. Among these metal-modified M/Ce-W-Ti catalysts (M represents Co, Mn, or Cu), the Cu/Ce-W-Ti catalyst with an optimized Cu content of 5 wt.% exhibited more than 90% conversion of nitrogen oxide (NOx) in the selective catalytic reduction by NH3 over a wide temperature range (260-400 °C). This catalyst likewise exhibited higher resistance to SO2 gas and water vapor under severe test conditions. On the basis of the characterization results by powder X-ray diffraction and X-ray photoelectron spectroscopy, we concluded that the superior catalytic properties of the Cu/Ce-W-Ti catalyst could be attributed to the highly dispersed Cu species, which increased the contents of Ce3+ species and adsorbed oxygen species in the catalysts. In addition, the NH3 temperature-programmed desorption results demonstrated that the Cu species doped into the Ce-W-Ti catalysts optimized surface acid content.

  8. A SCR Model Calibration Approach with Spatially Resolved Measurements and NH3 Storage Distributions

    DOE PAGESBeta

    Song, Xiaobo; Parker, Gordon G.; Johnson, John H.; Naber, Jeffrey D.; Pihl, Josh A.

    2014-11-27

    The selective catalytic reduction (SCR) is a technology used for reducing NO x emissions in the heavy-duty diesel (HDD) engine exhaust. In this study, the spatially resolved capillary inlet infrared spectroscopy (Spaci-IR) technique was used to study the gas concentration and NH3 storage distributions in a SCR catalyst, and to provide data for developing a SCR model to analyze the axial gaseous concentration and axial distributions of NH3 storage. A two-site SCR model is described for simulating the reaction mechanisms. The model equations and a calculation method was developed using the Spaci-IR measurements to determine the NH3 storage capacity andmore » the relationships between certain kinetic parameters of the model. Moreover, a calibration approach was then applied for tuning the kinetic parameters using the spatial gaseous measurements and calculated NH3 storage as a function of axial position instead of inlet and outlet gaseous concentrations of NO, NO2, and NH3. The equations and the approach for determining the NH3 storage capacity of the catalyst and a method of dividing the NH3 storage capacity between the two storage sites are presented. It was determined that the kinetic parameters of the adsorption and desorption reactions have to follow certain relationships for the model to simulate the experimental data. Finally, the modeling results served as a basis for developing full model calibrations to SCR lab reactor and engine data and state estimator development as described in the references (Song et al. 2013a, b; Surenahalli et al. 2013).« less

  9. NH 3 soil and soil surface gas measurements in a triticale wheat field

    NASA Astrophysics Data System (ADS)

    Neftel, A.; Blatter, A.; Gut, A.; Högger, D.; Meixner, F.; Ammann, C.; Nathaus, F. J.

    We present a new approach for a continuous determination of NH 3 concentration in the open pore space of the soil and on the soil surface. In a semi-permeable membrane of 0.5 m length a flow of 0.5 s1pm maintained. In the tube the NH 3 concentration adjusts itself to the surrounding air concentration by diffusion through the membrane. Continuous measurements have been performed in a triticale wheat field over a period of several weeks in a field experiment at Bellheim (FRG) during June and July 1995 within the frame of the European program EXAMINE (Exchange of Atmospheric Ammonia with European Ecosystems). Soil concentrations are generally below the detection limit of 0.1 μg m -3. We conclude, that the investigated soil is generally a sink for NH 3. The NH 3 concentration on the soil surface shows a diurnal variation due to a combination of physico-chemical desorption and adsorption phenomena associated with changes in wetness of the surrounding surfaces and the NH 3 concentration in the canopy.

  10. Awaruite and Tetrataenite Driven NH3 Synthesis

    NASA Astrophysics Data System (ADS)

    Li, B.; Lemke, K.

    2015-12-01

    The deep biosphere hypothesis postulates that life emerged from a hydrothermal system beginning with small molecules such as CO2, N2, H2, CO, and CS2. (M. J. Russell, A. J Hall, and W. Martin, Geobiology, 2010, 8, 355). Key catalysts/surfaces at the ocean crust boundary would have interacted with these dissolved gases, giving rise to larger biomolecules and ultimately life. Among the catalysts found at present in hydrothermal system, Ni3Fe (Awaruite) and NiFe (Tetrataenite) stand out because they convert simple di and triatomic molecules to more complex structures; for example, Awaruite has been shown to produce NH3 from hydrogen and nitrogen precursors (Alexander Smirnov, Douglas Hausner, Richard Laffers, Daniel R Strongin, and Marton AA Schoonen, Geochemical Transactions, 2008, 9:5). The goal of this study is to examine the role of iron nickel clusters with Awaruite and Tetrataenite stoichiometries in converting atomic nitrogen and hydrogen to ammonia. Using a basin-hopping algorithmic procedure, the global minima of Awaruite and Tetrataenite clusters with up to 35 atoms have been identified along with their affinity to nitrogen and hydrogen attachment has been examined (i.e. atom position, cluster edges, and surface sites). Preliminary results indicate that atomic nitrogen attaches onto mixed iron nickel cluster surface sites, with distinct discontinuities in the binding energy profile at magic cluster number positions. We also studied the effects of cluster composition on the affinity of nitrogen and hydrogen to attach to Ni13-xFex with up to x=13. These results, for both scenarios (size and compositional variation), indicate that nano-sized iron-nickel clusters would drive the initial transformation of nitrogen and hydrogen toward NH3, with important implications for the chemistry of Earth's early atmosphere.

  11. Theoretical and experimental analysis of ammonia ionic clusters produced by 252Cf fragment impact on an NH3 ice target.

    PubMed

    Fernandez-Lima, F A; Ponciano, C R; Chaer Nascimento, M A; da Silveira, E F

    2006-08-24

    Positive and negatively charged ammonia clusters produced by the impact of (252)Cf fission fragments (FF) on an NH(3) ice target have been examined theoretical and experimentally. The ammonia clusters generated by (252)Cf FF show an exponential dependence of the cluster population on its mass, and the desorption yields for the positive (NH(3))(n)NH(4)(+) clusters are 1 order of magnitude higher than those for the negative (NH(3))(n)NH(2)(-) clusters. The experimental population analysis of (NH(3))(n)NH(4)(+) (n = 0-18) and (NH(3))(n)NH(2)(-) (n = 0-8) cluster series show a special stability at n = 4 and 16 and n = 2, 4, and 6, respectively. DFT/B3LYP calculations of the (NH(3))(0)(-)(8)NH(4)(+) clusters show that the structures of the more stable conformers follow a clear pattern: each additional NH(3) group makes a new hydrogen bond with one of the hydrogen atoms of an NH(3) unit already bound to the NH(4)(+) core. For the (NH(3))(0)(-)(8)NH(2)(-) clusters, the DFT/B3LYP calculations show that, within the calculation error, the more stable conformers follow a clear pattern for n = 1-6: each additional NH(3) group makes a new hydrogen bond to the NH(2)(-) core. For n = 7 and 8, the additional NH(3) groups bind to other NH(3) groups, probably because of the saturation of the NH(2)(-) core. Similar results were obtained at the MP2 level of calculation. A stability analysis was performed using the commonly defined stability function E(n)(-)(1) + E(n)(+1) - 2E(n), where E is the total energy of the cluster, including the zero point correction energy (E = E(t) + ZPE). The trend on the relative stability of the clusters presents an excellent agreement with the distribution of experimental cluster abundances. Moreover, the stability analysis predicts that the (NH(3))(4)NH(4)(+) and the even negative clusters [(NH(3))(n)NH(2)(-), n = 2, 4, and 6] should be the most stable ones, in perfect agreement with the experimental results. PMID:16913675

  12. Growth of an Ultrathin Zirconia Film on Pt3Zr Examined by High-Resolution X-ray Photoelectron Spectroscopy, Temperature-Programmed Desorption, Scanning Tunneling Microscopy, and Density Functional Theory

    PubMed Central

    2014-01-01

    Ultrathin (∼3 Å) zirconium oxide films were grown on a single-crystalline Pt3Zr(0001) substrate by oxidation in 1 × 10–7 mbar of O2 at 673 K, followed by annealing at temperatures up to 1023 K. The ZrO2 films are intended to serve as model supports for reforming catalysts and fuel cell anodes. The atomic and electronic structure and composition of the ZrO2 films were determined by synchrotron-based high-resolution X-ray photoelectron spectroscopy (HR-XPS) (including depth profiling), low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. Oxidation mainly leads to ultrathin trilayer (O–Zr–O) films on the alloy; only a small area fraction (10–15%) is covered by ZrO2 clusters (thickness ∼0.5–10 nm). The amount of clusters decreases with increasing annealing temperature. Temperature-programmed desorption (TPD) of CO was utilized to confirm complete coverage of the Pt3Zr substrate by ZrO2, that is, formation of a closed oxide overlayer. Experiments and DFT calculations show that the core level shifts of Zr in the trilayer ZrO2 films are between those of metallic Zr and thick (bulklike) ZrO2. Therefore, the assignment of such XPS core level shifts to substoichiometric ZrOx is not necessarily correct, because these XPS signals may equally well arise from ultrathin ZrO2 films or metal/ZrO2 interfaces. Furthermore, our results indicate that the common approach of calculating core level shifts by DFT including final-state effects should be taken with care for thicker insulating films, clusters, and bulk insulators. PMID:25688293

  13. Condensation and vaporization studies of CH3OH and NH3 ices: Major implications for astrochemistry

    NASA Technical Reports Server (NTRS)

    Sandford, Scott A.; Allamandola, Louis J.

    1993-01-01

    In an extension of previously reported work on ices containing H2O, CO, CO2, SO2, H2S, and H2, we present measurements of the physical and infrared spectral properties of ices containing CH3OH and NH3. The condensation and sublimation behavior of these ice systems is discussed and surface binding energies are presented for all of these molecules. The surface binding energies can be used to calculate the residence times of the molecules on grain surfaces as a function of temperature. It is demonstrated that many of the molecules used to generate radio maps of and probe conditions in dense clouds, for example CO and NH3, will be significantly depleted from the gas phase by condensation onto dust grains. Attempts to derive total column densities solely from radio maps that do not take condensation effects into account may vastly underestimate the true column densities of any given species. Simple CO condensation onto and vaporization off of grains appears to be capable of explaining the observed depletion of gas phase CO in cold, dense molecular cores. This is not the case for NH3, however, where thermal considerations alone predict that all of the NH3 should be condensed onto grains. The fact that some gas phase NH3 is observed indicates that additional desorption processes must be involved. The surface binding energies of CH3OH, in conjunction with this molecule's observed behavior during warm up in H2O-rich ices, is shown to provide an explanation of the large excess of CH3OH seen in many warm, dense molecular cores. The near-infrared spectrum and associated integrated band strengths of CH3OH-containing ice are given, as are middle infrared absorption band strengths for both CH3OH and NH3.

  14. Condensation and Vaporization Studies of CH3OH and NH3 Ices: Major Implications for Astrochemistry

    NASA Technical Reports Server (NTRS)

    Sandford, Scott A.; Allamandola, Louis J.

    1993-01-01

    In an extension of previously reported work on ices containing H20, CO, CO2, SO2, H2S, and H2, We present measurements of the physical and infrared spectral properties of ices containing CH30H and NH3.The condensation and sublimation behavior of these ice systems is discussed and surface binding energies are presented for all of these molecules. The surface binding energies can be used to calculate the residence times of the molecules on grain surfaces as a function of temperature. It is demonstrated that many of the molecules used to generate radio maps of and probe conditions in dense clouds, for example CO and NH3, will be significantly depleted from the gas phase by condensation onto dust grains. Attempts to derive total column densities solely from radio maps that do not take condensation effects into account may vastly underestimate the true column densities of any given species. Simple CO condensation onto and vaporization off of grains appears to be capable of explaining the observed 87 of gas phase CO in cold, dense molecular cores. This is not the case for NH3, however, where thermal considerations alone predict that all of the NH3 should be condensed onto grains. The fact that some gas phase NH3 is observed indicates that additional desorption processes must be involved. The surface binding energies of CH3OH, in conjunction with this molecule's observed behavior during warm up in H2O-rich ices, is shown to provide an explanation of the large excess of CH3OH seen in many warm, dense molecular cores. The near-infrared spectrum and associated integrated band strengths of CH3OH-containing ice are given, as are middle infrared absorption band strengths for both CH3OH and NH3.

  15. Condensation and vaporization studies of CH3OH and NH3 ices: major implications for astrochemistry.

    PubMed

    Sandford, S A; Allamandola, L J

    1993-11-10

    In an extension of previously reported work on ices containing H2O, CO, CO2, SO2, H2S, and H2, we present measurements of the physical and infrared spectral properties of ices containing CH3OH and NH3. The condensation and sublimation behavior of these ice systems is discussed and surface binding energies are presented for all of these molecules. The surface binding energies can be used to calculate the residence times of the molecules on grain surfaces as a function of temperature. It is demonstrated that many of the molecules used to generate radio maps of and probe conditions in dense clouds, for example CO and NH3, will be significantly depleted from the gas phase by condensation onto dust grains. Attempts to derive total column densities solely from radio maps that do not take condensation effects into account may vastly underestimate the true column densities of any given species. Simple CO condensation onto and vaporization off of grains appears to be capable of explaining the observed depletion of gas phase CO in cold, dense molecular cores. This is not the case for NH3, however, where thermal considerations alone predict that all of the NH3 should be condensed onto grains. The fact that some gas phase NH3 is observed indicates that additional desorption processes must be involved. The surface binding energies of CH3OH, in conjunction with this molecule's observed behavior during warm up in H2O-rich ices, is shown to provide an explanation of the large excess of CH3OH seen in many warm, dense molecular cores. The near-infrared spectrum and associated integrated band strengths of CH3OH-containing ice are given, as are middle infrared absorption band strengths for both CH3OH and NH3. PMID:11540092

  16. Effects of Si/Al Ratio on Cu/SSZ-13 NH3-SCR Catalysts: Implications for the active Cu species and the Roles of Brønsted Acidity

    SciTech Connect

    Gao, Feng; Washton, Nancy M.; Wang, Yilin; Kollar, Marton; Szanyi, Janos; Peden, Charles HF

    2015-09-03

    Cu/SSZ-13 catalysts with three Si/Al ratios of 6, 12 and 35 were synthesized with Cu incorporation via solution ion exchange. The implications of varying Si/Al ratios on the nature of the multiple Cu species that can be present in the SSZ-13 zeolite are a major focus of this work, as highlighted by the results of a variety of catalyst characterization and reaction kinetics measurements. Specifically, catalysts were characterized with surface area/pore volume measurements, temperature programmed reduction by H2 (H2-TPR), NH3 temperature programmed desorption (NH3-TPD), and DRIFTS and solid-state nuclear magnetic resonance (NMR) spectroscopies. Catalytic properties were examined using NO oxidation, ammonia oxidation, and standard ammonia selective catalytic reduction (NH3-SCR) reactions on selected catalysts under differential conditions. Besides indicating possible variably active multiple Cu species for these reactions, the measurements are also used to untangle some of the complexities caused by the interplay between redox of Cu ion centers and Brønsted acidity. All three reactions appear to follow a redox reaction mechanism, yet the roles of Brønsted acidity are quite different. For NO oxidation, increasing Si/Al ratio lowers Cu redox barriers, thus enhancing reaction rates. Brønsted acidity appears to play essentially no role for this reaction. For standard NH3-SCR, residual Brønsted acidity plays a significant beneficial role at both low- and high-temperature regimes. For NH3 oxidation, no clear trend is observed suggesting both Cu ion center redox and Brønsted acidity play important and perhaps competing roles. The authors 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 in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of

  17. Degradation mechanism of CH3NH3PbI3 perovskite materials upon exposure to humid air

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    Low stability of organic-inorganic perovskite (CH3NH3PbI3) solar cells in humid air environments is a serious drawback which could limit practical application of this material severely. In this study, from real-time spectroscopic ellipsometry characterization, the degradation mechanism of ultra-smooth CH3NH3PbI3 layers prepared by a laser evaporation technique is studied. We present evidence that the CH3NH3PbI3 degradation in humid air proceeds by two competing reactions of (i) the PbI2 formation by the desorption of CH3NH3I species and (ii) the generation of a CH3NH3PbI3 hydrate phase by H2O incorporation. In particular, rapid phase change occurs in the near-surface region and the CH3NH3PbI3 layer thickness reduces rapidly in the initial 1 h air exposure even at a low relative humidity of 40%. After the prolonged air exposure, the CH3NH3PbI3 layer is converted completely to hexagonal platelet PbI2/hydrate crystals that have a distinct atomic-scale multilayer structure with a period of 0.65 ± 0.05 nm. We find that conventional x-ray diffraction and optical characterization in the visible region, used commonly in earlier works, are quite insensitive to the surface phase change. Based on results obtained in this work, we discuss the degradation mechanism of CH3NH3PbI3 in humid air.

  18. A Comparative Study of N2O Formation during the Selective Catalytic Reduction of NOx with NH3 on Zeolite Supported Cu Catalysts

    SciTech Connect

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

    2015-09-01

    A comparative study was carried out on a small-pore CHA.Cu and a large-pore BEA.Cu zeolite catalyst to understand the lower N2O formation on small-pore zeolite supported Cu catalysts in the selective catalytic reduction (SCR) of NOx with NH3. On both catalysts, the N2O yield increases with an increase in the NO2/NOx ratios of the feed gas, suggesting N2O formation via the decomposition of NH4NO3. Temperature-programmed desorption experiments reveal that NH4NO3 is more stable on CHA.Cu than on BEA.Cu. In situ FTIR spectra following stepwise (NO2 + O2) and (15NO + NH3 + O2) adsorption and reaction, and product distribution analysis using isotope-labelled reactants, unambiguously prove that surface nitrate groups are essential for the formation of NH4NO3. Furthermore, CHA.Cu is shown to be considerably less active than BEA.Cu in catalyzing NO oxidation and the subsequent formation of surface nitrate groups. Both factors, i.e., (1) the higher thermal stability of NH4NO3 on CHA.Cu, and (2) the lower activity for this catalyst to catalyze NO oxidation and the subsequent formation of surface nitrates, likely contribute to the higher SCR selectivity with less N2O formation on this catalyst as compared to BEA.Cu. The latter is determined as the primary reason since surface nitrates are the source that leads to the formation of NH4NO3 on the catalysts.

  19. Herschel/HIFI deepens the circumstellar NH3 enigma

    NASA Astrophysics Data System (ADS)

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

    2010-10-01

    Context. Circumstellar envelopes (CSEs) of a variety of evolved stars have been found to contain ammonia (NH3) in amounts that exceed predictions from conventional chemical models by many orders of magnitude. Aims: The observations reported here were performed in order to better constrain the NH3 abundance in the CSEs of four, quite diverse, oxygen-rich stars using the NH3 ortho JK = 10-00 ground-state line. Methods: We used the Heterodyne Instrument for the Far Infrared aboard Herschel to observe the NH3 JK = 10-00 transition near 572.5 GHz, simultaneously with the ortho-H2O JKa , Kc = 11,0 - 10,1 transition, toward VY CMa, OH 26.5+0.6, IRC+10420, and IK Tau. We conducted non-LTE radiative transfer modeling with the goal to derive the NH3 abundance in these objects' CSEs. For the last two stars, Very Large Array imaging of NH3 radio-wavelength inversion lines were used to provide further constraints, particularly on the spatial extent of the NH3-emitting regions. Results: We find remarkably strong NH3 emission in all of our objects with the NH3 line intensities rivaling those of the ground state H2O line. The NH3 abundances relative to H2 are very high and range from 2×10-7 to 3×10-6 for the objects we have studied. Conclusions: Our observations confirm and even deepen the circumstellar NH3 enigma. While our radiative transfer modeling does not yield satisfactory fits to the observed line profiles, it does lead to abundance estimates that confirm the very high values found in earlier studies. New ways to tackle this mystery will include further Herschel observations of more NH3 lines and imaging with the Expanded Very Large Array. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.Appendix A (page 5) is only available in electronic form at http://www.aanda.org

  20. Bias in modeled bi-directional NH3 fluxes associated with temporal averaging of atmospheric NH3 concentrations

    EPA Science Inventory

    Direct flux measurements of NH3 are expensive, time consuming, and require detailed supporting measurements of soil, vegetation, and atmospheric chemistry for interpretation and model parameterization. It is therefore often necessary to infer fluxes by combining measurements of...

  1. NH_3 Emission in the Perseus Molecular Cloud Complex

    NASA Astrophysics Data System (ADS)

    Ladd, E. F.; Myers, P. C.; Goodman, A. A.

    1993-12-01

    We present a survey for dense material around young IRAS sources in the Perseus molecular cloud complex in the NH_3 (J,K) = (1,1) line at 1.3 cm. NH_3 emission was detected in eight, and mapped in seven, out of ten positions chosen for study. The dense cores found typically have lower masses and narrower linewidths than cores previously studied in Perseus, and are located near sources of lower luminosity. NH_3 cores are found throughout the Perseus complex; however, much of the detected dense gas is concentrated into two filamentary ``ridges'' located in the western part. As group, NH_3 cores in Perseus have mean linewidth 0.6 kms(-1) , radius 0.12 pc, kinetic temperature 13 K, and mass 9 M_sun. These mean values are larger than the mean values for NH_3 cores with associated stars in Taurus, but smaller than the mean values for cores associated with stars in Orion A. Some of the cores in Perseus are ``thermally-dominated,'' with thermal and nonthermal linewidths similar to most Taurus cores, while others are ``nonthermally-dominated,'' and are more similar to the cores in Orion A. We conclude that the Perseus complex is intermediate in its star forming potential betweeen the predominantly low-mass star producing regions like Taurus and the regions capable of the producing high mass stars such as Orion A.

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

    NASA Astrophysics Data System (ADS)

    Esmaili, Sasan

    2015-08-01

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

  3. UF6 and UF4 in liquid ammonia: [UF7(NH3)]3- and [UF4(NH3)4].

    PubMed

    Kraus, Florian; Baer, Sebastian A

    2009-08-17

    From the reaction of uranium hexafluoride UF6 with dry liquid ammonia, the [UF7(NH3)]3- anion and the [UF4(NH3)4] molecule were isolated and identified for the first time. They are found in signal-green crystals of trisammonium monoammine heptafluorouranate(IV) ammonia (1:1; [NH4]3[UF7(NH3)].NH3) and emerald-green crystals of tetraammine tetrafluorouranium(IV) ammonia (1:1; [UF4(NH3)4].NH3). [NH4]3[UF7(NH3)].NH3 features discrete [UF7(NH3)]3- anions with a coordination geometry similar to a bicapped trigonal prism, hitherto unknown for U(IV) compounds. The emerald-green [UF4(NH3)4].NH3 contains discrete tetraammine tetrafluorouranium(IV) [UF4(NH3)4] molecules. [UF4(NH3)4].NH3 is not stable at room temperature and forms pastel-green [UF4(NH3)4] as a powder that is surprisingly stable up to 147 degrees C. The compounds are the first structurally characterized ammonia complexes of uranium fluorides. PMID:19585645

  4. Gaseous NH3 Confers Porous Pt Nanodendrites Assisted by Halides

    NASA Astrophysics Data System (ADS)

    Lu, Shuanglong; Eid, Kamel; Li, Weifeng; Cao, Xueqin; Pan, Yue; Guo, Jun; Wang, Liang; Wang, Hongjing; Gu, Hongwei

    2016-05-01

    Tailoring the morphology of Pt nanocrystals (NCs) is of great concern for their enhancement in catalytic activity and durability. In this article, a novel synthetic strategy is developed to selectively prepare porous dendritic Pt NCs with different structures for oxygen reduction reaction (ORR) assisted by NH3 gas and halides (F‑, Cl‑, Br‑). The NH3 gas plays critical roles on tuning the morphology. Previously, H2 and CO gas are reported to assist the shape control of metallic nanocrystals. This is the first demonstration that NH3 gas assists the Pt anisotropic growth. The halides also play important role in the synthetic strategy to regulate the formation of Pt NCs. As-made porous dendritic Pt NCs, especially when NH4F is used as a regulating reagent, show superior catalytic activity for ORR compared with commercial Pt/C catalyst and other previously reported Pt-based NCs.

  5. Gaseous NH3 Confers Porous Pt Nanodendrites Assisted by Halides.

    PubMed

    Lu, Shuanglong; Eid, Kamel; Li, Weifeng; Cao, Xueqin; Pan, Yue; Guo, Jun; Wang, Liang; Wang, Hongjing; Gu, Hongwei

    2016-01-01

    Tailoring the morphology of Pt nanocrystals (NCs) is of great concern for their enhancement in catalytic activity and durability. In this article, a novel synthetic strategy is developed to selectively prepare porous dendritic Pt NCs with different structures for oxygen reduction reaction (ORR) assisted by NH3 gas and halides (F(-), Cl(-), Br(-)). The NH3 gas plays critical roles on tuning the morphology. Previously, H2 and CO gas are reported to assist the shape control of metallic nanocrystals. This is the first demonstration that NH3 gas assists the Pt anisotropic growth. The halides also play important role in the synthetic strategy to regulate the formation of Pt NCs. As-made porous dendritic Pt NCs, especially when NH4F is used as a regulating reagent, show superior catalytic activity for ORR compared with commercial Pt/C catalyst and other previously reported Pt-based NCs. PMID:27184228

  6. Gaseous NH3 Confers Porous Pt Nanodendrites Assisted by Halides

    PubMed Central

    Lu, Shuanglong; Eid, Kamel; Li, Weifeng; Cao, Xueqin; Pan, Yue; Guo, Jun; Wang, Liang; Wang, Hongjing; Gu, Hongwei

    2016-01-01

    Tailoring the morphology of Pt nanocrystals (NCs) is of great concern for their enhancement in catalytic activity and durability. In this article, a novel synthetic strategy is developed to selectively prepare porous dendritic Pt NCs with different structures for oxygen reduction reaction (ORR) assisted by NH3 gas and halides (F−, Cl−, Br−). The NH3 gas plays critical roles on tuning the morphology. Previously, H2 and CO gas are reported to assist the shape control of metallic nanocrystals. This is the first demonstration that NH3 gas assists the Pt anisotropic growth. The halides also play important role in the synthetic strategy to regulate the formation of Pt NCs. As-made porous dendritic Pt NCs, especially when NH4F is used as a regulating reagent, show superior catalytic activity for ORR compared with commercial Pt/C catalyst and other previously reported Pt-based NCs. PMID:27184228

  7. First detection of ammonia (NH3) in the upper troposphere

    NASA Astrophysics Data System (ADS)

    Höpfner, Michael; Volkamer, Rainer; Grabowski, Udo; Grutter de la Mora, Michel; Orphal, Johannes; Stiller, Gabriele; von Clarmann, Thomas

    2016-04-01

    Ammonia (NH3) is the major alkaline trace gas in the troposphere. Neutralization of atmospheric acids, like HNO3 and H2SO4, leads to formation of ammonium nitrate and ammonium sulfate aerosols. Further, there are indications that NH3 may enhance nucleation of sulfuric acid aerosols by stabilization of sulfuric acid clusters. By far the largest source of ammonia is agricultural food production. Major global emissions are located in S-E Asia as e.g. shown by satellite nadir observations. Besides its importance with respect to air quality issues, an increase of ammonia emissions in the 21st century might lead to a significant climate radiative impact through aerosol formation. In spite of its significance, there is a lack of observational information on the global distribution of NH3 in the mid- and upper troposphere. Observational evidence, however, would be important for testing e.g. model results on the fate of ammonia from its source regions on ground to altitudes up to the tropopause. In this contribution we will show, to our knowledge, the first unequivocal detection of ammonia in the upper troposphere. This result has been achieved through analysis of infrared limb-emission observations performed with the MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) instrument on board the Envisat satellite from 2002-2012. On a global scale, enhanced values of ammonia have been measured in the upper tropospheric region influenced by the Asian monsoon. We will present a quantitative analysis of the retrieved concentrations of NH3 including an error assessment and further retrieval diagnostics. The results will be discussed with respect to the variability of NH3 locally within the Asian monsoon region's upper troposphere and at different years. Further, we will show comparisons between global distributions of NH3 from published model simulations and our observational dataset from MIPAS.

  8. Urban NH3 levels and sources in a Mediterranean environment

    NASA Astrophysics Data System (ADS)

    Reche, Cristina; Viana, Mar; Pandolfi, Marco; Alastuey, Andrés; Moreno, Teresa; Amato, Fulvio; Ripoll, Anna; Querol, Xavier

    2012-09-01

    Urban NH3 concentrations were mapped in Barcelona (Spain) by means of passive samplers (dosimeters). Average NH3 levels were 9.5 μg m-3 in summer and 4.4 μg m-3 in winter, higher than those reported in other urban background sites in Europe, this being especially notable in summer. During this season, values were significantly higher at urban background than at traffic sites, probably indicating the impact of emissions from biological sources, such as humans, sewage systems and garbage containers. Thus, the volatilization of NH3 from the aerosol phase seems to be significant enough during summer to dominate over traffic emissions. Conversely, in winter levels were higher at traffic sites, suggesting a contribution from vehicle emissions. Indeed, NH3 levels decreased by 55% with increasing distance (50 m) to the direct emissions from traffic. A significant correlation between NH3 concentrations averaged for the different districts of the city and the number of waste containers per hm2 was also obtained, highlighting the necessity for controlling and reducing the emissions from garbage collection systems. The urban topography of the Barcelona historical city centre, characterised by narrow streets with a high population density, seemed to exert a strong influence on NH3 levels, with levels reaching up to 30 μg m-3 as a consequence of limited dispersion and ventilation conditions. The impact of the sewage system emissions was also detected with an increase of levels when measuring immediately above the source, even though further studies are required to evaluate the relevance of these emissions.

  9. Enhanced NH3 emission from swine liquid waste

    NASA Astrophysics Data System (ADS)

    Lee, S.; Robarge, W. P.; Walker, J. T.

    2010-12-01

    Swine animal feeding operations are sources of emissions for various gases [ammonia (NH3), hydrogen sulfide (H2S), carbon dioxide (CO2), volatile organic carbons (VOCs)], and fine particulate matter. Gaseous emissions from simple aqueous systems are typically controlled by temperature, pH, wind speed, total dissolved concentration of the chemical species of interest (e.g. NH3+NH4+ = TAN), and the Henry’s law constant. Ammonia emissions from three different sources [ammonium sulfate (AS), swine anaerobic lagoon liquid (SLL), and pit liquid (SPL) from swine housing units] were evaluated using a small flow-through teflon-lined chamber (SFTC; 0.3m × 0.2m × 0.15m) under controlled laboratory conditions. The SFTC was designed for 100% collection efficiency of NH3 gas emitted from the liquids. The internal volume of the chamber, 9 L, was exchanged 1.1 times per minute. All three liquid formulations exhibit the expected response in emissions with changes in temperature and pH. However, NH3 emissions from the SPL and SLL are ~5 times those from pure solutions of AS. Furthermore, the enhancement in NH3 emissions was a function of TAN concentration, decreasing in intensity at higher TAN and approaching rates comparable to the pure solutions of AS. The difference in emissions with solutions of equivalent TAN suggests a synergistic mechanism that is enhancing NH3 emissions in SPL and SLL. Concurrent measurements as part of the National Air Emissions Monitoring Study at the swine operations originally sampled for SPL and SLL document the emissions of CO2, H2S and VOCs (primarily acetic, propionic and butyric acids) at levels that are comparable to observed NH3 emissions. To date, only additions of NaHCO3 to the SPL and SLL have been found to enhance NH3 emissions and exhibit the same response to increasing TAN as exhibited by the original SPL and SLL solutions. Possible reactions that could enhance emissions will be discussed.

  10. NARSTO EPA SS HOUSTON NH3 HNO3 DATA

    Atmospheric Science Data Center

    2014-04-25

    NARSTO EPA SS HOUSTON NH3 HNO3 DATA Project Title:  NARSTO ... Ion Chromatograph Location:  Houston, Texas Spatial Resolution:  Point Measurements ...   Order Data Guide Documents:  Houston HN3 HNO3 Guide Houston Project Plan  (PDF) ...

  11. NH3 in IRC plus 10216. [infrared astronomy

    NASA Technical Reports Server (NTRS)

    Betz, A. L.; Mclaren, R. A.; Spears, D. L.

    1978-01-01

    Ammonia was detected in the circumstellar envelope of IRC +10216 by means of three infrared absorption lines in the nu sup 2 band around 950/cm. The lines are fully resolved at a resolution of 0.22 km/sec and indicate that most of the circumstellar gas is accelerated to expansion velocities around 14 km/sec within a few stellar radii. The NH3 profiles indicate a rotational temperature between 400 and 700 K, and H2 density between 10 to the 8th power/cu cm and 10 to the 10th power/cu cm, and NH3 column density of 10 to the 17th power/sq cm. The H2 density indicates that the mass of the circumstellar envelope within a 1 arcsec radius is approximately 0.1 solar masses.

  12. Communication: overtone (2NH) spectroscopy of NH3-Ar.

    PubMed

    Didriche, K; Földes, T; Vanfleteren, T; Herman, M

    2013-05-14

    The Π (1(1)) ← Σ (0(0)) 2NH (ν1+ν3) band of the NH3-Ar van der Waals complex formed in a supersonic jet expansion, with origin at 6628 cm(-1) was recorded at high-resolution using cavity ring down spectroscopy. The analysis leads to upper state rotational constants and J-dependent predissociation lifetimes estimated from linewidth analysis, with a mean value about 0.6 ns. PMID:23676017

  13. Scattering resonances in slow NH3-He collisions

    NASA Astrophysics Data System (ADS)

    Gubbels, Koos B.; van de Meerakker, Sebastiaan Y. T.; Groenenboom, Gerrit C.; Meijer, Gerard; van der Avoird, Ad

    2012-02-01

    We theoretically study slow collisions of NH3 molecules with He atoms, where we focus in particular on the observation of scattering resonances. We calculate state-to-state integral and differential cross sections for collision energies ranging from 10-4 cm-1 to 130 cm-1, using fully converged quantum close-coupling calculations. To describe the interaction between the NH3 molecules and the He atoms, we present a four-dimensional potential energy surface, based on an accurate fit of 4180 ab initio points. Prior to collision, we consider the ammonia molecules to be in their antisymmetric umbrella state with angular momentum j = 1 and projection k = 1, which is a suitable state for Stark deceleration. We find pronounced shape and Feshbach resonances, especially for inelastic collisions into the symmetric umbrella state with j = k = 1. We analyze the observed resonant structures in detail by looking at scattering wavefunctions, phase shifts, and lifetimes. Finally, we discuss the prospects for observing the predicted scattering resonances in future crossed molecular beam experiments with a Stark-decelerated NH3 beam.

  14. Preformance Analysis of NH3-H2O Absorption Cycle

    NASA Astrophysics Data System (ADS)

    Tsujimori, Atsushi; Ozaki, Eiichi

    Different from H2O-LiBr absorption cycle, it is necessary to have rectifier between generator and condenser in NH3-H2O absorption cycle, because there mixes some steam in refrigerant vapor in the process of regenerating refrigerant from the ammonia strong aqueous solution. And in some case ex. partial load or heating, the efficiency of rectifier might decrease, if the flow rate of refrigerant vapor and ammonia aqueous solution decrease. As a result, steam flow into condenser with ammonia refrigerant vapor, which reduces cycle COPs of cooling and heating. Accordingly in order to evaluate the effect of ammonia concentration in refrigerant for the performance of NH3-H2O absorption heat pump, the simple design approach of modeling condenser and evaporator is introduced in this paper. In the model, the calculation of heat rate in condenser and evaporator was simplified considering the characteristic of NH3-H2O liquid-vapor equilibrium. Then the simulation for cycle perforance based on GAX absorption cycle was made using the efficiency of rectifier that established the ammonia concentration in refrigerant and it was derived that 3 [%] decrease of ammonia concentration in refrigerant induced 15 [%] decrcase of cooling COP and 7 [%] decrease of heating COP and that there existed the most suitable circulation ratio for each ammonia concentration in refrigerant.

  15. NH3-SCR denitration catalyst performance over vanadium-titanium with the addition of Ce and Sb.

    PubMed

    Xu, Chi; Liu, Jian; Zhao, Zhen; Yu, Fei; Cheng, Kai; Wei, Yuechang; Duan, Aijun; Jiang, Guiyuan

    2015-05-01

    Selective catalytic reduction technology using NH3 as a reducing agent (NH3-SCR) is an effective control method to remove nitrogen oxides. TiO2-supported vanadium oxide catalysts with different levels of Ce and Sb modification were prepared by an impregnation method and were characterized by X-ray diffractometer (XRD), Brunauer-Emmett-Teller (BET), Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), Raman and Hydrogen temperature-programmed reduction (H2-TPR). The catalytic activities of V5CexSby/TiO2 catalysts for denitration were investigated in a fixed bed flow microreactor. The results showed that cerium, vanadium and antimony oxide as the active components were well dispersed on TiO2, and the catalysts exhibited a large number of d-d electronic transitions, which were helpful to strengthen SCR reactivity. The V5CexSby/TiO2 catalysts exhibited a good low temperature NH3-SCR catalytic activity. In the temperature range of 210 to 400°C, the V5CexSby/TiO2 catalysts gave NO conversion rates above 90%. For the best V5Ce35Sb2/TiO2 catalyst, at a reaction temperature of 210°C, the NO conversion rate had already reached 90%. The catalysts had different catalytic activity with different Ce loadings. With the increase of Ce loading, the NO conversion rate also increased. PMID:25968261

  16. Preparation of highly active manganese oxides supported on functionalized MWNTs for low temperature NOx reduction with NH3

    NASA Astrophysics Data System (ADS)

    Pourkhalil, Mahnaz; Moghaddam, Abdolsamad Zarringhalam; Rashidi, Alimorad; Towfighi, Jafar; Mortazavi, Yadollah

    2013-08-01

    Manganese oxide catalysts (MnOx) supported on functionalized multi-walled carbon nanotubes (FMWNTs) for low temperature selective catalytic reduction (LTSCR) of nitrogen oxides (NOx) with NH3 in the presence of excess O2 were prepared by the incipient wetness impregnation method. These catalysts were characterized by N2 adsorption, Fourier transform infrared spectroscopy (FTIR), transmission electron microscope (TEM), X-ray diffraction (XRD), thermal gravimetric analysis (TGA) and H2-temperature programmed reduction (H2-TPR) methods. The effects of reaction temperature, MnOx loading, calcination temperature and calcination time were investigated. The presence of surface nitrate species under moderate calcination conditions may play a favorable role in the LTSCR of NOx with NH3. Under the reaction conditions of 200 °C, 1 bar, NO = NH3 = 900 ppm, O2 = 5 vol%, GHSV = 30,000 h-1 and 12 wt% MnOx, NOx conversion and N2 selectivity were 97% and 99.5%, respectively. The SCR activity was reduced in the presence of 100 ppm SO2 and 2.5 vol% H2O from 97% to 92% within 6 h at 200 °C, however such an effect was shown to be reversible by exposing the catalyst to a helium flow for 2 h at 350 °C due to thermal decomposition of ammonium sulphate salts.

  17. Cs5Sn9(OH)·4NH3

    PubMed Central

    Friedrich, Ute; Korber, Nikolaus

    2014-01-01

    The title compound, penta­caesium nona­stannide hydroxide tetra­ammonia, crystallized from a solution of CsSnBi in liquid ammonia. The Sn9 4− unit forms a monocapped quadratic anti­prism. The hydroxide ion is surrounded by five caesium cations, which form a distorted quadratic pyramidal polyhedron. A three-dimensional network is formed by Cs—Sn [3.8881 (7) Å to 4.5284 (7) Å] and Cs—NH3 [3.276 (7)–3.636 (7) Å] contacts. PMID:24940189

  18. The ground state far infrared spectrum of NH3

    NASA Technical Reports Server (NTRS)

    Poynter, R. L.; Margolis, J. S.

    1983-01-01

    The NH3 far infrared spectrum is particularly useful for the study of planetary composition and atmospheric dynamics. Studies of this spectrum were conducted by Dowling (1969), Helminger et al. (1971), and Urban et al. (1981). Sattler et al. (1981) have reported measurements of a few nu2 lines with tunable diode lasers. By using simple sum rules, these lines and accurate ground state inversion lines considered by Poynter and Kakar (1975) have been employed in the present investigation to deduce a few of the far infrared ground state transitions. An extensive set of high signal/noise, high resolution (0.0048 per cm) scans of the nu2 bands of NH3 from about 600 per cm through about 1300 per cm ait a series of low pressures have been made in order to accurately determine both the line positions and strengths. The obtained data provide line positions with an absolute accuracy of about 0.0001 per cm in the more favorable cases.

  19. Is CH3NH3PbI3 Polar?

    PubMed

    G, Sharada; Mahale, Pratibha; Kore, Bhushan P; Mukherjee, Somdutta; Pavan, Mysore S; De, Chandan; Ghara, Somnath; Sundaresan, A; Pandey, Anshu; Guru Row, Tayur N; Sarma, D D

    2016-07-01

    In view of the continued controversy concerning the polar/nonpolar nature of the hybrid perovskite system, CH3NH3PbI3, we report the first investigation of a time-resolved pump-probe measurement of the second harmonic generation efficiency as well as using its more traditional form as a sensitive probe of the absence/presence of the center of inversion in the system both in its excited and ground states, respectively. Our results clearly show that SHG efficiency, if nonzero, is below the limit of detection, strongly indicative of a nonpolar or centrosymmetric structure. Our results on the same samples, based on temperature dependent single crystal X-ray diffraction and P-E loop measurements, are entirely consistent with the above conclusion of a centrosymmetric structure for this compound in all three phases, namely the high temperature cubic phase, the intermediate temperature tetragonal phase and the low temperature orthorhombic phase. It is important to note that all our experimental probes are volume averaging and performed on bulk materials, suggesting that basic material properties of CH3NH3PbI3 are consistent with a centrosymmetric, nonpolar structure. PMID:27282976

  20. Sensing Mechanisms for Carbon Nanotube Based NH3 Gas Detection

    SciTech Connect

    Peng, Ning; Zhang, Qing; Chow, Chee L.; Tan, Ooi K.; Marzari, Nicola N.

    2009-03-31

    There has been an argument on carbon nanotube (CNT) based gas detectors with a field-effect transistor (FET) geometry: do the response signals result from charge transfer between adsorbed gas molecules and the CNT channel and/or from the gas species induced Schottky barrier modulation at the CNT/metal contacts? To differentiate the sensing mechanisms, we employed three CNTFET structures, i.e., (1) the entire CNT channel and CNT/electrode contacts are accessible to NH3 gas; (2) the CNT/electrode contacts are passivated with a Si3N4 thin film, leaving the CNT channel open to the gas and, in contrast, (3) the CNT channel is covered with the film, while the contacts are open to the gas. We suggest that the Schottky barrier modulation at the contacts is the dominant mechanism from room temperature to 150°C. At higher temperatures, the charge transfer process contributes to the response signals. There is a clear evidence that the adsorption of NH3 on the CNT channel is facilitated by environmental oxygen.

  1. Photodesorption and product formation in UV-irradiated N2 and NH3 ices under ultra-high-vacuum conditions

    NASA Astrophysics Data System (ADS)

    Cruz-Diaz, G. A.; Muñoz Caro, G. M.; Jiménez-Escobar, A.

    2012-02-01

    The accretion and desorption processes of gas molecules on cold grains play an important role in the evolution of dense clouds and circumstellar regions around YSOs. Given the low temperatures in dark cloud interiors (10-20 K), thermal desorption is negligible and most molecules are expected to stick to grains leading to depletion in the gas phase. Laboratory simulations of these processes under astrophysically relevant conditions are required for their understanding. The use of ultra-high-vacuum conditions minimalizes contamination by background water accretion. This introduces a radical improvement, allowing the study of photodesorption and the detection of products at very low abundances in a water-free ice matrix. We studied UV-photoprocessing of pure NH3 and N2 ices under ultra-high-vacuum conditions using the Interstellar Astrochemistry Chamber. The photodesorbed molecules, and the volatile products released upon photolysis and warm-up, were detected in situ by quadrupole mass spectroscopy.

  2. Parallel operation of NH3 screw compressors - the optimum way

    NASA Astrophysics Data System (ADS)

    Pijnenburg, B.; Ritmann, J.

    2015-08-01

    The use of more smaller industrial NH3 screw compressors operating in parallel seems to offer the optimum way when it comes to fulfilling maximum part load efficiency, increased redundancy and other highly requested features in the industrial refrigeration industry today. Parallel operation in an optimum way can be selected to secure continuous operation and can in most applications be configured to ensure lower overall operating economy. New compressors are developed to meet requirements for flexibility in operation and are controlled in an intelligent way. The intelligent control system keeps focus on all external demands, but yet striving to offer always the lowest possible absorbed power, including in future scenarios with connection to smart grid.

  3. A variationally computed line list for hot NH3

    NASA Astrophysics Data System (ADS)

    Yurchenko, S. N.; Barber, R. J.; Tennyson, J.

    2011-05-01

    We present 'BYTe', a comprehensive 'hot' line list for the ro-vibrational transitions of ammonia, 14NH3, in its ground electronic state. This line list has been computed variationally using the program suite TROVE, a new spectroscopically determined potential energy surface and an ab initio dipole moment surface. BYTe, is designed to be used at all temperatures up to 1500 K. It comprises 1138 323 351 transitions in the frequency range from 0 to 12 000 cm-1, constructed from 1373 897 energy levels below 18 000 cm-1 having J values ≤36. Comparisons with laboratory data confirm the accuracy of the line list which is suitable for modelling a variety of astrophysical problems including the atmospheres of extrasolar planets and brown dwarfs.

  4. MetNH3: Metrology for ammonia in ambient air

    NASA Astrophysics Data System (ADS)

    Braban, Christine; Twigg, Marsailidh; Tang, Sim; Leuenberger, Daiana; Ferracci, Valerio; Martin, Nick; Pascale, Celine; Hieta, Tuomas; Pogany, Andrea; Persijn, Stefan; van Wijk, Janneke; Gerwig, Holger; Wirtze, Klaus; Tiebe, Carlo; Balslev-Harder, David; Niederhausen, Bernhardt

    2015-04-01

    Measuring ammonia in ambient air is a sensitive and priority issue due to its harmful effects on human health and ecosystems. The European Directive 2001/81/EC on 'National Emission Ceilings for Certain Atmospheric Pollutants (NEC)' regulates ammonia emissions in the member states. However, there is a lack of regulation to ensure reliable ammonia measurements namely in applicable analytical technology, maximum allowed uncertainty, quality assurance and quality control (QC/QA) procedures as well as in the infrastructure to attain metrological traceability. Validated ammonia measurement data of high quality from air monitoring networks are vitally important for identifying changes due to implementations of environment policies, for understanding where the uncertainties in current emission inventories are derived from and for providing independent verification of atmospheric model predictions. The new EURAMET project MetNH3 aims to develop improved reference gas mixtures by static and dynamic gravimetric generation methods, develop and characterise laser based optical spectrometric standards and establish the transfer from high-accuracy standards to field applicable methods. MetNH3started in June 2014 and in this presentation the first results from the metrological characterisation of a commercially available cavity ring-down spectrometer (CRDS) will be discussed. Also first tests and results from a new design, Controlled Atmosphere Test Facility (CATFAC), which is to be characterised and used to validate the performance of diffusive samplers, denuders and on-line instruments, will be reported. CAFTEC can be used to control test parameters such as ammonia concentration, relative humidity and wind speed. Outline plans for international laboratory and field intercomparisons in 2016 will be presented.

  5. Elevated CO2 decreases the Photorespiratory NH3 production but does not decrease the NH3 compensation point in rice leaves.

    PubMed

    Miyazawa, Shin-Ichi; Hayashi, Kentaro; Nakamura, Hirofumi; Hasegawa, Toshihiro; Miyao, Mitsue

    2014-09-01

    The exchange of gaseous NH3 between the atmosphere and plants plays a pivotal role in controlling the global NH3 cycle. Photorespiration generates NH3 through oxygenation instead of carboxylation by the CO2-fixing enzyme, ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO). The future increase in the atmospheric CO2 concentration, [CO2], is expected to reduce plant NH3 production by suppressing RuBisCO oxygenation (Vo). We measured the net leaf NH3 uptake rate (FNH3) across NH3 concentrations in the air (na) ranging from 0.2 to 1.6 nmol mol(-1) at three [CO2] values (190, 360 and 750 µmol mol(-1)) using rice plants. We analyzed leaf NH3 gas exchange using a custom-made whole-leaf chamber system, and determined the NH3 compensation point (γ), a measure of potential NH3 emission, as the x-intercept of the linear relationship of FNH3 as a function of na. Our γ values were lower than those reported for other plant species. γ did not decrease under elevated [CO2], although leaf NH4 (+) content decreased with decreasing Vo at higher [CO2]. This was also the case for γ estimated from the pH and NH4 (+) concentration of the leaf apoplast solution (γ'). γ' of rice plants, grown at elevated [CO2] for months in a free-air CO2 enrichment facility, was also not decreased by elevated [CO2]. These results suggest that suppression of RuBisCO oxygenation by elevated [CO2] does not decrease potential leaf NH3 emission in rice plants. PMID:24951312

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

    PubMed

    Woidy, Patrick; Bühl, Michael; Kraus, Florian

    2015-04-28

    Pentaammine dioxido uranium(VI) dibromide ammonia (1/1), [UO2(NH3)5]Br2·NH3, was synthesized in the form of yellow crystals by the reaction of uranyl bromide, UO2Br2, with dry liquid ammonia. The compound crystallizes orthorhombic in space group Cmcm and is isotypic to [UO2(NH3)5]Cl2·NH3 with a = 13.2499(2), b = 10.5536(1), c = 8.9126(1) Å, V = 1246.29(3) Å(3) and Z = 4 at 123 K. The UO2(2+) cation is coordinated by five ammine ligands and the coordination polyhedron can be best described as pentagonal bipyramid. Car-Parrinello molecular dynamics simulations are reported for [UO2(NH3)5](2+) in the gas phase and in liquid NH3 solution (using the BLYP density functional). According to free-energy simulations, solvation by ammonia has only a small effect on the uranyl-NH3 bond strength. PMID:25797497

  7. Analyte separation utilizing temperature programmed desorption of a preconcentrator mesh

    DOEpatents

    Linker, Kevin L.; Bouchier, Frank A.; Theisen, Lisa; Arakaki, Lester H.

    2007-11-27

    A method and system for controllably releasing contaminants from a contaminated porous metallic mesh by thermally desorbing and releasing a selected subset of contaminants from a contaminated mesh by rapidly raising the mesh to a pre-determined temperature step or plateau that has been chosen beforehand to preferentially desorb a particular chemical specie of interest, but not others. By providing a sufficiently long delay or dwell period in-between heating pulses, and by selecting the optimum plateau temperatures, then different contaminant species can be controllably released in well-defined batches at different times to a chemical detector in gaseous communication with the mesh. For some detectors, such as an Ion Mobility Spectrometer (IMS), separating different species in time before they enter the IMS allows the detector to have an enhanced selectivity.

  8. Ultrasensitive gaseous NH3 sensor based on ionic liquid-mediated signal-on electrochemiluminescence.

    PubMed

    Chen, Lichan; Huang, Danjun; Zhang, Yuanjin; Dong, Tongqing; Zhou, Chen; Ren, Shuyan; Chi, Yuwu; Chen, Guonan

    2012-08-01

    This work reports that ammonia (NH(3)) can be used as an efficient co-reactant for tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)(3)(2+)) electrochemiluminescence (ECL) in ionic liquids (ILs), on the basis of which a signal-on ECL sensor for directly detecting gaseous NH(3) has been developed. The NH(3) ECL sensor has a very high sensitivity, with a detection limit of 10 ppt NH(3) (at signal-to-noise ratio of 3) without any preconcentration. The high sensitivity is mainly due to the zero ECL background of Ru(bpy)(3)(2+) in the ILs, strong co-reactant ECL activity of NH(3), and high solubility of NH(3) in imidazolium-based ILs. Additionally, the ECL sensor shows an excellent selectivity against common interfering gases and a wide linear response range from 10 ppt to 10 ppm. PMID:22728516

  9. Vibrations and reorientations of NH3 molecules in [Mn(NH3)6](ClO4)2 studied by infrared spectroscopy and theoretical (DFT) calculations.

    PubMed

    Hetmańczyk, Joanna; Hetmańczyk, Łukasz; Migdał-Mikuli, Anna; Mikuli, Edward

    2015-02-01

    The vibrational and reorientational motions of NH3 ligands and ClO4(-) anions were investigated by Fourier transform middle-infrared spectroscopy (FT-IR) in the high- and low-temperature phases of [Mn(NH3)6](ClO4)2. The temperature dependencies of full width at half maximum (FWHM) of the infrared bands at: 591 and 3385cm(-1), associated with: ρr(NH3) and νas(N-H) modes, respectively, indicate that there exist fast (correlation times τR≈10(-12)-10(-13)s) reorientational motions of NH3 ligands, with a mean values of activation energies: 7.8 and 4.5kJmol(-1), in the phase I and II, respectively. These reorientational motions of NH3 ligands are only slightly disturbed in the phase transition region and do not significantly contribute to the phase transition mechanism. Fourier transform far-infrared and middle-infrared spectra with decreasing of temperature indicated characteristic changes at the vicinity of PT at TC(c)=137.6K (on cooling), which suggested lowering of the crystal structure symmetry. Infrared spectra of [Mn(NH3)6](ClO4)2 were recorded and interpreted by comparison with respective theoretical spectra calculated using DFT method (B3LYP functional, LANL2DZ ECP basis set (on Mn atom) and 6-311+G(d,p) basis set (on H, N, Cl, O atoms) for the isolated equilibrium two models (Model 1 - separate isolated [Mn(NH3)6](2+) cation and ClO4(-) anion and Model 2 - [Mn(NH3)6(ClO4)2] complex system). Calculated optical spectra show a good agreement with the experimental infrared spectra (FT-FIR and FT-MIR) for the both models. PMID:25459713

  10. Vibrations and reorientations of NH3 molecules in [Mn(NH3)6](ClO4)2 studied by infrared spectroscopy and theoretical (DFT) calculations

    NASA Astrophysics Data System (ADS)

    Hetmańczyk, Joanna; Hetmańczyk, Łukasz; Migdał-Mikuli, Anna; Mikuli, Edward

    2015-02-01

    The vibrational and reorientational motions of NH3 ligands and ClO4- anions were investigated by Fourier transform middle-infrared spectroscopy (FT-IR) in the high- and low-temperature phases of [Mn(NH3)6](ClO4)2. The temperature dependencies of full width at half maximum (FWHM) of the infrared bands at: 591 and 3385 cm-1, associated with: ρr(NH3) and νas(N-H) modes, respectively, indicate that there exist fast (correlation times τR ≈ 10-12-10-13 s) reorientational motions of NH3 ligands, with a mean values of activation energies: 7.8 and 4.5 kJ mol-1, in the phase I and II, respectively. These reorientational motions of NH3 ligands are only slightly disturbed in the phase transition region and do not significantly contribute to the phase transition mechanism. Fourier transform far-infrared and middle-infrared spectra with decreasing of temperature indicated characteristic changes at the vicinity of PT at TCc = 137.6 K (on cooling), which suggested lowering of the crystal structure symmetry. Infrared spectra of [Mn(NH3)6](ClO4)2 were recorded and interpreted by comparison with respective theoretical spectra calculated using DFT method (B3LYP functional, LANL2DZ ECP basis set (on Mn atom) and 6-311 + G(d,p) basis set (on H, N, Cl, O atoms) for the isolated equilibrium two models (Model 1 - separate isolated [Mn(NH3)6]2+ cation and ClO4- anion and Model 2 - [Mn(NH3)6(ClO4)2] complex system). Calculated optical spectra show a good agreement with the experimental infrared spectra (FT-FIR and FT-MIR) for the both models.

  11. The selective catalytic reduction of NO with NH3 over a novel Ce-Sn-Ti mixed oxides catalyst: Promotional effect of SnO2

    NASA Astrophysics Data System (ADS)

    Yu, Ming'e.; Li, Caiting; Zeng, Guangming; Zhou, Yang; Zhang, Xunan; Xie, Yin'e.

    2015-07-01

    A series of novel catalysts (CexSny) for the selective catalytic reduction of NO by NH3 were prepared by the inverse co-precipitation method. The aim of this novel design was to improve the NO removal efficiency of CeTi by the introduction of SnO2. It was found that the Ce-Sn-Ti catalyst was much more active than Ce-Ti and the best Ce:Sn molar ratio was 2:1. Ce2Sn1 possessed a satisfied NO removal efficiency at low temperature (160-280 °C), while over 90% NO removal efficiency maintained in the temperature range of 280-400 °C at the gas hourly space velocity (GHSV) of 50,000 h-1. Besides, Ce2Sn1 kept a stable NO removal efficiency within a wide range of GHSV and a long period of reacting time. Meanwhile, Ce2Sn1 exhibited remarkable resistance to both respectively and simultaneously H2O and SO2 poisoning due to the introduction of SnO2. The promotional effect of SnO2 was studied by N2 adsorption-desorption, X-ray diffraction (XRD), Raman spectra, X-ray photoelectron spectroscopy (XPS) and H2 temperature programmed reduction (H2-TPR) for detail information. The characterization results revealed that the excellent catalytic performance of Ce2Sn1 was associated with the higher specific surface area, larger pore volume and poorer crystallization. Besides, the introduction of SnO2 could result in not only greater conversion of Ce4+ to Ce3+ but also the increase amount of chemisorbed oxygen, which are beneficial to improve the SCR activity. More importantly, a novel peak appearing at lower temperatures through the new redox equilibrium of 2Ce4+ + Sn2+ ↔ 2Ce3+ + Sn4+ and higher total H2 consumption can be obtained by the addition of SnO2. Finally, the possible reaction mechanism of the selective catalytic reduction over Ce2Sn1 was also proposed.

  12. Enhanced sensing of NH3 gas by decorated multiwalled carbon nanotube

    NASA Astrophysics Data System (ADS)

    Hasnahena, S. T.; Satpati, Biswarup; Roy, Madhusudan

    2016-05-01

    The present study describes synthesis of Barium Oxide Nanoparticles decorated Multiwalled Carbon Nanotubes and its gas sensing behavior towards NH3 and CO gases. The decorated MWCNT sensor has an enhanced sensing towards NH3 gas compare to pure MWCNT sensor and also has much reduced response and recovery time. The prepared sensing material is characterized by TEM, XRD and Thermal Gravimetric analysis.

  13. Urban NH3 levels and sources in six major Spanish cities.

    PubMed

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

    2015-01-01

    A detailed spatial and temporal assessment of urban NH3 levels and potential emission sources was made with passive samplers in six major Spanish cities (Barcelona, Madrid, A Coruña, Huelva, Santa Cruz de Tenerife and Valencia). Measurements were conducted during two different periods (winter-autumn and spring-summer) in each city. Barcelona showed the clearest spatial pattern, with the highest concentrations in the old city centre, an area characterised by a high population density and a dense urban architecture. The variability in NH3 concentrations did not follow a common seasonal pattern across the different cities. The relationship of urban NH3 with SO2 and NOX allowed concluding on the causes responsible for the variations in NH3 levels between measurement periods observed in Barcelona, Huelva and Madrid. However, the factors governing the variations in A Coruña, Valencia and Santa Cruz de Tenerife are still not fully understood. This study identified a broad variability in NH3 concentrations at the city-scale, and it confirms that NH3 sources in Spanish urban environments are vehicular traffic, biological sources (e.g. garbage containers), wastewater treatment plants, solid waste treatment plants and industry. The importance of NH3 monitoring in urban environments relies on its role as a precursor of secondary inorganic species and therefore PMX. Further research should be addressed in order to establish criteria to develop and implement mitigation strategies for cities, and to include urban NH3 sources in the emission inventories. PMID:25194477

  14. A relationship between agricultural NH 3 emissions and the atmospheric SO 2 content over industrial areas

    NASA Astrophysics Data System (ADS)

    Möller, Detlev; Schieferdecker, Helmut

    In an industrial area of the GDR, where there are major locations of lignite strip mines and lignite-fired power stations, a decline in the mean large-area SO 2 concentration was observed despite a slight increase in SO 2 emissions, between 1970 and 1980. It was found that the NH 3 emissions from biogenic sources had increased by some 20 per cent in the same period. This paper shows that a growing NH 3 concentration produces a nonlinear reduction of the SO 2 content of the atmosphere. In relative terms, the greatest such effect is observed in cases where NH 3 concentrations are low ( < 5 ppbv). Atmospheric NH 3 increases the relative percentage of the SO 2 wet deposition. Alkaline fly ashes derive their importance from the fact that NH 3 is formed from soil-deposited NH 4+ and can be re-released into the atmosphere, thus possibly giving rise to multiple cycles.

  15. Phase transition, thermal dissociation and dynamics of NH3 ligands in [Cd(NH3)4](ReO4)2

    NASA Astrophysics Data System (ADS)

    Hetmańczyk, Łukasz; Hetmańczyk, Joanna

    2016-07-01

    High temperature phase transition in [Cd(NH3)4](ReO4)2 at Tc = 368.5 K (on heating) was reported for the first time. Thermal stability was investigated by thermal analysis methods. The titled compound decomposes in three main stages. The first two are connected with deamination process whereas in the last step Re2O7 evaporates. The activation energy for NH3 lost processes was estimated from TG measurements. The dynamics of NH3 ligands in the low temperature phase was probed by various complementary techniques. Temperature dependent band shape analysis of properly chosen infrared and Raman scattering vibrational bands was performed. It was found that activation energy for NH3 reorientational motion (below 300 K) is rather small and is equal to ca. 4 kJ mol- 1. The quasielastic neutron scattering measurements revealed that NH3 groups perform fast stochastic reorientational motion even in the low temperatures. The neutron and X-ray powder diffraction data do not revealed any drastic changes in the crystal structure in the wide temperature range.

  16. Phase transition, thermal dissociation and dynamics of NH3 ligands in [Cd(NH3)4](ReO4)2.

    PubMed

    Hetmańczyk, Łukasz; Hetmańczyk, Joanna

    2016-07-01

    High temperature phase transition in [Cd(NH3)4](ReO4)2 at Tc=368.5K (on heating) was reported for the first time. Thermal stability was investigated by thermal analysis methods. The titled compound decomposes in three main stages. The first two are connected with deamination process whereas in the last step Re2O7 evaporates. The activation energy for NH3 lost processes was estimated from TG measurements. The dynamics of NH3 ligands in the low temperature phase was probed by various complementary techniques. Temperature dependent band shape analysis of properly chosen infrared and Raman scattering vibrational bands was performed. It was found that activation energy for NH3 reorientational motion (below 300K) is rather small and is equal to ca. 4kJmol(-1). The quasielastic neutron scattering measurements revealed that NH3 groups perform fast stochastic reorientational motion even in the low temperatures. The neutron and X-ray powder diffraction data do not revealed any drastic changes in the crystal structure in the wide temperature range. PMID:27070528

  17. Synthesis, structures and hydrogen storage properties of two new H-enriched compounds: Mg(BH4)2(NH3BH3)2 and Mg(BH4)2·(NH3)2(NH3BH3).

    PubMed

    Chen, Xiaowei; Yuan, Feng; Gu, Qinfen; Yu, Xuebin

    2013-10-28

    The synthesis, crystal structure and dehydrogenation performances of two new H-enriched compounds, Mg(BH4)2(NH3BH3)2 and Mg(BH4)2·(NH3)2(NH3BH3), are reported. Due to the introduction of ammonia ligands, the Mg(BH4)2·(NH3)2(NH3BH3) exhibits dramatically improved dehydrogenation properties over its parent compound. PMID:24002106

  18. Tetra­amminelithium triamminelithium tris­ulfide, [Li(NH3)4][Li(NH3)3S3

    PubMed Central

    Guentner, Christian; Korber, Nikolaus

    2012-01-01

    The title compound, [Li(NH3)4]+[Li(NH3)3S3]−, an ammo­niate of the previously unknown lithium tris­ulfide, was obtained from the reaction of lithium and sulfur in liquid ammonia. The asymmetric unit consists of two crystallographically independent formula units. The [Li(NH3)4]+ cations are close to regular LiN4 tetra­hedra. The anions contain LiSN3 tetra­hedra; the S—S—S bond angles are 110.43 (5) and 109.53 (5)°. In the crystal, the components are linked by multiple N—H⋯S hydrogen bonds. A weak N—H⋯N hydrogen bond is also present. PMID:23284314

  19. Tetra-amminelithium triamminelithium tris-ulfide, [Li(NH(3))(4)][Li(NH(3))(3)S(3)].

    PubMed

    Guentner, Christian; Korber, Nikolaus

    2012-11-01

    The title compound, [Li(NH(3))(4)](+)[Li(NH(3))(3)S(3)](-), an ammo-niate of the previously unknown lithium tris-ulfide, was obtained from the reaction of lithium and sulfur in liquid ammonia. The asymmetric unit consists of two crystallographically independent formula units. The [Li(NH(3))(4)](+) cations are close to regular LiN(4) tetra-hedra. The anions contain LiSN(3) tetra-hedra; the S-S-S bond angles are 110.43 (5) and 109.53 (5)°. In the crystal, the components are linked by multiple N-H⋯S hydrogen bonds. A weak N-H⋯N hydrogen bond is also present. PMID:23284314

  20. Rotational Dynamics of Organic Cations in CH3NH3PbI3 Perovskite

    NASA Astrophysics Data System (ADS)

    Chen, Tianran; Foley, Benjamin; Ipek, Bahar; Tyagi, Madhusudan; Copley, John; Brown, Craig; Choi, Joshua; Lee, Seung-Hun

    Methylammonium lead iodide (CH3NH3PbI3) based solar cells have shown impressive power conversion efficiencies of above 20%. However, the microscopic mechanism of the high photovoltaic performance is yet to be fully understood. Particularly, the dynamics of CH3NH3+ cations and their impact on relevant processes are still poorly understood. Using elastic and quasi-elastic neutron scattering techniques and group theoretical analysis, we studied rotational modes of the CH3NH3+ cation in CH3NH3PbI3. Our results show that, in the cubic and tetragonal phases, the CH3NH3+ ions exhibit four-fold rotational symmetry of the C-N axis (C4) along with three-fold rotation around the C-N axis (C3) , while in orthorhombic phase only C3 rotation is present. Around room temperature, the characteristic relaxation time for the C4 rotation is found to be 5ps while for the C3 rotation is 1ps. The T-dependent rotational relaxation times were fitted with Arrhenius equations to obtain activation energies. Our data show a close correlation between the C4 rotational mode and the temperature dependent dielectric permittivity. Our findings on the rotational dynamics of CH3NH3+ and the associated dipole have important implications on understanding the low exciton binding energy and slow charge recombination rate in CH3NH3PbI3 which are directly relevant for the high solar cell performance.

  1. Unaccounted variability in NH3 agricultural sources detected by IASI contributing to European spring haze episode

    NASA Astrophysics Data System (ADS)

    Fortems-Cheiney, A.; Dufour, G.; Hamaoui-Laguel, L.; Foret, G.; Siour, G.; Van Damme, M.; Meleux, F.; Coheur, P.-F.; Clerbaux, C.; Clarisse, L.; Favez, O.; Wallasch, M.; Beekmann, M.

    2016-05-01

    Ammonia (NH3), whose main source in the troposphere is agriculture, is an important gaseous precursor of atmospheric particulate matter (PM). We derived daily ammonia emissions using NH3 total columns measured from the Infrared Atmospheric Sounding Interferometer (IASI) on board Metop-A, at a relatively high spatial resolution (grid cell of 0.5° × 0.5°). During the European spring haze episodes of 24-31 March 2012 and 8-15 March 2014, IASI reveals NH3 total column magnitudes highlighting higher NH3 emissions over central Europe (especially over Germany, Czech Republic, and eastern France) from the ones provided by the European reference European Monitoring and Evaluation Programme inventory. These ammonia emissions exhibit in addition a large day-to-day variability, certainly due to spreading practices. The increase of NH3 emissions in the model, that reaches +300% locally, leads to an increase of both NH3 and PM2.5 surface concentrations and allows for a better comparison with independent measurements (in terms of bias, root-mean-square error, and correlation). This study suggests that there are good prospects for better quantifying NH3 emissions by atmospheric inversions.

  2. NH3 Emission from Fertilizer Application: A Collaborative Study in the Midwestern U.S.

    NASA Astrophysics Data System (ADS)

    Myles, L.; Koloutsou-Vakakis, S.; Bernacchi, C.; Lehmann, C.; Saylor, R. D.; Heuer, M.; Sibble, D.; Caldwell, J. A.; Balasubramanian, S.; Nelson, A. J.; Rood, M. J.

    2014-12-01

    Atmospheric ammonia (NH3) is a precursor for secondary particulate matter and a contributor to soil acidification and eutrophication when deposited to land and surface waters. Fertilizer application is a major source of atmospheric NH3, particularly in intensive agricultural regions such as the Midwestern U.S. Quantification of NH3 emission from fertilized crops remains highly uncertain, which limits the representativeness of NH3 emissions that are used in air quality models. A collaborative study to improve understanding of NH3 emission from fertilizer application focused on [1] measurement of above-canopy NH3 fluxes from a fertilized corn field in Illinois using the relaxed eddy accumulation (REA) and flux gradient methods and in-canopy fluxes with the inverse Lagrangian dispersion analysis method, [2] estimation of NH3 emissions at the regional scale using a process-based approach with available archived independent variables, and the currently used top-down approach, in order to compare and determine differences in predicted spatial and temporal variability of NH3 emissions, and [3] performance of spatial analysis to determine spatial and temporal patterns of ammonia emissions and relate them to independent variables characteristic of land use, soil, meteorology, and agricultural management practices. NH3 flux was measured over and within a maize canopy from pre-cultivation through senescence (May-September 2014) at the University of Illinois at Urbana-Champaign (UIUC) Energy Biosciences Institute Energy Farm, and data from the field study was incorporated into models to facilitate connection of local emissions with the regional scale and to improve understanding of the processes that drive emission and deposition.

  3. Validation of NH3 satellite observations by ground-based FTIR measurements

    NASA Astrophysics Data System (ADS)

    Dammers, Enrico; Palm, Mathias; Van Damme, Martin; Shephard, Mark; Cady-Pereira, Karen; Capps, Shannon; Clarisse, Lieven; Coheur, Pierre; Erisman, Jan Willem

    2016-04-01

    Global emissions of reactive nitrogen have been increasing to an unprecedented level due to human activities and are estimated to be a factor four larger than pre-industrial levels. Concentration levels of NOx are declining, but ammonia (NH3) levels are increasing around the globe. While NH3 at its current concentrations poses significant threats to the environment and human health, relatively little is known about the total budget and global distribution. Surface observations are sparse and mainly available for north-western Europe, the United States and China and are limited by the high costs and poor temporal and spatial resolution. Since the lifetime of atmospheric NH3 is short, on the order of hours to a few days, due to efficient deposition and fast conversion to particulate matter, the existing surface measurements are not sufficient to estimate global concentrations. Advanced space-based IR-sounders such as the Tropospheric Emission Spectrometer (TES), the Infrared Atmospheric Sounding Interferometer (IASI), and the Cross-track Infrared Sounder (CrIS) enable global observations of atmospheric NH3 that help overcome some of the limitations of surface observations. However, the satellite NH3 retrievals are complex requiring extensive validation. Presently there have only been a few dedicated satellite NH3 validation campaigns performed with limited spatial, vertical or temporal coverage. Recently a retrieval methodology was developed for ground-based Fourier Transform Infrared Spectroscopy (FTIR) instruments to obtain vertical concentration profiles of NH3. Here we show the applicability of retrieved columns from nine globally distributed stations with a range of NH3 pollution levels to validate satellite NH3 products.

  4. Concentration-dependent NH 3 deposition processes for moorland plant species with and without stomata

    NASA Astrophysics Data System (ADS)

    Jones, M. R.; Leith, I. D.; Raven, J. A.; Fowler, D.; Sutton, M. A.; Nemitz, E.; Cape, J. N.; Sheppard, L. J.; Smith, R. I.

    Currently, in operational modelling of NH 3 deposition a fixed value of canopy resistance ( Rc) is generally applied, irrespective of the plant species and NH 3 concentration. This study determined the effect of NH 3 concentration on deposition processes to individual moorland species. An innovative flux chamber system was used to provide accurate continuous measurements of NH 3 deposition to Deschampsia cespitosa (L.) Beauv., Calluna vulgaris (L.) Hull, Eriophorum vaginatum L., Cladonia spp., Sphagnum spp., and Pleurozium schreberi (Brid.) Mitt. Measurements were conducted across a wide range of NH 3 concentrations (1-140 μg m -3). NH 3 concentration directly affects the deposition processes to the vegetation canopy, with Rc, and cuticular resistance ( Rw) increasing with increasing NH 3 concentration, for all the species and vegetation communities tested. For example, the Rc for C. vulgaris increased from 14 s m -1 at 2 μg m -3 to 112 s m -1 at 80 μg m -3. Diurnal variations in NH 3 uptake were observed for higher plants, due to stomatal uptake; however, no diurnal variations were shown for non-stomatal plants. Rc for C. vulgaris at 80 μg m -3 was 66 and 112 s m -1 during day and night, respectively. Differences were found in NH 3 deposition between plant species and vegetation communities: Sphagnum had the lowest Rc (3 s m -1 at 2 μg m -3 to 23 at 80 μg m -3), and D. cespitosa had the highest nighttime value (18 s m -1 at 2 μg m -3 to 197 s m -1 at 80 μg m -3).

  5. Manipulating bedding materials and PLTto reduce NH(3) emissions from broiler manure.

    PubMed

    Tasistro, Armando S; Cabrera, Miguel L; Ritz, Casey W; Kissel, David E

    2008-04-01

    We studied the effect of five bedding materials (wood shavings, sawdust, peanut hulls, wheat straw and shredded paper) and PLTtrade mark (a commercial formulation of Na bisulfate) in factorial combinations, on NH(3) emissions from broiler manure. Treatments were incubated for 11 days at 25 degrees C and 98% relative humidity. Ammonia was trapped in 0.1N H(2)SO(4) and measured colorimetrically as NH(4)(+), and CO(2) was monitored with an infrared analyzer. Ammonia and CO(2) emissions were suppressed by PLT throughout the study. Wheat straw, wood shavings, and sawdust, with C(total)/N(total)>50 or C(biodegradable)/N>20, had low NH(3) emissions. Total NH(3) emissions from peanut hulls and shredded paper were the highest, probably due to peanut hulls' low C/N ratio and shredded paper's alkaline pH. No significant interactions on NH(3) emissions were detected between PLT and bedding materials. PMID:17572086

  6. Worldwide spatiotemporal atmospheric ammonia (NH3) columns variability revealed by satellite

    NASA Astrophysics Data System (ADS)

    Van Damme, M.; Erisman, J. W.; Clarisse, L.; Dammers, E.; Whitburn, S.; Clerbaux, C.; Dolman, A. J.; Coheur, P.-F.

    2015-10-01

    We exploit 6 years of measurements from the Infrared Atmospheric Sounding Interferometer (IASI)/MetOp-A instrument to identify seasonal patterns and interannual variability of atmospheric NH3. This is achieved by analyzing the time evolution of the monthly mean NH3 columns in 12 subcontinental areas around the world, simultaneously considering measurements from IASI morning and evening overpasses. For most regions, IASI has a sufficient sensitivity throughout the years to capture the seasonal patterns of NH3 columns, and we show that each region is characterized by a well-marked and distinctive cycle, with maxima mainly related to underlying emission processes. The largest column abundances and seasonal amplitudes throughout the years are found in southwestern Asia, with maxima twice as large as what is observed in southeastern China. The relation between emission sources and retrieved NH3 columns is emphasized at a smaller regional scale by inferring a climatology of the month of maximum columns.

  7. Indirect measurement of N-14 quadrupolar coupling for NH3 intercalated in potassium graphite

    NASA Technical Reports Server (NTRS)

    Tsang, T.; Fronko, R. M.; Resing, H. A.

    1987-01-01

    A method for indirect measurement of the nuclear quadrupolar coupling was developed and applied to NH3 molecules in the graphite intercalation compound K(NH3)4.3C24, which has a layered structure with alternating carbon and intercalant layers. Three triplets were observed in the H-1 NMR spectra of the compound. The value of the N-14 quadrupolar coupling constant of NH3 (3.7 MHz), determined indirectly from the H-1 NMR spectra, was intermediate between the gas value of 4.1 MHz and the solid-state value of 3.2 MHz. The method was also used to deduce the (H-1)-(H-1) and (N-14)-(H-1) dipolar interactions, the H-1 chemical shifts, and the molecular orientations and motions of NH3.

  8. Selective Catalytic Reduction of NO by NH3 with WO3-TiO2 Catalysts: Influence of Catalyst Synthesis Method

    SciTech Connect

    He, Yuanyuan; Ford, Michael E; Zhu, Minghui; Liu, Qingcai; Wu, Zili; Wachs, Israel

    2016-01-01

    A series of supported WO3/TiO2 catalysts was prepared by a new synthesis procedure involving co-precipitation of an aqueous TiO(OH)2 and (NH4)10W12O41*5H2O slurry under controlled pH conditions. The morphological properties, molecular structures, surface acidity and surface chemistry of the supported WO3/TiO2 catalysts were determined with BET, in situ Raman, in situ IR and temperature-programmed surface reaction (TPSR) spectroscopy, respectively. Isotopic 18O-16O exchange demonstrated that tungsten oxide was exclusively present as surface WOx species on the TiO2 support with mono-oxo W=O coordination. In contrast to previous studies employing impregnation synthesis that found only surface one mono-oxo O=WO4 site on TiO2, the co-precipitation procedure resulted in the formation of two distinct surface WOx species: mono-oxo O=WO4 (~1010-1017 cm-1) on low defect density patches of TiO2 and a second mono-oxo O=WO4 (~983-986 cm-1) on high defect density patches of TiO2. The concentration of the second WOx surface species increases as a function of solution pH. Both surface WOx sites, however, exhibited the same NO/NH3 SCR reactivity. The co-precipitated WO3-TiO2 catalysts synthesized in alkaline solutions exhibited enhanced performance for the NO/NH3 SCR reaction that is ascribed to the greater number of surface defects on the resulting TiO2 support. For the co-precipitated catalyst prepared at pH10, surface NH4+ species on Br nsted acid sites were found to be more reactive than surface NH3* species on Lewis acid sites for SCR of NO with NH3.

  9. Selective Catalytic Reduction of NO by NH3 with WO3-TiO2 Catalysts: Influence of Catalyst Synthesis Method

    DOE PAGESBeta

    He, Yuanyuan; Ford, Michael E.; Zhu, Minghui; Liu, Qingcai; Wu, Zili; Wachs, Israel E.

    2016-02-02

    A series of supported WO3/TiO2 catalysts was prepared by a new synthesis procedure involving co-precipitation of an aqueous TiO(OH)2 and (NH4)10W12O41*5H2O slurry under controlled pH conditions. The morphological properties, molecular structures, surface acidity and surface chemistry of the supported WO3/TiO2 catalysts were determined with BET, in situ Raman, in situ IR and temperature-programmed surface reaction (TPSR) spectroscopy, respectively. Isotopic 18O-16O exchange demonstrated that tungsten oxide was exclusively present as surface WOx species on the TiO2 support with mono-oxo W=O coordination. In contrast to previous studies employing impregnation synthesis that found only surface one mono-oxo O=WO4 site on TiO2, the co-precipitationmore » procedure resulted in the formation of two distinct surface WOx species: mono-oxo O=WO4 (~1010-1017 cm-1) on low defect density patches of TiO2 and a second mono-oxo O=WO4 (~983-986 cm-1) on high defect density patches of TiO2. The concentration of the second WOx surface species increases as a function of solution pH. Both surface WOx sites, however, exhibited the same NO/NH3 SCR reactivity. The co-precipitated WO3-TiO2 catalysts synthesized in alkaline solutions exhibited enhanced performance for the NO/NH3 SCR reaction that is ascribed to the greater number of surface defects on the resulting TiO2 support. For the co-precipitated catalyst prepared at pH10, surface NH4+ species on Br nsted acid sites were found to be more reactive than surface NH3* species on Lewis acid sites for SCR of NO with NH3.« less

  10. Quantifying Uncertainty in Daily Temporal Variations of Atmospheric NH3 Emissions Following Application of Chemical Fertilizers

    NASA Astrophysics Data System (ADS)

    Balasubramanian, S.; Koloutsou-Vakakis, S.; Rood, M. J.

    2014-12-01

    Improving modeling predictions of atmospheric particulate matter and deposition of reactive nitrogen requires representative emission inventories of precursor species, such as ammonia (NH3). Anthropogenic NH3 is primarily emitted to the atmosphere from agricultural sources (80-90%) with dominant contributions (56%) from chemical fertilizer usage (CFU) in regions like Midwest USA. Local crop management practices vary spatially and temporally, which influence regional air quality. To model the impact of CFU, NH3 emission inputs to chemical transport models are obtained from the National Emission Inventory (NEI). NH3 emissions from CFU are typically estimated by combining annual fertilizer sales data with emission factors. The Sparse Matrix Operator Kernel Emissions (SMOKE) model is used to disaggregate annual emissions to hourly scale using temporal factors. These factors are estimated by apportioning emissions within each crop season in proportion to the nitrogen applied and time-averaged to the hourly scale. Such approach does not reflect influence of CFU for different crops and local weather and soil conditions. This study provides an alternate approach for estimating temporal factors for NH3 emissions. The DeNitrification DeComposition (DNDC) model was used to estimate daily variations in NH3 emissions from CFU at 14 Central Illinois locations for 2002-2011. Weather, crop and soil data were provided as inputs. A method was developed to estimate site level CFU by combining planting and harvesting dates, nitrogen management and fertilizer sales data. DNDC results indicated that annual NH3 emissions were within ±15% of SMOKE estimates. Daily modeled emissions across 10 years followed similar distributions but varied in magnitudes within ±20%. Individual emission peaks on days after CFU were 2.5-8 times greater as compared to existing estimates from SMOKE. By identifying the episodic nature of NH3 emissions from CFU, this study is expected to provide improvements

  11. Kinematics, Kinetic Temperatures, and Column Densities of NH3 in the Orion Hot Core

    NASA Astrophysics Data System (ADS)

    Wilson, T. L.; Gaume, R. A.; Gensheimer, P.; Johnston, K. J.

    2000-08-01

    Using the VLA, we have mapped the Orion Hot Core region (full extent 10") with an angular resolution of ~1" in the (J,K)=(4,4) and (10, 9) inversion transitions of 14NH3 and an angular resolution of 4" in the (J,K)=(2,2) and (3, 3) inversion transitions of 15NH3. All of the single-dish flux density for the (10, 9) transition was recovered by the VLA, but a substantial fraction of the flux density in the (4, 4) and 15NH3 (3, 3) lines was not detected. The missing flux density is from the spatially extended ``spike'' component. Assuming that local thermodynamic equilibrium (LTE) holds, we have calculated the optical depths of the (4, 4) inversion transition for all positions where the main and satellite lines were detected with sufficient signal-to-noise ratio. We combined our (10, 9) data with these (4, 4) line results to produce images of the rotational temperature, Trot, and the column density of ammonia, N(NH3). For the H2 densities in the Hot Core, Trot=Tkin, the kinetic temperature. An additional determination of Tkin and N(NH3) was made by combining our (10, 9) inversion line data with our 15NH3 (3, 3) inversion line results. The 15NH3 inversion transitions have no quadrupole hyperfine structure so that the line shapes are simpler. The moment distribution of the 15NH3 (3, 3) line shows that the largest intensity-weighted line width arises close to the center of the Hot Core region. Thus, we may have discovered a low-luminosity outflow source embedded in the Hot Core. Alternatively, this may be a result of gas motions related to source ``I,'' which is about half a beamwidth from this feature.

  12. Global distributions, time series and error characterization of atmospheric ammonia (NH3) from IASI satellite observations

    NASA Astrophysics Data System (ADS)

    Van Damme, M.; Clarisse, L.; Heald, C. L.; Hurtmans, D.; Ngadi, Y.; Clerbaux, C.; Dolman, A. J.; Erisman, J. W.; Coheur, P. F.

    2014-03-01

    Ammonia (NH3) emissions in the atmosphere have increased substantially over the past decades, largely because of intensive livestock production and use of fertilizers. As a short-lived species, NH3 is highly variable in the atmosphere and its concentration is generally small, except near local sources. While ground-based measurements are possible, they are challenging and sparse. Advanced infrared sounders in orbit have recently demonstrated their capability to measure NH3, offering a new tool to refine global and regional budgets. In this paper we describe an improved retrieval scheme of NH3 total columns from the measurements of the Infrared Atmospheric Sounding Interferometer (IASI). It exploits the hyperspectral character of this instrument by using an extended spectral range (800-1200 cm-1) where NH3 is optically active. This scheme consists of the calculation of a dimensionless spectral index from the IASI level1C radiances, which is subsequently converted to a total NH3 column using look-up tables built from forward radiative transfer model simulations. We show how to retrieve the NH3 total columns from IASI quasi-globally and twice daily above both land and sea without large computational resources and with an improved detection limit. The retrieval also includes error characterization of the retrieved columns. Five years of IASI measurements (1 November 2007 to 31 October 2012) have been processed to acquire the first global and multiple-year data set of NH3 total columns, which are evaluated and compared to similar products from other retrieval methods. Spatial distributions from the five years data set are provided and analyzed at global and regional scales. In particular, we show the ability of this method to identify smaller emission sources than those previously reported, as well as transport patterns over the ocean. The five-year time series is further examined in terms of seasonality and interannual variability (in particular as a function of fire

  13. Concentration-dependent NH 3 deposition processes for mixed moorland semi-natural vegetation

    NASA Astrophysics Data System (ADS)

    Jones, M. R.; Leith, I. D.; Fowler, D.; Raven, J. A.; Sutton, M. A.; Nemitz, E.; Cape, J. N.; Sheppard, L. J.; Smith, R. I.; Theobald, M. R.

    Dry deposition modelling typically assumes that canopy resistance ( Rc) is independent of ammonia (NH 3) concentration. An innovative flux chamber system was used to provide accurate continuous measurements of NH 3 deposition to a moorland composed of a mixture of Calluna vulgaris (L.) Hull, Eriophorum vaginatum L. and Sphagnum spp. Ammonia was applied at a wide range of concentrations (1-100 μg m -3). The physical and environmental properties and the testing of the chamber are described, as well as results for the moorland vegetation using the 'canopy resistance' and 'canopy compensation point' interpretations of the data. Results for moorland plant species demonstrate that NH 3 concentration directly affects the rate of NH 3 deposition to the vegetation canopy, with Rc and cuticular resistance ( Rw) increasing with increasing NH 3 concentrations. Differences in Rc were found between night and day: during the night Rc increases from 17 s m -1 at 10 μg m -3 to 95 s m -1 at 80 μg m -3, whereas during the day Rc increases from 17 s m -1 at 10 μg m -3 to 48 s m -1 at 80 μg m -3. The lower resistance during the day is caused by the stomata being open and available as a deposition route to the plant. Rw increased with increasing NH 3 concentrations and was not significantly different between day and night (at 80 μg m -3 NH 3 day Rw=88 s m -1 and night Rw=95 s m -1). The results demonstrate that assessments using fixed Rc will over-estimate NH 3 deposition at high concentrations (over ˜15 μg m -3).

  14. On the Interaction of CO and NH3 with BH3 and BF3

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Ricca, Alessandra; Langhoff, Stephen R. (Technical Monitor)

    1994-01-01

    BH3CO, BF3CO, BH3NH3, and BF3NH3 have been studied using density functional theory (DFT). The computed geometries are in reasonable agreement with experiment. BF3CO is found to be weakly bound. The binding energies of BH3CO, BH3NH3 , and BF3NH3 have also been computed using the coupled cluster singles and doubles level of theory, including a perturbational estimate of the connected triples [CCSD(T)]. These CCSD(T) calculations are performed using correlation consistent polarized-valence triple-zeta basis sets. These are expected to be the most accurate binding energies to date. The DFT binding energies are in good agreement with those obtained at the CCSD(T) level. The bonding is analyzed using the constrained space orbital variation (CSOV) technique. In addition to analyzing the bonding in BH3CO, BH3NH3, and BF3NH3, the CSOV approach is used to study why the bonding in BF3CO is so weak.

  15. Understanding of the mechanism of pulsed NH3 growth in metalorganic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Song, Jie; Chen, Danti; Han, Jung

    2015-04-01

    We have studied the mechanism of pulsed NH3 growth in metalorganic chemical vapor deposition by investigating the influence of interruption duration of NH3, growth temperature, pressure and NH3 flow rate on the growth behavior of GaN selective area growth (SAG). The essential mechanism of pulsed NH3 is to create a short-term metal-rich growth condition, thus facilitating the growth of { 1 0 1 bar 1 } facets. Optimized pulse duration, growth temperature, pressure and NH3 flow rate balance the amount of Ga atoms on the surface and create an appropriate metal-rich condition, resulting in an enhanced lateral growth rate by dramatically increasing the growth rate of { 1 0 1 bar 1 } facet. We have achieved hexagonal GaN plates with flat c-plane top surfaces and { 1 0 1 bar 0 } vertical sidewalls on substrates with a fill factor of about 0.1%. The understanding of pulsed NH3 growth technique will significantly promote the preparation of crystals by SAG or epitaxial lateral overgrowth, especially on substrates with a very low fill factor.

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

    PubMed

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

    2016-10-01

    Two water-filled transmembrane cyclic peptide nanotubes (CPNTs) of 8×cyclo-(WL)n=4,5/POPE were chosen to investigate the dependences of the transport properties of the positive NH4 (+) and neutral NH3 on the channel radius. Molecular dynamic simulations revealed that molecular charge, size, ability to form H-bonds and channel radius all significantly influence the behaviors of NH4 (+) and NH3 in a CPNT. Higher electrostatic interactions, more H-bonds, and water-bridges were found in the NH4 (+) system, resulting in NH4 (+) meeting higher energy barriers, while NH3 can enter, exit and permeate the channels effortlessly. This work sheds a first light on the differences between the mechanisms of NH4 (+) and NH3 moving in a CPNT at an atomic level. Graphical Abstract Snapshot of the simulation system of NH4 (+)_octa-CPNT with an NH4 (+) initially positioned at one mouth of the tube, PMF profiles for single NH4 (+) ion and NH3 molecule moving through water-filled transmembrane CPNTs of 8×cyclo-(WL)n=4,5/POPE and sketch graphs of the possible H-bond forms of NH3 and NH4 (+) with the neighboring water. PMID:27600817

  17. Dynamics and fragmentation of van der Waals and hydrogen bonded cluster cations: (NH3)n and (NH3BH3)n ionized at 10.51 eV.

    PubMed

    Yuan, Bing; Shin, Joong-Won; Bernstein, Elliot R

    2016-04-14

    A 118 nm laser is employed as a high energy, single photon (10.51 eV/photon) source for study of the dynamics and fragmentation of the ammonia borane (NH3BH3) cation and its cluster ions through time of flight mass spectrometry. The behavior of ammonia ion and its cluster ions is also investigated under identical conditions in order to explicate the ammonia borane results. Charge distributions, molecular orbitals, and spin densities for (NH3BH3)n and its cations are explored at both the second-order perturbation theory (MP2) and complete active space self-consistent field (CASSCF) theory levels. Initial dissociation mechanisms and potential energy surfaces for ionized NH3BH3, NH3, and their clusters are calculated at the MP2/6-311++G(d,p) level. Protonated clusters (NH3)xH(+) dominate ammonia cluster mass spectra: our calculations show that formation of (NH3)n-1H(+) and NH2 from the nascent (NH3)n(+) has the lowest energy barrier for the system. The only common features for the (NH3)n(+) and (NH3BH3)n(+) mass spectra under these conditions are found to be NHy(+) (y = 0,…,4) at m/z = 14-18. Molecular ions with both (11)B and (10)B isotopes are observed, and therefore, product ions observed for the (NH3BH3)n cluster system derive from (NH3BH3)n clusters themselves, not from the NH3 moiety of NH3BH3 alone. NH3BH2(+) is the most abundant ionization product in the (NH3BH3)n(+) cluster spectra: calculations support that for NH3BH3(+), an H atom is lost from the BH3 moiety with an energy barrier of 0.67 eV. For (NH3BH3)2(+) and (NH3BH3)3(+) clusters, a B(δ+)⋯H(δ-)⋯(δ-)H⋯(δ+)B bond can form in the respective cluster ions, generating a lower energy, more stable ion structure. The first step in the (NH3BH3)n(+) (n = 2, 3) dissociation is the breaking of the B(δ+)⋯H(δ-)⋯(δ-)H⋯(δ+)B moiety, leading to the subsequent release of H2 from the latter cluster ion. The overall reaction mechanisms calculated are best represented and understood employing a CASSCF

  18. Dynamics and fragmentation of van der Waals and hydrogen bonded cluster cations: (NH3)n and (NH3BH3)n ionized at 10.51 eV

    NASA Astrophysics Data System (ADS)

    Yuan, Bing; Shin, Joong-Won; Bernstein, Elliot R.

    2016-04-01

    A 118 nm laser is employed as a high energy, single photon (10.51 eV/photon) source for study of the dynamics and fragmentation of the ammonia borane (NH3BH3) cation and its cluster ions through time of flight mass spectrometry. The behavior of ammonia ion and its cluster ions is also investigated under identical conditions in order to explicate the ammonia borane results. Charge distributions, molecular orbitals, and spin densities for (NH3BH3)n and its cations are explored at both the second-order perturbation theory (MP2) and complete active space self-consistent field (CASSCF) theory levels. Initial dissociation mechanisms and potential energy surfaces for ionized NH3BH3, NH3, and their clusters are calculated at the MP2/6-311++G(d,p) level. Protonated clusters (NH3)xH+ dominate ammonia cluster mass spectra: our calculations show that formation of (NH3)n-1H+ and NH2 from the nascent (NH3)n+ has the lowest energy barrier for the system. The only common features for the (NH3)n+ and (NH3BH3)n+ mass spectra under these conditions are found to be NHy+ (y = 0,…,4) at m/z = 14-18. Molecular ions with both 11B and 10B isotopes are observed, and therefore, product ions observed for the (NH3BH3)n cluster system derive from (NH3BH3)n clusters themselves, not from the NH3 moiety of NH3BH3 alone. NH3BH2+ is the most abundant ionization product in the (NH3BH3)n+ cluster spectra: calculations support that for NH3BH3+, an H atom is lost from the BH3 moiety with an energy barrier of 0.67 eV. For (NH3BH3)2+ and (NH3BH3)3+ clusters, a Bδ+⋯Hδ-⋯δ-H⋯δ+B bond can form in the respective cluster ions, generating a lower energy, more stable ion structure. The first step in the (NH3BH3)n+ (n = 2, 3) dissociation is the breaking of the Bδ+⋯Hδ-⋯δ-H⋯δ+B moiety, leading to the subsequent release of H2 from the latter cluster ion. The overall reaction mechanisms calculated are best represented and understood employing a CASSCF natural bond orbital

  19. Movement of NH3 through the human urea transporter B: a new gas channel

    PubMed Central

    Musa-Aziz, Raif; Enkavi, Giray; Mahinthichaichan, P.; Tajkhorshid, Emad; Boron, Walter F.

    2013-01-01

    Aquaporins and Rh proteins can function as gas (CO2 and NH3) channels. The present study explores the urea, H2O, CO2, and NH3 permeability of the human urea transporter B (UT-B) (SLC14A1), expressed in Xenopus oocytes. We monitored urea uptake using [14C]urea and measured osmotic water permeability (Pf) using video microscopy. To obtain a semiquantitative measure of gas permeability, we used microelectrodes to record the maximum transient change in surface pH (ΔpHS) caused by exposing oocytes to 5% CO2/33 mM HCO3− (pHS increase) or 0.5 mM NH3/NH4+ (pHS decrease). UT-B expression increased oocyte permeability to urea by >20-fold, and Pf by 8-fold vs. H2O-injected control oocytes. UT-B expression had no effect on the CO2-induced ΔpHS but doubled the NH3-induced ΔpHS. Phloretin reduced UT-B-dependent urea uptake (Jurea*) by 45%, Pf* by 50%, and (−ΔpHS*)NH3 by 70%. p-Chloromercuribenzene sulfonate reduced Jurea* by 25%, Pf* by 30%, and (ΔpHS*)NH3 by 100%. Molecular dynamics (MD) simulations of membrane-embedded models of UT-B identified the monomeric UT-B pores as the main conduction pathway for both H2O and NH3 and characterized the energetics associated with permeation of these species through the channel. Mutating each of two conserved threonines lining the monomeric urea pores reduced H2O and NH3 permeability. Our data confirm that UT-B has significant H2O permeability and for the first time demonstrate significant NH3 permeability. Thus the UTs become the third family of gas channels. Inhibitor and mutagenesis studies and results of MD simulations suggest that NH3 and H2O pass through the three monomeric urea channels in UT-B. PMID:23552862

  20. SEASONAL NH3 EMISSION ESTIMATES FOR THE EASTERN UNITED STATES BASED ON AMMONIUM WET CONCENTRATIONS AND AN INVERSE MODELING METHOD

    EPA Science Inventory

    Significant uncertainty exists in the magnitude and variability of ammonia (NH3) emissions. NH3 emissions are needed as input for air quality modeling of aerosols and deposition of nitrogen compounds. Approximately 85% of NH3 emissions are estimated to come from agricultural ...

  1. Study on adsorption and desorption of ammonia on graphene

    NASA Astrophysics Data System (ADS)

    Zhang, Zhengwei; Zhang, Xinfang; Luo, Wei; Yang, Hang; He, Yanlan; Liu, Yixing; Zhang, Xueao; Peng, Gang

    2015-09-01

    The gas sensor based on pristine graphene with conductance type was studied theoretically and experimentally. The time response of conductance measurements showed a quickly and largely increased conductivity when the sensor was exposed to ammonia gas produced by a bubble system of ammonia water. However, the desorption process in vacuum took more than 1 h which indicated that there was a larger number of transferred carriers and a strong adsorption force between ammonia and graphene. The desorption time could be greatly shortened down to about 2 min by adding the flow of water-vapor-enriched air at the beginning of the recovery stage which had been confirmed as a rapid and high-efficiency desorption process. Moreover, the optimum geometries, adsorption energies, and the charge transfer number of the composite systems were studied with first-principle calculations. However, the theoretical results showed that the adsorption energy between NH3 and graphene was too small to fit for the experimental phenomenon, and there were few charges transferred between graphene and NH3 molecules, which was completely different from the experiment measurement. The adsorption energy between NH4 and graphene increased stage by stage which showed NH4 was a strong donor. The calculation suggested that H2O molecule could help a quick desorption of NH4 from graphene by converting NH4 to NH3 or (NH3)n(H2O)m groups, which was consistent with the experimental results. This study demonstrates that the ammonia gas produced by a bubble system of ammonia water is mainly ammonium groups of NH3 and NH4, and the NH4 moleculars are ideal candidates for the molecular doping of graphene while the interaction between graphene and the NH3 moleculars is weak.

  2. Study on adsorption and desorption of ammonia on graphene.

    PubMed

    Zhang, Zhengwei; Zhang, Xinfang; Luo, Wei; Yang, Hang; He, Yanlan; Liu, Yixing; Zhang, Xueao; Peng, Gang

    2015-12-01

    The gas sensor based on pristine graphene with conductance type was studied theoretically and experimentally. The time response of conductance measurements showed a quickly and largely increased conductivity when the sensor was exposed to ammonia gas produced by a bubble system of ammonia water. However, the desorption process in vacuum took more than 1 h which indicated that there was a larger number of transferred carriers and a strong adsorption force between ammonia and graphene. The desorption time could be greatly shortened down to about 2 min by adding the flow of water-vapor-enriched air at the beginning of the recovery stage which had been confirmed as a rapid and high-efficiency desorption process. Moreover, the optimum geometries, adsorption energies, and the charge transfer number of the composite systems were studied with first-principle calculations. However, the theoretical results showed that the adsorption energy between NH3 and graphene was too small to fit for the experimental phenomenon, and there were few charges transferred between graphene and NH3 molecules, which was completely different from the experiment measurement. The adsorption energy between NH4 and graphene increased stage by stage which showed NH4 was a strong donor. The calculation suggested that H2O molecule could help a quick desorption of NH4 from graphene by converting NH4 to NH3 or (NH3)n(H2O)m groups, which was consistent with the experimental results. This study demonstrates that the ammonia gas produced by a bubble system of ammonia water is mainly ammonium groups of NH3 and NH4, and the NH4 moleculars are ideal candidates for the molecular doping of graphene while the interaction between graphene and the NH3 moleculars is weak. PMID:26377212

  3. Volatility of NH3 from internally mixed sodium succinate-NH4SO4 particles

    NASA Astrophysics Data System (ADS)

    Wang, Na; Zhang, Yunhong

    2016-04-01

    Contributing the complicacy of atmospheric constituents, aerosol particles may undergo complicated heterogeneous reactions that have profound consequences on their hygroscopic properties and volatility. Ammonia (NH3) is a ubiquitous trace atmospheric gas in the troposphere and has negative effects on human health and climate forcing of ambient aerosols. In addition, atmospheric cycle of NH3 is complex in atmosphere, therefore it necessary to get insights to the complexity of gas-to-aerosol NH3 partitioning, which results in large uncertainties in the sources and distributions of NH3. By using in-situ Fourier transform infrared spectroscopy and attenuated total reflection (FTIR-ATR), we report here the volatility of NH3 from the laboratory generated sodium succinate with ammonium sulfate ((NH4)2SO4) at a 1:1 molar ratio as well as its effect on the hygroscopicity of the mixtures. The loss of the NH4+ peak at 1451cm‑1 and the formation of peaks at 1718 and 1134 cm‑1 due to C = O stretching asymmetric vibration of -COOH and ν3 (SO42‑) stretching of sodium sulfate indicate that sodium succinate reacts with (NH4)2SO4, releasing NH3 and forming succinic acid and sodium sulfate on dehydration process. The formation of less hygroscopic succinic acid and volatility of NH3 in mixtures leads to a significant decrease in the total water content. To the best of our knowledge, this is the first report of the reaction between (NH4)2SO4 and dicarboxylate salts, which may represent an important particle-gas partitioning for ammonia and thus elucidate another underlying ammonia cycle in atmosphere. These results could be helpful to understand the mutual transformation process of dicarboxylic acids and dicarboxylate salts.

  4. Rotational dynamics of organic cations in the CH3NH3PbI3 perovskite.

    PubMed

    Chen, Tianran; Foley, Benjamin J; Ipek, Bahar; Tyagi, Madhusudan; Copley, John R D; Brown, Craig M; Choi, Joshua J; Lee, Seung-Hun

    2015-12-14

    Methylammonium lead iodide (CH3NH3PbI3) based solar cells have shown impressive power conversion efficiencies of above 20%. However, the microscopic mechanism of the high photovoltaic performance is yet to be fully understood. Particularly, the dynamics of CH3NH3(+) cations and their impact on relevant processes such as charge recombination and exciton dissociation are still poorly understood. Here, using elastic and quasi-elastic neutron scattering techniques and group theoretical analysis, we studied rotational modes of the CH3NH3(+) cation in CH3NH3PbI3. Our results show that, in the cubic (T > 327 K) and tetragonal (165 K < T < 327 K) phases, the CH3NH3(+) ions exhibit four-fold rotational symmetry of the C-N axis (C4) along with three-fold rotation around the C-N axis (C3), while in the orthorhombic phase (T < 165 K) only C3 rotation is present. At around room temperature, the characteristic relaxation times for the C4 rotation are found to be τC4 ≈ 5 ps while for the C3 rotation τC3 ≈ 1 ps. The T-dependent rotational relaxation times were fitted with Arrhenius equations to obtain activation energies. Our data show a close correlation between the C4 rotational mode and the temperature dependent dielectric permittivity. Our findings on the rotational dynamics of CH3NH3(+) and the associated dipole have important implications for understanding the low exciton binding energy and a slow charge recombination rate in CH3NH3PbI3 which are directly relevant for the high solar cell performance. PMID:26549203

  5. Accurate Potential Energy Surface, Rovibrational Energy Levels, and Transitions of Ammonia C_{3v} Isotopologues: ^{14}NH_3, ^{15}NH_3, ^{14}ND_3 and ^{14}NT_3

    NASA Astrophysics Data System (ADS)

    Huang, Xinchuan; Schwenke, David W.; Lee, Timothy J.

    2009-06-01

    A further refined, global potential energy surface (PES) is computed for the C_{3v} symmetry isotopologues of ammonia, including ^{14}NH_3, ^{15}NH_3, ^{14}ND_3 and ^{14}NT_3. The refinement procedure was similar to that used in our previously reported PES, but now extends to higher J energy levels and other isotopologues. Both the diagonal Born-Oppenheimer correction and the non-adiabatic correction were included. J=0-6 rovibrational energy levels and transition frequencies of ^{14}NH_3 computed on this PES are in excellent agreement with HITRAN data. Statistics on nearly 4100 transitions and more than 1000 energy levels demonstrate the accuracy achieved by the state-of-the-art "Best Theory + Experiment" strategy. Most transition frequencies are of ±0.01-0.02 cm^{-1} accuracy. Similar accuracy has been found on ^{15}NH_3 J=0-3 rovibrational energy levels. Several transitions and energy levels in HITRAN have been identified as unreliable or suspicious, and some have been re-assigned. For ^{14}ND_3 and ^{14}NT_3, J=0-3 calculations have been performed. Agreement for pure rotation-inversion transitions is nearly perfect, with more reliable energy levels presented. On the other hand, our J=0 results suggest a re-analysis on the ^{14}ND_3 ν_1 band origin is needed. Finally, we will discuss possible future refinements leading to an even better final PES for Ammonia. X. Huang, D.W. Schwenke, and T.J. Lee, J. Chem. Phys. 129, 214304 (2008).

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

    PubMed

    Krupa, S V

    2003-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Yu, Shanshan

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

  8. Photoelectric characteristics of CH3NH3PbI3/p-Si heterojunction

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  9. [Effects of superphosphate addition on NH3 and greenhouse gas emissions during vegetable waste composting].

    PubMed

    Yang, Yan; Sun, Qin-ping; Li, Ni; Liu, Chun-sheng; Li, Ji-jin; Liu, Ben-sheng; Zou, Guo-yuan

    2015-01-01

    To study the effects of superphosphate (SP) on the NH, and greenhouse gas emissions, vegetable waste composting was performed for 27 days using 6 different treatments. In addition to the controls, five vegetable waste mixtures (0.77 m3 each) were treated with different amounts of the SP additive, namely, 5%, 10%, 15%, 20% and 25%. The ammonia volatilization loss and greenhouse gas emissions were measured during composting. Results indicated that the SP additive significantly decreased the ammonia volatilization and greenhouse gas emissions during vegetable waste composting. The additive reduced the total NH3 emission by 4.0% to 16.7%. The total greenhouse gas emissions (CO2-eq) of all treatments with SP additives were decreased by 10.2% to 20.8%, as compared with the controls. The NH3 emission during vegetable waste composting had the highest contribution to the greenhouse effect caused by the four different gases. The amount of NH3 (CO2-eq) from each treatment ranged from 59.90 kg . t-1 to 81.58 kg . t-1; NH3(CO2-eq) accounted for 69% to 77% of the total emissions from the four gases. Therefore, SP is a cost-effective phosphorus-based fertilizer that can be used as an additive during vegetable waste composting to reduce the NH3 and greenhouse gas emissions as well as to improve the value of compost as a fertilizer. PMID:25985667

  10. Theoretical study of adsorption and dissociation of NH3 on pentanuclear Fe(111) surface

    NASA Astrophysics Data System (ADS)

    Purwiandono, G.; Triyono; Wijaya, K.

    2016-02-01

    Theoretical study regarding the adsorption and dissociation of NH3 molecule on Fe(111) surface has been carried out. The method used was DFT-B3LYP, and the basis sets used were ECP and 6-311G**. This research aimed at giving the theoretical understanding of adsorption and dissociation of NH3 molecule on Fe(111) surface. The adsorption and dissociation were studied based on the energetic parameter, bond length, electron population, vibration and orbital interaction. The result of theoretical calculation revealed that the on top position is the interaction position with the minimum energy for the adsorption of NH3 molecule on Fe(111) surface. The analysis of electron population of the two composing molecular orbitals indicated that the transfer of electron has an important role in the mechanism of adsorption. The visualization of molecular orbital showed that the transfer of electron occurred in the electron pairs of the interacting orbital. Relating to the adsorption mechanism and the overlapping of interaction orbitals, NH3 molecule provides the Highest Occupied Molecular Orbital (HOMO) as the interaction pair for the Lowest Unoccupied Molecular Orbital (LUMO) on Fe surface. The insignificant difference between the oxidation state of N and H atoms as well as the higher hemolytic N-H bond dissociation energy (compared to heterolytic dissociation) cause the adsorption mechanism of NH3 on Fe(111) model to occur through homolytic-dissociative chemisorption.

  11. Thermal Durability of Cu-CHA NH3-SCR Catalysts for Diesel NOx Reduction

    SciTech Connect

    Schmieg, Steven J.; Oh, Se H.; Kim, Chang H.; Brown, David B.; Lee, Jong H.; Peden, Charles HF; Kim, Do Heui

    2012-04-30

    Multiple catalytic functions (NOx conversion, NO and NH3 oxidation, NH3 storage) of a commercial Cu-zeolite urea/NH3-SCR catalyst were assessed in a laboratory fixed-bed flow reactor system after differing degrees of hydrothermal aging. Catalysts were characterized by using x-ray diffraction (XRD), 27Al solid state nuclear magnetic resonance (NMR) and transmission electron microscopy (TEM) / energy dispersive X-ray (EDX) spectroscopy to develop an understanding of the degradation mechanisms during catalyst aging. The catalytic reaction measurements of laboratory-aged catalysts were performed, which allows us to obtain a universal curve for predicting the degree of catalyst performance deterioration as a function of time at each aging temperature. Results show that as the aging temperature becomes higher, the zeolite structure collapses in a shorter period of time after an induction period. The decrease in SCR performance was explained by zeolite structure destruction and/or Cu agglomeration, as detected by XRD/27Al NMR and by TEM/EDX, respectively. Destruction of the zeolite structure and agglomeration of the active phase also results in a decrease in the NO/NH3 oxidation activity and the NH3 storage capacity of the catalyst. Selected laboratory aging conditions (16 h at 800oC) compare well with a 135,000 mile vehicle-aged catalyst for both performance and characterization criteria.

  12. Electric polarization of CH3NH3PbI3 and enhancement by Cl substitution

    NASA Astrophysics Data System (ADS)

    Yan, Wen-Li; Lu, Guang-Hong; Liu, Feng

    As a prototype of organic-inorganic hybrid perovskite, CH3NH3PbI3 has attracted extensive attention recently due to its applications in high power-conversion-efficiency solar cells. In comparison with its inorganic perovskite counterparts such as CsPbI3, the organic cation CH3NH3+ is expected to play multiple important roles in distorting crystal structures and thus band structures as well as creating local electrically polarized domains to help separate charge carriers. Using first-principles method and berry phase theory, the electric polarization vectors of CH3NH3PbI3 have been calculated. The off-center displacement of Pb within the PbI6 octahedral is shown to introduce major intrinsic polarization, with additional contributions from off-center displacement of CH3NH3+ within PbI3 cage and charge polarization within the organic cation. With chlorine substitution of iodine, the electronegativity difference between halogen and Pb becomes larger, and the lattice distortion and hence the electric polarization increases, which provides a possible mechanism to further assist charge carrier separation in solar cell devices. This is consistent with enhanced photovoltaics properties of CH3NH3PbI3-xClx found in recent experiments. This work is supported by China Scholarship Council (Grant No. 201306020117) and US DOE-BES (Grant No. DE-FG02-04ER46148).

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

    PubMed

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

    2016-02-01

    V-MCM-41, a mesoporous catalyst doped with V2O5, was applied for the first time to the removal of atmospheric NO. The quantity of V2O5 added was 10 wt% and 30 wt%. The characteristics of the synthesized catalysts were examined using XRD, N2 soprtion, and NH3-TPD. With increasing quantity of V2O5 added, specific surface area decreased and pore size increased. When the quantity of V2O5 was 10 wt%, the MCM-41 structure was retained, whereas considerable collapse of mesoporous structure was observed when 30 wt% V2O5 was added. The examination of acid characteristics using NH3-TPD showed that 30 wt% V-MCM-41 had the higher NH3 adsorption ability, implying that it would exhibit high activity for NH3 SCR reaction. In the NO removal experiments, 30 wt% V-MCM-41 showed much higher NO removal efficiency than 10 wt% V-MCM-41, which was attributed to its high NH3 adsorption ability. PMID:27433662

  14. Role of NH3 in the dehydrogenation of calcium amidoborane ammoniate and magnesium amidoborane ammoniate: a first-principles study.

    PubMed

    Li, Wen; Wu, Guotao; Chua, Yongshen; Feng, Yuan Ping; Chen, Ping

    2012-01-01

    First-principles calculations show that [NH(3)] molecules play crucial roles as both activator for the break-up of B-H bond and supplier of protic H for the establishment of dihydrogen bonding, which could facilitate the dehydrogenation of Ca(NH(2)BH(3))(2)·2NH(3) or Mg(NH(2)BH(3))(2)·NH(3) occurring at lower temperatures compared to those of Ca(NH(2)BH(3))(2) and Mg(NH(2)BH(3))(2). Moreover, the calculations of Helmholtz Free energy and [NH(3)] molecule removal energy evidence that coordination between [NH(3)] and Mg cation is stronger than that between [NH(3)] and Ca cation; therefore, Mg(NH(2)BH(3))(2)·NH(3) will undergo directly dehydrogenation rather than deammoniation at lower temperatures. PMID:22148858

  15. Quantifying local traffic contributions to NO2 and NH3 concentrations in natural habitats.

    PubMed

    Gadsdon, Sally R; Power, Sally A

    2009-10-01

    NO(2) and NH(3) concentrations were measured across a Special Area for Conservation in southern England, at varying distances from the local road network. Exceedances of the critical levels for these pollutants were recorded at nearly all roadside locations, extending up to 20 m away from roads at some sites. Further, paired measurements of NH(3) and NO(2) concentrations revealed differences between ground and tree canopy levels. At "background" sites, away from the direct influence of roads, concentrations were higher within tree canopies than at ground level; the reverse pattern was, however, seen at roadside locations. Calculations of pollutant deposition rates showed that nitrogen inputs are dominated by NH(3) at roadside sites. This study demonstrates that local traffic emissions contribute substantially to the exceedance of critical levels and critical loads, and suggests that on-site monitoring is needed for sites of nature conservation value which are in close proximity to local transport routes. PMID:19427723

  16. Facile route to freestanding CH3NH3PbI3 crystals using inverse solubility

    PubMed Central

    Kadro, Jeannette M.; Nonomura, Kazuteru; Gachet, David; Grätzel, Michael; Hagfeldt, Anders

    2015-01-01

    CH3NH3PbI3 was found to exhibit inverse solubility at high temperatures in γ-butyrolactone. Making use of this unusual, so far unreported phenomenon, we present a facile method for the growth of freestanding crystals of CH3NH3PbI3 from solution without addition of any capping agents or seed particles. Large, strongly faceted crystals could be grown within minutes. This finding may aid in understanding the crystallization process of CH3NH3PbI3 from solution that may lead to improved morphological control of film deposition for a range of device architectures. Our process offers a facile and rapid route to freestanding crystals for use in a broad range of characterization techniques. PMID:26123285

  17. Resonances in rotationally inelastic scattering of NH3 and ND3 with H2.

    PubMed

    Ma, Qianli; van der Avoird, Ad; Loreau, Jérôme; Alexander, Millard H; van de Meerakker, Sebastiaan Y T; Dagdigian, Paul J

    2015-07-28

    We present theoretical studies on the scattering resonances in rotationally inelastic collisions of NH3 and ND3 molecules with H2 molecules. We use the quantum close-coupling method to compute state-to-state integral and differential cross sections for the NH3/ND3-H2 system for collision energies between 5 and 70 cm(-1), using a previously reported potential energy surface [Maret et al., Mon. Not. R. Astron. Soc. 399, 425 (2009)]. We identify the resonances as shape or Feshbach resonances. To analyze these, we use an adiabatic bender model, as well as examination at the scattering wave functions and lifetimes. The strength and width of the resonance peaks suggest that they could be observed in a crossed molecular beam experiment involving a Stark-decelerated NH3 beam. PMID:26233134

  18. NH3 sensing characteristics of nano-WO3 thin films deposited on porous silicon.

    PubMed

    Sun, Fengyun; Hu, Ming; Sun, Peng; Zhang, Jie; Liu, Bo

    2010-11-01

    The NH3 sensing characteristics of nano-tungsten trioxide (WO3) thin films deposited on porous silicon (PS) were investigated in the present study. Porous silicon layer was first prepared by electrochemical etching in an HF-based solution on a p(+)-type silicon substrate. Then, WO3 nano-films were deposited on the porous silicon layer by DC magnetron sputtering. Pt electrodes were deposited on the top surface of the WO3 films to obtain the WO3/PS gas sensor. The WO3 films deposited on PS were characterized by SEM, XRD and XPS. The NH3 sensing characteristics for WO3/PS gas sensor were tested at room temperature and 50 degrees C. The results showed that the NH3 sensing characteristics of WO3/PS were superior to WO3/Al2O3 at room temperature. The sensing mechanism of the nano-WO3 thin films based on PS was also discussed. PMID:21138022

  19. NH3 sensing properties polyaniline: TiO2 nanorods heterostructure

    NASA Astrophysics Data System (ADS)

    Patil, U. V.; Ramgir, Niranjan S.; Debnath, A. K.; Karmakar, N.; Aswal, D. K.; Kothari, D. C.; Gupta, S. K.

    2016-05-01

    NH3 sensing properties of polyaniline: TiO2 nanorods heterostructures have been investigated. TiO2 nanorods were synthesized using hydrothermal method. Thin layer of polyanilene was deposited by in-situ oxidative polymerization of aniline over TiO2 nanorods film. The heterostructure film exhibited an enhanced sensor response towards NH3 at room temperature. For example, heterostructure films exhibited a sensor response of 610% towards 100 ppm of NH3 with a response and recovery times of 40 and 60 s, respectively. This response and response kinetics is better than pure PANI films that exhibited a response of 210% with a response and recovery time of 21 and 160 s, respectively.

  20. Correlation of superconductivity with crystal structure in (NH3)yC sxFeSe

    NASA Astrophysics Data System (ADS)

    Zheng, Lu; Miao, Xiao; Sakai, Yusuke; Goto, Hidenori; Uesugi, Eri; Eguchi, Ritsuko; Nishiyama, Saki; Sugimoto, Kunihisa; Fujiwara, Akihiko; Kubozono, Yoshihiro

    2016-03-01

    The superconducting transition temperature Tc of ammoniated metal-doped FeSe (NH3)yMxFeSe (M : metal atom) has been scaled with the FeSe plane spacing, and it has been suggested that the FeSe plane spacing depends on the location of metal atoms in (NH3)yMxFeSe crystals. Although the crystal structure of (NH3)yL ixFeSe exhibiting a high Tc (˜44 K) was determined from neutron diffraction, the structure of (NH3)yMxFeSe exhibiting a low Tc (˜32 K) has not been determined thus far. Here, we determined the crystal structure of (NH3)yC s0.4FeSe (Tc=33 K ) through the Rietveld refinement of the x-ray diffraction (XRD) pattern measured with synchrotron radiation at 30 K. The XRD pattern was analyzed based on two different models, on-center and off-center, under a space group of I 4 /m m m . In the on-center structure, the Cs occupies the 2 a site and the N of N H3 may occupy either the 4 c or 2 b site, or both. In the off-center structure, the Cs may occupy either the 4 c or 2 b site, or both, while the N occupies the 2 a site. Only an on-center structure model in which the Cs occupies the 2 a and the N of N H3 occupies the 4 c site provided reasonable results in the Rietveld analysis. Consequently, we concluded that (NH3)yC s0.4FeSe can be assigned to the on-center structure, which produces a smaller FeSe plane spacing leading to the lower Tc.

  1. Mixing of Dust and NH3 Observed Globally over Anthropogenic Dust Sources

    NASA Technical Reports Server (NTRS)

    Ginoux, P.; Clarisse, L.; Clerbaux, C.; Coheur, P.-F.; Dubovik, O.; Hsu, N. C.; Van Damme, M.

    2012-01-01

    The global distribution of dust column burden derived from MODIS Deep Blue aerosol products is compared to NH3 column burden retrieved from IASI infrared spectra. We found similarities in their spatial distributions, in particular their hot spots are often collocated over croplands and to a lesser extent pastures. Globally, we found 22% of dust burden collocated with NH3, with only 1% difference between land-use databases. This confirms the importance of anthropogenic dust from agriculture. Regionally, the Indian subcontinent has the highest amount of dust mixed with NH3 (26 %), mostly over cropland and during the pre-monsoon season. North Africa represents 50% of total dust burden but accounts for only 4% of mixed dust, which is found over croplands and pastures in Sahel and the coastal region of the Mediterranean. In order to evaluate the radiative effect of this mixing on dust optical properties, we derive the mass extinction efficiency for various mixtures of dust and NH3, using AERONET sunphotometers data. We found that for dusty days the coarse mode mass extinction efficiency decreases from 0.62 to 0.48 square meters per gram as NH3 burden increases from 0 to 40 milligrams per square meter. The fine mode extinction efficiency, ranging from 4 to 16 square mters per gram, does not appear to depend on NH3 concentration or relative humidity but rather on mineralogical composition and mixing with other aerosols. Our results imply that a significant amount of dust is already mixed with ammonium salt before its long range transport. This in turn will affect dust lifetime, and its interactions with radiation and cloud properties

  2. Scattering of NH3 and ND3 with rare gas atoms at low collision energy.

    PubMed

    Loreau, J; van der Avoird, A

    2015-11-14

    We present a theoretical study of elastic and rotationally inelastic collisions of NH3 and ND3 with rare gas atoms (He, Ne, Ar, Kr, Xe) at low energy. Quantum close-coupling calculations have been performed for energies between 0.001 and 300 cm(-1). We focus on collisions in which NH3 is initially in the upper state of the inversion doublet with j = 1, k = 1, which is the most relevant in an experimental context as it can be trapped electrostatically and Stark-decelerated. We discuss the presence of resonances in the elastic and inelastic cross sections, as well as the trends in the inelastic cross sections along the rare gas series and the differences between NH3 and ND3 as a colliding partner. We also demonstrate the importance of explicitly taking into account the umbrella (inversion) motion of NH3 in order to obtain accurate scattering cross sections at low collision energy. Finally, we investigate the possibility of sympathetic cooling of ammonia using cold or ultracold rare gas atoms. We show that some systems exhibit a large ratio of elastic to inelastic cross sections in the cold regime, which is promising for sympathetic cooling experiments. The close-coupling calculations are based on previously reported ab initio potential energy surfaces for NH3-He and NH3-Ar, as well as on new, four-dimensional, potential energy surfaces for the interaction of ammonia with Ne, Kr, and Xe, which were computed using the coupled-cluster method and large basis sets. We compare the properties of the potential energy surfaces corresponding to the interaction of ammonia with the various rare gas atoms. PMID:26567658

  3. LPG and NH3 sensing characteristics of DC electrochemically deposited Co3O4 films

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  4. A flexible and robust neural network IASI-NH3 retrieval algorithm

    NASA Astrophysics Data System (ADS)

    Whitburn, S.; Van Damme, M.; Clarisse, L.; Bauduin, S.; Heald, C. L.; Hadji-Lazaro, J.; Hurtmans, D.; Zondlo, M. A.; Clerbaux, C.; Coheur, P.-F.

    2016-06-01

    In this paper, we describe a new flexible and robust NH3 retrieval algorithm from measurements of the Infrared Atmospheric Sounding Interferometer (IASI). The method is based on the calculation of a spectral hyperspectral range index (HRI) and subsequent conversion to NH3 columns via a neural network. It is an extension of the method presented in Van Damme et al. (2014a) who used lookup tables (LUT) for the radiance-concentration conversion. The new method inherits the advantages of the LUT-based method while providing several significant improvements. These include the following: (1) Complete temperature and humidity vertical profiles can be accounted for. (2) Third-party NH3 vertical profile information can be used. (3) Reported positive biases of LUT retrieval are reduced, and finally (4) a full measurement uncertainty characterization is provided. A running theme in this study, related to item (2), is the importance of the assumed vertical NH3 profile. We demonstrate the advantages of allowing variable profile shapes in the retrieval. As an example, we analyze how the retrievals change when all NH3 is assumed to be confined to the boundary layer. We analyze different averaging procedures in use for NH3 in the literature, introduced to cope with the variable measurement sensitivity and derive global averaged distributions for the year 2013. A comparison with a GEOS-Chem modeled global distribution is also presented, showing a general good correspondence (within ±3 × 1015 molecules.cm-2) over most of the Northern Hemisphere. However, IASI finds mean columns about 1-1.5 × 1016 molecules.cm-2 (˜50-60%) lower than GEOS-Chem for India and the North China plain.

  5. Partial phase diagram for the system NH3-H2O - The water-rich region

    NASA Technical Reports Server (NTRS)

    Johnson, M. L.; Schwake, A.; Nicol, M.

    1984-01-01

    Phase boundaries of the H2O-NH3 system for (NH3)/x/(H2O)/1-x/ have been determined with diamond-anvil cells for mixtures in two composition ranges: (1) for x in the range from 0 to 0.3, at pressures up to 4 GPa at 21 C, and (2) for x in the range from 0.46 to 0.50, at pressures up to 5 GPa from 150 to 400 K. Phases were identified visually with a microscope and polarized optics. The NH3.2(H2O) phase is strongly anisotropic with a much smaller refractive index than that of ice VII and cracks in two nonperpendicular networks. NH3.H2O has a refractive index closer to that of Ice VII and does not appear to form cracks. Both phases are colorless. Phase boundaries were determined on both increasing and decreasing pressures, and compositions of the ammonia ices were determined by estimating relative amounts of water and ammonia ices at known overall compositions. For low-ammonia compositions (x equal to or less than 0.15), the following assemblages succedd one another as pressure increases: liquid; liquid and Ice VI (at 1.0 + GPa); liquid and Ice VII (at 2.1 GPa); Ice VII and NH3.H2O (at 3.5 GPa). For x in the range from 0.15 to 0.30, the water ice and liquid fields are replaced by the NH3.2(H2O) and liquid field at pressures down to 1.0 GPa and lower.

  6. Ultraviolet-gas phase and -photocatalytic synthesis from CO and NH3. [photolysis products

    NASA Technical Reports Server (NTRS)

    Hubbard, J. S.; Voecks, G. E.; Hobby, G. L.; Ferris, J. P.; Williams, E. A.; Nicodem, D. E.

    1975-01-01

    Ammonium cyanate is identified as the major product of the photolysis of gaseous NH3-CO mixtures at 206.2 or 184.9 nm. Lesser amounts of urea, biurea, biuret semicarbazide, formamide and cyanide are observed. A series of 18 reactions underlying the formation of photolysis products is presented and discussed. Photocatalytic syntheses of C-14-urea, -formamide, and -formaldehyde are carried out through irradiation of (C-14)O and NH3 in the presence of Vycor, silica gel, or volcanic ash shale surfaces. The possible contributions of the relevant reactions to the abiotic synthesis of organic nitrogen compounds on Mars, the primitive earth, and in interstellar space are examined.

  7. Biochemical pathways of breath ammonia (NH3) generation in patients with end-stage renal disease undergoing hemodialysis.

    PubMed

    Chen, W; Laiho, S; Vaittinen, O; Halonen, L; Ortiz, F; Forsblom, C; Groop, P-H; Lehto, M; Metsälä, M

    2016-01-01

    Breath ammonia (NH3) has been proposed as a potential biomarker in monitoring hemodialysis (HD) adequacy, since a strong correlation between blood urea and mouth-exhaled breath NH3 has been observed in patients with end-stage renal disease (ESRD) undergoing HD. However, the biochemical pathways for breath NH3 generation from blood urea have not been demonstrated. In this study, we show a strong correlation (r s  =  0.77, p  <  0.001) between blood and salivary urea, indicating that salivary urea levels reflect blood urea levels. Salivary urea is in turn strongly correlated to salivary ammonia ([Formula: see text] + NH3) in most of the patients. This confirms that the hydrolysis of urea by urease generates ammonia in the oral cavity. A further strong correlation between salivary ammonia and breath NH3 indicates that salivary ammonia evaporates into gas phase and turns to breath NH3. Therefore, blood urea is a major biochemical source of breath NH3. Since breath NH3 is generated predominantly in the oral cavity, the levels of breath NH3 are influenced significantly by the patient's oral condition including urease activity and salivary pH. Our results agree with previous studies that have shown a connection between salivary urea and breath NH3. PMID:27516572

  8. Effect of Ti or Sn doping on the catalytic performance of MnOx/CeO2 catalyst for low temperature selective catalytic reduction of NO with NH3

    NASA Astrophysics Data System (ADS)

    Xiong, Yan; Tang, Changjin; Dong, Lin

    2015-04-01

    The abatement of nitrogen oxides (NOx) emission from exhaust gases of diesel and stationary sources is a significant challenge for economic and social development. Ceria-based solid solutions were synthesized and used as supports to prepare MnOx/Ce0.8Ti0.2O2 and MnOx/Ce0.8Sn0.2O2 catalysts (Mn/CeTi and Mn/CeSn) for low temperature selective catalytic reduction of NO by NH3 (NH3-SCR). The effects of Ti or Sn doping on the catalytic performance of MnOx/CeO2 catalyst were investigated. Experimental results show that doping of Ti or Sn increases the NO removal efficiency of MnOx/CeO2. The NO conversion of Mn/CeTi catalyst is more than 90 % at temperature window of 175 ~ 300 °C under a gas hour space velocity of 60,000 mL•g-1•h-1. Modified catalysts are also found to exhibit greatly improved resistance to sulfur-poisoning. NH3-TPD results suggest that NH3 desorption on the catalysts is observed over a wide temperature range, due to the variability of adsorbed NH3 species with different thermal stabilities. Doping of Ti and Sn into Mn/CeO2 greatly increased the NH3 adsorption ability of the composites which could promote the SCR reaction. Characterization results also indicate that doping of Ti or Sn brings about catalysts with higher BET surface area, enhanced oxygen storage capacity and increased surface acidity. X-ray photoelectron spectroscopy (XPS) analysis of spent catalysts following SCR reaction in the presence of SO2 verify that the loss of surface Mn species was inhibited by doping of Ti, which contributes to extend the catalyst durability.

  9. Effect of metal ions doping (M = Ti4+, Sn4+) on the catalytic performance of MnOx/CeO2 catalyst for low temperature selective catalytic reduction of NO with NH3

    NASA Astrophysics Data System (ADS)

    Xiong, Yan; Tang, Changjin; Dong, Lin

    2015-04-01

    Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, PR China The abatement of nitrogen oxides (NOx) emission from exhaust gases of diesel and stationary sources is a significant challenge for economic and social development. Ceria-based solid solutions were synthesized and used as supports to prepare MnOx/Ce0.8Ti0.2O2 and MnOx/Ce0.8Sn0.2O2 catalysts (Mn/CeTi and Mn/CeSn) for low temperature selective catalytic reduction of NO by NH3 (NH3-SCR). The effects of Ti or Sn doping on the catalytic performance of MnOx/CeO2 catalyst were investigated. Experimental results show that doping of Ti or Sn increases the NO removal efficiency of MnOx/CeO2. The NO conversion of Mn/CeTi catalyst is more than 90 % at temperature window of 175 ~ 300 °C under a gas hour space velocity of 60,000 mL.g-1.h-1. Modified catalysts are also found to exhibit greatly improved resistance to sulfur-poisoning. NH3-TPD results suggest that NH3 desorption on the catalysts is observed over a wide temperature range, due to the variability of adsorbed NH3 species with different thermal stabilities. Doping of Ti and Sn into Mn/CeO2 greatly increased the NH3 adsorption ability of the composites which could promote the SCR reaction. Characterization results also indicate that doping of Ti or Sn brings about catalysts with higher BET surface area, enhanced oxygen storage capacity and increased surface acidity.

  10. Parametrization of electron impact ionization cross sections for CO, CO2, NH3 and SO2

    NASA Technical Reports Server (NTRS)

    Srivastava, Santosh K.; Nguyen, Hung P.

    1987-01-01

    The electron impact ionization and dissociative ionization cross section data of CO, CO2, CH4, NH3, and SO2, measured in the laboratory, were parameterized utilizing an empirical formula based on the Born approximation. For this purpose an chi squared minimization technique was employed which provided an excellent fit to the experimental data.

  11. NH3(3,3) and CH3OH near Supernova Remnants: GBT and VLA Observations

    NASA Astrophysics Data System (ADS)

    McEwen, Bridget C.; Pihlström, Ylva M.; Sjouwerman, Loránt O.

    2016-08-01

    We report on Green Bank Telescope 23.87 GHz NH3(3,3) emission observations in five supernova remnants (SNRs) interacting with molecular clouds (G1.4‑0.1, IC 443, W44, W51C, and G5.7‑0.0). The observations show a clumpy gas density distribution, and in most cases the narrow line widths of ˜3–4 km s‑1 are suggestive of maser emission. Very Large Array observations reveal 36 and/or 44 GHz CH3OH maser emission in a majority (72%) of the NH3 peak positions toward three of these SNRs. This good positional correlation is in agreement with the high densities required for the excitation of each line. Through these observations we have shown that CH3OH and NH3 maser emission can be used as indicators of high-density clumps of gas shocked by SNRs, and provide density estimates thereof. Modeling of the optical depth of the NH3(3,3) emission is compared to that of CH3OH, constraining the densities of the clumps to a typical density of the order of 105 cm‑3 for cospatial masers. Regions of gas with this density are found to exist in the post-shocked gas quite close to the SNR shock front, and may be associated with sites where cosmic rays produce gamma-ray emission via neutral pion decay.

  12. Kinetics of gas-liquid reaction between NO and Co(NH3)6(2+).

    PubMed

    Long, Xiang-li; Xiao, Wen-De; Yuan, Wei-kang

    2005-08-31

    Wet ammonia desulphurization process can be retrofitted for combined removal of SO2 and NO from the flue gas by adding soluble cobalt(II) salts into the aqueous ammonia solutions. The Co(NH3)6(2+) formed by ammonia binding with Co2+ is the active constituent of scrubbing NO from the flue gas streams. A stirred vessel with a plane gas-liquid interface was used to measure the chemical absorption rates of nitric oxide into the Co(NH3)6(2+) solution under anaerobic and aerobic conditions separately. The experiments manifest that the nitric oxide absorption reaction can be regarded as instantaneous when nitric oxide concentration levels are parts per million ranges. The gas-liquid reaction becomes gas film controlling as Co(NH3)6(2+) concentration exceeds 0.02 mol/l. The NO absorption rate is proportional to the nitric oxide inlet concentration. Oxygen in the gas phase is favorable to the absorption of nitric oxide. But it is of little significance to increase the oxygen concentration above 5.2%. The NO absorption rate decreases with temperature. The kinetic equation of NO absorption into the Co(NH3)6(2+) solution under aerobic condition can be written as. PMID:15869841

  13. NH3(3,3) and CH3OH near Supernova Remnants: GBT and VLA Observations

    NASA Astrophysics Data System (ADS)

    McEwen, Bridget C.; Pihlström, Ylva M.; Sjouwerman, Loránt O.

    2016-08-01

    We report on Green Bank Telescope 23.87 GHz NH3(3,3) emission observations in five supernova remnants (SNRs) interacting with molecular clouds (G1.4‑0.1, IC 443, W44, W51C, and G5.7‑0.0). The observations show a clumpy gas density distribution, and in most cases the narrow line widths of ∼3–4 km s‑1 are suggestive of maser emission. Very Large Array observations reveal 36 and/or 44 GHz CH3OH maser emission in a majority (72%) of the NH3 peak positions toward three of these SNRs. This good positional correlation is in agreement with the high densities required for the excitation of each line. Through these observations we have shown that CH3OH and NH3 maser emission can be used as indicators of high-density clumps of gas shocked by SNRs, and provide density estimates thereof. Modeling of the optical depth of the NH3(3,3) emission is compared to that of CH3OH, constraining the densities of the clumps to a typical density of the order of 105 cm‑3 for cospatial masers. Regions of gas with this density are found to exist in the post-shocked gas quite close to the SNR shock front, and may be associated with sites where cosmic rays produce gamma-ray emission via neutral pion decay.

  14. Conformation of NH 3 and C 2H 4 molecules approaching a metal surface

    NASA Astrophysics Data System (ADS)

    Flores, F.; Gabbay, I.; March, N. H.

    1981-10-01

    Using a semiempirical approach to the conformation of free space molecules, the HNH angle in NH 3 adsorbed on Ru(001) is estimated to increase by about 1°. For C 2H 4, both HCC and HCH angles are predicted to decrease.

  15. Towards a carbon independent and CO2-free electrochemical membrane process for NH3 synthesis.

    PubMed

    Kugler, K; Ohs, B; Scholz, M; Wessling, M

    2014-04-01

    Ammonia is exclusively synthesized by the Haber-Bosch process starting from precious carbon resources such as coal or CH4. With H2O, H2 is produced and with N2, NH3 can be synthesized at high pressures and temperatures. Regrettably, the carbon is not incorporated into NH3 but emitted as CO2. Valuable carbon sources are consumed which could be used otherwise when carbon sources become scarce. We suggest an alternative process concept using an electrochemical membrane reactor (ecMR). A complete synthesis process with N2 production and downstream product separation is presented and evaluated in a multi-scale model to quantify its energy consumption. A new micro-scale ecMR model integrates mass, species, heat and energy balances with electrochemical conversions allowing further integration into a macro-scale process flow sheet. For the anodic oxidation reaction H2O was chosen as a ubiquitous H2 source. Nitrogen was obtained by air separation which combines with protons from H2O to give NH3 using a hypothetical catalyst recently suggested from DFT calculations. The energy demand of the whole electrochemical process is up to 20% lower than the Haber-Bosch process using coal as a H2 source. In the case of natural gas, the ecMR process is not competitive under today's energy and resource conditions. In future however, the electrochemical NH3 synthesis might be the technology-of-choice when coal is easily accessible over natural gas or limited carbon sources have to be used otherwise but for the synthesis of the carbon free product NH3. PMID:24557153

  16. A Water Maser and NH3 Survey of GLIMPSE Extended Green Objects

    NASA Astrophysics Data System (ADS)

    Cyganowski, C. J.; Koda, J.; Rosolowsky, E.; Towers, S.; Donovan Meyer, J.; Egusa, F.; Momose, R.; Robitaille, T. P.

    2013-02-01

    We present the results of a Nobeyama 45 m H2O maser and NH3 survey of all 94 northern GLIMPSE extended green objects (EGOs), a sample of massive young stellar objects (MYSOs) identified based on their extended 4.5 μm emission. We observed the NH3(1,1), (2,2), and (3,3) inversion lines, and detected emission toward 97%, 63%, and 46% of our sample, respectively (median rms ~ 50 mK). The H2O maser detection rate is 68% (median rms ~ 0.11 Jy). The derived H2O maser and clump-scale gas properties are consistent with the identification of EGOs as young MYSOs. To explore the degree of variation among EGOs, we analyze subsamples defined based on mid-infrared (MIR) properties or maser associations. H2O masers and warm dense gas, as indicated by emission in the higher-excitation NH3 transitions, are most frequently detected toward EGOs also associated with both Class I and II CH3OH masers. Ninety-five percent (81%) of such EGOs are detected in H2O (NH3(3,3)), compared to only 33% (7%) of EGOs without either CH3OH maser type. As populations, EGOs associated with Class I and/or II CH3OH masers have significantly higher NH3 line widths, column densities, and kinetic temperatures than EGOs undetected in CH3OH maser surveys. However, we find no evidence for statistically significant differences in H2O maser properties (such as maser luminosity) among any EGO subsamples. Combining our data with the 1.1 mm continuum Bolocam Galactic Plane Survey, we find no correlation between isotropic H2O maser luminosity and clump number density. H2O maser luminosity is weakly correlated with clump (gas) temperature and clump mass.

  17. Nucleobases and Prebiotic Molecules in Organic Residues Produced from the Ultraviolet Photo-Irradiation of Pyrimidine in NH3 and H2O+NH3 Ices

    NASA Technical Reports Server (NTRS)

    Nuevo, Michel; Milam, Stefanie N.; Sandford, Scott

    2012-01-01

    Although not yet identified in the interstellar medium (ISM), N-heterocycles including nucleobases the information subunits of DNA and RNA are present in carbonaceous chondrites, which indicates that molecules of biological interest can be formed in non-terrestrial environments via abiotic pathways. Recent laboratory experiments and ab-initio calculations have already shown that the irradiation of pyrimidine in pure H2O ices leads to the formation of a suite of oxidized pyrimidine derivatives, including the nucleobase uracil. In the present work, NH3:pyrimidine and H2O:NH3:pyrimidine ice mixtures with different relative proportions were irradiated with UV photons under astrophysically relevant conditions. Liquid- and gas-chromatography analysis of the resulting organic residues has led to the detection of the nucleobases uracil and cytosine, as well as other species of prebiotic interest such as urea and small amino acids. The presence of these molecules in organic residues formed under abiotic conditions supports scenarios in which extraterrestrial organics that formed in space and were subsequently delivered to telluric planets via comets and meteorites could have contributed to the inventory of molecules that triggered the first biological reactions on their surfaces.

  18. Nucleobases and prebiotic molecules in organic residues produced from the ultraviolet photo-irradiation of pyrimidine in NH(3) and H(2)O+NH(3) ices.

    PubMed

    Nuevo, Michel; Milam, Stefanie N; Sandford, Scott A

    2012-04-01

    Although not yet identified in the interstellar medium (ISM), N-heterocycles including nucleobases-the information subunits of DNA and RNA-are present in carbonaceous chondrites, which indicates that molecules of biological interest can be formed in non-terrestrial environments via abiotic pathways. Recent laboratory experiments and ab initio calculations have already shown that the irradiation of pyrimidine in pure H(2)O ices leads to the formation of a suite of oxidized pyrimidine derivatives, including the nucleobase uracil. In the present work, NH(3):pyrimidine and H(2)O:NH(3):pyrimidine ice mixtures with different relative proportions were irradiated with UV photons under astrophysically relevant conditions. Liquid- and gas-chromatography analysis of the resulting organic residues has led to the detection of the nucleobases uracil and cytosine, as well as other species of prebiotic interest such as urea and small amino acids. The presence of these molecules in organic residues formed under abiotic conditions supports scenarios in which extraterrestrial organics that formed in space and were subsequently delivered to telluric planets via comets and meteorites could have contributed to the inventory of molecules that triggered the first biological reactions on their surfaces. PMID:22519971

  19. Interfacial Electron Transfer Barrier at Compact TiO2 /CH3 NH3 PbI3 Heterojunction.

    PubMed

    Xing, Guichuan; Wu, Bo; Chen, Shi; Chua, Julianto; Yantara, Natalia; Mhaisalkar, Subodh; Mathews, Nripan; Sum, Tze Chien

    2015-08-01

    Low-temperature solution-processed CH3 NH3 PbI3 interfaced with TiO2 has recently been demonstrated as a highly successful type-II light harvesting heterojunction with ≈20% efficiency. Therefore, an efficient ultrafast photoexcited electron transfer from CH3 NH3 PbI3 to TiO2 is expected. However, by probing the photoexcited charge carrier dynamics in CH3 NH3 PbI3 /quartz, CH3 NH3 PbI3 /TiO2 (compact), and CH3 NH3 PbI3 /PCBM in a comparative study, an electron transfer potential barrier between CH3 NH3 PbI3 and the compact TiO2 (prepared with the spray pyrolysis method) formed by surface states is uncovered. Consequently, the CH3 NH3 PbI3 photoluminescence intensity and lifetime is enhanced when interfaced to compact TiO2 . The electron accumulation within CH3 NH3 PbI3 needed to overcome this interfacial potential barrier results in the undesirable large current-voltage hysteresis observed for CH3 NH3 PbI3 /TiO2 planar heterojunctions. The findings in this study indicate that careful surface engineering to reduce this potential barrier is key to pushing perovskite solar cell efficiencies toward the theoretical limit. PMID:25824264

  20. Observation of lower defect density in CH3NH3Pb(I,Cl)3 solar cells by admittance spectroscopy

    NASA Astrophysics Data System (ADS)

    Jiang, Minlin; Lan, Fei; Zhao, Bingxin; Tao, Quan; Wu, Jiamin; Gao, Di; Li, Guangyong

    2016-06-01

    The introduction of Cl into CH3NH3PbI3 precursors is reported to enhance the performance of CH3NH3PbI3 solar cell, which is attributed to the significantly increased diffusion lengths of carriers in CH3NH3Pb(I,Cl)3 solar cell. It has been assumed but never experimentally approved that the defect density in CH3NH3Pb(I,Cl)3 solar cell should be reduced according to the higher carrier lifetime observed from photoluminescence (PL) measurement. We have fabricated CH3NH3Pb(I,Cl)3 solar cell by adding a small amount of Cl source into CH3NH3PbI3 precursor. The performance of CH3NH3Pb(I,Cl)3 solar cell is significantly improved from 15.39% to 18.60%. Results from scanning electron microscopy and X-ray diffraction indicate that the morphologies and crystal structures of CH3NH3PbI3 and CH3NH3Pb(I,Cl)3 thin films remain unchanged. Open circuit voltage decay and admittance spectroscopy characterization jointly approve that Cl plays an extremely important role in suppressing the formation of defects in perovskite solar cells.

  1. Selective catalytic reduction of NO with NH3 over CeO2-ZrO2-WO3 catalysts prepared by different methods

    NASA Astrophysics Data System (ADS)

    Ning, Ping; Song, Zhongxian; Li, Hao; Zhang, Qiulin; Liu, Xin; Zhang, Jinhui; Tang, Xiaosu; Huang, Zhenzhen

    2015-03-01

    The selective catalytic reduction (SCR) of NO by NH3 has been investigated over the CeO2-ZrO2-WO3 (CZW) catalysts prepared by hydrothermal synthesis, incipient impregnation, co-precipitation and sol-gel methods. The results indicate that the CZW catalyst prepared by hydrothermal method shows the best SCR activity, and more than 90% NO conversion is obtained at 195-450 °C with a gas hourly space velocity of 50,000 h-1. The samples are characterized by XRD, N2 adsorption-desorption, SEM, EDS, XPS, H2-TPR, NH3-TPD and Pyridine-IR techniques. The results imply that the superior SCR activity of CZW catalyst is contributed to the excellent redox property, strong acidity and highest content of chemisorbed oxygen species. Furthermore, the larger surface area and greater total pore volume improve the redox ability and enhance NO conversion at low temperature, while the co-existence of Lewis and Brønsted acid sites enhance the SCR activity at high temperature.

  2. Synthesis and Evaluation of Cu/SAPO-34 Catalysts for NH3-SCR 2: Solid-state Ion Exchange and One-pot Synthesis

    SciTech Connect

    Gao, Feng; Walter, Eric D.; Washton, Nancy M.; Szanyi, Janos; Peden, Charles HF

    2015-01-01

    Cu-SAPO-34 catalysts are synthesized using two methods: solid-state ion exchange (SSIE) and one-pot synthesis. SSIE is conducted by calcining SAPO-34/CuO mixtures at elevated temperatures. For the one-pot synthesis method, Cu-containing chemicals (CuO and CuSO4) are added during gel preparation. A high-temperature calcination step is also needed for this method. Catalysts are characterized with surface area/pore volume measurements, temperature programmed reduction (TPR), electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies, and scanning electron microscopy (SEM). Catalytic properties are examined using standard ammonia selective catalytic reduction (NH3-SCR) and ammonia oxidation reactions. In Cu-SAPO-34 samples formed using SSIE, Cu presents both as isolated Cu2+ ions and unreacted CuO. The former is highly active and selective in NH3-SCR, while the latter catalyzes a side reaction; notably, the non-selective oxidation of NH3 above 350 ºC. Using the one-pot method followed by a high-temperature aging treatment, it is possible to form Cu SAPO-34 samples with predominately isolated Cu2+ ions at low Cu loadings. However at much higher Cu loadings, isolated Cu2+ ions that bind weakly with the CHA framework and CuO clusters also form. These Cu moieties are very active in catalyzing non-selective NH3 oxidation above 350 ºC. Low-temperature reaction kinetics indicate that Cu-SAPO-34 samples formed using SSIE have core-shell structures where Cu is enriched in the shell layers; while Cu is more evenly distributed within the one-pot samples. Reaction kinetics also suggest that at low temperatures, the local environment next to Cu2+ ion centers plays little role on the overall catalytic properties. The authors 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

  3. Crystal structure of [Co(NH3)6][Co(CO)4]2.

    PubMed

    Müller, Thomas G; Kraus, Florian

    2015-11-01

    Hexaamminecobalt(II) bis-[tetra-carbonyl-cobaltate(-I)], [Co(NH3)6][Co(CO)4]2, was synthesized by reaction of liquid ammonia with Co2(CO)8. The Co(II) atom is coordinated by six ammine ligands. The resulting polyhedron, the hexa-amminecobalt(II) cation, exhibits point group symmetry -3. The Co(-I) atom is coordinated by four carbonyl ligands, leading to a tetra-carbonyl-cobaltate(-I) anion in the shape of a slightly distorted tetra-hedron, with point group symmetry 3. The crystal structure is related to that of high-pressure BaC2 (space group R-3m), with the [Co(NH3)6](2+) cations replacing the Ba sites and the [Co(CO)4](-) anions replacing the C sites. N-H⋯O hydrogen bonds between cations and anions stabilize the structural set-up in the title compound. PMID:26594524

  4. Crystal structure of Ag2(μ-SCN)2(NH3)4

    PubMed Central

    Müller, Thomas G.; Kraus, Florian

    2016-01-01

    Di-μ-thio­cyanato-bis­[diamminesilver(I)], [Ag2(μ-SCN)2(NH3)4], was synthesized by the reaction of AgSCN with anhydrous liquid ammonia. In the binuclear mol­ecule, the AgI atom is coordinated by two ammine ligands and the S atom of one thio­cyanate ligand. Two of these [Ag(SCN)(NH3)2] units are bridged by the S atoms of the thio­cyanate anions at longer distances, leading to a dimer with point group symmetry C 2. The distance between the AgI atoms in the dimer is at 3.0927 (6) Å within the range of argentophilic inter­actions. The crystal structure displays N—H⋯N and N—H⋯S hydrogen-bonding inter­actions that build up a three-dimensional network. PMID:27555922

  5. The self-associating behavior of NH3 and ND3 in liquid xenon

    NASA Astrophysics Data System (ADS)

    De Beuckeleer, Liene I.; Herrebout, Wouter A.

    2016-08-01

    In this study we report on the analysis of isothermal spectra of NH3 and ND3 solutions in liquid xenon at 203 K using newly developed and validated least-squares approaches to investigate the its self-associating behavior. For both species we observe clear dimer bands in the spectral area of the ν1+ν4, ν3+ν4 and ν1+ν2, ν3+ν2 combination bands. The analysis of the N-D stretching area, allows us to characterize clear contributions of dimers and trimers. The analysis of the Nsbnd H stretching area is hampered by the occurrence of a time dependent band due to solid water traces during the experiments. For NH3 we also performed an investigation of the Nsbnd H bending region, ν2, which demonstrated a small dimer absorption band. These obtained results compare well with literature data.

  6. Potential energy surface and bound states of the NH3-Ar and ND3-Ar complexes.

    PubMed

    Loreau, J; Liévin, J; Scribano, Y; van der Avoird, A

    2014-12-14

    A new, four-dimensional potential energy surface for the interaction of NH3 and ND3 with Ar is computed using the coupled-cluster method with single, double, and perturbative triple excitations and large basis sets. The umbrella motion of the ammonia molecule is explicitly taken into account. The bound states of both NH3-Ar and ND3-Ar are calculated on this potential for total angular momentum values from J = 0 to 10, with the inclusion of Coriolis interactions. The energies and splittings of the rovibrational levels are in excellent agreement with the extensive high-resolution spectroscopic data accumulated over the years in the infrared and microwave regions for both complexes, which demonstrates the quality of the potential energy surface. PMID:25494745

  7. Porous Anatase TiO2 Thin Films for NH3 Vapour Sensing

    NASA Astrophysics Data System (ADS)

    Ponnusamy, Dhivya; Madanagurusamy, Sridharan

    2015-12-01

    Anatase titanium dioxide (TiO2) thin films were deposited onto cleaned glass substrates by a direct current (DC) reactive magnetron sputtering technique for different deposition times from 10 min to 40 min, which resulted in films of different thicknesses. Characterization techniques, such as x-ray diffraction (XRD) and field emission-scanning electron microscopy (FE-SEM) were used to characterize the structural and morphological properties of the TiO2 thin films. XRD patterns showed the formation of (101) crystal anatase facets. The grain size values of the film increased with increased deposition time, and the films deposited at 40 min exhibited a porous structure. Anatase TiO2 thin films exhibited excellent sensing response, fast response and recovery time, as well as good stability and selectivity towards ammonia (NH3). The enhanced NH3 sensing behavior of anatase TiO2 films is attributed to the porous morphology and oxygen vacancies.

  8. Comparison of the biological NH3 removal characteristics among four inorganic packing materials.

    PubMed

    Hirai, M; Kamamoto, M; Yani, M; Shoda, M

    2001-01-01

    Four inorganic packing materials were evaluated in terms of their availability as a packing material of a packed tower deodorization apparatus (biofilter) from the viewpoints of biological NH3 removal characteristics and some physical properties. Porous ceramics (A), calcinated cristobalite (B), calcinated and formed obsidian (C), granulated and calculated soil (D) were used. The superiority of these packing materials determined based on the values of non-biological removal per unit weight or unit volume of packing material, complete removal capacity of NH3 per unit weight of packing material per day or unit volume of packing material per day and pressure drop of the packed bed was in the order of A approximately = C > B > or = D. Packing materials A and C with high porosity, maximum water content, and suitable mean pore diameter showed excellent removal capacity. PMID:16233018

  9. Crystal structure of Ag2(μ-SCN)2(NH3)4.

    PubMed

    Müller, Thomas G; Kraus, Florian

    2016-07-01

    Di-μ-thio-cyanato-bis-[diamminesilver(I)], [Ag2(μ-SCN)2(NH3)4], was synthesized by the reaction of AgSCN with anhydrous liquid ammonia. In the binuclear mol-ecule, the Ag(I) atom is coordinated by two ammine ligands and the S atom of one thio-cyanate ligand. Two of these [Ag(SCN)(NH3)2] units are bridged by the S atoms of the thio-cyanate anions at longer distances, leading to a dimer with point group symmetry C 2. The distance between the Ag(I) atoms in the dimer is at 3.0927 (6) Å within the range of argentophilic inter-actions. The crystal structure displays N-H⋯N and N-H⋯S hydrogen-bonding inter-actions that build up a three-dimensional network. PMID:27555922

  10. Relativity, gold, closed-shell interactions, and CsAu.NH3.

    PubMed

    Pyykkö, Pekka

    2002-10-01

    The chemical properties of gold are strongly influenced by relativistic effects. One example is the large electronegativity of Au, which qualitatively explains the stability of (solid or liquid) cesium auride, Cs(+)Au(-), and other systems with Au(-) ions. An especially impressive compound is CsAu.NH(3), the structure and bonding of which are discussed. Future possibilities for finding further aurides are outlined. PMID:12370896

  11. Effect of TiO2 calcination temperature on the photocatalytic oxidation of gaseous NH3.

    PubMed

    Wu, Hongmin; Ma, Jinzhu; Zhang, Changbin; He, Hong

    2014-03-01

    Carbon-modified titanium dioxide (TiO2) was prepared by a sol-gel method using tetrabutyl titanate as precursor, with calcination at various temperatures, and tested for the photocatalytic oxidation (PCO) of gaseous NH3 under visible and UV light. The test results showed that no samples had visible light activity, while the TiO2 calcined at 400°C had the best UV light activity among the series of catalysts, and was even much better than the commercial catalyst P25. The catalysts were then characterized by X-ray diffractometry, Brunauer-Emmett-Teller adsorption analysis, Raman spectroscopy, thermogravimetry/differential scanning calorimetry coupled with mass spectrometry, ultraviolet-visible diffuse reflectance spectra, photoluminescence spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy. It was shown that the carbon species residuals on the catalyst surfaces induced the visible light adsorption of the samples calcined in the low temperature range (< 300°C). However, the surface acid sites played a determining role in the PCO of NH3 under visible and UV light over the series of catalysts. Although the samples calcined at low temperatures had very high SSA, good crystallinity, strong visible light absorption and also low PL emission intensity, they showed very low PCO activity due to their very low number of acid sites for NH3 adsorption and activation. The TiO2 sample calcined at 400°C contained the highest number of acid sites among the series of catalysts, therefore showing the highest performance for the PCO of NH3 under UV light. PMID:25079281

  12. NH3 quantum rotators in Hofmann clathrates: intensity and width of rotational transition lines

    NASA Astrophysics Data System (ADS)

    Vorderwisch, Peter; Sobolev, Oleg; Desmedt, Arnaud

    2004-07-01

    Inelastic structure factors for rotational transitions of uniaxial NH3 quantum rotators, measured in a Hofmann clathrate with biphenyl as guest molecule, agree with those calculated for free rotators. A finite intrinsic line width, found for rotational transitions involving the rotational level j=3 at low temperature, supports a recently suggested model based on resonant rotor-rotor coupling. Present address: LPCM, CNRS-Université de Bordeaux I, 351 Cours de Libération, Talence F-33405, France.

  13. Photovoltaic performance and the energy landscape of CH3NH3PbI3.

    PubMed

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

    2015-09-21

    Photovoltaic cells with absorbing layers of certain perovskites have power conversion efficiencies up to 20%. Among these materials, CH3NH3PbI3 is widely used. Here we use density-functional theory to calculate the energies and rotational energy barriers of a methylammonium ion in the α or β phase of CH3NH3PbI3 with differently oriented neighbouring methylammonium ions. Our results suggest the methylammonium ions in CH3NH3PbI3 prefer to rotate collectively, and to be parallel to their neighbours. Changes in polarization on rotation of methylammonium ions are two to three times larger than those on relaxation of the lead ion from the centre of its coordination shell. The preferences for parallel configuration and concerted rotation, with the polarisation changes, are consistent with ferroelectricity in the material, and indicate that this polarisation is governed by methylammonium orientational correlations. We show that the field due to this polarisation is strong enough to screen the field hindering charge transport, and find this screening field in agreement with experiment. We examine two possible mechanisms for the effect of methylammonium ion rotation on photovoltaic performance. One is that rearrangement of methylammoniums promotes the creation and transport of charge carriers. Some effective masses change greatly, but changes in band structure with methylammonium rotation are not large enough to explain current-voltage hysteresis behaviour. The second possible mechanism is that polarization screens the hindering electric field, which arises from charge accumulation in the transport layers. Polarization changes on methylammonium rotation favour this second mechanism, suggesting that collective reorientation of methylammonium ions in the bulk crystal are in significant part responsible for the hysteresis and power conversion characteristics of CH3NH3PbI3 photovoltaic cells. PMID:26269196

  14. Computational investigation of NH3 adsorption and dehydrogenation on a W-modified Fe(111) surface.

    PubMed

    Hsiao, Ming-Kai; Su, Chia-Hao; Liu, Ching-Yang; Chen, Hui-Lung

    2015-11-11

    Hydrogen gas will play an important role in the future since it could be a replacement for gasoline, heating oil, natural gas, and other fuels. In previous reports ammonia (NH3), which has a high hydrogen content, provides a promising mode for the transferring and storing of hydrogen for its on-site generation. Therefore, the dehydrogenation of NH3 on a metal surface has been studied widely in the last few decades. In our study, we employed monolayer tungsten metal to modify the Fe(111) surface, denoted as W@Fe(111), and calculated the adsorption and dehydrogenation behaviors of NH3 on W@Fe(111) surface via first-principles calculations based on density functional theory (DFT). The three adsorption sites of the surface, top (T), 3-fold-shallow (S), and 3-fold-deep (D) were considered. The most stable structure of the NHx (x = 0-3) species on the surface of W@Fe(111) have been predicted. The calculated activation energies for NHx (x = 1-3) dehydrogenations are 19.29 kcal mol(-1) (for H2N-H bond activation), 29.17 kcal mol(-1) (for HN-H bond activation) and 27.94 kcal mol(-1) (for N-H bond activation), and the entire process is exothermic by 33.05 kcal mol(-1). To gain detailed knowledge of the catalytic processes of the NH3 molecule on the W@Fe(111) surface, the physical insights between the adsorbate/substrate interaction and interface morphology were subjected to a detailed electronic analysis. PMID:26524324

  15. Comparison among NH3 and GHGs emissive patterns from different housing solutions of dairy farms

    NASA Astrophysics Data System (ADS)

    Baldini, Cecilia; Borgonovo, Federica; Gardoni, Davide; Guarino, Marcella

    2016-09-01

    Agriculture and livestock farming are known to be activities emitting relevant quantities of atmospheric pollutants. In particular, in intensive animal farming, buildings can be identified as a relevant source of ammonia and greenhouse gases. This study aimed at: i) determining the emission factors of NH3, N2O, CH4, and CO2 from different dairy farms in Italy, and ii) assessing the effects of the different floor types and manure-handling systems used, in order to minimize the impact of this important productive sector. A measurement campaign was carried out for 27 months in four naturally ventilated dairy cattle buildings with different floor types, layouts and manure management systems, representative of the most common technologies in the north of Italy. Gas emissions were measured with the "static chamber method": a chamber was placed above the floor farm and an infrared photoacoustic detector (IPD) was used to monitor gas accumulation over time. In the feeding alleys, emissions of NH3 were higher from solid floors than from flushing systems and perforated floors. N2O emissions were significantly different among farms but the absolute values were relatively low. CH4 and CO2 emissions were higher from perforated floors than from other types of housing solution. Regarding the cubicles, the emissions of NH3 were approximately equal from the two housing solution studied. Contrariwise, N2O, CH4 and CO2 emissions were different between the cubicles with rubber mat and those with straw where the highest values were found.

  16. Carbamic acid and carbamate formation in NH{3}:CO{2} ices - UV irradiation versus thermal processes

    NASA Astrophysics Data System (ADS)

    Bossa, J. B.; Theulé, P.; Duvernay, F.; Borget, F.; Chiavassa, T.

    2008-12-01

    Context: We study carbamic acid [ NH{2}COOH] and ammonium carbamate [ NH{2}COO-] [ NH{4}+] formation in interstellar ice analogs. Aims: We demonstrate how carbamic acid [ NH{2}COOH] and ammonium carbamate [ NH{2}COO-] [ NH{4}+] can be formed from both thermal reactions and energetic photons in an NH{3}:CO{2} ice mixture. Methods: Infrared and mass spectroscopy are used to monitor NH{3}:CO{2} ice mixture evolution during both warming and VUV photon irradiation. Results: Carbamic acid and ammonium carbamate can be produced thermally in a 1:1 ratio from NH{3} and CO{2} above 80 K. They can be also formed in a 28:1 ratio by less efficient processes such as energetic photons. Our study and its results provide fresh insight into carbamic acid formation in interstellar ices. Conclusions: We demonstrate that care is required to separate irradiation-induced reactivity from purely thermal reactivity in ices in which ammonia and carbon dioxide are both present. From an interstellar chemistry point of view, carbamic acid and ammonium carbamate are readily produced from the ice mantle of a typical interstellar grain and should therefore be a detectable species in molecular clouds.

  17. Illumination dependent carrier dynamics of CH3NH3PbBr3 perovskite

    NASA Astrophysics Data System (ADS)

    Chen, Sheng; Wen, Xiaoming; Huang, Shujuan; Sheng, Rui; Green, Martin A.; Ho-Baillie, Anita

    2015-12-01

    The excellent light harvesting properties and potentially low cost fabrication of organometal halide perovskites have attracted great attention in their application as solar cell device. Apart from the general advantages of organic-inorganic perovskite, CH3NH3PbBr3 has a larger bandgap (~2.3eV) suitable to be the top cell in a tandem solar device. Here we use steady-state and time-resolved photoluminescence (PL) techniques to investigate the photophysical behaviour of CH3NH3PbBr3 perovskite including its carrier dynamics under continuous illumination. Samples were studied under different illumination conditions and the following observations were made: (1) defect assisted recombination is dominant under low excitation under nano-second scale measurement, (2) bimolecular and Auger recombinations dominate under high excitation under the minute timescale measurement, (3) the magnitude PL decay traces decrease over time under continuous excitation. We propose that both the density of photo-generated free carriers and the density of mobile ions have an impact on the carrier dynamic of CH3NH3PbBr3. This finding provides insights into the photophysical properties of perovskite materials.

  18. Development and evaluation of optical fiber NH3 sensors for application in air quality monitoring

    NASA Astrophysics Data System (ADS)

    Huang, Yu; Wieck, Lucas; Tao, Shiquan

    2013-02-01

    Ammonia is a major air pollutant emitted from agricultural practices. Sources of ammonia include manure from animal feeding operations and fertilizer from cropping systems. Sensor technologies with capability of continuous real time monitoring of ammonia concentration in air are needed to qualify ammonia emissions from agricultural activities and further evaluate human and animal health effects, study ammonia environmental chemistry, and provide baseline data for air quality standard. We have developed fiber optic ammonia sensors using different sensing reagents and different polymers for immobilizing sensing reagents. The reversible fiber optic sensors have detection limits down to low ppbv levels. The response time of these sensors ranges from seconds to tens minutes depending on transducer design. In this paper, we report our results in the development and evaluation of fiber optic sensor technologies for air quality monitoring. The effect of change of temperature, humidity and carbon dioxide concentration on fiber optic ammonia sensors has been investigated. Carbon dioxide in air was found not interfere the fiber optic sensors for monitoring NH3. However, the change of humidity can cause interferences to some fiber optic NH3 sensors depending on the sensor's transducer design. The sensitivity of fiber optic NH3 sensors was found depends on temperature. Methods and techniques for eliminating these interferences have been proposed.

  19. Ammonia mobility in chabazite: insight into the diffusion component of the NH3-SCR process.

    PubMed

    O'Malley, Alexander J; Hitchcock, Iain; Sarwar, Misbah; Silverwood, Ian P; Hindocha, Sheena; Catlow, C Richard A; York, Andrew P E; Collier, P J

    2016-06-29

    The diffusion of ammonia in commercial NH3-SCR catalyst Cu-CHA was measured and compared with H-CHA using quasielastic neutron scattering (QENS) and molecular dynamics (MD) simulations to assess the effect of counterion presence on NH3 mobility in automotive emission control relevant zeolite catalysts. QENS experiments observed jump diffusion with a jump distance of 3 Å, giving similar self-diffusion coefficient measurements for both Cu- and H-CHA samples, in the range of ca. 5-10 × 10(-10) m(2) s(-1) over the measured temperature range. Self-diffusivities calculated by MD were within a factor of 6 of those measured experimentally at each temperature. The activation energies of diffusion were also similar for both studied systems: 3.7 and 4.4 kJ mol(-1) for the H- and Cu-chabazite respectively, suggesting that counterion presence has little impact on ammonia diffusivity on the timescale of the QENS experiment. An explanation is given by the MD simulations, which showed the strong coordination of NH3 with Cu(2+) counterions in the centre of the chabazite cage, shielding other molecules from interaction with the ion, and allowing for intercage diffusion through the 8-ring windows (consistent with the experimentally observed jump length) to carry on unhindered. PMID:27306298

  20. Ultraviolet-gas phase and -photocatalytic synthesis from CO and NH3.

    PubMed

    Hubbard, J S; Voecks, G E; Hobby, G L

    1975-08-01

    The major photoproduct obtained on irradiation of gaseous NH3 and CO mixtures is ammonium cyanate; lesser amounts of urea, biurea, biuret semi-carbazide, formamide and cyanide were observed. The formation of the major gas phase photolysis product may be rationalized by the following reaction sequence: (see article). Urea is probably formed from NH4NCO in a thermal reaction while formamide may result from the disproportionation of NH2CO. Photocatalytic syntheses of 14C-urea, -formamide, and -formadehyde are effected by irradiation of 14CO and NH3 in the presence of Vycor, silica gel, or volcanic ash shale surfaces. These syntheses are catalyzed by ultraviolet wavelengths longer than those absorbed by the gaseous reactants. The syntheses are also effected when the surface material is first irradiated in the presence of CO followed by a dark incubation with NH3. Apparently, the initiating step is a light dependent formation of a reactive form of CO on the surface. A discussion is given on the possible contribution of these reactions to the abiotic synthesis of organic nitrogen compounds on Mars, on the primitive Earth and in interstellar space. PMID:1159801

  1. VizieR Online Data Catalog: MSX high-contrast IRDCs with NH3 (Chira+,

    NASA Astrophysics Data System (ADS)

    Chira, R.-A.; Beuther, H.; Linz, H.; Walmsley, C. M.; Menten; K. M.; Bonfman, L.

    2013-02-01

    Based on MSX data, a catalogue of more than 10,000 candidate IRDCs was compiled. From this catalogue we selected a complete sample of northern hemisphere high-contrast IRDCs with Galactic longitudes >=19.27° (and nine exceptions with Galactic longitudes <19°). The sample was observed in ammonia (1,1) and (2,2) inversion transitions with the Effelsberg 100-m telescope. NH3 parameters are derived for 109 sample sources. For each source galactic coordinates, brightness temperatures, line width FWHMs and optical depths of (1,1) and (2,2) inversion lines and LSR velocity of (1,1) inversion line are given. Furthermore, we derived the rotation and kinetic temperatures, ammonia column densities, kinematic distances and virial masses using the NH3 data. In addition, notes about whether the sources being associated with Spitzer sources or not are given. Using ATLASGAL data, the 870 micron flux densities gas masses, virial parameters, H2 column densities and NH3 abundances are given. In addition, we listed the sample sources where no ammonia which did not fulfil our selection criteria. (4 data files).

  2. Imaging studies of the photodissociation of NH3+ and ND3+ cations.

    PubMed

    Webb, Alexander D; Nahler, N Hendrik; Ashfold, Michael N R

    2009-04-23

    Velocity map ion imaging methods have been used to study the photofragmentation dynamics of state-selected NH3+ and ND3+ cations. The cations were prepared in selected nu2+ bending vibrational levels of the ground (x2A'') electronic state by two-photon resonant, three-photon ionization of NH3(ND3), via several different nu2' levels of the and ' Rydberg states. Subsequent excitation to the A2E state by absorption of a 207.6 nm photon resulted in N-H(D) bond fission and NH2+(ND2+) fragment ion formation. These fragments exhibit isotropic recoil velocity distributions, which peak at low kinetic energy but extend to the maximum allowed by energy conservation. Such findings accord with conclusions from earlier electron induced photoionization and photoelectron-photoion coincidence studies of NH3 at similar total energies (defined relative to the ground-state neutral) and, as previously, can be rationalized in terms of excitation to the Jahn-Teller distorted state, rapid radiationless transfer via one or more conical intersections linking the and state potential energy surfaces (PESs) and subsequent unimolecular decay on the latter PES. Weak NH2+ and NH+ fragment ion signals are also observed when exciting with the ionization laser only; imaging these fragment ions provides some insights into their likely formation mechanisms. PMID:19216561

  3. SIMPLE DESIGN FOR AUTOMATION OF TUNGSTEN(VI) OXIDE TECHNIQUE FOR MEASUREMENT OF NH3, AND HNO3

    EPA Science Inventory

    The tungstic acid technique for collection and analysis of NH3 and HNO3 concentrations in the ambient air has been automated in a simple and cost-effective design. The design allows complete separation of HNO3 and NH3 during detection. Unattended operation in field trials has bee...

  4. Kinetics and gas-surface dynamics of GaN homoepitaxial growth using NH 3-seeded supersonic molecular beams

    NASA Astrophysics Data System (ADS)

    McGinnis, A. J.; Thomson, D.; Davis, R. F.; Chen, E.; Michel, A.; Lamb, H. H.

    2001-11-01

    The kinetics of homoepitaxial growth of GaN thin films on metal-organic chemical vapor deposition (MOCVD)-grown GaN(0 0 0 1)/AlN/6H-SiC substrates was probed using NH 3-seeded supersonic molecular beams. NH 3 was seeded in H 2 and He and antiseeded in N 2 and Ar in order to obtain incident kinetic energies of 0.08-1.8 eV. Nozzle temperatures of 35-600 °C were used to adjust the NH 3 internal energy. Intense NH 3 beams (fluxes >2×10 15 cm-2 s-1 at the substrate) are produced for low seeding percentages (<5%) in the lighter carrier gases, because the heavier species (NH 3) is focused along the centerline of the beam. The NH 3 flux is proportional to the ratio of its molecular weight to the average molecular weight of the binary gas mixture. A steady-state Langmuir-Hinshelwood kinetics model was used to extract zero-coverage NH 3 sticking coefficient ( αNH 30) values from GaN growth kinetics data. An αNH 30 value of 0.14 at 750 °C was determined using seeded supersonic beams of NH 3 in He with incident kinetic energies of 0.4-0.5 eV. In comparison, GaN growth rates using low-energy NH 3 molecules (0.03 eV) from a leak valve indicate an αNH 30 of 0.29. Growth rate measurements using NH 3 beams with kinetic energies of 0.08-1.8 eV confirmed that αNH 30 generally decreases with increasing incident kinetic energy, leading us to conclude that NH 3 chemisorption on GaN(0 0 0 1) is unactivated and occurs via a precursor-mediated mechanism. Internal energy enhancement of NH 3 chemisorption via a precursor-mediated channel is proposed to explain the effects of nozzle temperature on GaN growth kinetics. The effects of NH 3 incident kinetic energy on film morphology are indirect. Rough, highly faceted films are observed under Ga-limited growth conditions. The surface morphology of films grown under NH 3-limited conditions changes from rough to smooth as the effective V/III ratio is decreased.

  5. Transparent CH3NH3SnCl3/Al-ZnO p-n heterojunction diode

    NASA Astrophysics Data System (ADS)

    Kumar, Sunil; Ansari, Mohd. Zubair; Khare, Neeraj

    2016-05-01

    A p-type Organic inorganic tin chloride (CH3NH3SnCl3) perovskite thin film has been synthesized by solution method. An n-type 1% Al doped ZnO (AZO) film has been deposited on FTO substrate by ultrasonic assisted chemical vapor deposition technique. A transparent CH3NH3SnCl3/AZO p-n heterojunction diode has been fabricated by spin coating technique. CH3NH3SnCl3/AZO p-n heterojunction shows 75% transparency in the visible region. I-V characteristic of CH3NH3SnCl3/AZO p-n heterojunction shows rectifying behavior of the diode. The diode parameters calculated as ideality factor η=2.754 and barrier height V= 0.76 eV. The result demonstrates the potentiality of CH3NH3SnCl3/AZO p-n heterojunction for transparent electronics.

  6. Melting phase relations in the system H2O - NH3 at high pressure

    NASA Astrophysics Data System (ADS)

    Sugimura, E.; Hirose, K.; Komabayashi, T.; Ohishi, Y.; Hirao, N.; Dubrovinsky, L. S.

    2012-12-01

    The density models of Uranus and Neptune constrained by their gravitational moments from Voyager mission suggest that mantles of these planets may be predominantly comprised of water (H2O), methane (CH4), and ammonia (NH3). The impurities in pure water would greatly influence the phase relations in the water-rich system expected in the icy mantle, which must be known to construct a plausible planetary model. One of important effects of the impurity is on the liquidus temperature (Tliq), since it decides the actual presence of solid phase within the icy mantle. In order to determine Tliq in H2O-rich region of the H2O - CH4 - NH3 ternary system, the melting phase relations in the H2O - CH4 and H2O - NH3 systems must be accurately known. However, previous melting experiments on each binary system were limited to several gigapascals, thus need to be explored to higher P-T conditions for application in interiors of Uranus and Neptune. We have investigated high-pressure (P) and -temperature (T) melting phase relations in the H2O - NH3 system based on a combination of visual observation and angle-dispersive x-ray diffraction (XRD) measurements at BL10XU, SPring-8. High-P-T conditions were generated in an externally-resistive heated diamond anvil cell (DAC). Starting material was 20wt% NH3 aqueous solution whose composition was checked via Tliq of the solution measured in a DAC at near atmospheric pressure. The aqueous solution was loaded into a gold-lined hole in a preindented rhenium gasket in order to insulate the sample from rhenium. Pressure was determined from the unit-cell volume of gold liner. Melting and freezing of the sample were detected by monitoring disappearance/appearance of diffraction peaks of solid and diffuse scattering of liquids, as well as observing melting/crystallization of crystal grains under microscope. Up to 20 GPa at room temperature, in addition to ice VII, diffraction peaks of bcc-like phase, which is most likely to be the reported phase VI

  7. Two-center three-electron bonding in ClNH3 revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH3 → ClNH2 + H reaction

    NASA Astrophysics Data System (ADS)

    Moradi, Christopher P.; Xie, Changjian; Kaufmann, Matin; Guo, Hua; Douberly, Gary E.

    2016-04-01

    Pyrolytic dissociation of Cl2 is employed to dope helium droplets with single Cl atoms. Sequential addition of NH3 to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH3 → ClNH2 + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C3v symmetric top. Frequency shifts from NH3 and dipole moment measurements are consistent with a ClNH3 complex containing a relatively strong two-center three-electron (2c-3e) bond. The nature of the 2c-3e bonding in ClNH3 is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. Computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH3Cl and Cl-HNH2, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH3 → HCl + NH2.

  8. Two-center three-electron bonding in ClNH3 revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH3 → ClNH2 + H reaction.

    PubMed

    Moradi, Christopher P; Xie, Changjian; Kaufmann, Matin; Guo, Hua; Douberly, Gary E

    2016-04-28

    Pyrolytic dissociation of Cl2 is employed to dope helium droplets with single Cl atoms. Sequential addition of NH3 to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH3 → ClNH2 + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C3v symmetric top. Frequency shifts from NH3 and dipole moment measurements are consistent with a ClNH3 complex containing a relatively strong two-center three-electron (2c-3e) bond. The nature of the 2c-3e bonding in ClNH3 is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. Computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH3Cl and Cl-HNH2, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH3 → HCl + NH2. PMID:27131544

  9. Rovibrational spectra of ammonia. II. Detailed analysis, comparison, and prediction of spectroscopic assignments for 14NH3,15NH3, and 14ND3

    NASA Astrophysics Data System (ADS)

    Huang, Xinchuan; Schwenke, David W.; Lee, Timothy J.

    2011-01-01

    Several aspects of ammonia rovibrational spectra have been investigated using the new HSL-2 potential energy surface that includes an approximate correction for nonadiabatic effects. The unprecedented accuracy of rovibrational energy levels and transition energies computed using HSL-2 was demonstrated in Part I of this study. For 14NH3, new assignments for a few ν3 + ν4 band transitions and energy levels are suggested, and discrepancies between computed and HITRAN energy levels in the 2ν4 band are analyzed (2ν4 is the most difficult band below 5000 cm-1). New assignments are suggested for existing or missing 2ν4 levels. Several new vibrational bands are identified from existing, unassigned HITRAN data, including 2ν2 + ν4, (ν3 + ν4) -A'/A'', ν1 + 2ν2, and 2ν2 + 2ν4. The strong mixing between the 2ν4 and 2ν2 + ν4 bands is carefully examined and found to be the source of the difficulties in the experimental modeling of 2ν4. Discussion is presented for preliminary J = 10 results, where the overall root-mean-square error is estimated to be less than 0.039 cm-1. The analysis of the 4ν2 band demonstrates both the reliability and the accuracy of predictions from HSL-2. The full list of computed J = 0 band origins (with assignments) and the inversion splittings up to 7000-8000 cm-1 above the zero-point energy are presented. J = 0-2 levels are reported for those bands below 5100 cm-1 that are missing from the HITRAN database. For 15NH3, excellent agreement is found for the available ν2 and ν3 + ν4(E) transition energies, but significant deficiencies are shown for HITRAN levels and several corrections are suggested. The 15N isotopic effects are presented for the J = 0-6 levels of 13 HITRAN bands. For 14ND3, we reproduce the pure rotational inversion spectra line frequencies with an accuracy similar to that for 14NH3. However, it is not possible to reproduce simultaneously all four pairs of inversion-split vibrational fundamentals to better than 0.05 cm-1

  10. Rovibrational spectra of ammonia. II. Detailed analysis, comparison, and prediction of spectroscopic assignments for 14NH3, 15NH3, and 14ND3.

    PubMed

    Huang, Xinchuan; Schwenke, David W; Lee, Timothy J

    2011-01-28

    Several aspects of ammonia rovibrational spectra have been investigated using the new HSL-2 potential energy surface that includes an approximate correction for nonadiabatic effects. The unprecedented accuracy of rovibrational energy levels and transition energies computed using HSL-2 was demonstrated in Part I of this study. For (14)NH(3), new assignments for a few ν(3) + ν(4) band transitions and energy levels are suggested, and discrepancies between computed and HITRAN energy levels in the 2ν(4) band are analyzed (2ν(4) is the most difficult band below 5000 cm(-1)). New assignments are suggested for existing or missing 2ν(4) levels. Several new vibrational bands are identified from existing, unassigned HITRAN data, including 2ν(2) + ν(4), (ν(3) + ν(4)) -A(')∕A("), ν(1) + 2ν(2), and 2ν(2) + 2ν(4). The strong mixing between the 2ν(4) and 2ν(2) + ν(4) bands is carefully examined and found to be the source of the difficulties in the experimental modeling of 2ν(4). Discussion is presented for preliminary J = 10 results, where the overall root-mean-square error is estimated to be less than 0.039 cm(-1). The analysis of the 4ν(2) band demonstrates both the reliability and the accuracy of predictions from HSL-2. The full list of computed J = 0 band origins (with assignments) and the inversion splittings up to 7000-8000 cm(-1) above the zero-point energy are presented. J = 0-2 levels are reported for those bands below 5100 cm(-1) that are missing from the HITRAN database. For (15)NH(3), excellent agreement is found for the available ν(2) and ν(3) + ν(4)(E) transition energies, but significant deficiencies are shown for HITRAN levels and several corrections are suggested. The (15)N isotopic effects are presented for the J = 0-6 levels of 13 HITRAN bands. For (14)ND(3), we reproduce the pure rotational inversion spectra line frequencies with an accuracy similar to that for (14)NH(3). However, it is not possible to reproduce simultaneously all four

  11. Investigation of the Hydrolysis of Perovskite Organometallic Halide CH3NH3PbI3 in Humidity Environment

    PubMed Central

    Zhao, Jiangtao; Cai, Bing; Luo, Zhenlin; Dong, Yongqi; Zhang, Yi; Xu, Han; Hong, Bin; Yang, Yuanjun; Li, Liangbin; Zhang, Wenhua; Gao, Chen

    2016-01-01

    Instability of emerging perovskite organometallic halide in humidity environment is the biggest obstacle for its potential applications in solar energy harvest and electroluminescent display. Understanding the detailed decay mechanism of these materials in moisture is a critical step towards the final appropriate solutions. As a model study presented in this work, in situ synchrotron radiation x-ray diffraction was combined with microscopy and gravimetric analysis to study the degradation process of CH3NH3PbI3 in moisture, and the results reveal that: 1) intermediate monohydrated CH3NH3PbI3·H2O is detected in the degradation process of CH3NH3PbI3 and the final decomposition products are PbI2 and aqueous CH3NH3I; 2) the aqueous CH3NH3I could hardly further decompose into volatile CH3NH2, HI or I2; 3) the moisture disintegrate CH3NH3PbI3 and then alter the distribution of the decomposition products, which leads to an incompletely-reversible reaction of CH3NH3PbI3 hydrolysis and degrades the photoelectric properties. These findings further elucidate the picture of hydrolysis process of perovskite organometallic halide in humidity environment. PMID:26924112

  12. Investigation of the Hydrolysis of Perovskite Organometallic Halide CH3NH3PbI3 in Humidity Environment

    NASA Astrophysics Data System (ADS)

    Zhao, Jiangtao; Cai, Bing; Luo, Zhenlin; Dong, Yongqi; Zhang, Yi; Xu, Han; Hong, Bin; Yang, Yuanjun; Li, Liangbin; Zhang, Wenhua; Gao, Chen

    2016-02-01

    Instability of emerging perovskite organometallic halide in humidity environment is the biggest obstacle for its potential applications in solar energy harvest and electroluminescent display. Understanding the detailed decay mechanism of these materials in moisture is a critical step towards the final appropriate solutions. As a model study presented in this work, in situ synchrotron radiation x-ray diffraction was combined with microscopy and gravimetric analysis to study the degradation process of CH3NH3PbI3 in moisture, and the results reveal that: 1) intermediate monohydrated CH3NH3PbI3·H2O is detected in the degradation process of CH3NH3PbI3 and the final decomposition products are PbI2 and aqueous CH3NH3I; 2) the aqueous CH3NH3I could hardly further decompose into volatile CH3NH2, HI or I2; 3) the moisture disintegrate CH3NH3PbI3 and then alter the distribution of the decomposition products, which leads to an incompletely-reversible reaction of CH3NH3PbI3 hydrolysis and degrades the photoelectric properties. These findings further elucidate the picture of hydrolysis process of perovskite organometallic halide in humidity environment.

  13. Investigation of the Hydrolysis of Perovskite Organometallic Halide CH3NH3PbI3 in Humidity Environment.

    PubMed

    Zhao, Jiangtao; Cai, Bing; Luo, Zhenlin; Dong, Yongqi; Zhang, Yi; Xu, Han; Hong, Bin; Yang, Yuanjun; Li, Liangbin; Zhang, Wenhua; Gao, Chen

    2016-01-01

    Instability of emerging perovskite organometallic halide in humidity environment is the biggest obstacle for its potential applications in solar energy harvest and electroluminescent display. Understanding the detailed decay mechanism of these materials in moisture is a critical step towards the final appropriate solutions. As a model study presented in this work, in situ synchrotron radiation x-ray diffraction was combined with microscopy and gravimetric analysis to study the degradation process of CH3NH3PbI3 in moisture, and the results reveal that: 1) intermediate monohydrated CH3NH3PbI3·H2O is detected in the degradation process of CH3NH3PbI3 and the final decomposition products are PbI2 and aqueous CH3NH3I; 2) the aqueous CH3NH3I could hardly further decompose into volatile CH3NH2, HI or I2; 3) the moisture disintegrate CH3NH3PbI3 and then alter the distribution of the decomposition products, which leads to an incompletely-reversible reaction of CH3NH3PbI3 hydrolysis and degrades the photoelectric properties. These findings further elucidate the picture of hydrolysis process of perovskite organometallic halide in humidity environment. PMID:26924112

  14. Growth of large CH3NH3PbX3 (X=I, Br) single crystals in solution

    NASA Astrophysics Data System (ADS)

    Su, J.; Chen, D. P.; Lin, C. T.

    2015-07-01

    We present the results on the successful growth of CH3NH3PbX3 (X=I, Br) single crystals sized up to centimeters using hydrohalic acid solution method. Large crystals with perfect morphology were obtained by a very slow cooling rate of 0.1-0.2 °C/h. The lattice parameters of tetragonal CH3NH3PbI3 and cubic CH3NH3PbBr3 were estimated using the Rietveld refinement method. Study of crystal nucleus, habits and dimensions indicates that these are strongly dependent on the supercooling of solution during crystal growth, in which the (0 0 1)/(0 1 0) for CH3NH3PbI3 and {1 0 0} for CH3NH3PbBr3 always exhibit the largest faces on the as-grown crystals. A structural phase transition of tetragonal/cubic and cubic/tetragonal for the CH3NH3PbI3 single crystals was observed to occur at 62 and 60 °C during the heating and cooling process, respectively. The nonlinear relationship of temperature-dependent solubility for CH3NH3PbI3 in hydrohalic acid was also determined.

  15. Role of phase composition for electronic states in CH3NH3PbI3 prepared from CH3NH3I/PbCl2 solution

    NASA Astrophysics Data System (ADS)

    Naikaew, Atittaya; Prajongtat, Pongthep; Lux-Steiner, Martha Ch.; Arunchaiya, Marisa; Dittrich, Thomas

    2015-06-01

    Modulated surface photovoltage (SPV) spectra have been correlated with the phase composition in layers of CH3NH3PbI3 (MAPbI3) prepared from MAI and PbCl2 and annealed at 100 °C. Depending on the annealing time, different compositions of MAPbI3, MAPbCl3, MACl, PbI2, and an un-identified phase were found. It has been demonstrated that evaporation of MAI and HI is crucial for the development of electronic states in MAPbI3 and that only the appearance and evolution of the phase PbI2 has an influence on electronic states in MAPbI3. With ongoing annealing, (i) a transition from p- to n-type doping was observed with the appearance of PbI2, (ii) shallow acceptor states were distinguished and disappeared in n-type doped MAPbI3, and (iii) a minimum of the SPV response related to deep defect states was found at the transition from p- to n-type doping. The results are discussed with respect to the further development of highly efficient and stable MAPbI3 absorbers for solar cells.

  16. Estimation of NH3 emissions from a naturally ventilated livestock farm using local-scale atmospheric dispersion modelling

    NASA Astrophysics Data System (ADS)

    Hensen, A.; Loubet, B.; Mosquera, J.; van den Bulk, W. C. M.; Erisman, J. W.; Dämmgen, U.; Milford, C.; Löpmeier, F. J.; Cellier, P.; Mikuška, P.; Sutton, M. A.

    2009-12-01

    Agricultural livestock represents the main source of ammonia (NH3) in Europe. In recent years, reduction policies have been applied to reduce NH3 emissions. In order to estimate the impacts of these policies, robust estimates of the emissions from the main sources, i.e. livestock farms are needed. In this paper, the NH3 emissions were estimated from a naturally ventilated livestock farm in Braunschweig, Germany during a joint field experiment of the GRAMINAE European project. An inference method was used with a Gaussian-3D plume model and with the Huang 3-D model. NH3 concentrations downwind of the source were used together with micrometeorological data to estimate the source strength over time. Mobile NH3 concentration measurements provided information on the spatial distribution of source strength. The estimated emission strength ranged between 6.4±0.18 kg NH3 d-1 (Huang 3-D model) and 9.2±0.7 kg NH3 d-1 (Gaussian-3D model). These estimates were 94% and 63% of what was obtained using emission factors from the German national inventory (9.6 kg d-1 NH3). The effect of deposition was evaluated with the FIDES-2D model. This increased the emission estimate to 11.7 kg NH3 d-1, showing that deposition can explain the observed difference. The daily pattern of the source was correlated with net radiation and with the temperature inside the animal houses. The daily pattern resulted from a combination of a temperature effect on the source concentration together with an effect of variations in free and forced convection of the building ventilation rate. Further development of the plume technique is especially relevant for naturally ventilated farms, since the variable ventilation rate makes other emission measurements difficult.

  17. Estimation of NH3 emissions from a naturally ventilated livestock farm using local-scale atmospheric dispersion modelling

    NASA Astrophysics Data System (ADS)

    Hensen, A.; Loubet, B.; Mosquera, J.; van den Bulk, W. C. M.; Erisman, J. W.; Dämmgen, U.; Milford, C.; Löpmeier, F. J.; Cellier, P.; Mikuška, P.; Sutton, M. A.

    2009-01-01

    Agricultural livestock represents the main source of ammonia (NH3) in Europe. In recent years, reduction policies have been applied to reduce NH3 emissions. In order to estimate the impacts of these policies, robust estimates of the emissions from the main sources, i.e. livestock farms are needed. In this paper, the NH3 emissions were estimated from a naturally ventilated livestock farm in Braunschweig, Germany during a joint field experiment of the GRAMINAE European project. An inference method was used with a Gaussian-3-D plume model and a local-scale dispersion and deposition model (FIDES-2-D). NH3 concentrations downwind of the source were used together with micrometeorological data to estimate the source strength over time. Mobile NH3 concentration measurements provided information on the spatial distribution of source strength. The estimated emission strength ranged between 6.0±0.17 kg NH3 d-1 (FIDES-2-D model) and 9.2±0.7 kg NH3 d-1 (Gaussian model). These estimates were 94% and 63% of what was obtained using emission factors from the German national inventory (9.6 kg d-1 NH3. However, the FIDES-2-D approach was shown to be very sensitive to the source size, the roughness height and to whether deposition was taken into account downwind of the source. Accounting for deposition in FIDES-2-D gives a potential emission estimate of 11.7 kg NH3 d-1, showing that deposition can explain the observed difference. The daily pattern of the source was correlated with net radiation and with the temperature inside the animal houses. The daily pattern resulted from a combination of a temperature effect on the source concentration together with an effect of variations in free and forced convection of the building ventilation rate. Further development of the plume technique is especially relevant for naturally ventilated farms, since the variable ventilation rate makes other emission measurements difficult.

  18. Overtone, 2NH (ν1 + ν3) spectroscopy of 15NH3-Ar

    NASA Astrophysics Data System (ADS)

    Vanfleteren, T.; Földes, T.; Herman, M.; Di Lonardo, G.; Fusina, L.

    2015-12-01

    We report on the observation of the Π (11; 2NH) ← Σ (00; ground state) band in 15NH3-Ar, with origin at 6615.943 cm-1, using jet-cooled cw-cavity ring-down spectroscopy. The rotational temperature is estimated to be 7 K. Nineteen rotational lines were assigned. Perturbations were evidenced from anomalous line positions and line widths, but not unraveled. Upper state rotational constants were obtained from the analysis of the nine unperturbed R/P lines. The e-symmetry upper state predissociation lifetimes appear to decrease with J‧, from about 1.2 ns to 250 ps from J‧ = 1 to 9.

  19. Femtosecond two-photon ionization of fluid NH3 at 9.3 eV

    NASA Astrophysics Data System (ADS)

    Urbanek, Janus; Dahmen, Annika; Torres-Alacan, Joel; Vöhringer, Peter

    2013-03-01

    Liquid and supercritical ammonia (NH3) is photo-ionized at an energy of 9.3 eV with 100-fs duration pulses at a wavelength of 266 nm. The ionization involves two photons and generates fully solvated electrons via the conduction band of the solvent within the time resolution of the experiment. The dynamics of their ensuing geminate recombination is followed in real time with femtosecond near-infrared (IR) probe pulses. The recombination mechanism can be understood as an ion-pair mediated reaction. The electron survival probability is found to be in quantitative agreement with the classical Onsager theory for the initial recombination of ions.

  20. Spectroscopic line parameters of NH3 and PH3 in the far infrared

    NASA Technical Reports Server (NTRS)

    Husson, N.; Goldman, A.; Orton, G.

    1982-01-01

    NH3 and PH3 rotation and rotation-inversion line parameters in the far to medium IR are calculated for remote sounding purposes of planetary atmospheres; 1607 lines of (N-14)H3, 362 lines of (N-15)H3 and 325 lines of PH3 are compiled. The absolute intensity formulation has been reviewed in the case of rotation and rotation-inversion lines of molecules with C(3v) symmetry. The justification for the general agreement between the authors, and comparisons with other published expressions are given.

  1. H2O/Ni(100) and NH3/Ni(100) - A computational approach

    NASA Technical Reports Server (NTRS)

    Bauschlicher, C. W., Jr.

    1985-01-01

    The adsorption of NH3 and H2O on the Ni(100) is treated using a cluster model. The adsorption is found to have only a small effect on the HXH angle. Rotation about the principal ligand axis requires virtually no energy. Ligand tilts of 15 deg are found to require small amounts of energy, leading to the suggestion that the ESDIAD signal is a result of excited tilting modes, not a change in the HXH angle. For H2O additional bending modes are considered and all are found to be quite flat in energy.

  2. Construction of Spectroscopically Accurate IR Linelists for NH3 and CO2

    NASA Astrophysics Data System (ADS)

    Huang, X.; Schwenke, D. W.; Lee, T. J.

    2011-05-01

    The strategy of using the best theory together with high-resolution experi-ment was applied to NH3 and CO2: that is, refine a highly accurate ab initio PES with the most reliable HITRAN or pure experimental data. With 0.01 - 0.02 cm-1 accuracy, our calculations are clearly far beyond simply reproducing experimental data, but are also capable of revealing many deficiencies in the cur- rent experimental analysis of the various isotopologues, as well as provide reliable predictions with similar accuracy.

  3. Comparison of Recombination Dynamics in CH3NH3PbBr3 and CH3NH3PbI3 Perovskite Films: Influence of Exciton Binding Energy.

    PubMed

    Yang, Ye; Yang, Mengjin; Li, Zhen; Crisp, Ryan; Zhu, Kai; Beard, Matthew C

    2015-12-01

    Understanding carrier recombination in semiconductors is a critical component when developing practical applications. Here we measure and compare the monomolecular, bimolecular, and trimolecular (Auger) recombination rate constants of CH3NH3PbBr3 and CH3NH3PbI3. The monomolecular and bimolecular recombination rate constants for both samples are limited by trap-assisted recombination. The bimolecular recombination rate constant for CH3NH3PbBr3 is ∼3.3 times larger than that for CH3NH3PbI3 and both are in line with that found for radiative recombination in other direct-gap semiconductors. The Auger recombination rate constant is 4 times larger in lead-bromide-based perovskite compared with lead-iodide-based perovskite and does not follow the reduced Auger rate when the bandgap increases. The increased Auger recombination rate, which is enhanced by Coulomb interactions, can be ascribed to the larger exciton binding energy, ∼40 meV, in CH3NH3PbBr3 compared with ∼13 meV in CH3NH3PbI3. PMID:26551036

  4. Crystal structure of [Co(NH3)6][Co(CO)4]2

    PubMed Central

    Müller, Thomas G.; Kraus, Florian

    2015-01-01

    Hexaamminecobalt(II) bis­[tetra­carbonyl­cobaltate(-I)], [Co(NH3)6][Co(CO)4]2, was synthesized by reaction of liquid ammonia with Co2(CO)8. The CoII atom is coordinated by six ammine ligands. The resulting polyhedron, the hexa­amminecobalt(II) cation, exhibits point group symmetry -3. The Co-I atom is coordinated by four carbonyl ligands, leading to a tetra­carbonyl­cobaltate(−I) anion in the shape of a slightly distorted tetra­hedron, with point group symmetry 3. The crystal structure is related to that of high-pressure BaC2 (space group R-3m), with the [Co(NH3)6]2+ cations replacing the Ba sites and the [Co(CO)4]− anions replacing the C sites. N—H⋯O hydrogen bonds between cations and anions stabilize the structural set-up in the title compound. PMID:26594524

  5. Enhanced NH3-Sensitivity of Reduced Graphene Oxide Modified by Tetra-α-Iso-Pentyloxymetallophthalocyanine Derivatives.

    PubMed

    Li, Xiaocheng; Wang, Bin; Wang, Xiaolin; Zhou, Xiaoqing; Chen, Zhimin; He, Chunying; Yu, Zheying; Wu, Yiqun

    2015-12-01

    Three kinds of novel hybrid materials were prepared by noncovalent functionalized reduced graphene oxide (rGO) with tetra-α-iso-pentyloxyphthalocyanine copper (CuPc), tetra-α-iso-pentyloxyphthalocyanine nickel (NiPc) and tetra-α-iso-pentyloxyphthalocyanine lead (PbPc) and characterized by Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV-vis), Raman spectra, X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), and atomic force microscope (AFM). The as-synthesized MPc/rGO hybrids show excellent NH3 gas-sensing performance with high response value and fast recovery time compared with bare rGO. The enhancement of the sensing response is mainly attributed to the synergism of gas adsorption of MPc to NH3 gas and conducting network of rGO with greater electron transfer efficiency. Strategies for combining the good properties of rGO and MPc derivatives will open new opportunities for preparing and designing highly efficient rGO chemiresistive gas-sensing hybrid materials for potential applications in gas sensor field. PMID:26403926

  6. Enhanced NH3-Sensitivity of Reduced Graphene Oxide Modified by Tetra-α-Iso-Pentyloxymetallophthalocyanine Derivatives

    NASA Astrophysics Data System (ADS)

    Li, Xiaocheng; Wang, Bin; Wang, Xiaolin; Zhou, Xiaoqing; Chen, Zhimin; He, Chunying; Yu, Zheying; Wu, Yiqun

    2015-09-01

    Three kinds of novel hybrid materials were prepared by noncovalent functionalized reduced graphene oxide (rGO) with tetra-α-iso-pentyloxyphthalocyanine copper (CuPc), tetra-α-iso-pentyloxyphthalocyanine nickel (NiPc) and tetra-α-iso-pentyloxyphthalocyanine lead (PbPc) and characterized by Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV-vis), Raman spectra, X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), and atomic force microscope (AFM). The as-synthesized MPc/rGO hybrids show excellent NH3 gas-sensing performance with high response value and fast recovery time compared with bare rGO. The enhancement of the sensing response is mainly attributed to the synergism of gas adsorption of MPc to NH3 gas and conducting network of rGO with greater electron transfer efficiency. Strategies for combining the good properties of rGO and MPc derivatives will open new opportunities for preparing and designing highly efficient rGO chemiresistive gas-sensing hybrid materials for potential applications in gas sensor field.

  7. Paper based platform for colorimetric sensing of dissolved NH3 and CO2.

    PubMed

    Chen, Yu; Zilberman, Yael; Mostafalu, Pooria; Sonkusale, Sameer R

    2015-05-15

    Paper, a cheap and ubiquitous material, has great potential to be used as low-cost, portable and biodegradable platform for chemical and biological sensing application. In this paper, we are exploring a low-cost, flexible and reliable method to effectively pattern paper for capturing optical dyes and for flow-based delivery of target samples for colorimetric chemical sensing. In this paper, we target the detection of ammonia (NH3) and carbon dioxide (CO2), two of the important environmental and health biomarkers. By functionalizing the paper platform with diverse cross-reactive dyes sensitive to NH3 and CO2, their selective sensing within a certain pH range, as well as their detection at different concentrations can be achieved. The images of paper based device were captured by a flatbed scanner and processed in MATLAB(®) using a RGB model and PCA for quantitative analysis. Paper based devices with readout using ubiquitous consumer electronic devices (e.g. smartphones, flatbed scanner) are considered promising approaches for disease screening in developing countries with limited resources. PMID:25241151

  8. Decomposition of NH3 and H2 on ZrB2 (0001) surface

    NASA Astrophysics Data System (ADS)

    Walkosz, Weronika; Manandhar, Kedar; Trenary, Michael; Zapol, Peter

    2012-02-01

    Group III nitride semiconductors (AlN, GaN, InN, and their alloys) are important materials for applications in solid-state lighting, optoelectronics, and photovoltaics. However, the lack of lattice--matched substrates for their growth results in less than optimal material quality. In the last decade, zirconium diboride (ZrB2) has been demonstrated as a promising substrate for GaN growth because of its similar lattice constant and thermal expansion properties when compared to the nitride. Moreover, the high electrical conductivity of ZrB2 makes it desirable for many GaN-based device applications. In this talk, we present results of density functional theory calculations for the reactivity of the ZrB2(0001) surface towards the N precursor, NH3, and the carrier gas, H2, commonly used in metal organic chemical vapor deposition and molecular beam epitaxy of nitrides. Two different terminations of ZrB2(0001) surface, the Zr and B terminations, are considered and assessed in terms of their catalytic properties toward NH3 and H2 decomposition. The theoretical results are analyzed in connection with our recent XPS and RAIRS measurements.

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

    PubMed

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

    2016-06-28

    Probes of the Born-Oppenheimer potential energy surfaces governing polyatomic molecules often rely on spectroscopy for the bound regions or collision experiments in the continuum. A combined spectroscopic and half-collision approach to image nuclear dynamics in a multidimensional and multichannel system is reported here. The Rydberg radical NH4 and the double Rydberg anion NH4 (-) represent a polyatomic system for benchmarking electronic structure and nine-dimensional quantum dynamics calculations. Photodetachment of the H(-)(NH3) ion-dipole complex and the NH4 (-) DRA probes different regions on the neutral NH4 PES. Photoelectron energy and angular distributions at photon energies of 1.17, 1.60, and 2.33 eV compare well with quantum dynamics. Photoelectron-photofragment coincidence experiments indicate dissociation of the nascent NH4 Rydberg radical occurs to H + NH3 with a peak kinetic energy of 0.13 eV, showing the ground state of NH4 to be unstable, decaying by tunneling-induced dissociation on a time scale beyond the present scope of multidimensional quantum dynamics. PMID:27369519

  10. NH3 and NH2 in the coma of Comet Brorsen-Metcalf

    NASA Technical Reports Server (NTRS)

    Tegler, Stephen C.; Burke, Luke F.; Wyckoff, Susan; Womack, Maria; Fink, Uwe; Disanti, Michael

    1992-01-01

    Evidence consistent with NH3 ice in the nucleus of Comet Brorsen-Metcalf as the source of the NH2 observed in the comet coma is presented. The distribution of NH2 is symmetric and shows no evidence for jet structure at the 3-sigma significance level above background emission. An azimuthal average of the NH2 image produces an NH2 surface brightness profile for Comet Brorsen-Metcalf which yields a factor of about-10 improvement in the signal-to-noise ratio over previous 1D long-slit NH2 observations, and provides a significant constraint on the NH2 photodissociation time scale in comets. A Monte Carlo simulation of the comet coma, assuming that NH2 is the primary source of NH2, is described and compared with the observations. For an observed production rate, Q(H2O) is approximately equal to 7 x 10 exp 28 molecules/s, collisional effects on the NH3 and NH2 outflow had at most an approximately 10-percent effect on the NH2 surface brightness profile. Because Comet Brorsen-Metcalf showed no significant dust or gas production rate variability, it is argued that steady state conditions best match the comet at the time of the observations.

  11. Rotationally elastic total cross sections for NH3 on electron impact over a wide energy range

    NASA Astrophysics Data System (ADS)

    Vinodkumar, Minaxi; Limbachiya, Chetan; Antony, Bobby

    2011-10-01

    Electron molecule collisions are important over incident energy from very low (0.01 eV) to intermediate and high energies (10 keV). We present rotationally elastic total cross sections for electron scattering for NH3 from 0.01 eV to 2 keV using two different theoretical formalisms. We use Quantemol-N formalism for calculating total cross sections up to threshold of the target and the Spherical Optical Complex Potential (SCOP) method for calculating total cross sections beyond threshold up to 2 keV. Electron molecule collisions are important over incident energy from very low (0.01 eV) to intermediate and high energies (10 keV). We present rotationally elastic total cross sections for electron scattering for NH3 from 0.01 eV to 2 keV using two different theoretical formalisms. We use Quantemol-N formalism for calculating total cross sections up to threshold of the target and the Spherical Optical Complex Potential (SCOP) method for calculating total cross sections beyond threshold up to 2 keV. MVK and BA thank DST, CGL thanks UGC new Delhi.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  13. High resolution NH3 studies of nearby star-forming regions

    NASA Astrophysics Data System (ADS)

    Friesen, Rachel

    2014-07-01

    Stars form within dense molecular cores. These cores are often embedded within larger structures, such as clumps and filaments, particularly in clustered star-forming environments. Indeed, large-scale maps of the continuum emission from dust have revealed the ubiquity of filaments in star-forming regions. The condensation and fragmentation of cores within larger structures is therefore a critical step in the star formation process, but continuum data alone do not provide key information, such as the gas kinematics, needed to discern between evolutionary scenarios. I will present new results from large NH3 studies of nearby star-forming regions, including Taurus and Serpens South. While NH3 primarily traces high density gas, sensitive observations over Serpens South reveal extensive, low brightness emission between the prominent cores and filaments, and show directly the frequently (but not invariably) sharp transitions between turbulent and quiescent gas in the high density regions. I will discuss the hierarchical structure of the dense gas in Serpens South, with comparisons between two- and three-dimensional analysis, and analyze the importance of thermal fragmentation in the filaments and cores over a range of physical scales.

  14. Ambient Ammonia Impact Determined by a Novel NH3 Sensor Utilizing a Quantum Cascade Laser and Photoacoustic Spectroscopy

    NASA Astrophysics Data System (ADS)

    McKarns, T.; Kutter, M. F.

    2015-12-01

    Despite the impact of ambient ammonia (NH3) concentrations on the ecology and our health, the continuous monitoring of NH3 is not yet commonplace. The ammonia molecule has reactive and sticky properties making it difficult to sample, and measuring techniques with sufficient sensitivity and selectivity have been difficult to source. The technique presented is based on photo acoustic spectroscopy (PAS) with a quantum cascade laser (QCL). Developed for a wide range of environments, from the cleanest Swiss mountaintops to rural alpine pastures for cows, the novel detector has shown its reliability and ruggedness for sensing NH3 concentrations from 0-5,000 ppb (part per billions) levels. Rural background measurements performed with the new ECO PHYSICS PAS 87 system and in cooperation with the German Institute for Tropospheric Research, will prove the suitability of this approach to reach continuous automated ambient NH3 values for environmental campaigns.

  15. Control of charge transport in the perovskite CH3 NH3 PbI3 thin film.

    PubMed

    Shi, Jiangjian; Wei, Huiyun; Lv, Songtao; Xu, Xin; Wu, Huijue; Luo, Yanhong; Li, Dongmei; Meng, Qingbo

    2015-03-16

    Carrier density and transport properties in the CH3 NH3 PbI3 thin film have been investigated. It is found that the carrier density, the depletion field, and the charge collection and transport properties in the CH3 NH3 PbI3 absorber film can be controlled effectively by different concentrations of reactants. That is, the carrier properties and the self-doping characteristics in CH3 NH3 PbI3 films are strongly influenced by the reaction thermodynamic and kinetic processes. Furthermore, by employing mixed solvents with ethanol and isopropanol to deposit the CH3 NH3 PbI3 film, the charge collection and transport efficiencies are improved significantly, thereby yielding an overall enhanced cell performance. PMID:25581504

  16. Sources and Impacts of Atmospheric NH3: Current Understanding and Frontiers for Modeling, Measurements, and Remote Sensing in North America

    EPA Science Inventory

    Ammonia (NH3) contributes to widespread adverse health impacts, affects the climate forcing of ambient aerosols, and is a significant component of reactive nitrogen, deposition of which threatens many sensitive ecosystems. Historically, the scarcity of in situ measurements and th...

  17. Detection of a CO and NH3 gas mixture using carboxylic acid-functionalized single-walled carbon nanotubes

    PubMed Central

    2013-01-01

    Carbon nanotubes (CNT) are extremely sensitive to environmental gases. However, detection of mixture gas is still a challenge. Here, we report that 10 ppm of carbon monoxide (CO) and ammonia (NH3) can be electrically detected using a carboxylic acid-functionalized single-walled carbon nanotubes (C-SWCNT). CO and NH3 gases were mixed carefully with the same concentrations of 10 ppm. Our sensor showed faster response to the CO gas than the NH3 gas. The sensing properties and effect of carboxylic acid group were demonstrated, and C-SWCNT sensors with good repeatability and fast responses over a range of concentrations may be used as a simple and effective detection method of CO and NH3 mixture gas. PMID:23286690

  18. A two-color infrared-vacuum ultraviolet laser pulsed field ionization photoelectron study of NH3.

    PubMed

    Bahng, Mi-Kyung; Xing, Xi; Baek, Sun Jong; Ng, C Y

    2005-08-22

    We have observed fully rotationally resolved transitions of the photoelectron vibrational bands 2(4), 2(5), 1(1)2(1), and 1(1)2(3) for ammonia cation (NH3+) by two-color infrared (IR)-vacuum ultraviolet (VUV)- pulsed field-ionization photoelectron (PFI-PE) measurements. By preparing an intermediate rovibrational state of neutral NH(3) with a known parity by IR excitation followed by VUV-PFI-PE measurements, we show that the photoelectron parity can be determined unambiguously. The IR-VUV-PFI-PE measurement of the 2(4) band clearly reveals the formation of both even and odd l states for the photoelectrons, where l is the orbital angular momentum quantum number. This observation is consistent with the conclusion that the lack of inversion symmetry for NH3 and NH3+ allows odd/even l mixings, rendering the production of both odd and even l states for the photoelectrons. Evidence is also found, indicating that the photoionization transitions with DeltaK=0 are strongly favored compared to that with DeltaK=3. For the 2(5), 1(1)2(1), and 1(1)2(3) bands, only DeltaK=0 transitions for the production of even l photoelectron states from the J'K'=2(0) rotational level of NH3(nu1=1) are observed. The preferential formation of even l photoelectron states for these vibrational bands is attributed to the fact that the DeltaK=0 transitions for the formation of odd l photoelectron states from the 2(0) rotational level of NH3(nu1=1) are suppressed by the constraint of nuclear-spin statistics. In addition to information obtained on the photoionization dynamics of NH3, this experiment also provides a more precise value of 3232+/-10 cm-1 for the nu1+ (N-H stretch) vibrational frequency of NH3+. PMID:16164295

  19. Infrared spectra of 15NH3ṡH2O, 2 15NH3ṡH2O, and deuterated forms of ammonia hemihydrate at 90 °K

    NASA Astrophysics Data System (ADS)

    Bertie, John E.; Morrison, Mary M.

    1981-04-01

    The infrared spectra of various deuterated samples of ammonia hemihydrate are reported with some infrared absorption frequencies of 2 15NH3ṡH2O and 15NH3ṡH2O. The spectra of the 15N-substituted samples confirm the previous general assignments, and reveal a third component of ν3(NH3) in NH3ṡH2O. The absorption by 2ND3ṡD2O, NDH2 isolated in 2NH3ṡH2O, and ND2H isolated in 2ND3ṡD2O, show, with the aid of normal coordinate calculations, that the primary splitting of the bands due to ν2 and ν3 of ammonia is multiple site splitting, due to the existence of two types of ammonia molecule in the hemihydrate. The Cs site symmetry of the ammonia molecules is revealed by the stretching vibrations of NH2D in 2NH3ṡH2O but not by the symmetric deformation vibrations of NH2D or ND2H. The stretching vibrations of NH2D in 2NH3ṡH2O at 90 °K also indicate that the type II ammonia molecules occupy both of the orientations which preserve the plane of symmetry. The uncoupled O-D stretching frequencies of HDO in 2NH3ṡH2O confirm the assignment of the two νOH(H2O) bands in the spectrum of 2NH3ṡH2O as largely due to site splitting. The low-frequency νOD(HDO) stretching band is very broad and the corresponding νOH(HDO) band is even broader, as has been seen previously for analogous bands in hexamethylenetetramine hexahydrate. Similarly, one set of isolated νND(NH2D) stretching bands is sharp while the corresponding νNH(ND2H) bands are very broad, as has also been reported previously for solid ammonia. The assignment to rotational vibrations of features below 850 cm-1 in 2NH3ṡH2O is confirmed, but no evidence indicates the degree of mixing of ammonia and water displacements in these vibrations.

  20. Enhanced performance of CH3NH3PbI3- x Cl x perovskite solar cells by CH3NH3I modification of TiO2-perovskite layer interface

    NASA Astrophysics Data System (ADS)

    Wang, Wen; Zhang, Zongbao; Cai, Yangyang; Chen, Jinshan; Wang, Jianming; Huang, Riyan; Lu, Xubing; Gao, Xingsen; Shui, Lingling; Wu, Sujuan; Liu, Jun-Ming

    2016-06-01

    In this work, perovskite solar cells (PSCs) with CH3NH3PbI3- x Cl x as active layer and spiro-OMeTAD as hole-transport media have been fabricated by one-step method. The methylammonium iodide (CH3NH3I) solution with different concentrations is used to modify the interface between mesoporous TiO2 (meso-TiO2) film and CH3NH3PbI3- x Cl x perovskite layer. Several techniques including X-ray diffraction, scanning electron microscopy, optical absorption, electrochemical impedance spectroscopy (EIS) and photoluminescence are used to investigate the effect of the interfacial modification. It is found that the interfacial modification by CH3NH3I enhance the crystallinity and increase the grain size of CH3NH3PbI3- x Cl x layer, and improve the surface wetting properties of perovskite precursor on meso-TiO2 film. The sunlight absorption and external quantum efficiency of PSCs in the visible region with wavelength less than 600 nm have been improved. The Nyquist plots obtained from the EIS suggest that the CH3NH3I modification can reduce the charge recombination rates. The photoluminescence measurement shows that the exciton dissociation in the modified devices is more effective than that in the control samples. The photovoltaic performance of the modified devices can be significantly improved with respect to the reference (control) devices. The CH3NH3I modified devices at the optimized concentration demonstrate the average power conversion efficiency of 12.27 % in comparison with the average efficiency of 9.68 % for the reference devices.

  1. Enhanced performance of CH3NH3PbI3-x Cl x perovskite solar cells by CH3NH3I modification of TiO2-perovskite layer interface.

    PubMed

    Wang, Wen; Zhang, Zongbao; Cai, Yangyang; Chen, Jinshan; Wang, Jianming; Huang, Riyan; Lu, Xubing; Gao, Xingsen; Shui, Lingling; Wu, Sujuan; Liu, Jun-Ming

    2016-12-01

    In this work, perovskite solar cells (PSCs) with CH3NH3PbI3-x Cl x as active layer and spiro-OMeTAD as hole-transport media have been fabricated by one-step method. The methylammonium iodide (CH3NH3I) solution with different concentrations is used to modify the interface between mesoporous TiO2 (meso-TiO2) film and CH3NH3PbI3-x Cl x perovskite layer. Several techniques including X-ray diffraction, scanning electron microscopy, optical absorption, electrochemical impedance spectroscopy (EIS) and photoluminescence are used to investigate the effect of the interfacial modification. It is found that the interfacial modification by CH3NH3I enhance the crystallinity and increase the grain size of CH3NH3PbI3-x Cl x layer, and improve the surface wetting properties of perovskite precursor on meso-TiO2 film. The sunlight absorption and external quantum efficiency of PSCs in the visible region with wavelength less than 600 nm have been improved. The Nyquist plots obtained from the EIS suggest that the CH3NH3I modification can reduce the charge recombination rates. The photoluminescence measurement shows that the exciton dissociation in the modified devices is more effective than that in the control samples. The photovoltaic performance of the modified devices can be significantly improved with respect to the reference (control) devices. The CH3NH3I modified devices at the optimized concentration demonstrate the average power conversion efficiency of 12.27 % in comparison with the average efficiency of 9.68 % for the reference devices. PMID:27356563

  2. Desorption Kinetics of Methanol, Ethanol, and Water from Graphene

    SciTech Connect

    Smith, R. Scott; Matthiesen, Jesper; Kay, Bruce D.

    2014-09-18

    The desorption kinetics of methanol, ethanol, and water from graphene covered Pt(111) are investigated. The temperature programmed desorption (TPD) spectra for both methanol and ethanol have well-resolved first, second, third, and multilayer layer desorption peaks. The alignment of the leading edges is consistent with zero-order desorption kinetics from all layers. In contrast, for water the first and second layers are not resolved. At low water coverages (< 1 ML) the initial desorption leading edges are aligned but then fall out of alignment at higher temperatures. For thicker water layers (10 to 100 ML), the desorption leading edges are in alignment throughout the desorption of the film. The coverage dependence of the desorption behavoir suggests that at low water coverages the non-alignment of the desorption leading edges is due to water dewetting from the graphene substrate. Kinetic simulations reveal that the experimental results are consistent with zero-order desorption. The simulations also show that fractional order desorption kinetics would be readily apparent in the experimental TPD spectra.

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

    NASA Astrophysics Data System (ADS)

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

    Vehicular emissions of reactive nitrogen compounds (RNCs) such as nitric oxide (NO), nitrogen dioxide (NO 2), and ammonia (NH 3) have a substantial impact on urban air quality. NO and NO 2 support the photochemical formation of ozone, and NH 3 is involved in the atmospheric formation of secondary aerosols. Vehicular NO is mainly formed during combustion, whereas NO 2 and NH 3 are both secondary pollutants of the catalytic converter systems. Herein we report on tail-pipe RNC emissions of gasoline-fueled Euro-3- and Euro-4-passenger cars at transient driving from 0 to 150 km h -1. Two sets of 10 in-use vehicles with comparable engine size and mileage were studied with time-resolved chemical ionization-mass spectrometry (CI-MS). Each vehicle was tested in 7 different driving cycles including the legislative European (EDC) and the US FTP-75 driving cycles. Mean emission factors (EFs) for different traffic situations are reported and effects of cold start, velocity, acceleration, and deceleration are discussed. Furthermore, critical operating conditions supporting the de novo formation of NH 3 have been identified. In the EDC, mean NO- and NH 3-EFs of 57±26 and 16±12 mg km -1 were obtained for Euro-3-vehicles; those of the Euro-4-technology were lower by about 25% and 33% at the levels of 43±46 and 10±7 mg km -1, respectively. NO 2 emissions of the investigated three-way catalyst (TWC) vehicles accounted for <1% of the detected RNCs, whereas NH 3 was found to be the dominant RNC for most vehicle conditions. Molar NH 3 proportions varied from about 0.4-0.8, as soon as catalyst light-off occurred. NO was found in large excess only during the cold-start period. Catalyst light-off is indicated by a fast transition from NO- to NH 3-rich exhaust. Velocity and acceleration had pronounced effects on the RNC emission characteristics. Mean velocity-dependent EFs for NO and NH 3 varied by about one order of magnitude from 10 to 74 and 15 to 161 mg km -1 for Euro-3-vehicles and

  4. Improving the Photoluminescence Properties of Perovskite CH3NH3PbBr3-xClx Films by Modulating Organic Cation and Chlorine Concentrations.

    PubMed

    Yan, Jun; Zhang, Bing; Chen, Yunlin; Zhang, Ao; Ke, Xiaohan

    2016-05-25

    The photoluminescence (PL) properties of inorganic-organic perovskites can be drastically changed by tuning the halogen composition, especially the Cl content. However, our research demonstrated that in addition to the influence of Cl concentration, the PL emission intensity of CH3NH3PbBr3 strongly depends on the content of CH3NH3Br in the coating solution. The effects of CH3NH3Br and Cl concentrations on the PL properties of CH3NH3PbBr3-xClx were investigated. We found that a strong PL emission intensity of CH3NH3PbBr3 can be obtained from solutions with a high CH3NH3Br concentration. The PL emission intensities of CH3NH3PbBr3-xClx films were enhanced by adjusting the molar ratio of PbBr to PbCl2 only in a highly concentrated CH3NH3Br environment. Moreover, it was found that an optimum CH3NH3Br/PbBr2/PbCl2 ratio in the precursor solutions can be used to obtain the strongest PL emission intensity of CH3NH3PbBr3-xClx films. Further studies revealed that both CH3NH3Br and Cl concentrations significantly influence the CH3NH3PbBr3-xClx films evolution, which affects their PL properties. PMID:27163386

  5. NH3D(+) ions in ammonium perchlorate - The N-D stretching bands of different sites

    NASA Astrophysics Data System (ADS)

    Weier, Jane E.; Strauss, Herbert L.

    1993-03-01

    The N-D stretching region of the infrared spectrum of doped NH4ClO4 has been reexamined at low temperatures. The spectra are found to be still changing at 2 K, indicating the existence of energy differences of this order. The N-H spectrum in ND4ClO4 was also examined. Comparison of the two sets of spectra led to an assignment of the small energy differences as due to tunneling among the distinct positions the NX3Y(+) ions can assume in the lattice. The distinct orientation of NH3D(+) and the ND3H(+) ions have slightly different energies and this, plus the tunneling, accounts for all the eight observed lines. A complete assignment of the tunneling levels will, however, require more information.

  6. Intense Pulsed Light Sintering of CH3NH3PbI3 Solar Cells.

    PubMed

    Lavery, Brandon W; Kumari, Sudesh; Konermann, Hannah; Draper, Gabriel L; Spurgeon, Joshua; Druffel, Thad

    2016-04-01

    Perovskite solar cells utilizing a two-step deposited CH3NH3PbI3 thin film were rapidly sintered using an intense pulsed light source. For the first time, a heat treatment has shown the capability of sintering methylammonium lead iodide perovskite and creating large crystal sizes approaching 1 μm without sacrificing surface coverage. Solar cells with an average efficiency of 11.5% and a champion device of 12.3% are reported. The methylammonium lead iodide perovskite was subjected to 2000 J of energy in a 2 ms pulse of light generated by a xenon lamp, resulting in temperatures significantly exceeding the degradation temperature of 150 °C. The process opens up new opportunities in the manufacturability of perovskite solar cells by eliminating the rate-limiting annealing step, and makes it possible to envision a continuous roll-to-roll process similar to the printing press used in the newspaper industry. PMID:26943510

  7. Zwitterion formation in titan ice analogs: reaction between HC3N and NH3.

    PubMed

    Couturier-Tamburelli, Isabelle; Sessouma, Bintou; Chiavassa, Thierry; Piétri, Nathalie

    2012-11-01

    A zwitterion is formed in the laboratory at low temperatures in the solid phase from the thermal reaction of HC(3)N and NH(3). We report for the first time its infrared spectrum. We study its reaction using Fourier transform infrared spectroscopy. Its reaction rate is estimated to be k(T) = 2.9 × 10(5) exp(-2.3 ± 0.1 (kJ mol(-1))/RT). Calculations using density functional theory (B3LYP/6-31g**) are used to characterize all the species (complexes, zwitterions, and transition states) and are in good agreement with the infrared spectra. The structure of the zwitterion is determined planar and it is characterized by a N-C bond around 1.5 Å. PMID:23075265

  8. Theoretical study of geometry relaxation following core excitation: H2O, NH3, and CH4

    NASA Astrophysics Data System (ADS)

    Takahashi, Osamu; Kunitake, Naoto; Takaki, Saya

    2015-10-01

    Single core-hole (SCH) and double core-hole excited state molecular dynamics (MD) calculations for neutral and cationic H2O, NH3, and CH4 have been performed to examine geometry relaxation after core excitation. We observed faster X-H (X = C, N, O) bond elongation for the core-ionized state produced from the valence cationic molecule and the double-core-ionized state produced from the ground and valence cationic molecules than for the first resonant SCH state. Using the results of SCH MD simulations of the ground and valence cationic molecules, Auger decay spectra calculations were performed. We found that fast bond scission leads to peak broadening of the spectra.

  9. Electronic structure evolution of fullerene on CH3NH3PbI3

    DOE PAGESBeta

    Wang, Chenggong; Wang, Congcong; Liu, Xiaoliang; Kauppi, John; Shao, Yuchuan; Xiao, Zhengguo; Bi, Cheng; Huang, Jinsong; Gao, Yongli

    2015-03-19

    The thickness dependence of fullerene on CH3NH3PbI3 perovskitefilm surface has been investigated by using ultraviolet photoemission spectroscopy (UPS), X-ray photoemission spectroscopy(XPS), and inverse photoemission spectroscopy (IPES). The lowest unoccupied molecular orbital and highest occupied molecular orbital (HOMO) can be observed directly with IPES and UPS. It is observed that the HOMO level in fullerene shifts to lower binding energy. The XPS results show a strong initial shift of core levels to lower binding energy in the perovskite, which indicates that electrons transfer from the perovskitefilm to fullerene molecules. Further deposition of fullerene forms C60 solid, accompanied by the reduction ofmore » the electron transfer. As a result, the strongest electron transfer happened at 1/4 monolayer of fullerene.« less

  10. Electronic transport properties of BN sheet on adsorption of ammonia (NH3) gas.

    PubMed

    Srivastava, Anurag; Bhat, Chetan; Jain, Sumit Kumar; Mishra, Pankaj Kumar; Brajpuriya, Ranjeet

    2015-03-01

    We report the detection of ammonia gas through electronic and transport properties analysis of boron nitride sheet. The density functional theory (DFT) based ab initio approach has been used to calculate the electronic and transport properties of BN sheet in presence of ammonia gas. Analysis confirms that the band gap of the sheet increases due to presence of ammonia. Out of different positions, the bridge site is the most favorable position for adsorption of ammonia and the mechanism of interaction falls between weak electrostatic interaction and chemisorption. On relaxation, change in the bond angles of the ammonia molecule in various configurations has been reported with the distance between NH3 and the sheet. An increase in the transmission of electrons has been observed on increasing the bias voltage and I-V relationship. This confirms that, the current increases on applying the bias when ammonia is introduced while a very small current flows for pure BN sheet. PMID:25666919

  11. Structure and stability in TMC-1: Analysis of NH3 molecular line and Herschel continuum data

    NASA Astrophysics Data System (ADS)

    Fehér, O.; Tóth, L. V.; Ward-Thompson, D.; Kirk, J.; Kraus, A.; Pelkonen, V.-M.; Pintér, S.; Zahorecz, S.

    2016-05-01

    Aims: We examined the velocity, density, and temperature structure of Taurus molecular cloud-1 (TMC-1), a filamentary cloud in a nearby quiescent star forming area, to understand its morphology and evolution. Methods: We observed high signal-to-noise (S/N), high velocity resolution NH3(1,1), and (2, 2) emission on an extended map. By fitting multiple hyperfine-split line profiles to the NH3(1, 1) spectra, we derived the velocity distribution of the line components and calculated gas parameters on several positions. Herschel SPIRE far-infrared continuum observations were reduced and used to calculate the physical parameters of the Planck Galactic Cold Clumps (PGCCs) in the region, including the two in TMC-1. The morphology of TMC-1 was investigated with several types of clustering methods in the parameter space consisting of position, velocity, and column density. Results: Our Herschel-based column density map shows a main ridge with two local maxima and a separated peak to the south-west. The H2 column densities and dust colour temperatures are in the range of 0.5-3.3 × 1022 cm-2 and 10.5-12 K, respectively. The NH3 column densities and H2 volume densities are in the range of 2.8-14.2 × 1014 cm-2 and 0.4-2.8 × 104 cm-3. Kinetic temperatures are typically very low with a minimum of 9 K at the maximum NH3 and H2 column density region. The kinetic temperature maximum was found at the protostar IRAS 04381+2540 with a value of 13.7 K. The kinetic temperatures vary similarly to the colour temperatures in spite of the fact that densities are lower than the critical density for coupling between the gas and dust phase. The k-means clustering method separated four sub-filaments in TMC-1 with masses of 32.5, 19.6, 28.9, and 45.9 M⊙ and low turbulent velocity dispersion in the range of 0.13-0.2 km s-1. Conclusions: The main ridge of TMC-1 is composed of four sub-filaments that are close to gravitational equilibrium. We label these TMC-1F1 through F4. The sub-filaments TMC

  12. Field inter-comparison of three systems for NH3 concentration and flux measurements

    NASA Astrophysics Data System (ADS)

    Voglmeier, Karl; Ammann, Christof; Neftel, Albrecht; Häni, Christoph; Richter, Undine; Brümmer, Christian

    2016-04-01

    Ambient air ammonia analyzer systems that are not only used for concentration but also for flux measurements have to meet special requirements. They either have to provide a fast response detection (c. 1 sec) for the application of the eddy covariance technique (EC) or they have to resolve relatively small horizontal or vertical concentration gradients. The Posieux intercomparison experiment in fall 2015 was designed to compare three advanced and different approaches to determine concentration and fluxes of NH3 of a grazed pasture during several weeks. The methods involved: [1] a two channel reactive N converter measuring in parallel the sum of oxidized N species with the exception of N2O and the sum of the total reactive N species. The difference of the two channels corresponds to the sum of reduced reactive N species; [2] a QC laser analyzer with a special designed inlet system that minimize wall effects and separates particles from the gas sampling stream; [3] two MiniDOAS instruments for line integrated concentration without any inlet system. The experimental setup and the environmental conditions resulted in a high temporal and spatial dynamic of NH3 concentrations and fluxes. Systems [1] and [2] are designed to perform flux measurements by the Eddy Covariance technique, whereas the DOAS technique has a temporal resolution of 1 min. Fluxes are calculated from the horizontal concentration increase across an emitting surface with back lagrangian stochastic trajectory dispersion model. We present a comparison of the measured concentrations and fluxes and discuss the advantages and limitations of the three chosen systems.

  13. Characterizing the excess electron of Li(NH3)4.

    PubMed

    Sommerfeld, Thomas; Dreux, Katelyn M

    2012-12-28

    Small lithium ammonia clusters are model systems for the dissociation of metals into solvated cations and electrons in ammonia. Metal-ammonia solutions display a complex behavior with increasing metal concentration including a phase change from a paramagnetic to a metallic diamagnetic phase, and small clusters should be useful models in the low concentration regime, where one may expect the ammoniated electron to show a behavior similar to that of the hydrated electron. Yet, even in the low concentration regime the nature of the ammoniated electron is still controversial with cavity models supported by optical and density measurements whereas localized radical models have been invoked to explain magnetic measurements. Small clusters can shed light on these open questions, and in particular the Li-NH(3) tetramer represents the smallest cluster with a complete solvation shell for the Li(+) cation. In view of the controversies about the character of the excess electron, the first question investigated is whether different theoretical characterizations of the "excess electron" lead to different conclusions about it. Only small differences are found between orbital-based and spin density-based and between self-consistent-field and coupled-cluster-based methods. Natural orbitals from equation-of-motion coupled-cluster calculations are then used to analyze the excess electron's distribution of Li(NH(3))(4) with particular emphasis on the portion of the excess electron's density that is closely associated with the N atoms. Three different comparisons show that only about 6% of the excess electron's density are closely associated with the atoms, with about 1% being closely associated with any N atom, and that the electron is best characterized as a Rydberg-like electron of the whole cluster. Finally, it is shown that in spite of the small amount of density close to the N atoms, the spin-density at the N nuclei is substantial, and that the magnetic observations can plausibly

  14. Relative CO2/NH3 selectivities of AQP1, AQP4, AQP5, AmtB, and RhAG

    PubMed Central

    Musa-Aziz, Raif; Chen, Li-Ming; Pelletier, Marc F.; Boron, Walter F.

    2009-01-01

    The water channel aquaporin 1 (AQP1) and certain Rh-family members are permeable to CO2 and NH3. Here, we use changes in surface pH (pHS) to assess relative CO2 vs. NH3 permeability of Xenopus oocytes expressing members of the AQP or Rh family. Exposed to CO2 or NH3, AQP1 oocytes exhibit a greater maximal magnitude of pHS change (ΔpHS) compared with day-matched controls injected with H2O or with RNA encoding SGLT1, NKCC2, or PepT1. With CO2, AQP1 oocytes also have faster time constants for pHS relaxation (τpHs). Thus, AQP1, but not the other proteins, conduct CO2 and NH3. Oocytes expressing rat AQP4, rat AQP5, human RhAG, or the bacterial Rh homolog AmtB also exhibit greater ΔpHS(CO2) and faster τpHs compared with controls. Oocytes expressing AmtB and RhAG, but not AQP4 or AQP5, exhibit greater ΔpHS(NH3) values. Only AQPs exhibited significant osmotic water permeability (Pf). We computed channel-dependent (*) ΔpHS or Pf by subtracting values for H2O oocytes from those of channel-expressing oocytes. For the ratio ΔpHS(CO2)*/Pf*, the sequence was AQP5 > AQP1 ≅ AQP4. For ΔpHS(CO2)*/ΔpHS(NH3)*, the sequence was AQP4 ≅ AQP5 > AQP1 > AmtB > RhAG. Thus, each channel exhibits a characteristic ratio for indices of CO2 vs. NH3 permeability, demonstrating that, like ion channels, gas channels can exhibit selectivity. PMID:19273840

  15. Conductivity of p(AAc) Cryogel and Its Li+, Na+, and K+ Salts for NH3 Sensing

    NASA Astrophysics Data System (ADS)

    Sahiner, Nurettin; Demirci, Sahin; Sel, Kivanc

    2016-07-01

    Poly(acrylic acid) [p(AAc)] cryogel has been synthesized by a cryopolymerization technique under cryogenic conditions. The synthesized p(AAc) cryogel was treated with LiOH, NaOH, and KOH to generate corresponding salt forms of carboxylic acid groups within the p(AAc) cryogel network for activation as p(AAc)-Li+, p(AAc)-Na+, and p(AAc)-K+, respectively. The synthesized p(AAc)-based cryogels were characterized via Fourier-transform infrared (FT-IR) spectroscopy, thermogravimetric analysis, and scanning electron microscopy. The room-temperature electrical conductivity of the p(AAc), p(AAc)-Li+, p(AAc)-Na+, and p(AAc)-K+ cryogels was measured as 10-11 S cm-1, 10-10 S cm-1, 10-9 S cm-1, and 10-8 S cm-1, respectively. Furthermore, the p(AAc) cryogel and its salt forms were tested as sensor materials for NH3 gas by exposing them to NH3 vapor for 60 min under ambient conditions. Upon exposure to NH3 vapor, it was found that the conductivity of the bare p(AAc) and p(AAc)-K+ cryogels increased by up to 105- and 102-fold, respectively, compared with their NH3 unexposed states. The increase in conductivity for the other salt forms of p(AAc) cryogel was about 60-fold compared with their bare form. The conductivity increase for the p(AAc) and p(AAc)-K+ cryogels was therefore further investigated by changing the NH3 vapor exposure time, revealing that these materials could be used as sensors for NH3. It was further found that a 5 min NH3 gas exposure time was sufficient for p(AAc)-K+ cryogel to generate a detectable response via a change in the conductivity of the matrix.

  16. Conductivity of p(AAc) Cryogel and Its Li+, Na+, and K+ Salts for NH3 Sensing

    NASA Astrophysics Data System (ADS)

    Sahiner, Nurettin; Demirci, Sahin; Sel, Kivanc

    2016-04-01

    Poly(acrylic acid) [p(AAc)] cryogel has been synthesized by a cryopolymerization technique under cryogenic conditions. The synthesized p(AAc) cryogel was treated with LiOH, NaOH, and KOH to generate corresponding salt forms of carboxylic acid groups within the p(AAc) cryogel network for activation as p(AAc)-Li+, p(AAc)-Na+, and p(AAc)-K+, respectively. The synthesized p(AAc)-based cryogels were characterized via Fourier-transform infrared (FT-IR) spectroscopy, thermogravimetric analysis, and scanning electron microscopy. The room-temperature electrical conductivity of the p(AAc), p(AAc)-Li+, p(AAc)-Na+, and p(AAc)-K+ cryogels was measured as 10-11 S cm-1, 10-10 S cm-1, 10-9 S cm-1, and 10-8 S cm-1, respectively. Furthermore, the p(AAc) cryogel and its salt forms were tested as sensor materials for NH3 gas by exposing them to NH3 vapor for 60 min under ambient conditions. Upon exposure to NH3 vapor, it was found that the conductivity of the bare p(AAc) and p(AAc)-K+ cryogels increased by up to 105- and 102-fold, respectively, compared with their NH3 unexposed states. The increase in conductivity for the other salt forms of p(AAc) cryogel was about 60-fold compared with their bare form. The conductivity increase for the p(AAc) and p(AAc)-K+ cryogels was therefore further investigated by changing the NH3 vapor exposure time, revealing that these materials could be used as sensors for NH3. It was further found that a 5 min NH3 gas exposure time was sufficient for p(AAc)-K+ cryogel to generate a detectable response via a change in the conductivity of the matrix.

  17. DFT study of NH 3 dissociation on Si(1 1 1)-7 × 7. The role of intermolecular interactions

    NASA Astrophysics Data System (ADS)

    Ferullo, Ricardo M.; Fuente, Silvia A.; Belelli, Patricia G.; Castellani, Norberto J.

    2007-04-01

    The adsorption of NH 3 molecule on the Si(1 1 1)-7 × 7 surface modelled with a cluster has been studied using density functional theory (DFT). The results indicate the existence of a precursor state for the non-dissociative chemisorption. The active site for the molecular chemisorption is the adatom; while the NH 3 molecule adsorbs on the Si restatom via this preadsorbed state, the adsorption on the Si adatom is produced practically without an energy barrier. The ammonia adsorption on the adatom induces an electron transfer from the dangling bond of this atom to the dangling bond of the adjacent Si restatom, hindering this site for the adsorption of a second NH 3 incoming molecule. However, this second molecule links strongly by means of two H-bonds. The dissociative chemisorption process was studied considering one and two ammonia molecules. For the dissociation of a lonely NH 3 molecule an energy barrier of ˜0.3 eV was calculated, yielding NH 2 on the adatom and H on the restatom. When two molecules are adsorbed, the NH 3-NH 3 interaction yields the weakening of a N-H bond of the ammonia molecule adsorbed closer the Si surface. As a consequence, the dissociation barrier practically disappears. Thus, the presence of a second NH 3 molecule at the adatom-restatom pair of the Si(1 1 1)-7 × 7 surface makes the dissociative reaction self-assisted, the total adsorption process elapsing with a negligible activation barrier (less than 0.01 eV).

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

    PubMed

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

    2015-12-01

    Lichens are sensitive to the presence of ammonia (NH3) in the environment. However, in order to use them as reliable indicators in biomonitoring studies, it is necessary to establish unequivocally the occurrence of certain symptoms following the exposure to NH3 in the environment. In this paper, we simulated an episode of acute air pollution due to the release of NH3. The biological effects of acute air pollution by atmospheric NH3 have been investigated using N-sensitive (Flavoparmelia caperata) and N-tolerant (Xanthoria parietina) species. Lichen samples were exposed to ecologically relevant NH3 concentrations for 8 weeks, simulating three areas of impact: a control area (2 μg/m(3)), an area of intermediate impact (2-35 μg/m(3)) and an area of high impact (10-315 μg/m(3)), with a peak of pollution reached between the fourth and fifth week. Ammonia affected both the photobiont and the mycobiont in F. caperata, while in X. parietina only the photosynthetic performance of the photobiont was altered after exposure to the highest concentration. In the photobiont of F. caperata we recorded chlorophyll degradation as indicated by OD435/415 ratio, decrease of the photosynthetic performance (as reflected by the maximum quantum yield of primary photochemistry FV/FM and the performance index PIABS); in the mycobiont, ergosterol reduction, membrane lipid peroxidation (as reflected by the increase of thiobarbituric acid reactive substances), alteration (decrease) of the secondary metabolite usnic acid. No effects were detected on caperatic acid and dehydrogenase activity. In X. parietina, the only signal determined by NH3 was the alteration of FV/FM and the performance index PIABS. The results suggest that physiological parameters in N-sensitive lichens well reflect the effects of NH3 exposure and can be applied as early indicators in monitoring studies. PMID:26342688

  19. Lead-Halide Perovskite Solar Cells by CH3NH3I Dripping on PbI2-CH3NH3I-DMSO Precursor Layer for Planar and Porous Structures Using CuSCN Hole-Transporting Material.

    PubMed

    Ito, Seigo; Tanaka, Soichiro; Nishino, Hitoshi

    2015-03-01

    The sequential fabrication scheme of the CH3NH3PbI3 layer has been improved to fabricate planar-structure CH3NH3PbI3 perovskite solar cells using CuSCN hole-transporting material (HTM). In the PbI2 layer fabricated by the spin-coating method, at first, small amounts of CH3NH3I (MAI) and DMSO were incorporated as the first-drip precursor layer on a flat TiO2 layer. On the first-drip precursor layers, an MAI solution was applied by either soaking (MAI-soaking method) or dripping using successive spin coating (MAI-dripping). The morphology and crystal transformations were observed by SEM and XRD, respectively. Using the normal sequential MAI-soaking method, we were unable to fabricate planar CH3NH3PbI3 perovskite solar cells with CuSCN HTM. Using the MAI-dripping method, however, a significant photovoltaic effect has been observed to be planar NH3PbI3 perovskite/CuSCN> solar cells. PMID:26262667

  20. Characterization of Biochar using Temperature Programmed Oxidation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Biochar from the fast pyrolysis of biomass was characterized by Temperature Programmed Oxidation. This technique can be used to assess the oxidative reactivity of carbonaceous solids where higher temperature reactivity indicates greater structural order. The samples examined include soy and barley...

  1. The tropospheric abundances of NH3 and PH3 in Jupiter's Great Red Spot, from Voyager IRIS observations.

    PubMed

    Griffith, C A; Bezard, B; Owen, T; Gautier, D

    1992-01-01

    To investigate the chemistry and dynamics of Jupiter's Great Red Spot (GRS), the tropospheric abundances of NH3 and PH3 in the GRS are determined and compared to those of the surrounding region, the South Tropical Zone (STZ). These gases well up from deep in the atmosphere, and, in the upper troposphere, are depleted by condensation (in the case of NH3), chemical reactions, and UV photolysis. At Jupiter's tropopause, the chemical lifetimes of NH3 and PH3 are comparable to the time constant for vertical transport over the atmospheric scale height. The distributions of these gases are therefore diagnostic of the rate of vertical transport in the upper troposphere and lower stratosphere. Three groups of Voyager IRIS spectra are analyzed, two of the STZ and one of the GRS. The two groups of STZ spectra are defined on the basis of their radiances at 602 and 226 cm-1, which reflect, respectively, the temperature near 150 mbar and the cloud opacity in the 300-600 mbar region. One selection of STZ spectra is chosen to have the same radiance as does the GRS at 226 cm-1. The other STZ selection has a significantly greater radiance, indicative of reduced cloudiness. Variations in the abundances of NH3 and PH3 are determined within the STZ, as a background for our studies of the GRS. Within the uncertainty of our measurements (-55% and +75%), the PH3 mixing ratio at 600 mbar is 3 x 10(-7), the same for all three selections. The NH3 mixing ratio profile in the pressure region between 300 and 600 mbar is the same within error (-25% and +50% at 300 mbar) for both STZ selections. In the GRS, however, NH3 is significantly depleted at 300 mbar, with an abundance of 25% that derived for the STZ selections. Since the GRS is believed to be a region of strong vertical transport, our finding of a depletion of NH3 below the tropopause within the GRS is particularly unexpected. One of the STZ selections has a temperature-pressure profile similar to that of the GRS below the 300-mbar level

  2. Global analytical potential energy surface for the electronic ground state of NH3 from high level ab initio calculations.

    PubMed

    Marquardt, Roberto; Sagui, Kenneth; Zheng, Jingjing; Thiel, Walter; Luckhaus, David; Yurchenko, Sergey; Mariotti, Fabio; Quack, Martin

    2013-08-15

    The analytical, full-dimensional, and global representation of the potential energy surface of NH(3) in the lowest adiabatic electronic state developed previously (Marquardt, R.; et al. J. Phys. Chem. B 2005, 109, 8439–8451) is improved by adjustment of parameters to an enlarged set of electronic energies from ab initio calculations using the coupled cluster method with single and double substitutions and a perturbative treatment of connected triple excitations (CCSD(T)) and the method of multireference configuration interaction (MRCI). CCSD(T) data were obtained from an extrapolation of aug-cc-pVXZ results to the basis set limit (CBS), as described in a previous work (Yurchenko, S.N.; et al. J. Chem. Phys 2005, 123, 134308); they cover the region around the NH3 equilibrium structures up to 20,000 hc cm(–1). MRCI energies were computed using the aug-cc-pVQZ basis to describe both low lying singlet dissociation channels. Adjustment was performed simultaneously to energies obtained from the different ab initio methods using a merging strategy that includes 10,000 geometries at the CCSD(T) level and 500 geometries at the MRCI level. Characteristic features of this improved representation are NH3 equilibrium geometry r(eq)(NH(3)) ≈ 101.28 pm, α(eq)(NH(3)) ≈ 107.03°, the inversion barrier at r(inv)(NH(3)) ≈ 99.88 pm and 1774 hc cm(–1) above the NH(3) minimum, and dissociation channel energies 41,051 hc cm(–1) (for NH(3) → ((2)B(2))NH(2) + ((2)S(1/2))H) and 38,450 hc cm(–1) (for NH(3) → ((3)Σ(–))NH +((1)Σ(g)(+))H(2)); the average agreement between calculated and experimental vibrational line positions is 11 cm(–1) for (14)N(1)H(3) in the spectral region up to 5000 cm(–1). A survey of our current knowledge on the vibrational spectroscopy of ammonia and its isotopomers is also given. PMID:23688044

  3. Validation of flux measurements with artificial sources: simulating CH4 from cows and NH3 emissions from medium plot scales

    NASA Astrophysics Data System (ADS)

    Sintermann, Jörg; Felber, Raphael; Häni, Christoph; Ammann, Christof; Neftel, Albrecht

    2014-05-01

    Mitigation of ammonia (NH3) emissions with detrimental environmental effects as well as of greenhouse gas emissions (GHG: CO2, N2O, CH4) are key challenges faced by the agricultural production sector. While NH3 originates mainly from polluted surfaces, e.g. after slurry application, the main source for CH4 emissions are cows and other ruminating animals, representing point sources. There are two widespread state-of-the-art techniques to determine agricultural emissions: eddy covariance (EC) flux measurements and Lagrangian stochastic (LS) dispersion modelling, namely the WindTrax (WT) model. Whereas GHG emissions can be measured with both techniques, NH3 emissions are usually not feasible with EC measurements due to the stickiness of NH3 molecules on surfaces. In addition, point sources render difficulties for the interpretation of EC flux data. We tested the EC technique and the WT model using artificial sources with known gas release rates. i) The effect of a point source on EC fluxes was investigated by placing an artificial CH4 source with known release rate upwind of the EC tower at two different heights and during different wind conditions. ii) The WT model was checked with a NH3 release grid of 314 m2 of known source strength. Ambient NH3 concentrations were measured by open path DOAS systems and impinger sampling. The CH4 concentration timeseries influenced by the point source showed a similar pattern as in the presence of cows upwind of the EC system. CH4 release rates from the point source were reproduced by the EC flux measurement with stationary background conditions only. The experiments with the NH3 release showed that WT performs well for emission determination, even in complex terrain (asphalt surrounded by grassland) with associated micrometeorology, given a realistic description of the vertical profile of wind velocity. Calculated gas recoveries ranged between 73 to 105%. Such a result is encouraging considering the immanent uncertainties from a

  4. Formation of a passivating CH3NH3PbI3/PbI2 interface during moderate heating of CH3NH3PbI3 layers

    NASA Astrophysics Data System (ADS)

    Supasai, T.; Rujisamphan, N.; Ullrich, K.; Chemseddine, A.; Dittrich, Th.

    2013-10-01

    Layers of CH3NH3PbI3 are investigated by modulated surface photovoltage spectroscopy (SPV) during heating in vacuum. As prepared CH3NH3PbI3 layers behave as a p-type doped semiconductor in depletion with a band gap of 1.5 eV. After heating to 140 °C the sign of the SPV signals of CH3NH3PbI3 changed concomitant with the appearance of a second band gap at 2.36 eV ascribed to PbI2, and SPV signals related to charge separation from defect states were reduced after moderate heating.

  5. Fragmentation of doubly charged ammonia cations NH{3/++} studied by the photoion-photoion coincidence (PIPICO) method

    NASA Astrophysics Data System (ADS)

    Winkoun, D.; Dujardin, G.

    1986-03-01

    Doubly charged NH{3/++} cations were produced by double photoionization of neutral ammonia molecules by using the synchrotron radiation from ACO as a photon source of variable energy in the 35 49 eV energy range. The fragmentation of NH{3/++} was studied by the photoion-photoion coincidence (PIPICO) method. NH{3/++} cations were produced in thetilde X^1 A 1 andtilde B^1 electronic states of which the onset energies were measured at, respectively, 35.4±0.5 eV and 44.5±0.5 eV. It was shown that the NH{3/++} ions, initially produced in theirtilde X^1 A 1 state, rapidly dissociate (in less than 50 ns), into NH{2/+} + H+. Furthermore, the comparison with results obtained by other methods indicates that NH{3/++} ions can either be long-lived (τ>10 µs) or slowly dissociating (1 µs<τ<10 µs) or rapidly dissociating (τ<50 ns), depending on their geometry and/or internal energy in theirtilde X^1 E A 1 electronic state.

  6. Quantum-chemical study and FTIR jet spectroscopy of CHCl(3)-NH(3) association in the gas phase.

    PubMed

    Hippler, Michael; Hesse, Susanne; Suhm, Martin A

    2010-11-01

    High level ab initio quantum chemical calculations have been performed on the association of chloroform with ammonia in the gas phase (counterpoise corrected MP2 and coupled-cluster CCSD(T) calculations with 6-311++G(d,p) basis functions). Minimum energy equilibrium structures have been found for CHCl(3)-NH(3) dimer, CHCl(3)-(NH(3))(2) trimer and CHCl(3)-(NH(3))(3) tetramer. Association is characterised by a CHN hydrogen bond between a chloroform and an ammonia molecule, with further ammonia units attached by hydrogen bonds to ammonia and by an electrostatic NHCl interaction to chloroform. Cooperative effects provide additional stabilisation. The complexes exhibit characteristic shifts of vibrational bands and change of IR intensity; in particular there is a pronounced progressive shift of the CH-stretching vibration towards lower wavenumber with each unit of ammonia attached in the complex. The shift is accompanied by an up to 600 fold increase in IR intensity. The experimental FTIR jet spectra have provided firm evidence of CHCl(3)-NH(3) association, with the clearest effects seen in the region of the CH-stretching vibration. First tentative assignments have been made based on the dependence of relative intensities of cluster features on the concentration of monomers, and assignments have been corroborated by the quantum chemical calculations. The present combined ab initio and FTIR spectroscopy study reveals the structure and energetics of cluster formation and intermolecular bonding in CHCl(3)-NH(3) association. PMID:20694238

  7. Reversible flexible structural changes in multidimensional MOFs by guest molecules (I2, NH3) and thermal stimulation

    NASA Astrophysics Data System (ADS)

    Chen, Yang; Li, Libo; Yang, Jiangfeng; Wang, Shuang; Li, Jinping

    2015-03-01

    Three metal-organic frameworks (MOFs), [Cu(INA)2], [Cu(INA)2I2] and [Cu(INA)2(H2O)2(NH3)2], were synthesized with 3D, 2D, and 0D structures, respectively. Reversible flexible structural changes of these MOFs were reported. Through high temperature (60-100 °C) stimulation of I2 or ambient temperature stimulation of NH3, [Cu(INA)2] (3D) converted to [Cu(INA)2I2] (2D) and [Cu(INA)2(H2O)2(NH3)2] (0D); as the temperature increased to 150 °C, the MOFs changed back to their original form. In this way, this 3D MOF has potential application in the capture of I2 and NH3 from polluted water and air. XRD, TGA, SEM, NH3-TPD, and the measurement of gas adsorption were used to describe the changes in processes regarding the structure, morphology, and properties.

  8. On-road measurement of NH3 and N2O emissions from a Euro V heavy-duty vehicle

    NASA Astrophysics Data System (ADS)

    Suarez-Bertoa, Ricardo; Mendoza-Villafuerte, Pablo; Bonnel, Pierre; Lilova, Velizara; Hill, Leslie; Perujo, Adolfo; Astorga, Covadonga

    2016-08-01

    The use of selective catalytic reduction systems (SCR) to abate NOx vehicular emissions brings new concerns on the emissions of the byproducts NH3 and N2O. Therefore, NH3 and N2O on-road emissions from a Euro V truck equipped with a SCR were measured in real time using a QCL-IR. Results bring to light possibility to perform this kind of real time measurements for other pollutants besides, hydrocarbons, NOx, CO and CO2. The capability to measure NH3 and N2O in a second-by-second basis will allow applying the currently agreed regulatory emissions evaluation for gaseous compounds. Average N2O emission factors calculated applying the current PEMS-based data analysis to all available windows from the tests ranged from 0.063 g/kWh to 0.139 g/kWh. Average NH3 concentrations ranged from 0.9 ppm to 5.7 ppm. Although calculated average N2O and NH3 emissions were within current limits, NOx emissions were substantially higher than Euro V limits under the studied conditions.

  9. Evaluation of a regional air-quality model with bidirectional NH3 exchange coupled to an agroecosystem model

    NASA Astrophysics Data System (ADS)

    Bash, J. O.; Cooter, E. J.; Dennis, R. L.; Walker, J. T.; Pleim, J. E.

    2013-03-01

    Atmospheric ammonia (NH3) is the primary atmospheric base and an important precursor for inorganic particulate matter and when deposited NH3 contributes to surface water eutrophication, soil acidification and decline in species biodiversity. Flux measurements indicate that the air-surface exchange of NH3 is bidirectional. However, the effects of bidirectional exchange, soil biogeochemistry and human activity are not parameterized in air quality models. The US Environmental Protection Agency's (EPA) Community Multiscale Air-Quality (CMAQ) model with bidirectional NH3 exchange has been coupled with the United States Department of Agriculture's (USDA) Environmental Policy Integrated Climate (EPIC) agroecosystem model. The coupled CMAQ-EPIC model relies on EPIC fertilization timing, rate and composition while CMAQ models the soil ammonium (NH4+) pool by conserving the ammonium mass due to fertilization, evasion, deposition, and nitrification processes. This mechanistically coupled modeling system reduced the biases and error in NHx (NH3 + NH4+) wet deposition and in ambient aerosol concentrations in an annual 2002 Continental US (CONUS) domain simulation when compared to a 2002 annual simulation of CMAQ without bidirectional exchange. Fertilizer emissions estimated in CMAQ 5.0 with bidirectional exchange exhibits markedly different seasonal dynamics than the US EPA's National Emissions Inventory (NEI), with lower emissions in the spring and fall and higher emissions in July.

  10. Ultrasensitive Photodetectors Based on Island-Structured CH3NH3PbI3 Thin Films.

    PubMed

    Zhang, Yin; Du, Juan; Wu, Xiaohan; Zhang, Guoqian; Chu, Yingli; Liu, Dapeng; Zhao, Yixin; Liang, Ziqi; Huang, Jia

    2015-10-01

    CH3NH3PbI3 perovskite-based optoelectronics have attracted intense research interests recently because of their easy fabrication process and high power conversion efficiency. Herein, we report a novel photodetector based on unique CH3NH3PbI3 perovskite films with island-structured morphology. The light-induced electronic properties of the photodetectors were investigated and compared to those devices based on conventional compact CH3NH3PbI3 films. The island-structured CH3NH3PbI3 photodetectors exhibited a rapid response speed (<50 ms), good stability at a temperature of up to 100 °C, a large photocurrent to dark current ratio (Ilight/Idark > 1 × 10(4) under an incident light of ∼6.59 mW/cm(2), and Ilight/Idark > 1 × 10(2) under low incident light ∼0.018 mW/cm(2)), and excellent reproducibility. Especially, the performance of the island-structured devices markedly exceed that of the conventional compact CH3NH3PbI3 thin-film devices. These excellent performances render the island-structured device to be potentially applicable for a wide range of optoelectronics. PMID:26387552