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Sample records for objects iv nh3

  1. Parameters Affecting I-V Hysteresis of CH3NH3PbI3 Perovskite Solar Cells: Effects of Perovskite Crystal Size and Mesoporous TiO2 Layer.

    PubMed

    Kim, Hui-Seon; Park, Nam-Gyu

    2014-09-01

    Current-voltage (I-V) characteristics of CH3NH3PbI3 perovskite solar cells are studied using a time-dependent current response with stepwise sweeping of the bias voltage. Compared with the crystalline Si solar cell showing time-independent current at a given bias voltage, the perovskite solar cells exhibit time-dependent current response. The current increases with time and becomes steady at forward scan from short-circuit to open-circuit, whereas it is decayed and saturated with time at reverse scan from open-circuit to short-circuit. Time-dependent current response eventually leads to I-V hysteresis depending on the scan direction and the scan rate. Crystal size of CH3NH3PbI3 and the mesoporous TiO2 (mp-TiO2) film are found to influence I-V hysteresis, where the I-V hysteresis is alleviated as crystal size increases and in the presence of mp-TiO2. The capacitance observed at low frequency (0.1 to 1 Hz), associated with dipole polarization, tends to diminish as size of perovskite and mp-TiO2 layer thickness increases, which suggests that the origin of hysteresis correlates to the capacitive characteristic of CH3NH3PbI3 and the degree of hysteresis depends strongly on perovskite crystal size and mesoporous TiO2 layer.

  2. 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.

  3. NH_3_ and HCO^+^ towards luminous IRAS sources.

    NASA Astrophysics Data System (ADS)

    Schreyer, K.; Henning, T.; Koempe, C.; Harjunpaeae, P.

    1996-02-01

    We have selected 67 objects for observation that are presumably massive young stellar objects. They were from the IRAS Point Source Catalogue based on their infrared flux (Fnu_>=500Jy at 100μm). All objects have been surveyed in the NH_3_(1,1) and (2,2) lines, and a subsample of 53 objects in the rotational line of HCO^+^(J=1-0). 25 objects (37%) were detected in the NH_3_(1,1) line, 18 objects (27%) in the NH_3_(2,2) line, and 38 objects (72%) in the HCO^+^ line. Two objects, IRAS 06058+2138 and IRAS 06061+2151, have been mapped in the two ammonia transitions. From the molecular line data, we have derived the kinetic temperature T_kin_ and the NH_3_ column densities. These data were combined with data from the literature and data derived from the IRAS fluxes (dust colour temperature T_d_, optical depth τ, luminosity). No clear correlations were found; the data are, however, consistent with least square fits found by Wouterloot et al. (1988a). The probability to detect H_2_O maser sources is strongly correlated with the detection of NH_3_ emission: Water maser emission has been seen towards 83% of those objects with clear detections of NH_3_(1,1) and (2,2) lines.

  4. 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.

  5. Observational constraints on solar nebula nitrogen chemistry - N2/NH3

    NASA Technical Reports Server (NTRS)

    Womack, Maria; Wyckoff, Susan; Ziurys, L. M.

    1992-01-01

    Observations of N2(+) and NH2 in Comet Halley and N2H(+) and NH3 in nine Galactic star-forming regions are used to determine the average N2/NH3 abundance ratio in these objects. For Comet Halley, N2/NH3 of about 0.1 is found, and for the quiescent gas in a sample of star-forming regions, N2/NH3 of about 170 +/- 100. The cometary N2/NH3 ratio corrected for gas-phase elemental nitrogen depletion in Comet Halley indicates that the gas component in the comet-forming region of the solar nebula was N2/NH3 of about 4. It is concluded that more realistic models which include condensation fractionation effects are required before the N2 and NH3 abundances in comet volatiles can be related to star-forming regions.

  6. 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

  7. 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 ...

  8. 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 ...

  9. 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 ...

  10. Diode laser saturation spectroscopy of NH3

    NASA Technical Reports Server (NTRS)

    Jennings, D. E.

    1978-01-01

    Saturation of molecular transitions using a tuneable diode laser was demonstrated for the first time using a standing-wave cavity configuration with an f/8 beam focussed at the sample. Observed saturation effects in NH3 transitions near 888/cm include sub-Doppler (Lamb-dip) resonances at line center.

  11. 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 ...

  12. Photolysis of solid NH3 and NH3-H2O mixtures at 193 nm

    NASA Astrophysics Data System (ADS)

    Loeffler, M. J.; Baragiola, R. A.

    2010-12-01

    We have studied UV photolysis of solid ammonia and ammonia-dihydrate samples at 40 K, using infrared spectroscopy, mass spectrometry, and microgravimetry. We have shown that in the pure NH3 sample, the main species ejected are NH3, H2, and N2, where the hydrogen and nitrogen increase with laser fluence. This increase in N2 ejection with laser fluence explains the increase in mass loss rate detected by a microbalance. In contrast, for the ammonia-water mixture, we see very weak signals of H2 and N2 in the mass spectrometer, consistent with the very small mass loss during the experiment and with a <5% decrease in the NH3 infrared absorption bands spectroscopy after a fluence of ˜3 × 1019 photons/cm2. The results imply that ammonia-ice mixtures in the outer solar system are relatively stable under solar irradiation.

  13. 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.

  14. 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).

  15. NH3-promoted ligand lability in eleven-vertex rhodathiaboranes.

    PubMed

    Calvo, Beatriz; Roy, Beatriz; Macías, Ramón; Artigas, Maria Jose; Lahoz, Fernando J; Oro, Luis A

    2014-12-01

    The reaction of the 11-vertex rhodathiaborane, [8,8-(PPh3)2-nido-8,7-RhSB9H10] (1), with NH3 affords inmediately the adduct, [8,8,8-(NH3)(PPh3)2-nido-8,7-RhSB9H10] (4). The NH3-Rh interaction induces the labilization of the PPh3 ligands leading to the dissociation product, [8,8-(NH3)(PPh3)-nido-8,7-RhSB9H10] (5), which can then react with another molecule of NH3 to give [8,8,8-(NH3)2(PPh3)-nido-8,7-RhSB9H10] (6). These clusters have been characterized in situ by multielement NMR spectroscopy at different temeperatures. The variable temperature behavior of the system demonstrates that the intermediates 4-6 are in equilibrium, involving ligand exchange processes. On the basis of low intensity signals present in the (1)H NMR spectra of the reaction mixture, some species are tentatively proposed to be the bis- and tris-NH3 ligated clusters, [8,8-(NH3)2-nido-8,7-RhSB9H10] (7) and [8,8,8-(NH3)3-nido-8,7-RhSB9H10] (8). After evaporation of the solvent and the excess of NH3, the system containing species 4-8 regenerates the starting reactant, 1, thus closing a stoichiometric cycle of ammonia addition and loss. After 40 h at room temperature, the reaction of 1 with NH3 gives the hydridorhodathiaborane, [8,8,8-(H)(PPh3)2-nido-8,7-RhSB9H9] (2), as a single product. The reported rhodathiaboranes show reversible H3N-promoted ligand lability, which implies weak Rh-N interactions, leading to a rare case of metal complexes that circumvent "classical" Werner chemistry.

  16. Quantum IR line list of NH3 and isotopologues for ISM and dwarf studies

    NASA Astrophysics Data System (ADS)

    Huang, Xinchuan; Schwenke, David W.; Lee, Timothy J.; Sung, Keeyoon; Brown, Linda R.

    2013-03-01

    Ammonia (NH3) was the first polyatomic molecule observed in the ISM. Its importance in interstellar molecules is only second to CO because its rovibrational spectroscopic signature can be used very effectively at deducing the conditions of the interstellar environment such as temperature and density, and because it is found in so many different interstellar objects in a wide temperature range. However, experimental determination of NH3 IR spectra is extremely difficult due to the large-amplutide inversion vibration, and the existing HITRAN2008 database for NH3 is limited in temperature, coverage, completeness, and accuracy. With rapid progress in theoretical chemistry and computational resources, now we are able to generate a highly reliable/accurate IR line list of NH3 (and its isotopologues) for astronomical studies. Exact quantum rovibrational computations on an empirically refined potential energy surface (with nonadiabatic corrections included) have achieved accuracies of 0.02-0.05 cm-1 (for line position) and better than 85-95% (for line intensity) for both NH3 and 15NH3 spectra. The unique feature of our work is that our predictions are essentially as accurate as reproducing existing measurements, suitable for synthetic simulation of various astrophysical environments or objects. The reliabilty and accuracy of our predictions for missing bands and higher energies computed on HSL-2 (Fig. 1) have been proved by the most recent high-resolution experiments and extended up to 7000 cm-1. See Huang et al. 2008, Huang et al. 2011, & Sung et al. 2012 for more details.

  17. 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...

  18. Validation of model calculation of ammonia deposition in the neighbourhood of a poultry farm using measured NH 3 concentrations and N deposition

    NASA Astrophysics Data System (ADS)

    Sommer, S. G.; Østergård, H. S.; Løfstrøm, P.; Andersen, H. V.; Jensen, L. S.

    Substantial emission of ammonia (NH 3) from animal houses and the related high local deposition of NH 3-N are a threat to semi-natural nitrogen-deficient ecosystems situated near the NH 3 source. In Denmark, there are regulations limiting the level of NH 3 emission from livestock houses near N-deficient ecosystems that are likely to change due to nitrogen (N) enrichment caused by NH 3 deposition. The models used for assessing NH 3 emission from livestock production, therefore, need to be precise, as the regulation will affect both the nature of the ecosystem and the economy of the farmer. Therefore a study was carried out with the objective of validating the Danish model used to monitor NH 3 transport, dispersion and deposition from and in the neighbourhood of a chicken farm. In the study we measured NH 3 emission with standard flux measuring methods, NH 3 concentrations at increasing distances from the chicken houses using passive diffusion samplers and deposition using 15N-enriched biomonitors and field plot studies. The dispersion and deposition of NH 3 were modelled using the Danish OML-DEP model. It was also shown that model calculations clearly reflect the measured NH 3 concentration and N deposition. Deposition of N measured by biomonitors clearly reflected the variation in NH 3 concentrations and showed that deposition was not significantly different from zero ( P < 0.05) at distances greater than 150-200 m from these chicken houses. Calculations confirmed this, as calculated N deposition 320 m away from the chicken farm was only marginally affected by the NH 3 emission from the farm. There was agreement between calculated and measured deposition showing that the model gives true estimates of the deposition in the neighbourhood of a livestock house emitting NH 3.

  19. Probing NH3 Formation in Oxygen-rich Circumstellar Envelopes

    NASA Astrophysics Data System (ADS)

    Wong, K. T.; Menten, K. M.; Kamiński, T.; Wyrowski, F.

    2015-08-01

    The chemistry of ammonia (NH3) in the circumstellar envelopes (CSEs) of AGB stars and red supergiants is poorly understood. Thermodynamic equilibrium (TE) chemistry predicts an abundance of ≲10-8, orders of magnitudes below values reported from observations (˜10-7-10-6). To date, there is no consistent model explaining the origin of such high abundances. To better understand the physical conditions necessary for the formation of NH3, we analysed the NH3 rotational and inversion lines observed in the spectrum of IK Tauri. The strength of the rotational lines clearly confirms the high abundances as compared to the TE predictions. From 1D radiative transfer modelling including infrared pumping via vibrational bands, we infer a total NH3 abundance of 7.5× 10-7, along with an ortho-to-para ratio (OPR) of ≤ 1.5 : 1, slightly above the statistical equilibrium value of 1. We discuss these preliminary results and the possible origin of NH3 in oxygen-rich CSEs.

  20. Objective assessment of image quality. IV. Application to adaptive optics

    PubMed Central

    Barrett, Harrison H.; Myers, Kyle J.; Devaney, Nicholas; Dainty, Christopher

    2008-01-01

    The methodology of objective assessment, which defines image quality in terms of the performance of specific observers on specific tasks of interest, is extended to temporal sequences of images with random point spread functions and applied to adaptive imaging in astronomy. The tasks considered include both detection and estimation, and the observers are the optimal linear discriminant (Hotelling observer) and the optimal linear estimator (Wiener). A general theory of first- and second-order spatiotemporal statistics in adaptive optics is developed. It is shown that the covariance matrix can be rigorously decomposed into three terms representing the effect of measurement noise, random point spread function, and random nature of the astronomical scene. Figures of merit are developed, and computational methods are discussed. PMID:17106464

  1. Objective assessment of image quality. IV. Application to adaptive optics.

    PubMed

    Barrett, Harrison H; Myers, Kyle J; Devaney, Nicholas; Dainty, Christopher

    2006-12-01

    The methodology of objective assessment, which defines image quality in terms of the performance of specific observers on specific tasks of interest, is extended to temporal sequences of images with random point spread functions and applied to adaptive imaging in astronomy. The tasks considered include both detection and estimation, and the observers are the optimal linear discriminant (Hotelling observer) and the optimal linear estimator (Wiener). A general theory of first- and second-order spatiotemporal statistics in adaptive optics is developed. It is shown that the covariance matrix can be rigorously decomposed into three terms representing the effect of measurement noise, random point spread function, and random nature of the astronomical scene. Figures of merit are developed, and computational methods are discussed.

  2. Objective assessment of image quality. IV. Application to adaptive optics.

    PubMed

    Barrett, Harrison H; Myers, Kyle J; Devaney, Nicholas; Dainty, Christopher

    2006-12-01

    The methodology of objective assessment, which defines image quality in terms of the performance of specific observers on specific tasks of interest, is extended to temporal sequences of images with random point spread functions and applied to adaptive imaging in astronomy. The tasks considered include both detection and estimation, and the observers are the optimal linear discriminant (Hotelling observer) and the optimal linear estimator (Wiener). A general theory of first- and second-order spatiotemporal statistics in adaptive optics is developed. It is shown that the covariance matrix can be rigorously decomposed into three terms representing the effect of measurement noise, random point spread function, and random nature of the astronomical scene. Figures of merit are developed, and computational methods are discussed. PMID:17106464

  3. 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

  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. 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.

  6. 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.

  7. 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.

  8. NARSTO EPA SS HOUSTON NH3 HNO3 DATA

    Atmospheric Science Data Center

    2014-04-25

    NARSTO EPA SS HOUSTON NH3 HNO3 DATA Project Title:  NARSTO Discipline:  ... Parameters:  Ammonia Nitric Acid Order Data:  ASDC Order Tool:   Order Data Guide Documents:  ... Earth Related Data:  Environmental Protection Agency Supersites Houston, Texas SCAR-B Block:  ...

  9. NH3 and PH3 adsorption through single walled ZnS nanotube: First principle insight

    NASA Astrophysics Data System (ADS)

    Khan, Md. Shahzad; Srivastava, Anurag; Chaurasiya, Rajneesh; Khan, Mohd. Shahid; Dua, Piyush

    2015-09-01

    The density functional theory (DFT) based adsorption analysis of NH3 and PH3 gas molecule has been made for confirming the sensing behaviour of ZnS nanotube. For a particular orientation of XH3 (X = N or P), the ZnS nanotube is found to be a good sensor with Zn as interactive site, discussed in terms of chemisorption and physisorption. Partial density of state (PDOS) analysis reveals strong interaction between few selected fragments from XH3 and ZnS nanotube. The quality of interaction for most favourable orientation is further scrutinized using charge decomposition analysis (CDA) analysis and sensing ability through current-voltage (I-V) characteristics.

  10. 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.

  11. Studies of elastic e-NH3 collisions

    NASA Technical Reports Server (NTRS)

    Pritchard, H. P.; Lima, M. A. P.; Mckoy, V.

    1989-01-01

    Differential and momentum-transfer cross sections for the elastic scattering of electrons by NH3 have been obtained for collision energies of between 2.5 and 20 eV using the fixed-nuclei static-exchange approximation of the Schwinger variational principle. At intermediate and large scattering angles, good agreement is found between calculated and relative experimental cross sections. The differential cross sections reveal evidence of a weak d-wave enhancement around 8 eV.

  12. First principles study of NH3 adsorption on carbon nanowires

    NASA Astrophysics Data System (ADS)

    Tapia, Jorge-Alejandro; Sanchez, Alvaro-Daniel; Acosta, Cesar; Canto, Gabriel

    2009-03-01

    Recently has been reported a new type of one-dimensional carbon structures. Carbon nanowires formed by a linear carbon-atom chain inside an armchair (5,5) carbon nanotube has been observed using high-resolution transmission electron microscopy. Theoretical and experimental studies of the NH3 adsorption in the carbon nanotubes report changes in the electronic properties of the carbon nanotubes. In the present work we have studied the electronic and structure properties of carbon nanowires (chain@SWCNT) when NH3 atoms are adsorbed. We used the Density Functional Theory and the calculations where performed by the pseudopotentials LCAO method (SIESTA code) and the Generalized Gradient Approximation (GGA) for the exchange-correlation potential. We have analyzed the changes in the atomic structure and density of states (DOS). We found that the electronic character of the carbon chain of the chain@SWCNT system, can be modulate by NH3 adsorption. This research was supported by SEP under Grant No. PROMEP/103.5/07/2595 and the Consejo Nacional de Ciencia y Tecnolog'ia (Conacyt) under Grants No. 82497 and 60534.

  13. Advanced ammonia (NH3) monitoring system for industrial applications

    NASA Astrophysics Data System (ADS)

    Spector, Oded; Jacobson, Esther

    1999-12-01

    The present paper describes an Electro-Optical Monitoring System developed for the real time in-situ monitoring of Ammonia (NH3) emissions, at very low concentrations in air, well below the hazardous levels. Ammonia is the starting chemical for almost all industrially produced nitrogen compounds and is therefore one of the most important inorganic raw materials. Due to its unique chemical and physical characteristics, the Ammonia (NH3) anhydrous gas is used in various industrial applications such as: Air Conditioning, Refrigeration (including space shuttles), Agriculture and Chemical Processing. NH3 gas, being a highly irritant toxic and flammable gas with a pungent odor detectable by human perception at 53 ppm, has a TLV-TWA of 25 ppm (TLV-STEL of 35 ppm) and a lower explosive limit (LEL) of 15% in air. Being extremely corrosive and irritating to the skin, eyes, nose and respiratory tract, (irritation begins at 130 - 200 ppm), exposures to high concentrations (above 2500 ppm) are life threatening, thus early detection of Ammonia at concentrations up to 50 ppm is essential to prevent its toxic influence. Existing detection methods for NH3 rely mainly on chemical sensors and analytical methods that require the gas to be sampled and introduced into the detection system via a probe, compared to various standards (for determining the concentration) and the result is not always reflecting the actual gas concentration. The emerging optical open path remote sensing technology that analyzes the specific 'finger print' absorption characteristics of NH3 in various narrow spectral bands, specifically in the UV solar blind band, is discussed including the rationale of the detection algorithm and system design. The system offers warning and alarm signals set at the above low concentration detection sensitivity, (10 - 50 ppm(DOT)m) thus providing reliable Ammonia detection over an air path from 3 (including air-duct applications) to 400 ft (1 - 120 m). Typical installations of

  14. Emission factor of ammonia (NH3) from on-road vehicles in China: tunnel tests in urban Guangzhou

    NASA Astrophysics Data System (ADS)

    Liu, Tengyu; Wang, Xinming; Wang, Boguang; Ding, Xiang; Deng, Wei; Lü, Sujun; Zhang, Yanli

    2014-05-01

    Ammonia (NH3) is the primary alkaline gas in the atmosphere that contributes to formation of secondary particles. Emission of NH3 from vehicles, particularly gasoline powered light duty vehicles equipped with three-way catalysts, is regarded as an important source apart from emissions from animal wastes and soils, yet measured emission factors for motor vehicles are still not available in China, where traffic-related emission has become an increasingly important source of air pollutants in urban areas. Here we present our tunnel tests for NH3 from motor vehicles under ‘real world conditions’ in an urban roadway tunnel in Guangzhou, a central city in the Pearl River Delta (PRD) region in south China. By attributing all NH3 emissions in the tunnel to light-duty gasoline vehicles, we obtained a fuel-based emission rate of 2.92 ± 0.18 g L-1 and a mileage-based emission factor of 229.5 ± 14.1 mg km-1. These emission factors were much higher than those measured in the United States while measured NO x emission factors (7.17 ± 0.60 g L-1 or 0.56 ± 0.05 g km-1) were contrastingly near or lower than those previously estimated by MOBILE/PART5 or COPERT IV models. Based on the NH3 emission factors from this study, on-road vehicles accounted for 8.1% of NH3 emissions in the PRD region in 2006 instead of 2.5% as estimated in a previous study using emission factors taken from the Emission Inventory Improvement Program (EIIP) in the United States.

  15. 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.

  16. 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

  17. 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.

  18. Enhanced Performance of Perovskite CH3NH3PbI3 Solar Cell by Using CH3NH3I as Additive in Sequential Deposition.

    PubMed

    Xie, Yian; Shao, Feng; Wang, Yaoming; Xu, Tao; Wang, Deliang; Huang, Fuqiang

    2015-06-17

    Sequential deposition is a widely adopted method to prepare CH3NH3PbI3 on mesostructured TiO2 electrode for organic lead halide perovskite solar cells. However, this method often suffers from the uncontrollable crystal size, surface morphology, and residual PbI2 in the resulting CH3NH3PbI3, which are all detrimental to the device performance. We herein present an optimized sequential solution deposition method by introducing different amount of CH3NH3I in PbI2 precursor solution in the first step to prepare CH3NH3PbI3 absorber on mesoporous TiO2 substrates. The addition of CH3NH3I in PbI2 precursor solution can affect the crystallization and composition of PbI2 raw films, resulting in the variation of UV-vis absorption and surface morphology. Proper addition of CH3NH3I not only enhances the absorption but also improves the efficiency of CH3NH3PbI3 solar cells from 11.13% to 13.37%. Photoluminescence spectra suggest that the improvement of device performance is attributed to the decrease of recombination rate of carriers in CH3NH3PbI3 absorber. This current method provides a highly repeatable route for enhancing the efficiency of CH3NH3PbI3 solar cell in the sequential solution deposition method.

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 Perovskites for Solar Cell Applications

    NASA Astrophysics Data System (ADS)

    Umari, Paolo; Mosconi, Edoardo; de Angelis, Filippo

    2014-03-01

    Hybrid AMX3 perovskites (A = Cs, CH3NH3; M = Sn, Pb; X = halide) have revolutionized the scenario of emerging photovoltaic technologies, with very recent results demonstrating 15% efficient solar cells. The CH3NH3PbI3/MAPb(I1-xClx)3 perovskites have dominated the field, while the similar CH3NH3SnI3 has not been exploited for photovoltaic applications. Replacement of Pb by Sn would facilitate the large uptake of perovskite-based photovoltaics. Despite the extremely fast progress, the materials electronic properties which are key to the photovoltaic performance are relatively little understood. Density Functional Theory electronic structure methods have so far delivered an unbalanced description of Pb- and Sn-based perovskites. Here we develop an effective GW method incorporating spin-orbit coupling which allows us to accurately model the electronic, optical and transport properties of CH3NH3SnI3 and CH3NH3PbI3, opening the way to new materials design. The different CH3NH3SnI3 and CH3NH3PbI3 electronic properties are discussed in light of their exploitation for solar cells, and found to be dominantly due to relativistic effects. These effects stabilize the CH3NH3PbI3 material towards oxidation, by inducing a deeper valence band edge. Relativistic effects, however, also increase the material band-gap compared to CH3NH3SnI3, due to the valence band energy downshift (~0.7 eV) being only partly compensated by the conduction band downshift (~0.2 eV).

  5. Removal of high concentrations of NH(3) by a combined photoreactor and biotrickling filter system.

    PubMed

    Wu, Li-Chun; Kuo, Cheng-Lang; Chung, Ying-Chien

    2011-01-01

    Average emission levels as high as 800 ppm(v) NH(3) have often been found during the anaerobic fermentation process. At these levels, NH(3) is regarded as an environmental toxic compound. High concentrations of NH(3) gas are difficult to treat in a single treatment process, suggesting that, in terms of economic cost and treatment performance, a coupled system may be a feasible technological alternative. In the coupled TiO(2) photocatalytic-biological treatment system evaluated here, the optimal gas retention time for NH(3) removal--in terms of removal efficiency and capital cost--was 26 s. High gas temperatures, high NH(3) concentrations, and low oxygen contents were unfavorable conditions for NH(3) removal by the photoreactor. The coupled system successfully removed concentrated NH(3) gas (R % > 97 %) under disrupted and shutdown conditions. The photoreactor component of the system successfully fulfilled its role as a pretreatment process and enhanced the performance of the biotrickling filter at a high inlet NH(3) load (2,277 g-N m(-3) day(-1)). Potential ammonia-oxidizing bacteria, including Bacillus cereus, Pseudomonas aeruginosa, and Stenotrophomonas sp., were isolated under the high inlet NH(3) load condition. These microbial strains have a potential as biological agents in the removal of high concentrations of NH(3) in waste gas or wastewater.

  6. 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

  7. 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.

  8. Rotational study of the NH3-CO complex: millimeter-wave measurements and ab initio calculations.

    PubMed

    Surin, L A; Potapov, A; Dolgov, A A; Tarabukin, I V; Panfilov, V A; Schlemmer, S; Kalugina, Y N; Faure, A; van der Avoird, A

    2015-03-21

    The rotational spectrum of the van der Waals complex NH3-CO has been measured with the intracavity OROTRON jet spectrometer in the frequency range of 112-139 GHz. Newly observed and assigned transitions belong to the K = 0-0, K = 1-1, K = 1-0, and K = 2-1 subbands correlating with the rotationless (jk)NH3 = 00 ground state of free ortho-NH3 and the K = 0-1 and K = 2-1 subbands correlating with the (jk)NH3 = 11 ground state of free para-NH3. The (approximate) quantum number K is the projection of the total angular momentum J on the intermolecular axis. Some of these transitions are continuations to higher J values of transition series observed previously [C. Xia et al., Mol. Phys. 99, 643 (2001)], the other transitions constitute newly detected subbands. The new data were analyzed together with the known millimeter-wave and microwave transitions in order to determine the molecular parameters of the ortho-NH3-CO and para-NH3-CO complexes. Accompanying ab initio calculations of the intermolecular potential energy surface (PES) of NH3-CO has been carried out at the explicitly correlated coupled cluster level of theory with single, double, and perturbative triple excitations and an augmented correlation-consistent triple zeta basis set. The global minimum of the five-dimensional PES corresponds to an approximately T-shaped structure with the N atom closest to the CO subunit and binding energy De = 359.21 cm(-1). The bound rovibrational levels of the NH3-CO complex were calculated for total angular momentum J = 0-6 on this intermolecular potential surface and compared with the experimental results. The calculated dissociation energies D0 are 210.43 and 218.66 cm(-1) for ortho-NH3-CO and para-NH3-CO, respectively.

  9. 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.

  10. 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.

  11. Ultrafast and sensitive room temperature NH3 gas sensors based on chemically reduced graphene oxide

    NASA Astrophysics Data System (ADS)

    Hu, Nantao; Yang, Zhi; Wang, Yanyan; Zhang, Liling; Wang, Ying; Huang, Xiaolu; Wei, Hao; Wei, Liangmin; Zhang, Yafei

    2014-01-01

    Ultrafast and sensitive room temperature NH3 gas sensors based on chemically reduced graphene oxide (rGO) are demonstrated in this work. rGO, which was prepared via the reduction of graphene oxide by pyrrole, exhibited excellent responsive sensitivity and selectivity to ammonia (NH3) gas. The high sensing performance of these rGO sensors with resistance change as high as 2.4% and response time as fast as 1.4 s was realized when the concentration of NH3 gas was as low as 1 ppb. Furthermore, the rGO sensors could rapidly recover to their initial states with IR illumination. The devices also showed excellent repeatability and selectivity to NH3. These rGO sensors, with low cost, low power, and easy fabrication, as well as scalable properties, showed great potential for ultrasensitive detection of NH3 gas in a wide variety of fields.

  12. 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.

  13. 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

  14. Fluxes of NH3 and CO2 over upland moorland in the vicinity of agricultural land

    NASA Astrophysics Data System (ADS)

    Milford, Celia; Hargreaves, Ken J.; Sutton, Mark A.; Loubet, Benjamin; Cellier, Pierre

    2001-10-01

    Intensive field measurements of NH3 and CO2 exchange were made over a wet heathland in the vicinity (<500 m) of sheep pastures in the Cairngorm mountains of Scotland for a two-week period in the summer. Fluxes of NH3 were determined using the aerodynamic gradient method with a 3-height continuous denuder system; fluxes of CO2 were determined using eddy correlation, while sensible and latent heat fluxes were determined by both methods. Few studies have measured NH3 and CO2 fluxes simultaneously, making these measurements relevant to compare exchange dynamics. Both NH3 and CO2 exchanged bidirectionally, in response to a combination of biological (foliar, soil) and physico-chemical controls (solubility). NH3 was deposited rapidly to leaf surfaces, although during warm, dry daytime conditions periods of emission occurred, explained by the existence of a compensation point concentration for NH3. By contrast, CO2 followed a characteristic pattern of absorption during the day associated with net photosynthesis and emission at night. Both gases showed net uptake from the atmosphere, at 30 μmol NH3 m-2 d-1 and 74 mmol CO2 m-2 d-1. In southeast winds, NH3 emissions from the sheep pasture caused a significant advection error to the measured fluxes (>10%). Corrections were applied using a local-scale dispersion-exchange model. The analysis highlights how advection modifies the classical one-dimensional inferential resistance approach. It is concluded that ecosystems in the vicinity of agricultural land receive more dry deposition than would be estimated using NH3 concentration monitoring and standard inferential models. In the present study, this effect represented an overall increase in total NH3 deposition of 32%.

  15. 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

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

    NASA Astrophysics Data System (ADS)

    Song, Hongwei; Yang, Minghui; Guo, Hua

    2016-10-01

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

  17. 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.

  18. Photosynthesis of Quercus suber is affected by atmospheric NH3 generated by multifunctional agrosystems.

    PubMed

    Pintó-Marijuan, Marta; Da Silva, Anabela Bernardes; Flexas, Jaume; Dias, Teresa; Zarrouk, Olfa; Martins-Loução, Maria Amélia; Chaves, Maria Manuela; Cruz, Cristina

    2013-12-01

    Montados are evergreen oak woodlands dominated by Quercus species, which are considered to be key to biodiversity conservation and ecosystem services. This ecosystem is often used for cattle breeding in most regions of the Iberian Peninsula, which causes plants to receive extra nitrogen as ammonia (NH(3)) through the atmosphere. The effect of this atmospheric NH(3) (NH(3atm)) on ecosystems is still under discussion. This study aimed to evaluate the effects of an NH(3atm) concentration gradient downwind of a cattle barn in a Montado area. Leaves from the selected Quercus suber L. trees along the gradient showed a clear influence of the NH(3) on δ(13)C, as a consequence of a strong limitation on the photosynthetic machinery by a reduction of both stomatal and mesophyll conductance. A detailed study of the impact of NH(3atm) on the photosynthetic performance of Q. suber trees is presented, and new mechanisms by which NH(3) affects photosynthesis at the leaf level are suggested.

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

    NASA Astrophysics Data System (ADS)

    Dammers, Enrico; Palm, Mathias; Van Damme, Martin; Vigouroux, Corinne; Smale, Dan; Conway, Stephanie; Toon, Geoffrey C.; Jones, Nicholas; Nussbaumer, Eric; Warneke, Thorsten; Petri, Christof; Clarisse, Lieven; Clerbaux, Cathy; Hermans, Christian; Lutsch, Erik; Strong, Kim; Hannigan, James W.; Nakajima, Hideaki; Morino, Isamu; Herrera, Beatriz; Stremme, Wolfgang; Grutter, Michel; Schaap, Martijn; Wichink Kruit, Roy J.; Notholt, Justus; Coheur, Pierre-F.; Erisman, Jan Willem

    2016-08-01

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

  20. 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.

  1. 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).

  2. Matrix Isolation Spectroscopy and Nuclear Spin Conversion of NH3 and ND3 in Solid Parahydrogen

    NASA Astrophysics Data System (ADS)

    Ruzi, Mahmut; Anderson, David T.

    2013-10-01

    We present matrix isolation infrared absorption spectra of NH3 and ND3 trapped in solid parahydrogen (pH2) at temperatures around 1.8 K. We used the relatively slow nuclear spin conversion (NSC) of NH3 and ND3 in freshly deposited pH2 samples as a tool to assign the sparse vibration-inversion-rotation (VIR) spectra of NH3 in the regions of the -2, -4, 2-4, -1, and -3 bands and ND3 in the regions of the -2, -4, -1, and -3 fundamentals. Partial assignments are also presented for various combination bands of NH3. Detailed analysis of the -2 bands of NH3 and ND3 indicates that both isotopomers are nearly free rotors; that the vibrational energy is blue-shifted by 1-2%; and that the rotational constants and inversion tunneling splitting are 91-94% and 67-75%, respectively, of the gas-phase values. The line shapes of the VIR absorptions are narrow (0.2-0.4 cm-1) for upper states that cannot rotationally relax and broad (>1 cm-1) for upper states that can rotationally relax. We report and assign a number of NH3-induced infrared absorption features of the pH2 host near 4150 cm-1, along with a cooperative transition that involves simultaneous vibrational excitation of a pH2 molecule and rotation-inversion excitation of NH3. The NSCs of NH3 and ND3 were found to follow first-order kinetics with rate constants at 1.8 K of k = 1.88(16) - 10-3 s-1 and k = 1.08(8) - 10-3 s-1, respectively. These measured rate constants are compared to previous measurements for NH3 in an Ar matrix and with the rate constants measured for other dopant molecules isolated in solid pH2.

  3. Electrical properties and conduction mechanism of [C2H5NH3]2CuCl4 compound

    NASA Astrophysics Data System (ADS)

    Mohamed, C. Ben; Karoui, K.; Jomni, F.; Guidara, K.; Rhaiem, A. Ben

    2015-02-01

    The [(C2H5)NH3]2CuCl4 compound was prepared and characterized by several technique: the X-ray powder diffraction confirms the purity of the synthetized compound, the differential scanning calorimetric show several phase transitions at 236 K, 330 K, 357 K and 371 K, the dialectical properties confirms the ferroelectric-paraelectric phase transition at 238 K, which is reported by V. Kapustianyk et al. (2007) [1]. The two semi-circles observed in the complex impedance identify the presence of the grain interior and grain boundary contributions to the electrical response in this material. The equivalent circuit is modeled by a combination series of two parallel RP-CPE circuits. The temperature dependence of the alternative current conductivity (σg) and direct current conductivity (σdc) confirm the observed transitions in the calorimetric study. The (AC) electrical conduction in [(C2H5)NH3]2CuCl4 was studied by two processes that can be attributed to a hopping transport mechanism: the non-overlapping small polaron tunneling (NSPT) model in phase III and the correlated barrier hopping (CBH) model in phases I, II, IV, V and VI.

  4. Seasonal variability of ambient NH3, NO, NO2 and SO2 over Delhi.

    PubMed

    Sharma, S K; Datta, A; Saud, T; Saxena, M; Mandal, T K; Ahammed, Y N; Arya, B C

    2010-01-01

    We present the diurnal and seasonal variability of ambient NH3, NO, NO2 and SO2 over Delhi, India. Ambient NH3, NO and NO2 were measured continuously during winter, summer and autumn seasons using NH3- and NOx-analyzer, which operates by chemiluminescence method with a higher estimation efficiency (> 90%) than the chemical trap method (reproducibility 4.7%). Prominent diurnal, day-to-day and seasonal variations of ambient mixing ratio of NH3, NO, NO2 and SO2 were observed during the study period. Seasonal variation with higher mixing ratio in winter was observed for all measured trace gases except NO. Day-night variation of all measured trace gases observed was higher in winter in comparison with summer. Late morning increase in NO2 mixing ratio might be attributed to conversion of NO to NO2 with the interaction of O3. PMID:21174992

  5. 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.

  6. 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

  7. 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.

  8. Optical monitoring of CH3NH3PbI3 thin films upon atmospheric exposure

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    CH3NH3PbI3 perovskite films of interest for photovoltaic (PV) devices have been prepared by (i) vapor deposition and (ii) solution processing. Complex dielectric function (ε  =  ε 1  +  iε 2) spectra and structural parameters of the films have been extracted using near infrared to ultraviolet spectroscopic ellipsometry. In situ real time spectroscopic ellipsometry (RTSE) over a 48 h period has been performed on vapor deposited CH3NH3PbI3 after the deposition in normal atmospheric laboratory ambient conditions. Analysis of RTSE data for vapor deposited CH3NH3PbI3 film prepared under un-optimized conditions identifies phase segregated PbI2 and CH3NH3I at the substrate/film interface and unreacted PbI2 and CH3NH3I on the film surface. This analysis also provides the time dependence of the effective thicknesses of perovskite film, unreacted components, and phase segregated layers to track CH3NH3PbI3 decomposition.

  9. Improvement of thermal stability of nickel silicide film using NH3 plasma treatment

    NASA Astrophysics Data System (ADS)

    Park, Jingyu; Jeon, Heeyoung; Kim, Hyunjung; Jang, Woochool; Kim, Jinho; Kang, Chunho; Yuh, Junhan; Jeon, Hyeongtag

    2014-09-01

    In this study, the effects of NH3 plasma pre-treatment on the characteristics of NiSi films were investigated. Nickel film was deposited on a Si(100) substrate by meal-organic chemical vapor deposition (MOCVD) using Ni(iPr-DAD)2 as a Ni precursor and NH3 gas as a reactant. Before the Ni deposition, silicon substrate was treated by NH3 plasma with various flow rates to adjust the amount of inserted hydrogen and nitrogen atoms. The Ni films showed a considerable low sheet resistance around 12 Ω/□, irrespective of the NH3 plasma pre-treatment conditions. The sheet resistance of the all Ni films was decreased after annealing at 500 °C due to formation of a low resistive NiSi phase. NiSi films with a high flow rate of NH3 plasma pre-treatment exhibited a lower sheet resistance and smoother interface between NiSi and the Si substrate than the low flow rate of the NH3 plasma pre-treated NiSi films because lots of nitrogen atoms incorporated at grain boundary of NiSi which result in reduce total surface/interface energy of NiSi and enhancement interface characteristics.

  10. Racemic monoperoxovanadium(V) complexes with achiral OO and ON donor set heteroligands: synthesis, crystal structure and stereochemistry of [NH3(CH2)2NH3][VO(O2)(ox)(pic)].2H2O and [NH3(CH2)2NH3][VO(O2)(ox)(pca)].

    PubMed

    Tatiersky, Jozef; Schwendt, Peter; Sivák, Michal; Marek, Jaromír

    2005-07-01

    Monoperoxovanadium(V) complexes, [NH3(CH2)2NH3][VO(O2)(ox)(pic)].2H2O (1) and [NH3(CH2)2NH3][VO(O2)(ox)(pca)] (2) [NH3(CH2)2NH3 = ethane-1,2-diammonium(2+), ox=oxalate(2-), pic=pyridine-2-carboxylate(1-), pca=pyrazine-2-carboxylate(1-)], were synthesized and characterized by X-ray analysis, IR and Raman spectroscopies. The five equatorial positions of the pentagonal bipyramid around the vanadium atoms are occupied by the eta2-peroxo ligand, two oxygen atoms of the ox, and the nitrogen atom of the pic or pca ligands, respectively. The oxo ligand and the oxygen atom of pic or pca are in the axial positions. Networks of X-HO (X=C, N or O) hydrogen bonds, and pi-pi interactions between aromatic rings in and anion-pi interactions in , determine the molecular packings and build up the supramolecular architecture. Three stereochemical rules for occupation of the donor sites in two-heteroligand [VO(O2)(L1)(L2)] complexes (L1, L2 are bidentate neutral or differently charged anionic heteroligands providing an OO, NN or ON donor set) are discussed. and crystallize as racemic compounds. The 51V NMR spectra proved that the parent complex anions of and partially decompose on dissolution in water to the monoperoxo-ox, -pic or -pca complexes.

  11. 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

  12. 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

  13. 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

  14. 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

  15. SUBSTELLAR OBJECTS IN NEARBY YOUNG CLUSTERS (SONYC). IV. A CENSUS OF VERY LOW MASS OBJECTS IN NGC 1333

    SciTech Connect

    Scholz, Alexander; Muzic, Koraljka; Bonavita, Mariangela; Jayawardhana, Ray; Geers, Vincent; Tamura, Motohide

    2012-01-01

    SONYC-Substellar Objects in Nearby Young Clusters-is a program to investigate the frequency and properties of young substellar objects with masses down to a few times that of Jupiter. Here we present a census of very low mass objects in the {approx}1 Myr old cluster NGC 1333. We analyze near-infrared spectra taken with Fiber Multi-Object Spectrograph/Subaru for 100 candidates from our deep, wide-field survey and find 10 new likely brown dwarfs with spectral types of M6 or later. Among them, there are three with {approx}>M9 and one with early L spectral type, corresponding to masses of 0.006 to {approx}< 0.02 M{sub Sun }, so far the lowest mass objects identified in this cluster. The combination of survey depth, spatial coverage, and extensive spectroscopic follow-up makes NGC 1333 one of the most comprehensively surveyed clusters for substellar objects. In total, there are now 51 objects with spectral type M5 or later and/or effective temperature of 3200 K or cooler identified in NGC 1333; 30-40 of them are likely to be substellar. NGC 1333 harbors about half as many brown dwarfs as stars, which is significantly more than in other well-studied star-forming regions, thus raising the possibility of environmental differences in the formation of substellar objects. The brown dwarfs in NGC 1333 are spatially strongly clustered within a radius of {approx}1 pc, mirroring the distribution of the stars. The disk fraction in the substellar regime is <66%, lower than for the total population (83%) but comparable to the brown dwarf disk fraction in other 2-3 Myr old regions.

  16. Comparison of preparation methods for ceria catalyst and the effect of surface and bulk sulfates on its activity toward NH3-SCR.

    PubMed

    Chang, Huazhen; Ma, Lei; Yang, Shijian; Li, Junhua; Chen, Liang; Wang, Wei; Hao, Jiming

    2013-11-15

    A series of CeO2 catalysts prepared with sulfate (S) and nitrate (N) precursors by hydrothermal (H) and precipitation (P) methods were investigated in selective catalytic reduction of NOx by NH3 (NH3-SCR). The catalytic activity of CeO2 was significantly affected by the preparation methods and the precursor type. CeO2-SH, which was prepared by hydrothermal method with cerium (IV) sulfate as a precursor, showed excellent SCR activity and high N2 selectivity in the temperature range of 230-450 °C. Based on the results obtained by temperature-programmed reduction (H2-TPR), transmission infrared spectra (IR) and thermal gravimetric analysis (TGA), the excellent performance of CeO2-SH was correlated with the surface sulfate species formed in the hydrothermal reaction. These results indicated that sulfate species bind with Ce(4+) on the CeO2-SH catalyst, and the specific sulfate species, such as Ce(SO4)2 or CeOSO4, were formed. The adsorption of NH3 was promoted by these sulfate species, and the probability of immediate oxidation of NH3 to N2O on Ce(4+) was reduced. Accordingly, the selective oxidation of NH3 was enhanced, which contributed to the high N2 selectivity in the SCR reaction. However, the location of sulfate on the CeO2-SP catalyst was different. Plenty of sulfate species were likely deposited on CeO2-SP surface, covering the active sites for NO oxidation, which resulted in poor SCR activity in the test temperature range. Moreover, the resistance to alkali metals, such as Na and K, was improved over the CeO2-SH catalyst.

  17. 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

  18. 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 ...

  19. New insights into the diurnal variability of animal NH3 emissions using in-situ, satellite and aloft observations

    NASA Astrophysics Data System (ADS)

    Bash, J. O.; Henze, D. K.; Zhu, L.; Jeong, G.; Walker, J. T.; Nowak, J. B.; Neuman, J. A.; Cady-Pereira, K. E.; Shephard, M. W.; Luo, M.; Pinder, R. W.

    2013-12-01

    Ammonia (NH3) is the primary atmospheric base and an important precursor for inorganic particulate matter. NH3 deposition contributes to surface water eutrophication, soil acidification and decline in species biodiversity. Despite its importance in atmospheric chemistry and the nitrogen biogeochemical cycle, the magnitude and temporal dynamics of NH3 emissions remain uncertain in regional and global scale models. This uncertainty stems from the lack of routine ambient NH3 observations and the complexity of NH3 emission sources. We will combine satellite, in-situ, and aircraft observations with model sensitivities to develop and evaluate process based improvements in NH3 emissions from animal production activities. First, we will show that initial model evaluations of ambient NH3 estimates using TES satellite and in-situ Carolina Ammonia Monitoring Network (CAMNet) observations paired in space and time indicated that the Community Multi-scale Air Quality (CMAQ) and GEOS-Chem overestimated CAMNet NH3 observations but underestimated TES observations. An evaluation of the differences in the timing of the measurement techniques indicated that the model errors are due to the dynamics of the temporal NH3 emissions, predominately from animal production. This was confirmed qualitatively using hourly in-situ NH3 observations. Then, a mechanistic NH3 animal emissions conceptual model was developed and implemented for use in both CMAQ and GEOS-Chem models. Finally, we will present improvements in model evaluations of gaseous NH3, NO3 aerosol concentrations and NH4 wet deposition against network, TES satellite and aircraft observations.

  20. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

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

    DOE PAGES

    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

  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. 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).

  5. 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

  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. 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).

  10. 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.

  11. Re-estimating NH3 Emissions from Chinese Cropland by a New Nonlinear Model.

    PubMed

    Zhou, Feng; Ciais, Philippe; Hayashi, Kentaro; Galloway, James; Kim, Dong-Gill; Yang, Changliang; Li, Shiyu; Liu, Bin; Shang, Ziyin; Gao, Shuoshuo

    2016-01-19

    Ammonia (NH3) released to the atmosphere leads to a cascade of impacts on the environment, yet estimation of NH3 volatilization from cropland soils (VNH3) in a broad spatial scale is still quite uncertain in China. This mainly stems from nonlinear relationships between VNH3 and relevant factors. On the basis of 495 site-years of measurements at 78 sites across Chinese croplands, we developed a nonlinear Bayesian tree regression model to determine how environmental factors modulate the local derivative of VNH3 to nitrogen application rates (Nrate) (VR, %). The VNH3-Nrate relationship was nonlinear. The VR of upland soils and paddy soils depended primarily on local water input and Nrate, respectively. Our model demonstrated good reproductions of VNH3 compared to previous models, i.e., more than 91% of the observed VR variance at sites in China and 79% of those at validation sites outside China. The observed spatial pattern of VNH3 in China agreed well with satellite-based estimates of NH3 column concentrations. The average VRs in China derived from our model were 14.8 ± 2.9% and 11.8 ± 2.0% for upland soils and paddy soils, respectively. The estimated annual NH3 emission in China (3.96 ± 0.76 TgNH3·yr(-1)) was 40% greater than that based on the IPCC Tier 1 guideline.

  12. 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

  13. [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.

  14. [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

  15. 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.

  16. Mechanism of NH4(+) Recruitment and NH3 Transport in Rh Proteins.

    PubMed

    Baday, Sefer; Orabi, Esam A; Wang, Shihao; Lamoureux, Guillaume; Bernèche, Simon

    2015-08-01

    In human cells, membrane proteins of the rhesus (Rh) family excrete ammonium and play a role in pH regulation. Based on high-resolution structures, Rh proteins are generally understood to act as NH3 channels. Given that cell membranes are permeable to gases like NH3, the role of such proteins remains a paradox. Using molecular and quantum mechanical calculations, we show that a crystallographically identified site in the RhCG pore actually recruits NH4(+), which is found in higher concentration and binds with higher affinity than NH3, increasing the efficiency of the transport mechanism. A proton is transferred from NH4(+) to a signature histidine (the only moiety thermodynamically likely to accept a proton) followed by the diffusion of NH3 down the pore. The excess proton is circulated back to the extracellular vestibule through a hydrogen bond network, which involves a highly conserved and functionally important aspartic acid, resulting in the net transport of NH3.

  17. 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.

  18. Determining the storage, availability and reactivity of NH3 within Cu-Chabazite-based Ammonia Selective Catalytic Reduction systems.

    PubMed

    Lezcano-Gonzalez, I; Deka, U; Arstad, B; Van Yperen-De Deyne, A; Hemelsoet, K; Waroquier, M; Van Speybroeck, V; Weckhuysen, B M; Beale, A M

    2014-01-28

    Three different types of NH3 species can be simultaneously present on Cu(2+)-exchanged CHA-type zeolites, commonly used in Ammonia Selective Catalytic Reduction (NH3-SCR) systems. These include ammonium ions (NH4(+)), formed on the Brønsted acid sites, [Cu(NH3)4](2+) complexes, resulting from NH3 coordination with the Cu(2+) Lewis sites, and NH3 adsorbed on extra-framework Al (EFAl) species, in contrast to the only two reacting NH3 species recently reported on Cu-SSZ-13 zeolite. The NH4(+) ions react very slowly in comparison to NH3 coordinated to Cu(2+) ions and are likely to contribute little to the standard NH3-SCR process, with the Brønsted groups acting primarily as NH3 storage sites. The availability/reactivity of NH4(+) ions can be however, notably improved by submitting the zeolite to repeated exchanges with Cu(2+), accompanied by a remarkable enhancement in the low temperature activity. Moreover, the presence of EFAl species could also have a positive influence on the reaction rate of the available NH4(+) ions. These results have important implications for NH3 storage and availability in Cu-Chabazite-based NH3-SCR systems. PMID:24322601

  19. Determining the storage, availability and reactivity of NH3 within Cu-Chabazite-based Ammonia Selective Catalytic Reduction systems.

    PubMed

    Lezcano-Gonzalez, I; Deka, U; Arstad, B; Van Yperen-De Deyne, A; Hemelsoet, K; Waroquier, M; Van Speybroeck, V; Weckhuysen, B M; Beale, A M

    2014-01-28

    Three different types of NH3 species can be simultaneously present on Cu(2+)-exchanged CHA-type zeolites, commonly used in Ammonia Selective Catalytic Reduction (NH3-SCR) systems. These include ammonium ions (NH4(+)), formed on the Brønsted acid sites, [Cu(NH3)4](2+) complexes, resulting from NH3 coordination with the Cu(2+) Lewis sites, and NH3 adsorbed on extra-framework Al (EFAl) species, in contrast to the only two reacting NH3 species recently reported on Cu-SSZ-13 zeolite. The NH4(+) ions react very slowly in comparison to NH3 coordinated to Cu(2+) ions and are likely to contribute little to the standard NH3-SCR process, with the Brønsted groups acting primarily as NH3 storage sites. The availability/reactivity of NH4(+) ions can be however, notably improved by submitting the zeolite to repeated exchanges with Cu(2+), accompanied by a remarkable enhancement in the low temperature activity. Moreover, the presence of EFAl species could also have a positive influence on the reaction rate of the available NH4(+) ions. These results have important implications for NH3 storage and availability in Cu-Chabazite-based NH3-SCR systems.

  20. 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

  1. X-shooter spectroscopy of young stellar objects. IV. Accretion in low-mass stars and substellar objects in Lupus

    NASA Astrophysics Data System (ADS)

    Alcalá, J. M.; Natta, A.; Manara, C. F.; Spezzi, L.; Stelzer, B.; Frasca, A.; Biazzo, K.; Covino, E.; Randich, S.; Rigliaco, E.; Testi, L.; Comerón, F.; Cupani, G.; D'Elia, V.

    2014-01-01

    We present VLT/X-shooter observations of a sample of 36 accreting low-mass stellar and substellar objects (YSOs) in the Lupus star-forming region, spanning a range in mass from ~0.03 to ~1.2 M⊙, but mostly with 0.1 M⊙object. The accretion luminosity (Lacc), and in turn the accretion rate (Ṁacc), was derived by modelling the excess emission from the UV to the near-infrared as the continuum emission of a slab of hydrogen. We computed the flux and luminosity (Lline) of many emission lines of H , He , and Ca ii, observed simultaneously in the range from ~330 nm to 2500 nm. The luminosity of all the lines is well correlated with Lacc. We provide empirical relationships between Lacc and the luminosity of 39 emission lines, which have a lower dispersion than relationships previously reported in the literature. Our measurements extend the Paβ and Brγ relationships to Lacc values about two orders of magnitude lower than those reported in previous studies. We confirm that different methodologies of measuring Lacc and Ṁacc yield significantly different results: Hα line profile modelling may underestimate Ṁacc by 0.6 to 0.8 dex with respect to Ṁacc derived from continuum-excess measures. These differences may explain the probably spurious bi-modal relationships between Ṁacc and other YSOs properties reported in the literature. We derived Ṁacc in the range 2 × 10-12-4 × 10-8 M⊙ yr-1 and conclude that Ṁacc ∝ M⋆1.8(±0.2), with a dispersion lower by a factor of about 2 than in previous studies. A number of properties indicate that the physical conditions of the accreting gas are similar over more than 5 orders of magnitude in Ṁacc, confirming previous suggestions that the geometry of the accretion flow

  2. 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.

  3. 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

  4. 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

  5. (CH3Br⋯NH3)@C60: The effect of nanoconfinement on halogen bonding

    NASA Astrophysics Data System (ADS)

    Srivastava, Ambrish Kumar; Pandey, Sarvesh Kumar; Misra, Neeraj

    2016-10-01

    Halogen bonds resemble hydrogen bonds in many aspects. How do the properties of halogen bonds change when confined to nanoregion? In order to explore this, we have encapsulated a halogen bonded complex, CH3Br⋯NH3 inside C60 fullerene and studied their properties using density functional theory and quantum theory of atoms in molecule. Our findings show that the geometry of CH3Br⋯NH3 complex is appreciably bent inside C60, interaction becomes covalent with larger interaction energy, unlike free CH3Br⋯NH3 complex, which is linear with closed shell interaction. Thus, the halogen bonded complexes show quite different properties at nanoscale.

  6. NH2 fluorescence efficiencies and the NH3 abundance in Comet Halley

    NASA Technical Reports Server (NTRS)

    Tegler, Stephen; Wyckoff, Susan

    1989-01-01

    If NH3 is the dominant source of the NH2 observed in comet spectra, then the NH3 abundance can in principle be accurately determined. Fluorescence efficiencies for the (0, v-prime/2/, O) to (0, 0, 0) progression of NH2 bands are calculated for NH2 bands likely to be observed in the 4500-8200-A region of comets. The results differ from previous determinations of the NH2 band fluorescence efficiencies by factors in the range 1.4-5.9, leading t6o significant changes in previously reported NH2 production rates in comets. A recalculation of the NH3/H2O abundance ratio in Comet Halley gives about (0.5 + or - 0.2) percent in better agreement with the Giotto ion-mass-spectrometer results of Allen et al (1987).

  7. 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.

  8. Silicene as a highly sensitive molecule sensor for NH3, NO and NO2.

    PubMed

    Hu, Wei; Xia, Nan; Wu, Xiaojun; Li, Zhenyu; Yang, Jinlong

    2014-04-21

    On the basis of first-principles calculations, we demonstrate the potential application of silicene as a highly sensitive molecule sensor for NH3, NO, and NO2 molecules. NH3, NO and NO2 molecules chemically adsorb on silicene via strong chemical bonds. With distinct charge transfer from silicene to molecules, silicene and chemisorbed molecules form charge-transfer complexes. The adsorption energy and charge transfer in NO2-adsorbed silicene are larger than those of NH3- and NO-adsorbed silicones. Depending on the adsorbate types and concentrations, the silicene-based charge-transfer complexes exhibit versatile electronic properties with tunable band gap opening at the Dirac point of silicene. The calculated charge carrier concentrations of NO2-chemisorbed silicene are 3 orders of magnitude larger than intrinsic charge carrier concentration of graphene at room temperature. The results present a great potential of silicene for application as a highly sensitive molecule sensor.

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. 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.

  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 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.

  15. 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.

  16. Low-temperature surface formation of NH3 and HNCO: hydrogenation of nitrogen atoms in CO-rich interstellar ice analogues

    NASA Astrophysics Data System (ADS)

    Fedoseev, G.; Ioppolo, S.; Zhao, D.; Lamberts, T.; Linnartz, H.

    2015-01-01

    Solid-state astrochemical reaction pathways have the potential to link the formation of small nitrogen-bearing species, like NH3 and HNCO, and prebiotic molecules, specifically amino acids. To date, the chemical origin of such small nitrogen-containing species is still not well understood, despite the fact that ammonia is an abundant constituent of interstellar ices towards young stellar objects and quiescent molecular clouds. This is mainly because of the lack of dedicated laboratory studies. The aim of this work is to experimentally investigate the formation routes of NH3 and HNCO through non-energetic surface reactions in interstellar ice analogues under fully controlled laboratory conditions and at astrochemically relevant temperatures. This study focuses on the formation of NH3 and HNCO in CO-rich (non-polar) interstellar ices that simulate the CO freeze-out stage in dark interstellar cloud regions, well before thermal and energetic processing start to become relevant. We demonstrate and discuss the surface formation of solid HNCO through the interaction of CO molecules with NH radicals - one of the intermediates in the formation of solid NH3 upon sequential hydrogenation of N atoms. The importance of HNCO for astrobiology is discussed.

  17. On the Surface Formation of NH3 and HNCO in Dark Molecular Clouds - Searching for Wöhler Synthesis in the Interstellar Medium

    NASA Astrophysics Data System (ADS)

    Fedoseev, Gleb; Lamberts, Thanja; Linnartz, Harold; Ioppolo, Sergio; Zhao, Dongfeng

    Despite its potential to reveal the link between the formation of simple species and more complex molecules (e.g., amino acids), the nitrogen chemistry of the interstellar medium (ISM) is still poorly understood. Ammonia (NH _{3}) is one of the few nitrogen-bearing species that have been observed in interstellar ices toward young stellar objects (YSOs) and quiescent molecular clouds. The aim of the present work is to experimentally investigate surface formation routes of NH _{3} and HNCO through non-energetic surface reactions in interstellar ice analogues under fully controlled laboratory conditions and at astrochemically relevant cryogenic temperatures. This study focuses on the formation of NH _{3} and HNCO in CO-rich (non-polar) interstellar ices that simulate the CO freeze-out stage in interstellar dark cloud regions, well before thermal and energetic processing start to become predominant. Our work confirms the surface formation of ammonia through the sequential addition of three hydrogen/deuterium atoms to a single nitrogen atom at low temperature. The H/D fractionation of the formed ammonia is also shown. Furthermore, we show the surface formation of solid HNCO through the interaction of CO molecules with NH radicals - one of the intermediates in the formation of solid NH _{3}. Finally, we discuss the implications of HNCO in astrobiology, as a possible starting point for the formation of more complex prebiotic species.

  18. Interaction of NH3 with Cu-SSZ-13 Catalyst: A Complementary FTIR, XANES, and XES Study.

    PubMed

    Giordanino, Filippo; Borfecchia, Elisa; Lomachenko, Kirill A; Lazzarini, Andrea; Agostini, Giovanni; Gallo, Erik; Soldatov, Alexander V; Beato, Pablo; Bordiga, Silvia; Lamberti, Carlo

    2014-05-01

    In the typical NH3-SCR temperature range (100-500 °C), ammonia is one of the main adsorbed species on acidic sites of Cu-SSZ-13 catalyst. Therefore, the study of adsorbed ammonia at high temperature is a key step for the understanding of its role in the NH3-SCR catalytic cycle. We employed different spectroscopic techniques to investigate the nature of the different complexes occurring upon NH3 interaction. In particular, FTIR spectroscopy revealed the formation of different NH3 species, that is, (i) NH3 bonded to copper centers, (ii) NH3 bonded to Brønsted sites, and (iii) NH4(+)·nNH3 associations. XANES and XES spectroscopy allowed us to get an insight into the geometry and electronic structure of Cu centers upon NH3 adsorption, revealing for the first time in Cu-SSZ-13 the presence of linear Cu(+) species in Ofw-Cu-NH3 or H3N-Cu-NH3 configuration. PMID:26270095

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. Simultaneous removal of H2S and NH3 in biofilter inoculated with Acidithiobacillus thiooxidans TAS.

    PubMed

    Lee, Eun Young; Cho, Kyung-Suk; Ryu, Hee Wook

    2005-06-01

    H2S and NH3 gases are toxic, corrosive and malodorous air pollutants. Although there are numerous well-established physicochemical techniques presently available for the treatment of these gases, the growing demand for a more economical and improved process has prompted investigations into biological alternatives. In biological treatment methods, H2S is oxidized to SO4(2-) by sulfur-oxidizing bacteria, and then NH3 is removed by chemical neutralization with SO4(2-) to (NH4)2SO4. Since the accumulated (NH4)2SO4 can inhibit microbial activity, it is important to utilize an effective sulfur-oxidizing bacterium that has tolerance to high concentrations of (NH4)2SO4 for the simultaneous removal of H2S and NH3. In this study, a sulfur-oxidizing bacterium with tolerance to high concentrations of (NH4)2SO4 was isolated from activated sludge and identified as Acidithiobacillus thiooxidans TAS. A. thiooxidans TAS could display its sulfur-oxidizing activity in a medium supplemented with 60 g.l(-1) (NH4)2SO4, even though its growth and sulfur-oxidizing activity were completely inhibited in 80 g.l(-1) (NH4)2SO4. When H2S alone was supplied to a ceramic biofilter inoculated with A. thiooxidans TAS, an almost 100% H2S removal efficiency was maintained until the inlet H2S concentration was increased up to 900 microl.l(-1) and the space velocity up to 500 h(-1), at which the amount of H2S eliminated was 810 g-S.m(-3).h(-1). However, when NH3 (50-500 microl.l(-1)) was simultaneously supplied to the biofilter with H2S, the maximum amount of H2S eliminated decreased to 650 g-S.m(-3).h(-1). The inhibition of H2S removal by low NH3 concentrations (50-200 microl.l(-1)) was similar to that by high NH3 concentrations (300-500 microl.l(-1)). The critical inlet H2S load that resulted in over 99% removal was determined as 400 g-S.m(-3).h(-1) in the presence of NH3.

  4. Photochemistry of NH3, CH4 and PH3. Possible applications to the Jovian planets.

    PubMed

    Ferris, J P; Morimoto, J Y; Benson, R; Bossard, A

    1982-09-01

    Photolysis of NH3 at 185 nm in the presence of a two-fold excess of CH4 results in the loss of about 0.25 mole of CH4 per mole of NH3 decomposed (delta CH4/delta NH3). The loss arises from the abstraction of hydrogen atoms from CH4 by photolytically generated hot hydrogen atoms, the presence of which is established by the constancy of delta CH4/delta NH3 between 298 and 156 K and by the quenching of the abstraction reaction when either H2 or SF6 is added. From the latter result, it can be concluded that NH3 photolysis in the H2-abundant atmosphere of Jupiter is not responsible for the presence of the carbon compounds observed there such as ethane, acetylene, and hydrogen cyanide, but may have had a role in the early atmosphere of Titan. Photolysis of PH3 with a 206 nm light source gives P2H4, which in turn is converted to a red-brown solid (P4?). The course of the photolysis is not changed appreciably when the temperatures is lowered to 157 K except that the concentration of P2H4 increases. The presence of H2 has no effect on the P2H4 yield. Photolysis of 9:1 NH3:PH3 gives a rate of decomposition of PH3 that is comparable with that observed by the direct photolysis of PH3. Comparable amounts of P2H4 and the red-brown solid are also observed. The mechanisms of these photochemical reactions together with their implications to the atmospheric chemistry of Jupiter are discussed. The structures of the compounds responsible for the wide array of colors e.g., brown, red and white, observed in the atmosphere of Jupiter have been the subject of extensive speculation. One theory suggests that these colors are due to organic materials formed by the action of either solar ultraviolet light or electric discharges on mixtures of CH4, NH3 and NH4HS in the Jovian atmosphere (Ponnamperuma, 1976; Khare et al., 1978). An alternative hypothesis is that the colors are due to inorganic compounds resulting from the photolysis of NH4HS and PH3 (Lewis and Prinn, 1970; Prinn and Lewis, 1975

  5. 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.

  6. 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

  7. 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.

  8. Low energy structural dynamics and constrained libration of Li(NH3)4, the lowest melting point metal.

    PubMed

    Seel, A G; Zurek, E; Ramirez-Cuesta, A J; Ryan, K R; Lodge, M T J; Edwards, P P

    2014-09-25

    The lattice and molecular dynamics for the solid phases of the lowest melting-point metal, Li(NH3)4, are determined by incoherent inelastic neutron scattering. Measurements of internal molecular displacements and distortions of the Li(NH3)4 units have been modelled and assigned using density functional theory calculations for the solid and molecular system. Inelastic neutron scattering measurement allow for the first determination of NH3 librational transitions.

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

    PubMed

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

    2013-12-01

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

  10. 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.

  11. Ferroelectric Polarization in CH3NH3PbI3 Perovskite.

    PubMed

    Kim, Hui-Seon; Kim, Sung Kyun; Kim, Byeong Jo; Shin, Kyung-Sik; Gupta, Manoj Kumar; Jung, Hyun Suk; Kim, Sang-Woo; Park, Nam-Gyu

    2015-05-01

    We report on ferroelectric polarization behavior in CH3NH3PbI3 perovskite in the dark and under illumination. Perovskite crystals with three different sizes of 700, 400, and 100 nm were prepared for piezoresponse force microscopy (PFM) measurements. PFM results confirmed the formation of spontaneous polarization in CH3NH3PbI3 in the absence of electric field, where the size dependency to polarization was not significant. Whereas the photoinduced stimulation was not significant without an external electric field, the stimulated polarization by poling was further enhanced under illumination. The retention of ferroelectric polarization was also observed after removal of the electric field, in which larger crystals showed longer retention behavior compared to the smaller sized one. Additionally, we suggest the effect of perovskite crystal size (morphology) on charge collection at the interface of the ferroelectric material even though insignificant size dependency in electric polarization was observed.

  12. 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.

  13. 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

  14. 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.

  15. Electrical and optical properties of Ar/NH3 atmospheric pressure plasma jet

    NASA Astrophysics Data System (ADS)

    Chang, Zheng-Shi; Yao, Cong-Wei; Chen, Si-Le; Zhang, Guan-Jun

    2016-09-01

    Inspired by the Penning effect, we obtain a glow-like plasma jet by mixing ammonia (NH3) into argon (Ar) gas under atmospheric pressure. The basic electrical and optical properties of an atmospheric pressure plasma jet (APPJ) are investigated. It can be seen that the discharge mode transforms from filamentary to glow-like when a little ammonia is added into the pure argon. The electrical and optical analyses contribute to the explanation of this phenomenon. The discharge mode, power, and current density are analyzed to understand the electrical behavior of the APPJ. Meanwhile, the discharge images, APPJ's length, and the components of plasma are also obtained to express its optical characteristics. Finally, we diagnose several parameters, such as gas temperature, electron temperature, and density, as well as the density number of metastable argon atoms of Ar/NH3 APPJ to help judge the usability in its applications.

  16. 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

  17. A surface penning ionization study of NH 3 on Ni(111)

    NASA Astrophysics Data System (ADS)

    Bozso, Ferenc; Arias, Jose M.; Hanrahan, Ciaran P.; Yates, John T.; Metiu, Horia; Martin, Richard M.

    1984-03-01

    Surface Penning ionization electron spectroscopy was used to investigate the properties of chemisorbed and condensed multilayers of ammonia on Ni(111). We find that the Penning spectroscopy of chemisorbed ammonia provides similar information to ultraviolet photoelectron spectroscopy: we detect emission from the 3a 1 and 1e molecular orbitals of NH 3. We also find a new peak which we assign to emission from Ni sites whose local work function differs from that of the clean Ni(111) surface. The Penning spectrum of condensed ammonia layers is similar to that of chemisorbed ammonia, but has higher intensity and different peak intensity ratios. Possible reasons for this behavior are suggested. Penning studies of NH 3 adsorbed on a Ni(111) surface precovered with hydrogen or oxygen show that the precoverage does not substantially modify the ammonia spectrum.

  18. 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.

  19. Calculations on the rate of the ion-molecule reaction between NH3(+) and H2

    NASA Technical Reports Server (NTRS)

    Herbst, Eric; Defrees, D. J.; Talbi, D.; Pauzat, F.; Koch, W.

    1991-01-01

    The rate coefficient for the ion-molecule reaction NH3(+) + H2 yields NH4(+) + H has been calculated as a function of temperature with the use of the statistical phase space approach. The potential surface and reaction complex and transition state parameters used in the calculation have been taken from ab initio quantum chemical calculations. The calculated rate coefficient has been found to mimic the unusual temperature dependence measured in the laboratory, in which the rate coefficient decreases with decreasing temperature until 50-100 K and then increases at still lower temperatures. Quantitative agreement between experimental and theoretical rate coefficients is satisfactory given the uncertainties in the ab initio results and in the dynamics calculations. The rate coefficient for the unusual three-body process NH3(+) + H2 + He yields NH4(+) + H + He has also been calculated as a function of temperature and the result found to agree well with a previous laboratory determination.

  20. 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.

  1. High-resolution absorption measurements of NH3 at high temperatures: 500-2100 cm-1

    NASA Astrophysics Data System (ADS)

    Barton, Emma J.; Yurchenko, Sergei N.; Tennyson, Jonathan; Clausen, Sønnik; Fateev, Alexander

    2015-12-01

    High-resolution absorption spectra of NH3 in the region 500-2100 cm-1 at temperatures up to 1027 °C and approximately atmospheric pressure (1013±20 mbar) are measured. NH3 concentrations of 1000 ppm, 0.5% and 1% in volume fraction were used in the measurements. Spectra are recorded in high temperature gas flow cells using a Fourier Transform Infrared (FTIR) spectrometer at a nominal resolution of 0.09 cm-1. Measurements at 22.7 °C are compared to high-resolution cross sections available from the Pacific Northwest National Laboratory (PNNL). The higher temperature spectra are analysed by comparison to a variational line list, BYTe, and experimental energy levels determined using the MARVEL procedure. Approximately 2000 lines have been assigned, of which 851 are newly assigned to mainly hot bands involving vibrational states as high as v2=5.

  2. 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

  3. 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

  4. Diagnosing shock temperature with NH3 and H2O profiles

    NASA Astrophysics Data System (ADS)

    Gómez-Ruiz, A. I.; Codella, C.; Viti, S.; Jiménez-Serra, I.; Navarra, G.; Bachiller, R.; Caselli, P.; Fuente, A.; Gusdorf, A.; Lefloch, B.; Lorenzani, A.; Nisini, B.

    2016-10-01

    In a previous study of the L1157 B1 shocked cavity, a comparison between NH3(10-00) and H2O(110-101) transitions showed a striking difference in the profiles, with H2O emitting at definitely higher velocities. This behaviour was explained as a result of the high-temperature gas-phase chemistry occurring in the post-shock gas in the B1 cavity of this outflow. If the differences in behaviour between ammonia and water are indeed a consequence of the high gas temperatures reached during the passage of a shock, then one should find such differences to be ubiquitous among chemically rich outflows. In order to determine whether the difference in profiles observed between NH3 and H2O is unique to L1157 or a common characteristic of chemically rich outflows, we have performed Herschel-HIFI observations of the NH3(10-00) line at 572.5 GHz in a sample of eight bright low-mass outflow spots already observed in the H2O(110-101) line within the Water In Star-forming regions with Herschel Key Programme. We detected the ammonia emission at high velocities at most of the outflows positions. In all cases, the water emission reaches higher velocities than NH3, proving that this behaviour is not exclusive of the L1157-B1 position. Comparisons with a gas-grain chemical and shock model confirms, for this larger sample, that the behaviour of ammonia is determined principally by the temperature of the gas.

  5. On the NH3 absorption depression observable at Northern low latitudes of Jupiter

    NASA Astrophysics Data System (ADS)

    Tejfel, Victor G.; Vdovichenko, Vladimir D.; Lysenko, Peter G.; Karimov, Alibek M.; Kirienko, Galina A.; Bondarenko, Natalya N.; Kharitonova, Galina

    2016-10-01

    From February to April of 2016, we carried out a special series of spectrophotometric observations of Jupiter to study the current behavior of the ammonia absorption at the low latitudes of the Northern hemisphere, where in 2004 we have found a well-defined depression of the 787 nm NH3 absorption band intensity (V.Tejfel et al., Bull.AAS, 2005, Vol. 37, p.682). In subsequent years, an existence of this depression was annually confirmed by spectral observations, although we were noticing its variable character. During observations of 2016 we obtained more than 2,500 CCD-spectrograms, including the spectra of the central meridian, the GRS, and 12 scans of Jovian disk on different dates (70 zonal spectra in each scan). The 787 nm NH3 absorption band was extracted with using of ratios of the Jovian spectra to the Saturn's disk spectrum that was taken as a reference. The depression of absorption in this band begins almost from the equator, and its maximum occurs at the planetographic latitude of 100N then the absorption increases again approaching to the latitude of 200N. The equivalent bandwidths corresponding to these latitudes are equal to 18.7 ± 1.4 A, 14.4 ± 1.0 A and 17.8 ± 0.8A. The 645 nm NH3 absorption band also shows depletion at the low latitudes of the Northern hemisphere, but it is less pronounced. At the temperate latitudes of the Northern hemisphere this band's absorption is systematically lower than the Southern Hemisphere's ones. We will continue research in this direction, especially because recently a significant depletion of gaseous NH3 has also been found with using of the VLA with high resolution (I. de Pater et al., Science, 2016, Vol. 352, Issue 6290, p.1290-1294) at the low latitudes of the Northern hemisphere in the region of the NEB.

  6. 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.

  7. The role of isolated Cu2+ location in structural stability of Cu-modified SAPO-34 in NH3-SCR of NO.

    PubMed

    Yan, Chundi; Cheng, Hao; Yuan, Zhongshan; Wang, Shudong

    2015-01-01

    In this study, three different methods (ion exchange, wet mixing and impregnation) were employed to prepare Cu-modified SAPO-34 molecular sieves. All these freshly prepared catalysts showed excellent activities towards the selective catalytic reduction (SCR) of NO with NH3 (NH3-SCR) no matter which preparation method was used. However, hydrothermal ageing significantly reduced the catalytic activities of those catalysts prepared by the wet-mixing and impregnation methods, respectively. The results of X-ray powder diffraction, H2-TPR and electron paramagnetic resonance measurements for these catalysts suggested that the decrease in catalytic activity may be attributed to the migration of Cu2+ ion to the centre of the hexagonal prism (site III), the formation of CuxOy and the collapse of the molecular framework during hydrothermal ageing. The degrees of structural collapse of each Cu-modified molecular sieve were different, probably due to Cu2+ species in different sites (in the ellipsoidal cavity (site I) for ion-exchange sample, near the eight-ring window (site IV) for the wet-mixing and impregnation samples). Cu2+ located at site I was more stable than that located at site IV.

  8. General working principles of CH3NH3PbX3 perovskite solar cells.

    PubMed

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

    2014-02-12

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

  9. Observation of orbiting resonances in He((3)S(1)) + NH3 Penning ionization.

    PubMed

    Jankunas, Justin; Jachymski, Krzysztof; Hapka, Michał; Osterwalder, Andreas

    2015-04-28

    Resonances are among the clearest quantum mechanical signatures of scattering processes. Previously, shape resonances and Feshbach resonances have been observed in inelastic and reactive collisions involving atoms or diatomic molecules. Structure in the integral cross section has been observed in a handful of elastic collisions involving polyatomic molecules. The present paper presents the observation of shape resonances in the reactive scattering of a polyatomic molecule, NH3. A merged-beam study of the gas phase He((3)S1) + NH3 Penning ionization reaction dynamics is described in the collision energy range 3.3 μeV < Ecoll < 10 meV. In this energy range, the reaction rate is governed by long-range attraction. Peaks in the integral cross section are observed at collision energies of 1.8 meV and 7.3 meV and are assigned to ℓ = 15,16 and ℓ = 20,21 partial wave resonances, respectively. The experimental results are well reproduced by theoretical calculations with the short-range reaction probability Psr = 0.035. No clear signature of the orbiting resonances is visible in the branching ratio between NH3 (+) and NH2 (+) formation.

  10. 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.

  11. 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

  12. 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.

  13. Diffusion measurements of CO, HNCO, H2CO, and NH3 in amorphous water ice

    NASA Astrophysics Data System (ADS)

    Mispelaer, F.; Theulé, P.; Aouididi, H.; Noble, J.; Duvernay, F.; Danger, G.; Roubin, P.; Morata, O.; Hasegawa, T.; Chiavassa, T.

    2013-07-01

    Context. Water is the major component of the interstellar ice mantle. In interstellar ice, chemical reactivity is limited by the diffusion of the reacting molecules, which are usually present at abundances of a few percent with respect to water. Aims: We want to study the thermal diffusion of H2CO, NH3, HNCO, and CO in amorphous water ice experimentally to account for the mobility of these molecules in the interstellar grain ice mantle. Methods: In laboratory experiments performed at fixed temperatures, the diffusion of molecules in ice analogues was monitored by Fourier transform infrared spectroscopy. Diffusion coefficients were extracted from isothermal experiments using Fick's second law of diffusion. Results: We measured the surface diffusion coefficients and their dependence with the temperature in porous amorphous ice for HNCO, H2CO, NH3, and CO. They range from 10-15 to 10-11 cm2 s-1 for HNCO, H2CO, and NH3 between 110 K and 140 K, and between 5-8 × 10-13 cm2 s-1 for CO between 35 K and 40 K. The bulk diffusion coefficients in compact amorphous ice are too low to be measured by our technique and a 10-15 cm2 s-1 upper limit can be estimated. The amorphous ice framework reorganization at low temperature is also put in evidence. Conclusions: Surface diffusion of molecular species in amorphous ice can be experimentally measured, while their bulk diffusion may be slower than the ice mantle desorption kinetics.

  14. Laboratory rotational ground state transitions of NH3D+ and CF+

    NASA Astrophysics Data System (ADS)

    Stoffels, A.; Kluge, L.; Schlemmer, S.; Brünken, S.

    2016-09-01

    Aims: This paper reports accurate laboratory frequencies of the rotational ground state transitions of two astronomically relevant molecular ions, NH3D+ and CF+. Methods: Spectra in the millimetre-wave band were recorded by the method of rotational state-selective attachment of He atoms to the molecular ions stored and cooled in a cryogenic ion trap held at 4 K. The lowest rotational transition in the A state (ortho state) of NH3D+ (JK = 10-00), and the two hyperfine components of the ground state transition of CF+ (J = 1-0) were measured with a relative precision better than 10-7. Results: For both target ions, the experimental transition frequencies agree with recent observations of the same lines in different astronomical environments. In the case of NH3D+ the high-accuracy laboratory measurements lend support to its tentative identification in the interstellar medium. For CF+ the experimentally determined hyperfine splitting confirms previous quantum-chemical calculations and the intrinsic spectroscopic nature of a double-peaked line profile observed in the J = 1-0 transition towards the Horsehead photon-dominated region (PDR).

  15. 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.

  16. An analytical approach to evaluate the performance of graphene and carbon nanotubes for NH3 gas sensor applications.

    PubMed

    Akbari, Elnaz; Arora, Vijay Kumar; Enzevaee, Aria; Ahmadi, Mohamad T; Saeidmanesh, Mehdi; Khaledian, Mohsen; Karimi, Hediyeh; Yusof, Rubiyah

    2014-01-01

    Carbon, in its variety of allotropes, especially graphene and carbon nanotubes (CNTs), holds great potential for applications in variety of sensors because of dangling π-bonds that can react with chemical elements. In spite of their excellent features, carbon nanotubes (CNTs) and graphene have not been fully exploited in the development of the nanoelectronic industry mainly because of poor understanding of the band structure of these allotropes. A mathematical model is proposed with a clear purpose to acquire an analytical understanding of the field-effect-transistor (FET) based gas detection mechanism. The conductance change in the CNT/graphene channel resulting from the chemical reaction between the gas and channel surface molecules is emphasized. NH3 has been used as the prototype gas to be detected by the nanosensor and the corresponding current-voltage (I-V) characteristics of the FET-based sensor are studied. A graphene-based gas sensor model is also developed. The results from graphene and CNT models are compared with the experimental data. A satisfactory agreement, within the uncertainties of the experiments, is obtained. Graphene-based gas sensor exhibits higher conductivity compared to that of CNT-based counterpart for similar ambient conditions. PMID:24991510

  17. 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

  18. 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

  19. 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

  20. 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.

  1. 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

  2. Two-Center Three-Electron Bonding in ClNH3 Revealed via Helium Droplet Infrared Spectroscopy: Entrance Channel Complex Along the cl + NH3 → ClNH2 + H Reaction

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    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 of two other complexes, NH3Cl and Cl-HNH2, which are predicted in the entry valley to the hydrogen abstraction reaction, Cl + NH3 → HCl + NH2

  3. Experimental Study of Coaxial Cylinder Dielectric Barrier Discharge in Ar/NH3 Mixtures under the Atmosphere-Pressure.

    PubMed

    Li, Yan-qin; Bu, De-cai; Di, Lan-bo; Zhang, Xiu-ling; Liu, Zhi-sheng; Li, Xue-hui

    2015-03-01

    An atmosphere-pressure Dielectric Barrier Discharge in Ar/NH3 mixtures between cylinder electrodes is studied by Optical Emission Spectroscopy and the main particles of atmosphere-pressure Ar/NH3 DBD plasma are NH, N, N+, N2, Ar, H(α) and OH. NH is decomposition products of NH3, and NH(c 1π) and NH(A 3π) are two kinds of excited-state neutral particles and produced by penning ionization of Ar* and NH3. The nitrogen active atom is detected at 674.5 nm which may provide the experimental foundation for the synthesis of ε-Fe3N ferroparticles by the atmosphere-pressure Ar/NH3 DBD plasma. The intensities of main particles are analyzed at different NH3 flow rate and applied voltage peak-peak value. The results show that the spectral line intensities of various particles increase with the rise of the applied voltage peak-peak value at the same NH3 flow rate, and first increase and then decrease with the increase of the NH3 flow rate at the same applied voltage peak-peak value. The applied voltage peak-peak value being kept constant, the spectral line intensity of nitrogen active atom first increases and then decreases with the increase of the NH3 flow rate. When NH3 flow rate is 20 mL x min(-1), the spectral line intensity of nitrogen active atom reaches a maximum at the same applied voltage peak-peak value. The spectral line intensity of nitrogen active atom decreases gradually with increasing the applied voltage peak-peak value at the same NH3 flow rate and it is mainly because of the translation of discharge mode from multi-pulse APGD to filamentary discharge in the atmosphere-pressure Ar/NH3 DBD. The microdischarge channels overlap and the microdischarges affect each other in multi-pulse APGD; hence the increasing rate of the spectral line intensity is quicker in multi-pulse APGD than in filamentary discharge with increasing the applied voltage peak-peak value. When the applied voltage peak-peak value is up from 4 600 to 6 400 V, the single-pulse and two-pulse APGD

  4. The Cu-CHA deNOx Catalyst in Action: Temperature-Dependent NH3-Assisted Selective Catalytic Reduction Monitored by Operando XAS and XES.

    PubMed

    Lomachenko, Kirill A; Borfecchia, Elisa; Negri, Chiara; Berlier, Gloria; Lamberti, Carlo; Beato, Pablo; Falsig, Hanne; Bordiga, Silvia

    2016-09-21

    The small-pore Cu-CHA zeolite is today the object of intensive research efforts to rationalize its outstanding performance in the NH3-assisted selective catalytic reduction (SCR) of harmful nitrogen oxides and to unveil the SCR mechanism. Herein we exploit operando X-ray spectroscopies to monitor the Cu-CHA catalyst in action during NH3-SCR in the 150-400 °C range, targeting Cu oxidation state, mobility, and preferential N or O ligation as a function of reaction temperature. By combining operando XANES, EXAFS, and vtc-XES, we unambiguously identify two distinct regimes for the atomic-scale behavior of Cu active-sites. Low-temperature SCR, up to ∼200 °C, is characterized by balanced populations of Cu(I)/Cu(II) sites and dominated by mobile NH3-solvated Cu-species. From 250 °C upward, in correspondence to the steep increase in catalytic activity, the largely dominant Cu-species are framework-coordinated Cu(II) sites, likely representing the active sites for high-temperature SCR. PMID:27532483

  5. The Cu-CHA deNOx Catalyst in Action: Temperature-Dependent NH3-Assisted Selective Catalytic Reduction Monitored by Operando XAS and XES.

    PubMed

    Lomachenko, Kirill A; Borfecchia, Elisa; Negri, Chiara; Berlier, Gloria; Lamberti, Carlo; Beato, Pablo; Falsig, Hanne; Bordiga, Silvia

    2016-09-21

    The small-pore Cu-CHA zeolite is today the object of intensive research efforts to rationalize its outstanding performance in the NH3-assisted selective catalytic reduction (SCR) of harmful nitrogen oxides and to unveil the SCR mechanism. Herein we exploit operando X-ray spectroscopies to monitor the Cu-CHA catalyst in action during NH3-SCR in the 150-400 °C range, targeting Cu oxidation state, mobility, and preferential N or O ligation as a function of reaction temperature. By combining operando XANES, EXAFS, and vtc-XES, we unambiguously identify two distinct regimes for the atomic-scale behavior of Cu active-sites. Low-temperature SCR, up to ∼200 °C, is characterized by balanced populations of Cu(I)/Cu(II) sites and dominated by mobile NH3-solvated Cu-species. From 250 °C upward, in correspondence to the steep increase in catalytic activity, the largely dominant Cu-species are framework-coordinated Cu(II) sites, likely representing the active sites for high-temperature SCR.

  6. Four-Terminal Tandem Solar Cells Using CH3NH3PbBr3 by Spectrum Splitting.

    PubMed

    Sheng, Rui; Ho-Baillie, Anita W Y; Huang, Shujuan; Keevers, Mark; Hao, Xiaojing; Jiang, Liangcong; Cheng, Yi-Bing; Green, Martin A

    2015-10-01

    In this work, the use of a high bandgap perovskite solar cell in a spectrum splitting system is demonstrated. A remarkable energy conversion efficiency of 23.4% is achieved when a CH3NH3PbBr3 solar cell is coupled with a 22.7% efficient silicon passivated emitter rear locally diffused solar cell. Relative enhancements of >10% are demonstrated by CH3NH3PbBr3/CH3NH3PbI3 and CH3NH3PbBr3/multicrystalline-screen-printed-Si spectral splitting systems with tandem efficiencies of 13.4% and 18.8%, respectively. The former is the first demonstration of an all perovskite split spectrum system. The CH3NH3PbBr3 cell on a mesoporous structure was fabricated by the vapor-assisted method while the planar CH3NH3PbI3 cell was fabricated by the gas-assisted method. This work demonstrates the advantage of the higher voltage output from the high bandgap CH3NH3PbBr3 cell and its suitability in a tandem system. PMID:26722894

  7. 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

  8. Four-Terminal Tandem Solar Cells Using CH3NH3PbBr3 by Spectrum Splitting.

    PubMed

    Sheng, Rui; Ho-Baillie, Anita W Y; Huang, Shujuan; Keevers, Mark; Hao, Xiaojing; Jiang, Liangcong; Cheng, Yi-Bing; Green, Martin A

    2015-10-01

    In this work, the use of a high bandgap perovskite solar cell in a spectrum splitting system is demonstrated. A remarkable energy conversion efficiency of 23.4% is achieved when a CH3NH3PbBr3 solar cell is coupled with a 22.7% efficient silicon passivated emitter rear locally diffused solar cell. Relative enhancements of >10% are demonstrated by CH3NH3PbBr3/CH3NH3PbI3 and CH3NH3PbBr3/multicrystalline-screen-printed-Si spectral splitting systems with tandem efficiencies of 13.4% and 18.8%, respectively. The former is the first demonstration of an all perovskite split spectrum system. The CH3NH3PbBr3 cell on a mesoporous structure was fabricated by the vapor-assisted method while the planar CH3NH3PbI3 cell was fabricated by the gas-assisted method. This work demonstrates the advantage of the higher voltage output from the high bandgap CH3NH3PbBr3 cell and its suitability in a tandem system.

  9. 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.

  10. 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.

  11. Identification of forbidden vibration-rotation transitions in 15NH3

    NASA Astrophysics Data System (ADS)

    Urban, Š.; D'Cunha, Romola; Narahari Rao, K.

    1984-07-01

    Forbidden Δk - l = 3 vibration-rotation transitions have been observed in the ν4 band of 15NH3. The analysis of these transitions, together with previously published data on the allowed transitions, has made it possible to determine a set of molecular parameters, including for the first time the rotational constant C as well as the centrifugal distortion constants DK and HKKK, which are necessary for the calculation of energy levels. Some weak forbidden transitions in the ν2 band have also been observed.

  12. 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.

  13. IR and polarized Raman spectra of (NH 3) 2(CH 2) 2HPO 4

    NASA Astrophysics Data System (ADS)

    Philip, Daizy; Aruldhas, G.

    1989-11-01

    The IR and polarized Raman spectra of (NH 3) 2(CH 2) 2HPO 4 have been recorded and analyzed. In the crystal, symmetry of the HPO 4 ion is found to be reduced from C3 v to C1. The observed splittings indicate that the site symmetry and the correlation field effects are appreciable in the crystal. Strong vibrational coupling between the PO(H) stretching and POH out-of-plane bending modes is observed. Ethylene diammonium groups are crystallographically different in the unit cell.

  14. Enhancement of NH3 Gas Sensitivity at Room Temperature by Carbon Nanotube-Based Sensor Coated with Co Nanoparticles

    PubMed Central

    Nguyen, Lich Quang; Phan, Pho Quoc; Duong, Huyen Ngoc; Nguyen, Chien Duc; Nguyen, Lam Huu

    2013-01-01

    Multi-walled carbon nanotube (MWCNT) film has been fabricated onto Pt-patterned alumina substrates using the chemical vapor deposition method for NH3 gas sensing applications. The MWCNT-based sensor is sensitive to NH3 gas at room temperature. Nanoclusters of Co catalysts have been sputtered on the surface of the MWCNT film to enhance gas sensitivity with respect to unfunctionalized CNT films. The gas sensitivity of Co-functionalized MWCNT-based gas sensors is thus significantly improved. The sensor exhibits good repeatability and high selectivity towards NH3, compared with alcohol and LPG. PMID:23364198

  15. Plasma nitridation of silicon by N2 and NH3 in PECVD reactor

    NASA Astrophysics Data System (ADS)

    Bakardjieva, V. S.; Alexieva, Z. I.; Beshkov, G. D.; Mateev, E. S.

    2010-04-01

    The effect was investigated of nitrogen and ammonia plasma treatment of monocrystalline Si wafers. The experiments were carried out in a plasma-enhanced chemical vapor deposition reactor. The wafers were subjected to N2 and NH3 plasma treatment for varying times at temperature of 380 °C. The plasma treated surfaces were studied by transmission electron microscopy with C-Pt replicas, reflection high-energy electron diffraction and Auger electron spectroscopy. The results point to the growth of an amorphous layer on the surface. The Auger electron spectroscopy depth profiles obtained by sputtering show the presence of an oxynitride layer with varying composition depending on the time of plasma treatment. The Auger electron spectroscopy analysis shows that after 60 s of treatment in N2 plasma, the nitrogen content is 8 at.%, while after 300 s it is 22 at.%, the thickness of the oxynitride nanolayer being 2.5-7.2 nm. In the case of NH3 plasma the thickness calculated from the sputtering time (from 50 s to 15 min) varies between 2 and 12 nm, and the nitrogen content, between 5 and 35 at.%.

  16. The ν 1 and ν 3 band system of 15NH3

    NASA Astrophysics Data System (ADS)

    Fusina, Luciano; Nivellini, Giandomenico; Spezzano, Silvia

    2011-09-01

    The infrared spectrum of 15NH3 has been investigated by high-resolution Fourier transform infrared spectroscopy in the region of the stretching fundamentals. A large number of ro-vibration transitions in the 3050-3650 cm-1 spectral range has been recorded and assigned to the fundamentals ν 1 and ν 3, and to the 2ν 4 overtone bands. In total, 1606 transitions involving the (s) and (a) inversion-rotation-vibration levels have been identified and assigned. They include 256 perturbation-allowed transitions with selection rules ΔK = ±2, Δl = -1 in ν 3 and Δl = +2 in ? , and ΔK = ±3, Δl = 0 in ν 1 and ? . All assigned transitions were fitted simultaneously to a model Hamiltonian that includes all symmetry-allowed interactions between and within the excited state levels in order to obtain accurate sets of spectroscopic parameters for both inversion states. The standard deviation of the fit, 0.034 cm-1, is about 70 times larger than the estimated measurement precision. This result is similar to that reported for the same band system in 14NH3 by Kleiner et al. [J. Mol. Spectrosc. 193, 46 (1999)] and is a consequence of the neglect of vibration and ro-vibration interactions between the analysed states and vibrationally excited states with close energies.

  17. 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

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. A theoretical analysis of the reaction between CN radicals and NH3.

    PubMed

    Talbi, Dahbia; Smith, Ian W M

    2009-10-14

    The reaction between CN radicals and NH3 molecules has been studied experimentally over an unusually wide range of temperature (25-716 K). Below 295 K, the rate constant exhibits a strong negative dependence on temperature; that is, it increases sharply as the temperature is lowered. The present work analyses the kinetics of this reaction theoretically, both to explain this unusual temperature-dependence and to identify the major products of the reaction--which have not been well established by experiment. Quantum chemical calculations at the CCSD(T) theoretical level show that the minimum energy path for reaction proceeds: (a) first, via a potential well, which is 39.3 kJ mol(-1) below the energy of the separated reactants, when allowance is made for zero-point energies, corresponding to a quite strongly bound NC-NH3 complex, and (ii) then over a 'submerged' barrier with a crest 10.9 kJ mol(-1) below the energy of the reactants to the products HCN + NH2. These ab initio calculations also demonstrate that there is no low energy path to the products NCNH2 + H. The dynamics of the main reaction have been further investigated using the two transition state model of Klippenstein and co-workers, in which transition state theory is applied at the selected E, J microcanonical level. The rate constants calculated for temperatures between 25 and 200 K are in excellent agreement with the experimental values.

  5. HCN and NH3 formation during coal/char gasification in the presence of NO.

    PubMed

    Lin, Jian-Ying; Zhang, Shu; Zhang, Lian; Min, Zhenhua; Tay, Huiling; Li, Chun-Zhu

    2010-05-15

    Understanding the conversion of coal-N during gasification is an important part of the development of gasification-based power generation technologies to reduce NO(x) emissions from coal utilization. This study investigated the conversion of coal-N in the presence of NO during the gasification of three rank-ordered coals and their chars in steam and low-concentration O(2). Our results show that NO can be incorporated into the char structure during gasification. The inherent char-N and the N incorporated into the char from NO-char reactions behave very similarly during gasification. During the gasification in steam, significant amounts of HCN and NH(3) can be formed from the incorporated N structure in char, especially for the relatively "aged" chars, mainly due to the availability of abundant H radicals on the char surface during the gasification in steam. During the gasification in 2000 ppm O(2), the formation of HCN or NH(3) from the N structures in char, including those incorporated into the char from the NO-char reactions, was not a favored route of reaction mainly due to the lack of H on char surface in the presence of O(2).

  6. 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.

  7. Large-Size CH3NH3PbBr3 Single Crystal: Growth and In Situ Characterization of the Photophysics Properties.

    PubMed

    Zhao, Pengjun; Xu, Jinbao; Dong, Xiaoyu; Wang, Lei; Ren, Wei; Bian, Liang; Chang, Aimin

    2015-07-01

    We reported a facile single-solution fabrication method to grow large-scale CH3NH3PbBr3 hybrid perovskite single crystal at room temperature. The obtained single crystal in this experiment was 14 × 14 mm. The sample's in situ photophysics properties under dark and illumination, including the surface morphology, work function, surface current distribution, microcosmic I-V curves, as well as the polarization behavior, were in situ characterized by integrated utilization of a scanning probe microscopy, respectively. Piezoresponse force microscopy (PFM) phase angles indicated the existence of "polarization" in CH3NH3PbBr3 lattice. Interestingly, the "polarization effect" was enhanced by the plus light source. Moreover, a surface potential shift as large as 200 mV was observed under the condition of the illumination on and off. This research is proposed to provide an opportunity to take a fresh look at the architectural design and photovoltaic performance origin of the hybrid perovskite solar cells.

  8. 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...

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

    PubMed

    Dong, Ki-Young; Choi, Jinnil; Lee, Yang Doo; Kang, Byung Hyun; Yu, Youn-Yeol; Choi, Hyang Hee; Ju, Byeong-Kwon

    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.

  10. 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.

  11. 7-Methylguanine: protonation, formation of linkage isomers with trans-(NH3)2Pt(II), and base pairing properties.

    PubMed

    Kozma, Ágnes; Ibáñez, Susana; Silaghi-Dumitrescu, Radu; Sanz Miguel, Pablo J; Gupta, Deepali; Lippert, Bernhard

    2012-05-28

    Three protonated forms of 7-methylguanine (7-MeGH, 1) with different counter ions, [7-MeGH(2)]X (X = NO(3), 1a; ClO(4), 1b; BF(4), 1c) and two Pt(II) complexes, trans-[Pt(NH(3))(2)(7-MeGH-N9)(2)](ClO(4))(2) (4) and trans-[Pt(NH(3))(2)(7-MeGH-N9)(7-MeGH-N3)](ClO(4))(2)·3H(2)O (5) are described and their X-ray crystal structures are reported. 1a-1c form infinite ribbons via pairs of intermolecular hydrogen bonds between N1H···O6 and N3···N2H(2) sites, with anions connecting individual ribbons, thereby generating extended sheets. 4 and 5 do not display unusual features, except that 5 represents a rare case of a bis(nucleobase) complex of Pt(II) in which linkage isomers occur. Unlike in a previously reported compound, [Pt(dien)(7-MeGH-N9)](NO(3))(ClO(4)), the Pt coordination planes and the 7-MeGH planes are not coplanar in 4 and 5. The hydrogen bonding behaviour of 7-MeGH, free and when platinated at N9 (complex 4), was studied in Me(2)SO-d(6). It revealed the following: (i) there is no detectable self-association of 1 in Me(2)SO solution. (ii) 1 and 1-methylcytosine (1-MeC) form Watson-Crick pairs. (iii) 4 does not self-associate. (iv) 4 associates with 1-MeC in the Watson-Crick fashion. (v) 4 and 1 interact in solution, but no model can be proposed at present. (vi) Remarkable interaction shifts between 4 and 1 occur when NH(3) is liberated from trans-(NH(3))(2)Pt(II) to give NH(4)(+) in Me(2)SO-d(6). Feasible models, which imply the presence of deprotonated 7-MeG(-) species are proposed. Finally, DFT calculations were carried out to qualitatively estimate the effect of 7-MeGH acidity in [Pt(dien)(7-MeGH-N9)](2+) in dependence of the dihedral angle between the Pt coordination plane and the nucleobase.

  12. 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.

  13. Synergistic formation of sulfate and ammonium resulting from reaction between SO2 and NH3 on typical mineral dust.

    PubMed

    Yang, Weiwei; He, Hong; Ma, Qingxin; Ma, Jinzhu; Liu, Yongchun; Liu, Pengfei; Mu, Yujing

    2016-01-14

    The heterogeneous reactions of SO2 and NH3 on typical mineral oxides were investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). A new sulfate formation pathway was proposed where NH3 accelerated the formation of sulfate species. The results revealed that surface hydroxyls and oxygen played principal roles in the conversion of SO2 to sulfate. It was proposed that NH3 adsorbed onto Lewis acid sites, and hydroxyls and water molecules adsorbed on the surfaces of mineral dust. The enhancement of surface Lewis basicity by NH3 induced more SO2 molecules to adsorb on the surface, which were further oxidized to sulfate by interacting with surface hydroxyls and oxygen atoms. The formation of sulfate, in turn, contributed to the adsorption of NH3, mainly as NH4(+) due to enhanced Brønsted acid sites. The IC results showed that the synergistic effect between SO2 and NH3 was more significant on acidic oxides like γ-Al2O3 and α-Fe2O3 compared to basic oxides like MgO.

  14. NH3, H2S, and the Radio Brightness Temperature Spectra of the Giant Planets

    NASA Technical Reports Server (NTRS)

    Spilker, Thomas R.

    1995-01-01

    Recent radio interferometer observations of Neptune enable comparisons of the radio brightness temperature (T(sub B)) spectra of all four giant planets. This comparison reveals evidence for fundamental differences in the compositions of Uranus' and Neptune's upper tropospheres, particularly in their ammonia (NH3) and hydrogen sulfide (H2S) mixing ratios, despite those planets' outward similarities. The tropospheric abundances of these constituents yield information about their deep abundances, and ultimately about the formation of the planets from the presolar nebula (Atreya et al.). Figures 1, 2, 3, and 4 show the T(sub B) spectra of Jupiter, Saturn, Uranus, and Neptune, respectively, from 0.1 to tens of cm wavelength. The data shown are collected from many observers. Data for Jupiter, Saturn, and Uranus are those cataloged by de Pater and Massie (1985), plus the Saturn Very Large Array (VLA) data by Grossman et al. Figure 3, Uranus, shows only data acquired since 1973. Before 1973 Uranus' T(sub B) increased steadily as its pole moved into view, causing significant scatter in those data. Neptune data at greater than 1 cm, all taken at the VLA, are collected from de Pater and Richmond, de Pater et al., and Hofstadter. For a variety of reasons, such as susceptibility to source confusion, single-dish data at those wavelengths are much noisier than the more reliable VLA data and have been ignored. Single-dish data by Griffin and Orton shortward of 0.4 cm are shown, along with the Owens Valley Radio Observatory (interferometer) datum at 0.266 cm by Muhleman and Berge. Spectra of Jupiter, Saturn, and Neptune share certain gross characteristics. In each spectrum, T(sub B) at 1.3 cm is approximately 120-140 K, less than approximately 30 K different from that at 0.1 cm. All three spectra show a break in slope at or near 1.3 cm, with T(sub B) increasing fairly rapidly with wavelength longward of 1.3 cm. Visible and IR spectroscopy show that NH3, whose strong inversion

  15. 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.

  16. 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.

  17. 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

  18. Electronic structure evolution of fullerene on CH3NH3PbI3

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    The thickness dependence of fullerene on CH3NH3PbI3 perovskite film 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 perovskite film to fullerene molecules. Further deposition of fullerene forms C60 solid, accompanied by the reduction of the electron transfer. The strongest electron transfer happened at 1/4 monolayer of fullerene.

  19. Determination of NH3 emissions from confined areas using backward Lagrangian stochastic dispersion modelling

    NASA Astrophysics Data System (ADS)

    Häni, Christoph; Neftel, Albrecht; Sintermann, Jörg

    2016-04-01

    Employing backward Lagrangian stochastic (bLS) dispersion modelling to infer emission strengths from confined areas using trace gas concentration measurements is a convenient way of emission estimation from field measurements (see Wilson et al., 2012 and references therein). The freely available software 'WindTrax' (www.thunderbeachscientific.com), providing a graphical interface for the application of a bLS model, has spurred its utilisation in the past decade. Investigations include mainly methane (CH4) and ammonia (NH3) emissions based on experimental plots with dimensions between approximately 102 to 104 m2. Whereas for CH4 deposition processes can be neglected, NH3 has a strong affinity to any surface and is therefore efficiently deposited. Neglecting dry deposition will underestimate NH3 emissions, e.g. with a standard WindTrax approach. We extended the bLS model described in Flesch et al. (2004) by a dry deposition process using a simple, one-directional deposition velocity approach. At every contact of the model trajectories with ground level (here at the height of the roughness length Zo), deposition is modelled as: Fdep = vdep × CT raj (1) where vdep represents deposition velocity, and CTraj is the actual concentration of the specific trajectory at contact. A convenient way to model vdep is given by a resistances approach. The deposition velocity is modelled as the inverse of the sum of a series of different resistances to deposition. The aerodynamic resistance is already implicitly included in the bLS model, thus vdep is given as: v = ---1--- dep Rb + Rc (2) Rb and Rc represent resistances of different model layers between Zo and the surfaces where deposition take place. With this approach we analysed a dataset from measurements with an artificial NH3 source that consisted of 36 individual orifices mimicking a circular area source with a radius of 10 m. The use of three open-path miniDOAS (Sintermann et al., submitted to AMT) systems allowed to measure

  20. Electronic structure evolution of fullerene on CH3NH3PbI3

    DOE PAGES

    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

  1. 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.

  2. An accurate global potential energy surface, dipole moment surface, and rovibrational frequencies for NH3

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

    A global potential energy surface (PES) that includes short and long range terms has been determined for the NH3 molecule. The singles and doubles coupled-cluster method that includes a perturbational estimate of connected triple excitations and the internally contracted averaged coupled-pair functional electronic structure methods have been used in conjunction with very large correlation-consistent basis sets, including diffuse functions. Extrapolation to the one-particle basis set limit was performed and core correlation and scalar relativistic contributions were included directly, while the diagonal Born-Oppenheimer correction was added. Our best purely ab initio PES, denoted "mixed," is constructed from two PESs which differ in whether the ic-ACPF higher-order correlation correction was added or not. Rovibrational transition energies computed from the mixed PES agree well with experiment and the best previous theoretical studies, but most importantly the quality does not deteriorate even up to 10300cm-1 above the zero-point energy (ZPE). The mixed PES was improved further by empirical refinement using the most reliable J =0-2 rovibrational transitions in the HITRAN 2004 database. Agreement between high-resolution experiment and rovibrational transition energies computed from our refined PES for J =0-6 is excellent. Indeed, the root mean square (rms) error for 13 HITRAN 2004 bands for J =0-2 is 0.023cm-1 and that for each band is always ⩽0.06cm-1. For J =3-5 the rms error is always ⩽0.15cm-1. This agreement means that transition energies computed with our refined PES should be useful in the assignment of new high-resolution NH3 spectra and in correcting mistakes in previous assignments. Ideas for further improvements to our refined PES and for extension to other isotopolog are discussed.

  3. 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.

  4. Anharmonic Calculation of the Structure, Vibrational Frequencies, and Intensities of the NH3···cis-HONO and NH3···cis-DONO Complexes.

    PubMed

    Bulychev, V P; Buturlimova, M V; Tokhadze, K G

    2016-08-25

    The geometrical parameters, the frequencies, and absolute intensities for transitions between vibrational states of NH3···cis-HONO and NH3···cis-DONO hydrogen-bonded complexes are calculated using the approach earlier tested in calculations of isolated molecules of nitrous acid and the NH3···trans-HONO and NH3··trans-DONO complexes. Vibrational wave functions and energy values of the complexes are derived from variational solutions of anharmonic equations in one to four dimensions. The equilibrium nuclear configuration and potential energy surfaces are calculated by the MP2/aug-cc-pVTZ method with the basis set superposition error taken into account. Comparison of the obtained results with the analogous data calculated in the same approximation for isolated cis- and trans-HONO (DONO) molecules and the NH3···trans-HONO (DONO) complexes provides information about the changes in the spectroscopic and geometrical parameters of nitrous acid upon cis-trans transition, H/D substitution, and H-bond formation. PMID:27472262

  5. 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

  6. 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

  7. 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.

  8. Effect of aeration modes on the characteristics of composting emissions and the NH3 removal efficiency by using biotrickling filter.

    PubMed

    Wu, Chuanfu; Wang, Qunhui; Sun, Xiaohong; Xue, Niantao; Liu, Shu; Xie, Weimin

    2011-08-01

    A pilot biotrickling filter (BTF) packed with ZX02 fibrous balls as packing material was tested for the treatment of ammonia (NH(3)) released from a composting plant of dairy manure. In order to investigate the effects of three compost aeration modes (mode Co-I, Co-II and In-II) on the NH(3) removal efficiency, a field experiment was continuously carried out for more than eight months. The results demonstrated that under the intermittent aeration mode (In-II), the NH(3) removal efficiency reached 99.2±0.1% when the inlet NH(3) concentration was 7.5-32.3mg m(-3) (9.8-42.5ppmv). The maximum and critical elimination capacity of the biotrickling filter was 22.6 and 4.9g NH(3)m(-3)h(-1), respectively. The effluent concentration of NH(3) was lower than 1.0mg m(-3), which meets the first class discharge standards of GB14554-93. When the concentration of free ammonia in the trickling liquid was varied from 0.1 to 0.4mg L(-1), the nitrification yield was between 47.9% and 103.8%. In addition, the optimum liquid tricking velocity (LTV) of the biotrickling filter was 0.5m(3)m(-2)h(-1) for low inlet concentrations and 2.2m(3)m(-2)h(-1) for high inlet concentrations. Therefore, the use of the biotrickling filter for the compost under the third aeration mode (In-II) yielded an effective optimum NH(3) removal and reduced the nitrogen loss in the compost.

  9. 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.

  10. 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

  11. 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

  12. 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.

  13. Shock-heated NH3 in a Molecular Jet Associated with a High-Mass Young Star.

    PubMed

    Zhang; Hunter; Sridharan; Cesaroni

    1999-12-20

    We present the discovery of shock-excited NH3 in a well-collimated jet associated with the extremely young high-mass star IRAS 20126+4104. The NH3 (3, 3) and (4, 4) emission is dominated by three clumps along the SiO jet. At the end of the jet, there exists strong and broad (+/-10 km s-1) NH3 (3, 3) emission. With typical brightness temperatures greater than 500 K, the overall emission indicates a weakly inverted population and appears in an arc, consistent with the excitation by bow shocks. There are two bright spots in the NH3 (3, 3) emission with brightness temperatures of approximately 2000 K. The narrow line width (1.5 km s-1 FWHM), the small sizes (<0&farcs;3), and the unusually high brightness temperature of the features are indicative of maser emission. Our observations provide clear evidence that NH3 (3, 3) masers are excited in shock regions in molecular outflows.

  14. 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.

  15. High Resolution Infrared and Microwave Spectra of NH3-HCCH and NH3-OCS Complexes: Studies of Weak C-H\\cdotsN Hydrogen Bond and Electric Multipole Interactions

    NASA Astrophysics Data System (ADS)

    Liu, Xunchen; Xu, Yunjie

    2011-06-01

    C-H\\cdotsN weak hydrogen bond is of much current interest. We report the first high resolution infrared spectroscopic study of a prototypical C-H\\cdotsN bonded system, i.e. NH3-HCCH, at the vicinity of the ν4 band of NH3. The spectrum has been recorded using an infrared spectrometer equipped with an astigmatic multipass cell aligned for 366 passes and a room temperature external cavity quantum cascade laser at the 6 μm region. The perpendicular band spectrum of symmetric top rotor observed is consistent with the previous microwave and infrared studies at 3 μm. We also extended the previous microwave measurement to higher J and K. For the related NH3-OCS complex, microwave spectrum of J up to 6 and infrared spectrum at the vicinity of the ν4 band of NH3 have been recorded and analyzed for the first time. Comparison has been made with the previously studied isoelectronic complexes such as NH3-N2O and NH3-CO2. The source of the difference will be discussed with the aid of ab initio calculations. G.T. Fraser, K.R. Leopold, and W. Klemperer, J. Chem. Phys. 80(4), 1423, (1984) G. Hilpert, G.T. Fraser, and A.S. Pine, J. Chem. Phys. 105(15), 6183, (1996) G.T. Fraser, D.D. Nelson, JR., G.J. Gerfen, and W. Klemperer, J. Chem. Phys. 83(11), 5442, (1985) G.T. Fraser, K.R. Leopold, and W. Klemperer, J. Chem. Phys. 81(6), 2577, (1984)

  16. Effects of molecular dipole orientation on the exciton binding energy of CH3NH3PbI3

    NASA Astrophysics Data System (ADS)

    Motta, Carlo; Mandal, Pankaj; Sanvito, Stefano

    2016-07-01

    We present a simple interacting tight-binding model for excitons, which is used to investigate the dependence of the exciton binding energy of CH3NH3PbI3 over the disorder induced by the molecular motion at room temperature. The model is fitted to the electronic structure of CH3NH3PbI3 by using data from density-functional theory and Born-Oppenheimer ab initio molecular dynamics, and it is solved in the mean-field approximation. When a finite-scale analysis is performed to extract the energetic of the excitons at experimental concentrations we find that disorder in general reduces the binding energy of about 10%. This suggests that the excitonic properties of CH3NH3PbI3 largely depend on the electronic structure of the PbI3 inorganic lattice.

  17. The Bonding of NO2, NH3, and CH2NY to Models of a (10,0) Carbon Nanotube

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.

    2004-01-01

    We have studied the bonding of NO2, NH3, and CH2NH to a (10,O) carbon nanotube using the MP2 and ONIOM methods with extended basis sets. We find bond strengths of 3.5, 3.6. and 6.3 kcal/mol for NO2, NH3, and CH2NH, respectively, using the ONIOM method with the high accuracy part treated at the MP2/aug-CC-pVTZ level and the remainder of the CNT approximated at the UFF level and including an estimate of basis set superposition error using the counterpoise method.

  18. Separation of H2S and NH3 gases from tofu waste water-based biogas using activated carbon adsorption

    NASA Astrophysics Data System (ADS)

    Harihastuti, Nani; Purwanto, P.; Istadi, I.

    2015-12-01

    Research on the separation of H2S and NH3 gases from tofu waste water-based biogas has been conducted to improve the content of CH4 of biogas in order to increase calorific value. Biogas from tofu waste water contained many kinds of gases such as: CH4 of 53-64%, CO2 of 36-45%, H2S of 3,724-5,880 mg/Nm3, NH3 of 0.19-70.36 mg/Nm3, and H2O of 33,800-19,770,000 mg/Nm3. In fact, CO2, H2S, NH3, and moisture are impurities that have disturbance to human and environment, so that they are necessary to be separated from biogas. Particularly, H2S and NH3 have high toxicity to people, particularly the workers in the tofu industry. Therefore, separation of H2S and NH3 from biogas to increase calorific value is the focus of this research. The method used in this research is by adsorption of H2S and NH3 gases using activated carbon as adsorbent. It also used condensation as pretreatment to remove moisture content in biogas. Biogas was flowed to adsorption column (70 cm height and 9 cm diameter containing activated carbon as much as 500 g) so that the H2S and NH3 gases were adsorbed. This research was conducted by varying flow rate and flow time of biogas. From this experiment, it was found that the optimum adsorption conditions were flow rate of 3.5 l/min and 4 hours flow time. This condition could reach 99.95% adsorption efficiency of H2S from 5,879.50 mg/Nm3 to 0.67 mg/Nm3, and 74.96% adsorption efficiency of NH3 from 2.93 mg/Nm3 to 0.73 mg/Nm3. The concentration of CH4 increased from 63.88% to 76.24% in the biogas.

  19. 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).

  20. Electronic promoter or reacting species? The role of LiNH2 on Ru in catalyzing NH3 decomposition.

    PubMed

    Guo, Jianping; Chen, Zheng; Wu, Anan; Chang, Fei; Wang, Peikun; Hu, Daqiang; Wu, Guotao; Xiong, Zhitao; Yu, Pei; Chen, Ping

    2015-10-21

    LiNH2 decomposes to NH3 rather than N2 and H2 because of a severe kinetic barrier in NHx (x = 1, 2) coupling. In the presence of Ru, however, a drastic enhancement in N2 and H2 formation is obtained, which enables the LiNH2-Ru composite to act as a highly active catalyst for NH3 decomposition. Experimental and theoretical investigations indicate that Li creates a NHx-rich environment and Ru mediates the electron transfer facilitating NHx coupling. A strategy in catalytic material design is thus proposed.

  1. DFT based study of transition metal nano-clusters for electrochemical NH3 production.

    PubMed

    Howalt, J G; Bligaard, T; Rossmeisl, J; Vegge, T

    2013-05-28

    Theoretical studies of the possibility of producing ammonia electrochemically at ambient temperature and pressure without direct N2 dissociation are presented. Density functional theory calculations were used in combination with the computational standard hydrogen electrode to calculate the free energy profile for the reduction of N2 admolecules and N adatoms on transition metal nanoclusters in contact with an acidic electrolyte. This work has established linear scaling relations for the dissociative reaction intermediates NH, NH2, and NH3. In addition, linear scaling relations for the associative reaction intermediates N2H, N2H2, and N2H3 have been determined. Furthermore, correlations between the adsorption energies of N, N2, and H have been established. These scaling relations and the free energy corrections are used to establish volcanoes describing the onset potential for electrochemical ammonia production and hence describe the potential determining steps for the electrochemical ammonia production. The competing hydrogen evolution reaction has also been analyzed for comparison. PMID:23598667

  2. Electronic Structure Evolution of Fullerene on CH3NH3PbI3

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    The thickness dependence of fullerene on CH3NH3PbI3 perovskite film 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 (LUMO) 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 an initial shift of core levels to lower binding energy in the perovskite, which indicates that electrons transfer from the perovskite film to fullerene molecules. We observed that the WF of the perovskite is 5.0 eV and the VBM is 0.6 eV. The band gap of the perovskite is 1.66 eV, which is in accordance with previous reports. We also observed the HOMO level of C60 shifts to lower binding energy, indicating a band bending in the C60 region. The perovskite core levels show a strong initial shift to lower binding energy, indicating electron transfer from the perovskite film to fullerene molecules. The strongest electron transfer happened at 1/4 monolayer of fullerene, and further deposition reduced the transfer as forms fullerene forms C60 solid film. NSF CBET-1437656.

  3. The efficiency limit of CH3NH3PbI3 perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Sha, Wei E. I.; Ren, Xingang; Chen, Luzhou; Choy, Wallace C. H.

    2015-06-01

    With the consideration of photon recycling effect, the efficiency limit of methylammonium lead iodide (CH3NH3PbI3) perovskite solar cells is predicted by a detailed balance model. To obtain convincing predictions, both AM 1.5 spectrum of Sun and experimentally measured complex refractive index of perovskite material are employed in the detailed balance model. The roles of light trapping and angular restriction in improving the maximal output power of thin-film perovskite solar cells are also clarified. The efficiency limit of perovskite cells (without the angular restriction) is about 31%, which approaches to Shockley-Queisser limit (33%) achievable by gallium arsenide (GaAs) cells. Moreover, the Shockley-Queisser limit could be reached with a 200 nm-thick perovskite solar cell, through integrating a wavelength-dependent angular-restriction design with a textured light-trapping structure. Additionally, the influence of the trap-assisted nonradiative recombination on the device efficiency is investigated. The work is fundamentally important to high-performance perovskite photovoltaics.

  4. Quadrupole splittings in the near-infrared spectrum of 14NH3

    NASA Astrophysics Data System (ADS)

    Twagirayezu, Sylvestre; Hall, Gregory E.; Sears, Trevor J.

    2016-10-01

    Sub-Doppler, saturation dip, spectra of lines in the v1 + v3, v1 + 2v4, and v3 + 2v4 bands of 14NH3 have been measured by frequency comb-referenced diode laser absorption spectroscopy. The observed spectral line widths are dominated by transit time broadening and show resolved or partially-resolved hyperfine splittings that are primarily determined by the 14N quadrupole coupling. Modeling of the observed line shapes based on the known hyperfine level structure of the ground state of the molecule shows that, in nearly all cases, the excited state level has hyperfine splittings similar to the same rotational level in the ground state. The data provide accurate frequencies for the line positions and easily separate lines overlapped in Doppler-limited spectra. The observed hyperfine splittings can be used to make and confirm rotational assignments and ground state combination differences obtained from the measured frequencies are comparable in accuracy to those obtained from conventional microwave spectroscopy. Several of the measured transitions do not show the quadrupole hyperfine splittings expected based on their existing rotational assignments. Either the assignments are incorrect or the upper levels involved are perturbed in a way that affects the nuclear hyperfine structure.

  5. Benchmarking of ONIOM method for the study of NH3 dissociation at open ends of BNNTs.

    PubMed

    Ahmadi, Ali; Beheshtian, Javad; Kamfiroozi, Mohammad

    2012-05-01

    The reliability of ONIOM approach have been examined in calculations of adsorption energies, transition structures, change of HOMO-LUMO energy gaps and equilibrium geometries of the interaction between NH(3) and N-enriched (A) or B-enriched (B) open ended boron nitride nanotubes. To these ends, four models of the A or B, with different inner and outer layers have been studied. In addition, various low-levels including, AM1, PM3, MNDO and UFF have been examined, applying B3LYP/6-31 G* in all high-levels. It was shown, that in the case of A, (choosing two atom layers of the tube open-end as inner layer) the results of ONIOM approach are in best agreement with those of the pure density functional theory (DFT) calculations, while their results significantly differ from those of DFT in the case of B in same conditions. All above and population analysis demonstrate that the ONIOM may be a reliable scheme in the study of weak interactions while it is a controversial approach and should be applied cautiously in the case of strong interactions. We also probed the effect of tube length and diameter on the consistency between ONIOM and DFT results, showing that this consistency is independent of the mentioned parameters. PMID:21833827

  6. Quadrupole splittings in the near-infrared spectrum of 14NH3

    DOE PAGES

    Twagirayezu, Sylvestre; Hall, Gregory E.; Sears, Trevor J.

    2016-10-13

    Sub-Doppler, saturation dip, spectra of lines in the v1 + v3, v1 + 2v4 and v3 + 2v4 bands of 14NH3 have been measured by frequency comb-referenced diode laser absorption spectroscopy. The observed spectral line widths are dominated by transit time broadening, and show resolved or partially-resolved hyperfine splittings that are primarily determined by the 14N quadrupole coupling. Modeling of the observed line shapes based on the known hyperfine level structure of the ground state of the molecule shows that, in nearly all cases, the excited state level has hyperfine splittings similar to the same rotational level in the groundmore » state. The data provide accurate frequencies for the line positions and easily separate lines overlapped in Doppler-limited spectra. The observed hyperfine splittings can be used to make and confirm rotational assignments and ground state combination differences obtained from the measured frequencies are comparable in accuracy to those obtained from conventional microwave spectroscopy. Furthermore, several of the measured transitions do not show the quadrupole hyperfine splittings expected based on their existing rotational assignments. Either the assignments are incorrect or the upper levels involved are perturbed in a way that affects the nuclear hyperfine structure.« less

  7. Selective catalytic reduction operation with heavy fuel oil: NOx, NH3, and particle emissions.

    PubMed

    Lehtoranta, Kati; Vesala, Hannu; Koponen, Päivi; Korhonen, Satu

    2015-04-01

    To meet stringent NOx emission limits, selective catalytic reduction (SCR) is increasingly utilized in ships, likely also in combination with low-priced higher sulfur level fuels. In this study, the performance of SCR was studied by utilizing NOx, NH3, and particle measurements. Urea decomposition was studied with ammonia and isocyanic acid measurements and was found to be more effective with heavy fuel oil (HFO) than with light fuel oil. This is suggested to be explained by the metals found in HFO contributing to metal oxide particles catalyzing the hydrolysis reaction prior to SCR. At the exhaust temperature of 340 °C NOx reduction was 85-90%, while at lower temperatures the efficiency decreased. By increasing the catalyst loading, the low temperature behavior of the SCR was enhanced. The drawback of this, however, was the tendency of particle emissions (sulfate) to increase at higher temperatures with higher loaded catalysts. The particle size distribution results showed high amounts of nanoparticles (in 25-30 nm size), the formation of which SCR either increased or decreased. The findings of this work provide a better understanding of the usage of SCR in combination with a higher sulfur level fuel and also of ship particle emissions, which are a growing concern.

  8. Hydrophobic recovery of VUV/NH3 modified polyolefin surfaces: Comparison with plasma treatments in nitrogen

    NASA Astrophysics Data System (ADS)

    Truica-Marasescu, F.; Guimond, S.; Jedrzejowski, P.; Wertheimer, M. R.

    2005-07-01

    Film samples of two very pure polyolefins (low density polyethylene, LDPE and biaxially oriented polypropylene, BOPP) were surface-modified by two different methods, namely vacuum ultraviolet (VUV) irradiation with a Kr resonant lamp in low-pressure NH3 gas, and atmospheric pressure glow discharge (APGD) plasma treatment in pure N2 gas. Samples were then stored in air and the time-dependence of surface properties (the surface energy and chemical composition) was monitored using several complementary surface-sensitive techniques: contact angle goniometry (CAG), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). We show that the main mechanism responsible for hydrophobic recovery is the motion of polymer chains and chain segments, which governs an apparent "loss" of functional groups, within the first monolayers of the surface (∼1 nm). Finally, comparing BOPP samples modified by both techniques, we show that aging can be reduced by crosslinking near the surface, as illustrated by depth-sensing nano-indentation measurements.

  9. Computed and Experimental Absorption Spectra of the Perovskite CH3NH3PbI3.

    PubMed

    Zhu, Xi; Su, Haibin; Marcus, Rudolph A; Michel-Beyerle, Maria E

    2014-09-01

    Electronic structure and light absorption properties of the perovskite CH3NH3PbI3 are investigated by relativistic density functional theory with quasiparticle GW corrections and many-body interactions. The nature of the Wannier exciton is studied by solving the Bethe-Salpeter equation augmented with the analysis of a conceptual hydrogen-like model. The computed absorption spectrum unravels a remarkable absorption "gap" between the first two absorption peaks. This discontinuity is maintained in the calculated tetragonal structure that, however, is not stable at low temperature. Most importantly, the discontinuity is also observed in the experimental absorption spectrum of the orthorhombic single crystal at low temperature (4 K). However, in contrast to the single crystal, in a polycrystalline perovskite film at 5 K the "gap" is filled by a monotonously increasing absorption throughout the visible range. This feature of thin films points to the potential significance of defect absorption for the excellent light harvesting properties of perovskite-based solar cells. PMID:26278260

  10. Hot ammonia around young O-type stars. I. JVLA imaging of NH3 (6, 6) to (14, 14) in NGC 7538 IRS1

    NASA Astrophysics Data System (ADS)

    Goddi, C.; Zhang, Q.; Moscadelli, L.

    2015-01-01

    Context. The formation of massive (O-type) stars through the same accretion processes as low-mass stars is problematic, mainly because of the feedback massive stars provide to the environment, which halts the accretion. In order to constrain theoretical models of high-mass star formation, observational signatures of mass accretion in O-type forming stars are desirable. The high-mass star forming region NGC 7538 IRS1 (distance = 2.7 kpc) is an ideal target, because VLBI measurements of CH3OH masers recently identified a triple system of high-mass young stellar object (YSOs) in the region: IRS1a, IRS1b, and IRS1c. The first two YSOs seem to be surrounded by rotating disks. Aims: We want to characterize physical conditions and kinematics of circumstellar molecular gas around O-type young stars. Sub-arcsecond resolution observations of highly-excited lines from high-density tracers are useful, since these probe the hottest and densest gas, which presumably is close to O-type forming stars, i.e., in disks and the innermost portions of envelopes. Methods: Using the Karl Jansky Very Large Array (JVLA), we have mapped the hot and dense molecular gas in the hot core associated with NGC 7538 IRS1, with ~0.''2 angular resolution, in seven metastable (J = K) inversion transitions of ammonia (NH3): (J,K) = (6, 6), (7, 7), (9, 9), (10, 10), (12, 12), (13, 13), and (14, 14). These lines arise from energy levels between ~400 K and ~1950 K above the ground state, and are observed in absorption against the HC-HII region associated with NGC 7538 IRS1. The CH3OH JK = 132 - 131 and CH3CN (2-1) lines were also included in our spectral setup, but only the former was detected. We also obtained sensitive continuum maps at frequencies between 25 and 35 GHz. Results: For each transition, we produced resolved images of total intensity and velocity field, as well as position-velocity diagrams. The intensity maps show that the NH3 absorption follows the continuum emission closely. With a 500 AU

  11. Analogues of Cis- and Transplatin with a Rich Solution Chemistry: cis-[PtCl2 (NH3 )(1-MeC-N3)] and trans-[PtI2 (NH3 )(1-MeC-N3)].

    PubMed

    Siebel, Sabine; Dammann, Claudia; Sanz Miguel, Pablo J; Drewello, Thomas; Kampf, Gunnar; Teubner, Natascha; Bednarski, Patrick J; Freisinger, Eva; Lippert, Bernhard

    2015-12-01

    Mono(nucleobase) complexes of the general composition cis-[PtCl2 (NH3 )L] with L=1-methylcytosine, 1-MeC (1 a) and L=1-ethyl-5-methylcytosine, as well as trans-[PtX2 (NH3 )(1-MeC)] with X=I (5 a) and X=Br (5 b) have been isolated and were characterized by X-ray crystallography. The Pt coordination occurs through the N3 atom of the cytosine in all cases. The diaqua complexes of compounds 1 a and 5 a, cis-[Pt(H2 O)2 (NH3 )(1-MeC)](2+) and trans-[Pt(H2 O)2 (NH3 )(1-MeC)](2+) , display a rich chemistry in aqueous solution, which is dominated by extensive condensation reactions leading to μ-OH- and μ-(1-MeC(-) -N3,N4)-bridged species and ready oxidation of Pt to mixed-valence state complexes as well as diplatinum(III) compounds, one of which was characterized by X-ray crystallography: h,t-[{Pt(NH3 )2 (OH)(1-MeC(-) -N3,N4)}2 ](NO3 )2 ⋅2 [NH4 ](NO3 )⋅2 H2 O. A combination of (1) H NMR spectroscopy and ESI mass spectrometry was applied to identify some of the various species present in solution and the gas phase, respectively. As it turned out, mass spectrometry did not permit an unambiguous assignment of the structures of +1 cations due to the possibilities of realizing multiple bridging patterns in isomeric species, the occurrence of different tautomers, and uncertainties regarding the Pt oxidation states. Additionally, compound 1 a was found to have selective and moderate antiproliferative activity for a human cervix cancer line (SISO) compared to six other human cancer cell lines.

  12. Emergence of superconductivity in (NH3)yMxMoSe2 (M: Li, Na and K)

    NASA Astrophysics Data System (ADS)

    Miao, Xiao; Nishiyama, Saki; Zheng, Lu; Goto, Hidenori; Eguchi, Ritsuko; Ota, Hiromi; Kambe, Takashi; Terashima, Kensei; Yokoya, Takayoshi; Nguyen, Huyen T. L.; Kagayama, Tomoko; Hirao, Naohisa; Ohishi, Yasuo; Ishii, Hirofumi; Liao, Yen-Fa; Kubozono, Yoshihiro

    2016-07-01

    We report syntheses of new superconducting metal-doped MoSe2 materials (MxMoSe2). The superconducting MxMoSe2 samples were prepared using a liquid NH3 technique, and can be represented as ‘(NH3)yMxMoSe2’. The Tcs of these materials were approximately 5.0 K, independent of x and the specific metal atom. X-ray diffraction patterns of (NH3)yNaxMoSe2 were recorded using polycrystalline powders. An increase in lattice constant c showed that the Na atom was intercalated between MoSe2 layers. The x-independence of c was observed in (NH3)yNaxMoSe2, indicating the formation of a stoichiometric compound in the entire x range, which is consistent with the x-independence of Tc. A metallic edge of the Fermi level was observed in the photoemission spectrum at 30 K, demonstrating its metallic character in the normal state. Doping of MoSe2 with Li and K also yielded superconductivity. Thus, MoSe2 is a promising material for designing new superconductors, as are other transition metal dichalcogenides.

  13. Emergence of superconductivity in (NH3)yMxMoSe2 (M: Li, Na and K).

    PubMed

    Miao, Xiao; Nishiyama, Saki; Zheng, Lu; Goto, Hidenori; Eguchi, Ritsuko; Ota, Hiromi; Kambe, Takashi; Terashima, Kensei; Yokoya, Takayoshi; Nguyen, Huyen T L; Kagayama, Tomoko; Hirao, Naohisa; Ohishi, Yasuo; Ishii, Hirofumi; Liao, Yen-Fa; Kubozono, Yoshihiro

    2016-01-01

    We report syntheses of new superconducting metal-doped MoSe2 materials (MxMoSe2). The superconducting MxMoSe2 samples were prepared using a liquid NH3 technique, and can be represented as '(NH3)yMxMoSe2'. The Tcs of these materials were approximately 5.0 K, independent of x and the specific metal atom. X-ray diffraction patterns of (NH3)yNaxMoSe2 were recorded using polycrystalline powders. An increase in lattice constant c showed that the Na atom was intercalated between MoSe2 layers. The x-independence of c was observed in (NH3)yNaxMoSe2, indicating the formation of a stoichiometric compound in the entire x range, which is consistent with the x-independence of Tc. A metallic edge of the Fermi level was observed in the photoemission spectrum at 30 K, demonstrating its metallic character in the normal state. Doping of MoSe2 with Li and K also yielded superconductivity. Thus, MoSe2 is a promising material for designing new superconductors, as are other transition metal dichalcogenides. PMID:27404919

  14. Emergence of superconductivity in (NH3)yMxMoSe2 (M: Li, Na and K)

    PubMed Central

    Miao, Xiao; Nishiyama, Saki; Zheng, Lu; Goto, Hidenori; Eguchi, Ritsuko; Ota, Hiromi; Kambe, Takashi; Terashima, Kensei; Yokoya, Takayoshi; Nguyen, Huyen T. L.; Kagayama, Tomoko; Hirao, Naohisa; Ohishi, Yasuo; Ishii, Hirofumi; Liao, Yen-Fa; Kubozono, Yoshihiro

    2016-01-01

    We report syntheses of new superconducting metal-doped MoSe2 materials (MxMoSe2). The superconducting MxMoSe2 samples were prepared using a liquid NH3 technique, and can be represented as ‘(NH3)yMxMoSe2’. The Tcs of these materials were approximately 5.0 K, independent of x and the specific metal atom. X-ray diffraction patterns of (NH3)yNaxMoSe2 were recorded using polycrystalline powders. An increase in lattice constant c showed that the Na atom was intercalated between MoSe2 layers. The x-independence of c was observed in (NH3)yNaxMoSe2, indicating the formation of a stoichiometric compound in the entire x range, which is consistent with the x-independence of Tc. A metallic edge of the Fermi level was observed in the photoemission spectrum at 30 K, demonstrating its metallic character in the normal state. Doping of MoSe2 with Li and K also yielded superconductivity. Thus, MoSe2 is a promising material for designing new superconductors, as are other transition metal dichalcogenides. PMID:27404919

  15. Effect of Morphology Control of Light Absorbing Layer on CH3NH3PbI3 Perovskite Solar Cells.

    PubMed

    Lei, Binglong; Eze, Vincent Obiozo; Mori, Tatsuo

    2016-04-01

    As one of the most significant components of perovskite solar cells, the perovskite light absorbing layer demands high quality to guarantee extraordinary power conversion efficiency (PCE). We have fabricated series of CH3NH3PbI3 perovskite solar cells by virtue of gas-flowing assisting (GFA), spin coating twice for the Pbl2 layer and dipping the semi-samples in a thermal CH3NH3I solution, by which some undesirable perovskite morphologies can be effectively avoided. The modified conductions have also dramatically improved the perovskite layer and elevated the coverage ratio from 53.6% to 79.5%. All the fabrication processes, except the steps for deposition of the hole transport material (HTM) and back gold electrode, have been conducted in air and an average PCE of 6.6% has been achieved by initiatively applying N,N'-bis(1-naphtyl)-N,N'-diphenyl-1,1'-biphenyl-4,4'-diamine (α-NPD) doped by MoO3 as HTM. The CH3NH3PbI3 perovskite's morphology and its coverage ratio to the underneath TiO2 mesoporic layer are evaluated to account for the cells' performance. It has demonstrated that higher homogeneity and coverage ratio of the CH3NH3PbI3 layer have most significantly contributed to the solar cells' light conversion efficiency. Keywords: Perovskite, Solar Cell, Morphology, Coverage Ratio, Hole Transport Material. PMID:27451600

  16. Acute toxicity of ammonia (NH3-N) in sewage effluent to Chironomus riparius: II. Using a generalized linear model

    USGS Publications Warehouse

    Monda, D.P.; Galat, D.L.; Finger, S.E.; Kaiser, M.S.

    1995-01-01

    Toxicity of un-ionized ammonia (NH3-N) to the midge, Chironomus riparius was compared, using laboratory culture (well) water and sewage effluent (≈0.4 mg/L NH3-N) in two 96-h, static-renewal toxicity experiments. A generalized linear model was used for data analysis. For the first and second experiments, respectively, LC50 values were 9.4 mg/L (Test 1A) and 6.6 mg/L (Test 2A) for ammonia in well water, and 7.8 mg/L (Test 1B) and 4.1 mg/L (Test 2B) for ammonia in sewage effluent. Slopes of dose-response curves for Tests 1A and 2A were equal, but mortality occurred at lower NH3-N concentrations in Test 2A (unequal intercepts). Response ofC. riparius to NH3 in effluent was not consistent; dose-response curves for tests 1B and 2B differed in slope and intercept. Nevertheless, C. riparius was more sensitive to ammonia in effluent than in well water in both experiments, indicating a synergistic effect of ammonia in sewage effluent. These results demonstrate the advantages of analyzing the organisms entire range of response, as opposed to generating LC50 values, which represent only one point on the dose-response curve.

  17. Observations and analysis of the Jovian spectrum in the 10-micron nu-2 band of NH3

    NASA Technical Reports Server (NTRS)

    Lacy, J. H.; Larrabee, A. I.; Wollman, E. R.; Geballe, T. R.; Townes, C. H.; Bregman, J. D.; Rank, D. M.

    1975-01-01

    Observations of the nu-2 band of NH3 in the Jovian atmosphere have been made at resolutions varying from 4 per cm to 0.15 per cm. The observations have been interpreted by computation of synthetic atmospheric spectra. Derived atmospheric parameters include a pressure of 0.5 atm at 145 K and a minimum temperature of 118 K.

  18. Chloride Incorporation Process in CH3NH3PbI3-xClx Perovskites via Nanoscale Bandgap Maps

    PubMed Central

    Chae, Jungseok; Dong, Qingfeng; Huang, Jinsong; Centrone, Andrea

    2016-01-01

    CH3NH3PbI3-xClx perovskites enable fabrication of highly efficient solar cells. Chloride ions benefit the morphology, carrier diffusion length and stability of perovskite films; however, whether those benefits stem from the presence of Cl− in the precursor solution or from their incorporation in annealed films is debated. In this work, the photothermal induced resonance (PTIR), an in situ technique with nanoscale resolution, is leveraged to measure the bandgap of CH3NH3PbI3-xClx films obtained by a multicycle coating process that produces high efficiency (≈ 16 %) solar cells. Because chloride ions modify the perovskite lattice, thereby widening the bandgap, measuring the bandgap locally yields the local chloride content. After a mild annealing (60 min, 60°C) the films consist of Cl-rich (x < 0.3) and Cl-poor phases that, upon further annealing (110 °C), evolve into a homogenous Cl-poorer (x < 0.06) phase, suggesting that methylammonium-chrloride is progressively expelled from the film. Despite the small chloride content, CH3NH3PbI3-xClx films show better thermal stability up to 140 °C with respect CH3NH3PbI3 films fabricated with the same methodology. PMID:26528710

  19. Formation of TiO2 Thin Films using NH3 as Catalyst by Metalorganic Chemical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Jung, Sung-Hoon; Kang, Sang-Won

    2001-05-01

    We have studied metalorganic chemical vapor deposition of TiO2 thin films using titanium tetra-isopropoxide [TTIP, Ti(O--C3H7)4] and NH3 as a catalyst at deposition temperatures ranging from 250 to 365°C. At deposition temperatures above 330°C, pyrolytic self-decomposition of TTIP is dominant regardless of the use of NH3, and the activation energy for TiO2 film formation is 152 kJ/mol. At deposition temperatures below 330°C, the films can be formed with the help of the catalytic activity of NH3, and the activation energy is reduced to 55 kJ/mol. TiO2 films deposited through the pyrolytic self-decomposition of TTIP have an anatase structure before and after performing post-deposition annealing in oxygen ambient for 30 min at 750°C. On the other hand, the as-deposited films formed through the catalytic reaction of TTIP with NH3 incorporate nitrogen impurities and have microcrystallites of the rutile structure within the amorphous matrix. However, the post-deposition annealing, the nitrogen impurities are completely removed from the films, and the films are converted into polycrystalline TiO2 films with the rutile structure, which have a high dielectric constant of 82 and a low leakage current.

  20. Understanding the Impact of Bromide on the Photovoltaic Performance of CH3 NH3 PbI3 Solar Cells.

    PubMed

    Ibrahim Dar, M; Abdi-Jalebi, Mojtaba; Arora, Neha; Moehl, Thomas; Grätzel, Michael; Nazeeruddin, Mohammad Khaja

    2015-11-25

    An optimum amount of lead bromide (1%) can enhance the power conversion efficiency of CH3 NH3 PbI3-x Brx (where x ≈ 0) devices from 14.7% to 16.9% without altering the bandgap of the perovskite material.

  1. Novel iron titanate catalyst for the selective catalytic reduction of NO with NH3 in the medium temperature range.

    PubMed

    Liu, Fudong; He, Hong; Zhang, Changbin

    2008-05-01

    An iron titanate catalyst with a crystallite phase, prepared by a co-precipitation method, showed excellent activity, stability, selectivity and SO(2)/H(2)O durability in the selective catalytic reduction of NO with NH(3) in the medium temperature range.

  2. Novel cerium-tungsten mixed oxide catalyst for the selective catalytic reduction of NO(x) with NH3.

    PubMed

    Shan, Wenpo; Liu, Fudong; He, Hong; Shi, Xiaoyan; Zhang, Changbin

    2011-07-28

    A novel Ce-W mixed oxide catalyst prepared by homogeneous precipitation method presented nearly 100% NO(x) conversion in a wide temperature range from 250 to 425 °C for the selective catalytic reduction of NO(x) with NH(3) under an extremely high GHSV of 500,000 h(-1).

  3. Triple-differential cross sections for the ionization of NH3 by positron impact. Comparison with electron impact ionization

    NASA Astrophysics Data System (ADS)

    Tóth, Istvan; Nagy, Ladislau; Campeanu, Radu I.

    2016-08-01

    Triple differential cross sections are calculated for the ionization of NH3 by positron impact in coplanar and perpendicular geometrical arrangements. The cross sections are determined for symmetrically emerging particles with equal energies. The positron cross sections are compared with previously calculated electron cross sections for the same kinematical conditions.

  4. Selective autocatalytic reduction of NO from sintering flue gas by the hot sintered ore in the presence of NH3.

    PubMed

    Chen, Wangsheng; Luo, Jing; Qin, Linbo; Han, Jun

    2015-12-01

    In this paper, the selective autocatalytic reduction of NO by NH3 combined with multi-metal oxides in the hot sintered ore was studied, and the catalytic activity of the hot sintered ore was investigated as a function of temperature, NH3/NO ratio, O2 content, H2O and SO2. The experimental results indicated that the hot sintered ore, when combined with NH3, had a maximum denitration efficiency of 37.67% at 450 °C, 3000 h(-1) gas hourly space velocity (GHSV) and a NH3/NO ratio of 0.4/1. Additionally, it was found that O2 played an important role in removing NOx. However, high O2 content had a negative effect on NO reduction. H2O was found to promote the denitration efficiency in the absence of SO2, while SO2 inhibited the catalytic activity of the sintered ore. In the presence of H2O and SO2, the catalytic activity of the sintered ore was dramatically suppressed.

  5. Fe2O3 particles as superior catalysts for low temperature selective catalytic reduction of NO with NH3.

    PubMed

    Wang, Xiaobo; Gui, Keting

    2013-12-01

    Fe2O3 particle catalysts were experimentally studied in the low temperature selective catalytic reduction (SCR) of NO with NH3. The effects of reaction temperature, oxygen concentration, [NH3]/[NO] molar ratio and residence time on SCR activity were studied. It was found that Fe2O3 catalysts had high activity for the SCR of NO with NH3 in a broad temperature range of 150-270 degrees C, and more than 95% NO conversion was obtained at 180 degrees C when the molar ratio [NH3]/[NO] = 1, the residence time was 0.48 seconds and O2 volume fraction was 3%. In addition, the effect of SO2 on SCR catalytic activity was also investigated at the temperature of 180 degrees C. The results showed that deactivation of the Fe2O3 particles occurred due to the presence of SO2 and the NO conversion decreased from 99.2% to 58% in 240 min, since SO2 gradually decreased the catalytic activity of the catalysts. In addition, X-ray diffraction, Thermogravimetric analysis and Fourier transform infrared spectroscopy were used to characterize the fresh and deactivated Fe2O3 catalysts. The results showed that the deactivation caused by SO2 was due to the formation of metal sulfates and ammonium sulfates on the catalyst surface during the de-NO reaction, which could cause pore plugging and result in suppression of the catalytic activity.

  6. Post-Cleaning Effect on a HfO2 Gate Stack Using a NF3/NH3 Plasma.

    PubMed

    Lee, Min-Seon; Oh, Hoon-Jung; Lee, Joo-Hee; Lee, In-Geun; Shin, Woo-Gon; Kim, Kyu-Dong; Park, Jin-Gu; Ko, Dae-Hong

    2016-05-01

    The effects of dry cleaning of a HfO2 gate stack using NF3 only and a NF3/NH3 gas mixture plasma were investigated. The plasma dry cleaning process was carried out after HfO2 deposition using an indirect down-flow capacitively coupled plasma (CCP) system. An analysis of the chemical composition of the HfO2 gate stacks by XPS indicated that fluorine was incorporated into the HfO2 films during the plasma dry cleaning. Significant changes in the HfO2 chemical composition were observed as a result of the NF3 dry cleaning, while they were not observed in this case of NF3/NH3 dry cleaning. TEM results showed that the interfacial layer (IL) between the HfO2 and Si thickness was increased by the plasma dry cleaning. However, in the case of NF3/NH3 dry cleaning using 150 W, the IL thickness was suppressed significantly compared to the sample that had not been dry cleaned. Its electrical properties were also improved, including the low gate leakage currents, and reduced EOT. Finally, the finding show that the IL thickness of the HfO2 gate stack can be controlled by using the novel NF3/NH3 dry cleaning process technique without any the significant changes in chemical composition and metal-oxide-semiconductor (MOS) capacitor characteristics. PMID:27483826

  7. Galvanic deposition of Rh and Ru on randomly structured Ti felts for the electrochemical NH3 synthesis.

    PubMed

    Kugler, Kurt; Luhn, Mareike; Schramm, Jean André; Rahimi, Khosrow; Wessling, Matthias

    2015-02-01

    Nowadays NH3 is exclusively synthesized by the Haber process. Unfortunately, the energy demand and the CO2 emissions due to H2 production are high. Hydrogen production utilizes precious carbon sources such as coal and natural gas. In the past we proposed an alternative process concept using a membrane electrode assembly in an electrochemical membrane reactor (ecMR). At the anode H2O is oxidized at an IrMMO catalyst to form protons. By applying an external potential to the ecMR N2 is reduced to NH3 at the cathode. Just recently Rh and Ru were identified as possible cathodic electrocatalysts by DFT calculations. We present an easy and highly efficient method for galvanic coatings of Rh and Ru on randomly structured Ti felts to be used in a membrane electrode assembly. Linear sweep voltammetry measurements give a slightly higher activity of Ru for the liquid phase electrochemical NH3 synthesis. The NH4(+) concentration reached is 8 times higher for Ru than for Rh. From an economical point of view, Ru is also more feasible for an electrochemical NH3 synthesis process. Such electrodes can now be evaluated in an ecMR in comparison to recently demonstrated Ti-based electrodes.

  8. Galvanic deposition of Rh and Ru on randomly structured Ti felts for the electrochemical NH3 synthesis.

    PubMed

    Kugler, Kurt; Luhn, Mareike; Schramm, Jean André; Rahimi, Khosrow; Wessling, Matthias

    2015-02-01

    Nowadays NH3 is exclusively synthesized by the Haber process. Unfortunately, the energy demand and the CO2 emissions due to H2 production are high. Hydrogen production utilizes precious carbon sources such as coal and natural gas. In the past we proposed an alternative process concept using a membrane electrode assembly in an electrochemical membrane reactor (ecMR). At the anode H2O is oxidized at an IrMMO catalyst to form protons. By applying an external potential to the ecMR N2 is reduced to NH3 at the cathode. Just recently Rh and Ru were identified as possible cathodic electrocatalysts by DFT calculations. We present an easy and highly efficient method for galvanic coatings of Rh and Ru on randomly structured Ti felts to be used in a membrane electrode assembly. Linear sweep voltammetry measurements give a slightly higher activity of Ru for the liquid phase electrochemical NH3 synthesis. The NH4(+) concentration reached is 8 times higher for Ru than for Rh. From an economical point of view, Ru is also more feasible for an electrochemical NH3 synthesis process. Such electrodes can now be evaluated in an ecMR in comparison to recently demonstrated Ti-based electrodes. PMID:25556769

  9. Hyperfine Splittings in the Near-Infrared Spectrum of 14NH_3

    NASA Astrophysics Data System (ADS)

    Twagirayezu, Sylvestre; Sears, Trevor; Hall, Gregory

    2016-06-01

    Sub-Doppler, saturation dip, measurements of transitions in the ν_1 + ν_3 band of 14NH_3 have been made by frequency comb-referenced diode laser absorption spectroscopy. The observed spectra exhibit either resolved or partially-resolved hyperfine splittings that are primarily determined by the 14N quadrupole coupling in the molecule. Modeling of the line shapes based on the known hyperfine level structure of the ground state of the molecule shows that, in nearly all cases, the upper state level has splittings similar to that of the same rotational level in the ground state. The data provide accurate frequencies for the line positions and the observed hyperfine splittings can be used to make or confirm rotational assignments. Of all the measurements, one transition, pP(5,4)_a at 195 994.73457 GHz, exhibits hyperfine structure which does not conform to that expected based on extrapolation from the known lower state hyperfine splittings. Examination of the known vibration-rotation level structure near the upper state energy shows that there exists a near degeneracy between this level and one in the ν_1 + 2ν_4 manifold which is of the appropriate symmetry to be mixed by magnetic hyperfine terms that couple ortho- and para- modifications of the molecule. It is possible that the unusual hyperfine splittings are a consequence of ortho-paro mixing, which has been predicted, but not previously seen in ammonia and further experimental measurements to investigate this possibility are ongoing. Acknowledgments: Work at Brookhaven National Laboratory was carried out under Contract No. DE-SC0012704 with the U.S. Department of Energy, Office of Science, and supported by its Division of Chemical Sciences, Geosciences and Biosciences within the Office of Basic Energy Sciences.

  10. Charge transport in bulk CH3NH3PbI3 perovskite

    NASA Astrophysics Data System (ADS)

    Slonopas, Andre; Foley, Benjamin J.; Choi, Joshua J.; Gupta, Mool C.

    2016-02-01

    The variation of leakage current and polarization hysteresis properties for bulk CH3NH3PbI3 perovskite was studied as a function of temperature to understand the reported hysteresis in photocurrent and the role of ferroelectricity. The leakage current decreased by two orders of magnitude when the temperature was lowered from 350 K to 100 K. The transitions in leakage current were observed at structural phase transition temperatures. The temperature dependence study allowed the identification of current conduction mechanism based on various models for ferroelectrics and insulating materials. Our results show that the leakage current is governed by the space charge limited conduction mechanism which should be considered in addition to ion conduction and ferroelectricity when analyzing current-voltage hysteresis for thin film and bulk materials. The Mott's variable range hopping model fits well to the experimental data indicating the charge conduction is through hopping mechanism from 300 K to 160 K and possibly tunneling below 160 K. The conclusions from polarization hysteresis study are: (1) the hysteresis loop shape is highly dependent upon frequency and show non-saturating behavior, an indicative of strong non-ferroelectric contributions such as resistive component. (2) No domain switching current was observed between the temperature range of 100 K-350 K. (3) An electric field off-set was observed in polarization-electric field curves and it was dependent upon the frequency and temperature. This offset could be caused by the accumulation of vacancies at one interface, which could give rise to hysteresis in forward and reverse bias photocurrent. (4) The time dependence study of instantaneous current as the voltage was increased linearly show strong resistive contribution to hysteresis loop at temperatures above 200 K and capacitive contribution at 100 K.

  11. Characterization of Cu-SSZ-13 NH3 SCR catalysts: an in situ FTIR study.

    PubMed

    Szanyi, János; Kwak, Ja Hun; Zhu, Haiyang; Peden, Charles H F

    2013-02-21

    The adsorption of CO and NO over Cu-SSZ-13 zeolite catalysts, highly active in the selective catalytic reduction of NO(x) with NH(3), was investigated by FTIR spectroscopy, and the results obtained were compared to those collected from other Cu-ion exchanged zeolites (Y,FAU and ZSM-5). Under low CO pressures and at room temperature (295 K), CO forms monocarbonyls exclusively on the Cu(+) ions, while in the presence of gas phase CO dicarbonyls on Cu(+) and adsorbed CO on Cu(2+) centers form, as well. At low (cryogenic) sample temperatures, tricarbonyl formation on Cu(+) sites was also observed. The adsorption of NO produces IR bands that can be assigned to nitrosyls bound to both Cu(+) and Cu(2+) centers, and NO(+) species located in charge compensating cationic positions of the chabasite framework. On the reduced Cu-SSZ-13 samples the formation of N(2)O was also detected. The assignment of the adsorbed NO(x) species was aided by adsorption experiments with isotopically labeled (15)NO. The movement of Cu ions from the sterically hindered six member ring position to the more accessible cavity positions as a result of their interaction with adsorbates (NO and H(2)O) was clearly evidenced. Comparisons of the spectroscopy data obtained in the static transmission IR system to those collected in the flow-through diffuse reflectance cell points out that care must be taken when general conclusions are drawn about the adsorptive and reactive properties of metal cation centers based on a set of data collected under well defined, specific experimental conditions. PMID:23301245

  12. Characterization of Cu-SSZ-13 NH3 SCR catalysts: an in situ FTIR study.

    PubMed

    Szanyi, János; Kwak, Ja Hun; Zhu, Haiyang; Peden, Charles H F

    2013-02-21

    The adsorption of CO and NO over Cu-SSZ-13 zeolite catalysts, highly active in the selective catalytic reduction of NO(x) with NH(3), was investigated by FTIR spectroscopy, and the results obtained were compared to those collected from other Cu-ion exchanged zeolites (Y,FAU and ZSM-5). Under low CO pressures and at room temperature (295 K), CO forms monocarbonyls exclusively on the Cu(+) ions, while in the presence of gas phase CO dicarbonyls on Cu(+) and adsorbed CO on Cu(2+) centers form, as well. At low (cryogenic) sample temperatures, tricarbonyl formation on Cu(+) sites was also observed. The adsorption of NO produces IR bands that can be assigned to nitrosyls bound to both Cu(+) and Cu(2+) centers, and NO(+) species located in charge compensating cationic positions of the chabasite framework. On the reduced Cu-SSZ-13 samples the formation of N(2)O was also detected. The assignment of the adsorbed NO(x) species was aided by adsorption experiments with isotopically labeled (15)NO. The movement of Cu ions from the sterically hindered six member ring position to the more accessible cavity positions as a result of their interaction with adsorbates (NO and H(2)O) was clearly evidenced. Comparisons of the spectroscopy data obtained in the static transmission IR system to those collected in the flow-through diffuse reflectance cell points out that care must be taken when general conclusions are drawn about the adsorptive and reactive properties of metal cation centers based on a set of data collected under well defined, specific experimental conditions.

  13. ZnO Nanoparticles/Reduced Graphene Oxide Bilayer Thin Films for Improved NH3-Sensing Performances at Room Temperature

    NASA Astrophysics Data System (ADS)

    Tai, Huiling; Yuan, Zhen; Zheng, Weijian; Ye, Zongbiao; Liu, Chunhua; Du, Xiaosong

    2016-03-01

    ZnO nanoparticles and graphene oxide (GO) thin film were deposited on gold interdigital electrodes (IDEs) in sequence via simple spraying process, which was further restored to ZnO/reduced graphene oxide (rGO) bilayer thin film by the thermal reduction treatment and employed for ammonia (NH3) detection at room temperature. rGO was identified by UV-vis absorption spectra and X-ray photoelectron spectroscope (XPS) analyses, and the adhesion between ZnO nanoparticles and rGO nanosheets might also be formed. The NH3-sensing performances of pure rGO film and ZnO/rGO bilayer films with different sprayed GO amounts were compared. The results showed that ZnO/rGO film sensors exhibited enhanced response properties, and the optimal GO amount of 1.5 ml was achieved. Furthermore, the optimal ZnO/rGO film sensor showed an excellent reversibility and fast response/recovery rate within the detection range of 10-50 ppm. Meanwhile, the sensor also displayed good repeatability and selectivity to NH3. However, the interference of water molecules on the prepared sensor is non-ignorable; some techniques should be researched to eliminate the effect of moisture in the further work. The remarkably enhanced NH3-sensing characteristics were speculated to be attributed to both the supporting role of ZnO nanoparticles film and accumulation heterojunction at the interface between ZnO and rGO. Thus, the proposed ZnO/rGO bilayer thin film sensor might give a promise for high-performance NH3-sensing applications.

  14. DFT study of coverage-depended adsorption of NH3 on TiO2-B (100) surface.

    PubMed

    Guo, Xiao-Jing; Liu, Weijia; Fang, Wei; Cai, Lu; Zhu, Yudan; Lu, Linghong; Lu, Xiaohua

    2012-12-28

    A previous study showed that TiO(2)-B (100) surface is very unique. It is characterised by high activity and a loose structure. In this study, we studied the adsorption of ammonia on TiO(2)-B (100) surface at coverages ranging from 1/6 ML to 1 ML using ab initio density functional calculations. We also investigated the adsorption of an isolated ammonia molecule on TiO(2)-B (001) surface to compare the different activities of TiO(2)-B (100) and (001) surfaces towards NH(3). The results showed that the TiO(2)-B (100) surface is more reactive towards NH(3) molecule than TiO(2)-B (001) surface, and the Lewis acid site on TiO(2)-B (100) surface is more acidic. The decrease rate of the average molecular adsorption energy of NH(3) with coverage on TiO(2)-B (100) surface is substantially lower than that on a rutile (011) surface above 1/2 ML coverage due to the open structure of TiO(2)-B (100) surface. The average molecular adsorption energy shows a linear dependence on the coverage of y = 111.0 - 36.3x on TiO(2)-B (100) surface. The possibility of NH(3) molecule onto the Ti(5c) site is nearly equal to forming a dimer with adsorbed NH(3) on TiO(2)-B (100) surface at 5/6 ML coverage. PMID:22955312

  15. Selective catalytic reduction of NOx with NH3 over a Cu-SSZ-13 catalyst prepared by a solid state ion exchange method

    SciTech Connect

    Wang, Di; Gao, Feng; Peden, Charles HF; Li, Junhui; Kamasamudram, Krishna; Epling, William S.

    2014-06-01

    A novel solid state method was developed to synthesize Cu-SSZ-13 catalysts with excellent NH3-SCR performance and durable hydrothermal stability. After the solid state ion exchange (SSIE) process, the SSZ framework structure and surface area was maintained. In-situ DRIFTS and NH3-TPD experiments provide evidence that isolated Cu ions were successfully exchanged into the pores, which are the active centers for the NH3-SCR reaction.

  16. Characterization of Cu-SSZ-13 NH3 SCR Catalysts: an in situ FTIR Study

    SciTech Connect

    Szanyi, Janos; Kwak, Ja Hun; Zhu, Haiyang; Peden, Charles HF

    2013-01-23

    The adsorption of CO and NO over Cu-SSZ-13 zeolite catalysts, highly active in the selective catalytic reduction of NOx with NH3, was investigated by FTIR spectroscopy, and the results obtained were compared to those collected from other Cu-ion exchanged zeolites (Y,FAU and ZSM-5). At low CO pressures at room temperature (295 K) CO form monocarbonyls exclusively on the Cu+ ions, while in the presence of gas phase CO dicarbonyls on Cu+ and adsorbed CO on Cu2+ centers form, as well. At low (cryogenic) sample temperatures tricarbonyl formation on Cu+ sites was also observed. The adsorption of NO produces IR bands that can be assigned to nitrosyls bound to both Cu+ and Cu2+ centers, and NO+ species located in charge compensating cationic positions of the chabasite framework. On the reduced Cu-SSZ-13 samples the formation of N2O was also detected. The assignment of the adsorbed NOx species was aided by adsorption experiments with isotopically labeled 15NO. The movement of Cu ions from the sterically hindered six member ring position to the more accessible cavity positions as a result of their interaction with adsorbates (NO and H2O) was clearly evidenced. Comparisons of the spectroscopy data obtained in the static transmission IR system to those collected in the flow-through diffuse reflectance cell points out that care must be taken when conclusions are drawn about the adsorptive and reactive properties of metal cation centers based on a set of data collected under well defined, specific experimental conditions. Financial support was provided by the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Program. This work was performed in the Environmental Molecular Sciences Laboratory (EMSL) at the Pacific Northwest National Laboratory (PNNL). The EMSL is a national scientific user facility supported by the US DOE, Office of Biological and Environmental Research. PNNL is a multi-program national laboratory operated for

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

    NASA Astrophysics Data System (ADS)

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

    1991-06-01

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

  18. Welding IV.

    ERIC Educational Resources Information Center

    Allegheny County Community Coll., Pittsburgh, PA.

    Instructional objectives and performance requirements are outlined in this course guide for Welding IV, a competency-based course in advanced arc welding offered at the Community College of Allegheny County to provide students with proficiency in: (1) single vee groove welding using code specifications established by the American Welding Society…

  19. ESO Very Large Telescope Optical Spectroscopy of BL Lacertae Objects. IV. New Spectra and Properties of the Full Sample

    NASA Astrophysics Data System (ADS)

    Landoni, M.; Falomo, R.; Treves, A.; Sbarufatti, B.; Barattini, M.; Decarli, R.; Kotilainen, J.

    2013-04-01

    We present the last chapter of a spectroscopy program aimed at deriving the redshift or a lower limit to the redshift of BL Lac objects using medium-resolution spectroscopy. Here we report new spectra for 33 BL Lac object candidates obtained in 2008-2009, confirming the BL Lac nature of 25 sources and obtaining new redshifts for 5 objects. These new observations are combined with our previous data in order to construct a homogeneous sample of ~70 BL Lac objects with high-quality spectroscopy. All these spectra can be accessed at the Web site http://www.oapd.inaf.it/zbllac/. The average spectrum, beaming properties of the full sample, discussion of intervening systems, and future perspectives are addressed.

  20. Eddy covariance measurements of NH3 fluxes over a natural grass land with an open-path quantum cascade laser-based sensor

    NASA Astrophysics Data System (ADS)

    Pan, D.; Benedict, K. B.; Ham, J. M.; Prenni, A. J.; Schichtel, B. A.; Collett, J. L., Jr.; Zondlo, M. A.

    2015-12-01

    NH3 is an important component of the bio-atmospheric N cycle with implications for regional air quality, human and ecosystem health degradation, and global climate change. However, measuring NH3 flux is challenging, requiring a sensor with high sensitivity (sub-ppbv), fast response time and the capability to account for NH3 adsorption effects. In this study, we address these issues with an open-path quantum-cascade-based sensor for eddy covariance (EC) measurements. Previously, our EC NH3 sensor was deployed over a feedlot in Colorado in 2013 and 2014, and the results showed the potential of the sensor to measure NH3 emissions from agricultural sources. In the summer of 2015, the sensor was installed at a remote monitoring site in Rocky Mountain National Park to measure NH3 flux over a natural grass land. During the deployment, the precision of the sensor was about 0.15 ppbv at 10 Hz, and the detection limit of the flux was estimated to be 0.7±0.5 ng NH3/s/m2. The cospectra of the NH3 flux closely resembled those of CO2 flux and sensible heat flux measured by a LI-7500 CO2 analyzer and a CSAT3 sonic anemometer. The ogive analyses indicated that the loss of NH3 fluxes due to various damping effects was about 15%. Examining initial results from a few days of measurement, the measured NH3 fluxes appear to have a strong diurnal pattern with local emissions during afternoon, a pattern not previously reported for remote grass land. The pattern is consistent with background NH3 concentration measured by PICARRO NH3 analyzer, although summertime afternoon concentration increases at the site have previously been associated with upslope transport from urban and agricultural regions to the east. The results demonstrate the sensor's capability to measure NH3 flux in low NH3 conditions and also show that more measurements are needed to investigate spatial and temporal variability of NH3 flux.

  1. A simple rule for determining the band offset at CH3NH3PbI3/organic semiconductor heterojunctions

    NASA Astrophysics Data System (ADS)

    Thibau, E. S.; Llanos, A.; Lu, Z. H.

    2016-01-01

    Organo-metal halide perovskites have recently emerged as a highly promising class of semiconductors for optoelectronic device applications. Integrating these hybrid materials within organic molecular thin film devices is key to fabricate functional devices. By evaporating ultra-thin films of organic semiconductor on thermally evaporated CH3NH3PbI3 and using in-situ ultraviolet photoemission spectroscopy, we directly measure the interfacial energy offset between CH3NH3PbI3 valence band maximum and the highest occupied molecular orbital for 5 different archetypal organic semiconductors. It is found that the energy offsets scale linearly as a function of the ionization energies of the organic semiconductors. The experimental data are in excellent agreement with a theoretical model for ideal semiconductor heterojunctions.

  2. Mor-Dalphos-Pd (II) oxidative addition complexes and related NH3 adducts: Insights into bonding and nonbonding interactions

    NASA Astrophysics Data System (ADS)

    de Lima Batista, Ana P.; Braga, Ataualpa A. C.

    2016-09-01

    The stabilizing effects and bonding properties of the Pd metallic center in [(κ2 -P,N-Mor-Dalphos)Pd(Ar)Cl] complexes and related NH3 adducts were investigated by density functional theory (DFT), the intrinsic bond orbital (IBO) approach and the Su-Li energy decomposition method (Su-Li EDA). The IBO analysis showed that the P atom from the P,N-Mor-Dalphos structure has stabilizing contributions in all Pd-Cl and Pd-NH3 bonds in the complexes. According to the Su-Li energy decomposition analysis, the main energy that drives the interaction between the [Mor-Dalphos-Pd(Ar)] moiety and Cl- is the electrostatic term, therefore, the electrostatic energy interaction between them might be an important factor for taking into account when designing other [Mor-Dalphos-Pd(Ar)]-Cl precatalysts.

  3. Synthesis, structure, and properties of SrC(NH)3 , a nitrogen-based carbonate analogue with the trinacria motif.

    PubMed

    Missong, Ronja; George, Janine; Houben, Andreas; Hoelzel, Markus; Dronskowski, Richard

    2015-10-01

    Strontium guanidinate, SrC(NH)3 , the first compound with a doubly deprotonated guanidine unit, was synthesized from strontium and guanidine in liquid ammonia and characterized by X-ray and neutron diffraction, IR spectroscopy, and density-functional theory including harmonic phonon calculations. The compound crystallizes in the hexagonal space group P63 /m, constitutes the nitrogen analogue of strontium carbonate, SrCO3 , and its structure follows a layered motif between Sr(2+) ions and complex anions of the type C(NH)3 (2-) ; the anions adopt the peculiar trinacria shape. A comparison of theoretical phonons with experimental IR bands as well as quantum-chemical bonding analyses yield a first insight into bonding and packing of the formerly unknown anion in the crystal.

  4. Effect of hydrogen generated by dielectric barrier discharge of NH3 on selective non-catalytic reduction process.

    PubMed

    Byun, Youngchul; Ko, Kyung Bo; Cho, Moohyun; Namkung, Won; Shin, Dong Nam; Koh, Dong Jun

    2009-05-01

    Plasma-assisted selective non-catalytic reduction (SNCR) has been investigated to clarify which species generated by the plasma play a crucial role in NO reduction. We find that the presence of O(2) is indispensable and only H(2) is observed to be a stable product by dielectric barrier discharge (DBD) of NH(3). As the extent of NH(3) decomposition by DBD increases, the commencement temperature of SNCR processes is lowered and the working temperature window is widened. This propensity may be attributed to the chemical reaction of H(2) with O(2) to generate OH and H radicals which make it possible to yield NH(2) radicals even at low temperature.

  5. Structural, energetic and thermodynamic analyses of Ca(BH4)2·2NH3 from first principles calculations

    NASA Astrophysics Data System (ADS)

    Yuan, Peng-Fei; Wang, Fei; Sun, Qiang; Jia, Yu; Guo, Zheng-Xiao

    2012-01-01

    Ca(BH4)2·2NH3 is a relatively new compound with potential application in hydrogen storage. Here the fundamental properties of the compound, such as electronic structure, energetic and thermodynamic properties, were comprehensively studied using first-principles calculations. Results from electronic density of states (DOS) and electron localization function (ELF) indicate the covalent bond nature of the N-H bond and the B-H bond. Charge density analyses show weak ionic interactions between the Ca atom and the NH3 complexes or the (BH4)- complexes. The calculated vibration frequencies of B-H and N-H are in good agreement with other theoretical and experimental results. Furthermore, we calculated the reaction enthalpy and reaction Gibbs free energy at a range of temperature 0-700 K. Our results are in good agreement with experimental results in literature. Possible reaction mechanism of the decomposition reaction is proposed.

  6. Ceria supported on sulfated zirconia as a superacid catalyst for selective catalytic reduction of NO with NH3.

    PubMed

    Gao, Shan; Chen, Xiongbo; Wang, Haiqiang; Mo, Jiansong; Wu, Zhongbiao; Liu, Yue; Weng, Xiaole

    2013-03-15

    In this paper, ceria supported on sulfated zirconia (CeSZ) as a superacid catalyst was synthesized and the resulted performances for selective catalytic reduction (SCR) of NO with NH(3) were investigated. Experimental results revealed that the sulfation of zirconia supports could greatly improve the SCR activity of the catalysts. Among the tested samples, the CeSZ catalyst with Ce/Zr mole ratio at 0.095 possessed the highest NO conversion (i.e., 98.6% at ca. 420 °C and 180,000 h(-1)). The sulfation had led to a formation of pure tetragonal phase of ZrO(2), a well dispersion of CeO(2), abundant stable superacid sites, increasing surface area and enrichment of Ce(3+) on the surface, all of which were responsible for its excellent performance in SCR of NO with NH(3).

  7. Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NOx with NH3

    SciTech Connect

    Kwak, Ja Hun; Tonkyn, Russell G.; Kim, Do Heui; Szanyi, Janos; Peden, Charles HF

    2010-10-21

    Superior activity and selectivity of a Cu ion-exchanged SSZ-13 zeolite in the selective catalytic reduction (SCR) of NOx with NH3 were observed, in comparison to Cu-beta and Cu-ZSM-5 zeolites. Cu-SSZ-13 was not only more active in the NOx SCR reaction over the entire temperature range studied (up to 550 °C), but also more selective toward nitrogen formation, resulting in significantly lower amounts of NOx by-products (i.e., NO2 and N2O) than the other two zeolites. In addition, Cu-SSZ-13 demonstrated the highest activity and N2 formation selectivity in the oxidation of NH3. The results of this study strongly suggest that Cu-SSZ-13 is a promising candidate as a catalyst for NOx SCR with great potential in after-treatment systems for either mobile or stationary sources.

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

    PubMed

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

    2015-10-01

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

  9. The role of copper species on Cu/γ-Al2O3 catalysts for NH3-SCO reaction

    NASA Astrophysics Data System (ADS)

    Liang, Chunxia; Li, Xinyong; Qu, Zhenping; Tade, Moses; Liu, Shaomin

    2012-02-01

    UV-vis spectra, XRD, H2-TPR, TEM and ESR were used to characterize a series of Cu/γ-Al2O3 catalysts, which were prepared by incipient wetness impregnation using copper nitrate, copper acetate or copper sulfate as precursors, to study the role of Cu species on Cu/γ-Al2O3 catalysts for NH3-SCO reaction. It was found that the mixture of CuO phase and CuAl2O4 phase formed on various Cu/γ-Al2O3 catalysts, and the Cu species and dispersion had significant influence on the Cu/γ-Al2O3 activity. Highly dispersed CuO phase on the support would be related with its high activity for the NH3-SCO reaction.

  10. Sonochemical synthesis of CH3NH3PbI3 perovskite ultrafine nanocrystal sensitizers for solar energy applications.

    PubMed

    Bhooshan Kumar, Vijay; Gouda, Laxman; Porat, Ze'ev; Gedanken, Aharon

    2016-09-01

    The organic-inorganic hybrid perovskite CH3NH3PbI3 is becoming an interesting material in the field of energy harvesting. This material is one of the cleanest and cheapest components in solar cells which is available in ample amounts. However, most of the previous research work was done on thin film of this material. In the present work we describe the preparation of a powder containing nanoparticles of CH3NH3PbI3 using a sonochemical method. Characterization of the product was done by various methods, such as HRTEM, FTIR, PL, DLS and XRD. The particles were found to be highly crystalline (tetragonal crystal structure), polygonal in shape and having diameters of 10-40nm.

  11. Evidence that fungal MEP proteins mediate diffusion of the uncharged species NH(3) across the cytoplasmic membrane.

    PubMed

    Soupene, E; Ramirez, R M; Kustu, S

    2001-09-01

    Methylammonium and ammonium (MEP) permeases of Saccharomyces cerevisiae belong to a ubiquitous family of cytoplasmic membrane proteins that transport only ammonium (NH(4)(+) + NH(3)). Transport and accumulation of the ammonium analog [(14)C]methylammonium, a weak base, led to the proposal that members of this family were capable of energy-dependent concentration of the ammonium ion, NH(4)(+). In bacteria, however, ATP-dependent conversion of methylammonium to gamma-N-methylglutamine by glutamine synthetase precludes its use in assessing concentrative transport across the cytoplasmic membrane. We have confirmed that methylammonium is not metabolized in the yeast S. cerevisiae and have shown that it is little metabolized in the filamentous fungus Neurospora crassa. However, its accumulation depends on the energy-dependent acidification of vacuoles. A Deltavph1 mutant of S. cerevisiae and a Deltavma1 mutant, which lack vacuolar H(+)-ATPase activity, had large (fivefold or greater) defects in the accumulation of methylammonium, with little accompanying defect in the initial rate of transport. A vma-1 mutant of N. crassa largely metabolized methylammonium to methylglutamine. Thus, in fungi as in bacteria, subsequent energy-dependent utilization of methylammonium precludes its use in assessing active transport across the cytoplasmic membrane. The requirement for a proton gradient to sequester the charged species CH(3)NH(3)(+) in acidic vacuoles provides evidence that the substrate for MEP proteins is the uncharged species CH(3)NH(2). By inference, their natural substrate is NH(3), a gas. We postulate that MEP proteins facilitate diffusion of NH(3) across the cytoplasmic membrane and speculate that human Rhesus proteins, which lie in the same domain family as MEP proteins, facilitate diffusion of CO(2).

  12. The role of NH3 and hydrocarbon mixtures in GaN pseudo-halide CVD: a quantum chemical study.

    PubMed

    Gadzhiev, Oleg B; Sennikov, Peter G; Petrov, Alexander I; Kachel, Krzysztof; Golka, Sebastian; Gogova, Daniela; Siche, Dietmar

    2014-11-01

    The prospects of a control for a novel gallium nitride pseudo-halide vapor phase epitaxy (PHVPE) with HCN were thoroughly analyzed for hydrocarbons-NH3-Ga gas phase on the basis of quantum chemical investigation with DFT (B3LYP, B3LYP with D3 empirical correction on dispersion interaction) and ab-initio (CASSCF, coupled clusters, and multireference configuration interaction including MRCI+Q) methods. The computational screening of reactions for different hydrocarbons (CH4, C2H6, C3H8, C2H4, and C2H2) as readily available carbon precursors for HCN formation, potential chemical transport agents, and for controlled carbon doping of deposited GaN was carried out with the B3LYP method in conjunction with basis sets up to aug-cc-pVTZ. The gas phase intermediates for the reactions in the Ga-hydrocarbon systems were predicted at different theory levels. The located π-complexes Ga…C2H2 and Ga…C2H4 were studied to determine a probable catalytic activity in reactions with NH3. A limited influence of the carbon-containing atmosphere was exhibited for the carbon doping of GaN crystal in the conventional GaN chemical vapor deposition (CVD) process with hydrocarbons injected in the gas phase. Our results provide a basis for experimental studies of GaN crystal growth with C2H4 and C2H2 as auxiliary carbon reagents for the Ga-NH3 and Ga-C-NH3 CVD systems and prerequisites for reactor design to enhance and control the PHVPE process through the HCN synthesis.

  13. Surface Properties of CH3NH3PbI3 for Perovskite Solar Cells.

    PubMed

    Haruyama, Jun; Sodeyama, Keitaro; Han, Liyuan; Tateyama, Yoshitaka

    2016-03-15

    Perovskite solar cells (PSCs) have attracted considerable interest because of their high potential for solar energy conversion. Power conversion efficiencies of the PSCs have rapidly increased from 3.8 to over 20% only in the past few years. PSCs have several similarities to dye-sensitized solar cells in their device compositions; mesoporous TiO2 (mp-TiO2) is sensitized by light-absorbing components and placed into a medium containing hole transporting materials (HTMs). On the other hand, the perovskite materials for the light-harvesting, for example, CH3NH3PbI3 (MAPbI3), have a greater advantage for the photovoltaic applications; extremely long photocarrier diffusion lengths (over 1 μm) enable carrier transports without singnificant loss. In this respect, the surface states, that can be possible recombination centers, are also of great importance. Availability of solution processes is another important aspect in terms of low cost fabrication of PSCs. Two-step methods, where PbI2 is first introduced from solution onto a mp-TiO2 film and subsequently transformed into the MAPbI3 by the exposition of a solution containing MAI, suggest that use of such a high PbI2 concentration is crucial to obtain higher performance. The experiments also indicate that the PbI2-rich growth condition modifies TiO2/ or HTM/MAPbI3 interfaces in such a way that the photocarrier transport is improved. Thus, the characteristics of surfaces and interfaces play key roles in the high efficiencies of the PSCs. In this Account, we focus on the structural stability and electronic states of the representative (110), (001), (100), and (101) surfaces of tetragonal MAPbI3, which can be regarded as reasonable model HTM/MAPbI3 interfaces, by use of first-principles calculations. By examining various types of PbIx polyhedron terminations, we found that there are two major phases on all of the four surface facets. They can be classified as vacant- and flat-type terminations, and the former is more stable

  14. Surface Properties of CH3NH3PbI3 for Perovskite Solar Cells.

    PubMed

    Haruyama, Jun; Sodeyama, Keitaro; Han, Liyuan; Tateyama, Yoshitaka

    2016-03-15

    Perovskite solar cells (PSCs) have attracted considerable interest because of their high potential for solar energy conversion. Power conversion efficiencies of the PSCs have rapidly increased from 3.8 to over 20% only in the past few years. PSCs have several similarities to dye-sensitized solar cells in their device compositions; mesoporous TiO2 (mp-TiO2) is sensitized by light-absorbing components and placed into a medium containing hole transporting materials (HTMs). On the other hand, the perovskite materials for the light-harvesting, for example, CH3NH3PbI3 (MAPbI3), have a greater advantage for the photovoltaic applications; extremely long photocarrier diffusion lengths (over 1 μm) enable carrier transports without singnificant loss. In this respect, the surface states, that can be possible recombination centers, are also of great importance. Availability of solution processes is another important aspect in terms of low cost fabrication of PSCs. Two-step methods, where PbI2 is first introduced from solution onto a mp-TiO2 film and subsequently transformed into the MAPbI3 by the exposition of a solution containing MAI, suggest that use of such a high PbI2 concentration is crucial to obtain higher performance. The experiments also indicate that the PbI2-rich growth condition modifies TiO2/ or HTM/MAPbI3 interfaces in such a way that the photocarrier transport is improved. Thus, the characteristics of surfaces and interfaces play key roles in the high efficiencies of the PSCs. In this Account, we focus on the structural stability and electronic states of the representative (110), (001), (100), and (101) surfaces of tetragonal MAPbI3, which can be regarded as reasonable model HTM/MAPbI3 interfaces, by use of first-principles calculations. By examining various types of PbIx polyhedron terminations, we found that there are two major phases on all of the four surface facets. They can be classified as vacant- and flat-type terminations, and the former is more stable

  15. Improved characteristics for MOHOS memory with oxygen-rich GdO as charge storage layer annealed by NH3

    NASA Astrophysics Data System (ADS)

    Liu, Lu; Xu, J. P.; Chen, J. X.; Lai, P. T.

    2014-06-01

    Characteristics of metal-oxide-high- k-oxide-silicon (MOHOS) memories with oxygen-rich or oxygen-deficient GdO as charge storage layer annealed by NH3 or N2 are investigated. Transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction are used to analyze the cross-sectional quality, composition and crystallinity, respectively, of the stacked gate dielectric with a structure of Al/Al2O3/GdO/SiO2/Si. The MOHOS capacitor with oxygen-rich GdO annealed in NH3 exhibits a good trade-off among its memory properties: large memory window (4.8 V at ±12 V, 1 s), high programming speed (2.6 V at ±12 V/100 μs), good endurance and retention properties (window degradation of 5 % after 105 program/erase cycles and charge loss of 18.6 % at 85 °C after 10 years, respectively) due to passivation of oxygen vacancies, generation of deep-level traps in the grain boundaries of the GdO layer and suppression of the interlayer between GdO and SiO2 by the NH3 annealing.

  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. Effects of co-processing sewage sludge in cement kiln on NOx, NH3 and PAHs emissions.

    PubMed

    Lv, Dong; Zhu, Tianle; Liu, Runwei; Lv, Qingzhi; Sun, Ye; Wang, Hongmei; Liu, Yu; Zhang, Fan

    2016-09-01

    The effects of co-processing sewage sludge in cement kiln on NOx, NH3 and PAHs emissions were systematically investigated in a cement production line in Beijing. The results show that co-processing the sewage sludge was helpful to reduce NOx emission, which primarily depends on the NH3 amount released from the sewage sludge. Meanwhile, NOx and NH3 concentrations in the flue gas have a negative correlation, and the contribution of feeding the sewage sludge to NOx removal decreased with the increase of injection amount of ammonia water in the SNCR system. Therefore, it is suggested that the injection amount of ammonia water in SNCR system may reduce to cut down the operating costs during co-processing the sewage sludge in cement kiln. In addition, the emission of total PAHs seems to increase with the increased amount of the sewage sludge feeding to the cement kiln. However, the distributions of PAHs were barely changed, and lower molecular weight PAHs were mainly distributed in gaseous phase, accounted for the major portion of PAHs when co-processing sewage sludge in cement kiln.

  18. Effects of co-processing sewage sludge in cement kiln on NOx, NH3 and PAHs emissions.

    PubMed

    Lv, Dong; Zhu, Tianle; Liu, Runwei; Lv, Qingzhi; Sun, Ye; Wang, Hongmei; Liu, Yu; Zhang, Fan

    2016-09-01

    The effects of co-processing sewage sludge in cement kiln on NOx, NH3 and PAHs emissions were systematically investigated in a cement production line in Beijing. The results show that co-processing the sewage sludge was helpful to reduce NOx emission, which primarily depends on the NH3 amount released from the sewage sludge. Meanwhile, NOx and NH3 concentrations in the flue gas have a negative correlation, and the contribution of feeding the sewage sludge to NOx removal decreased with the increase of injection amount of ammonia water in the SNCR system. Therefore, it is suggested that the injection amount of ammonia water in SNCR system may reduce to cut down the operating costs during co-processing the sewage sludge in cement kiln. In addition, the emission of total PAHs seems to increase with the increased amount of the sewage sludge feeding to the cement kiln. However, the distributions of PAHs were barely changed, and lower molecular weight PAHs were mainly distributed in gaseous phase, accounted for the major portion of PAHs when co-processing sewage sludge in cement kiln. PMID:27343866

  19. Solvent-Mediated Crystallization of CH3NH3SnI3 Films for Heterojunction Depleted Perovskite Solar Cells.

    PubMed

    Hao, Feng; Stoumpos, Constantinos C; Guo, Peijun; Zhou, Nanjia; Marks, Tobin J; Chang, Robert P H; Kanatzidis, Mercouri G

    2015-09-01

    Organo-lead halide perovskite solar cells have gained enormous significance and have now achieved power conversion efficiencies of ∼20%. However, the potential toxicity of lead in these systems raises environmental concerns for widespread deployment. Here we investigate solvent effects on the crystallization of the lead-free methylammonium tin triiodide (CH3NH3SnI3) perovskite films in a solution growth process. Highly uniform, pinhole-free perovskite films are obtained from a dimethyl sulfoxide (DMSO) solution via a transitional SnI2·3DMSO intermediate phase. This high-quality perovskite film enables the realization of heterojunction depleted solar cells based on mesoporous TiO2 layer but in the absence of any hole-transporting material with an unprecedented photocurrent up to 21 mA cm(-2). Charge extraction and transient photovoltage decay measurements reveal high carrier densities in the CH3NH3SnI3 perovskite device which are one order of magnitude larger than CH3NH3PbI3-based devices but with comparable recombination lifetimes in both devices. The relatively high background dark carrier density of the Sn-based perovskite is responsible for the lower photovoltaic efficiency in comparison to the Pb-based analogues. These results provide important progress toward achieving improved perovskite morphology control in realizing solution-processed highly efficient lead-free perovskite solar cells.

  20. Effects of NH3 PECVD treatment time on the performance of multiwall carbon nanotubes for antibody immobilization.

    PubMed

    Hu, Chih-Chung; Chiou, Ai-Huei; Hsu, Chun-Yao

    2016-10-01

    This work presents an amino plasma-enhanced chemical vapour deposition (NH3 PECVD) treatment to modify multiwall carbon nanotubes (MWCNTs) for the immobilization of antibodies (IgG-gold), and the effects of treatment time were studied. A titanium nitride (TiN) buffer layer and a nickel catalyst layer were deposited on silicon substrates for synthesis of MWCNTs using thermal CVD. The MWCNTs were modified by amine (NH2 (-) ) or amino (NH(-) ) functional groups for 1, 3, and 5 min by PECVD, respectively. Mouse IgG-golds were immobilized on the modified MWCNTs using glutaraldehyde (GA) as a crosslinker. The performance of the modified MWCNTs was characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), Fourier transform infrared spectroscopy (FT-IR), contact angle system (CA), X-ray photoelectron spectroscopy (XPS, ESCA), and UV-visible spectroscopy. Results show that the efficiency of IgG-gold immobilization was increased with the increase of NH3 PECVD treatment time. The NH3 PECVD treatment changed the surface properties of the MWCNTs, tuning them more hydrophilic without affecting their structure. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1343-1351, 2016. PMID:26138473

  1. Kinetics of selective catalytic reduction of NO by NH3 on Fe-Mo/ZSM-5 catalyst.

    PubMed

    Li, Zhe; Shen, Lin-tao; Huang, Wei; Xie, Ke-chang

    2007-01-01

    The catalyst of Fe-Mo/ZSM-5 has been found to be more active than Fe-ZSM-5 and Mo/ZSM-5 separately for selective catalytic reduction (SCR) of nitric oxide (NO) with NH3. The kinetics of the SCR reaction in the presence of O2 was studied in this work. The results showed that the observed reaction orders were 0.74-0.99, 0.01-0.13, and 0 for NO, O2 and NH3 at 350-450 degrees C, respectively. And the apparent activation energy of the SCR was 65 kJ/mol on the Fe-Mo/ZSM-5 catalyst. The SCR mechanism was also deduced. Adsorbed NO species can react directly with adsorbed ammonia species on the active sites to form N2 and H2O. Gaseous 02 might serve as a reoxidizing agent for the active sites that have undergone reduction in the SCR process. It is also important to note that a certain amount of NO was decomposed directly over the Fe-Mo/ZSM-5 catalyst in the absence of NH3.

  2. Ultrasound-assistant preparation of Cu-SAPO-34 nanocatalyst for selective catalytic reduction of NO by NH3.

    PubMed

    Panahi, Parvaneh Nakhostin; Niaei, Ali; Salari, Darush; Mousavi, Seyed Mahdi; Delahay, Gérard

    2015-09-01

    The influence of the various preparation methods of Cu-SAPO-34 nanocatalysts on the selective catalytic reduction of NO with NH3 under excess oxygen was studied. Cu-SAPO-34 nanocatalysts were prepared by using four techniques: conventional impregnation (IM), ultrasound-enhanced impregnation (UIM), conventional deposition precipitation (DP) using NaOH and homogeneous deposition precipitation (HDP) using urea. These catalysts were characterized in detail by various techniques such as N2-sorption, XRD, TEM, H2-TPR, NH3-TPD and XPS to understand the catalyst structure, the nature and the dispersed state of the copper species, and the acid sites for NH3 adsorption. All of the nanocatalysts showed high activities for NO removal. However, the activities were different and followed the sequence of Cu-SAPO-34 (UIM)>Cu-SAPO-34 (HDP)>Cu-SAPO-34 (IM)>Cu-SAPO-34 (DP). Based on the obtained results, it was concluded that the NO conversion on Cu-SAPO-34 nanocatalysts was mainly related to the high reducibility of the isolated Cu(2+) ions and CuO species, the number of the acid sites and the dispersion of CuO species on SAPO-34.

  3. Fiber-Amplifier-Enhanced QEPAS Sensor for Simultaneous Trace Gas Detection of NH3 and H2S

    PubMed Central

    Wu, Hongpeng; Dong, Lei; Liu, Xiaoli; Zheng, Huadan; Yin, Xukun; Ma, Weiguang; Zhang, Lei; Yin, Wangbao; Jia, Suotang

    2015-01-01

    A selective and sensitive quartz enhanced photoacoustic spectroscopy (QEPAS) sensor, employing an erbium-doped fiber amplifier (EDFA), and a distributed feedback (DFB) laser operating at 1582 nm was demonstrated for simultaneous detection of ammonia (NH3) and hydrogen sulfide (H2S). Two interference-free absorption lines located at 6322.45 cm−1 and 6328.88 cm−1 for NH3 and H2S detection, respectively, were identified. The sensor was optimized in terms of current modulation depth for both of the two target gases. An electrical modulation cancellation unit was equipped to suppress the background noise caused by the stray light. An Allan-Werle variance analysis was performed to investigate the long-term performance of the fiber-amplifier-enhanced QEPAS sensor. Benefitting from the high power boosted by the EDFA, a detection sensitivity (1σ) of 52 parts per billion by volume (ppbv) and 17 ppbv for NH3 and H2S, respectively, were achieved with a 132 s data acquisition time at atmospheric pressure and room temperature. PMID:26506351

  4. Revealing the role of organic cations in hybrid halide perovskite CH3NH3PbI3

    PubMed Central

    Motta, Carlo; El-Mellouhi, Fedwa; Kais, Sabre; Tabet, Nouar; Alharbi, Fahhad; Sanvito, Stefano

    2015-01-01

    The hybrid halide perovskite CH3NH3PbI3 has enabled solar cells to reach an efficiency of about 20%, demonstrating a pace for improvements with no precedents in the solar energy arena. Despite such explosive progress, the microscopic origin behind the success of such material is still debated, with the role played by the organic cations in the light-harvesting process remaining unclear. Here van der Waals-corrected density functional theory calculations reveal that the orientation of the organic molecules plays a fundamental role in determining the material electronic properties. For instance, if CH3NH3 orients along a (011)-like direction, the PbI6 octahedral cage will distort and the bandgap will become indirect. Our results suggest that molecular rotations, with the consequent dynamical change of the band structure, might be at the origin of the slow carrier recombination and the superior conversion efficiency of CH3NH3PbI3. PMID:25912782

  5. 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.

  6. Optical band gap transition from direct to indirect induced by organic content of CH3NH3PbI3 perovskite films

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    Most of the systematic studies on tuning the band gap in the family of organolead halide perovskites have focused on changing the compositions of halogens. Here, the effects of varying the organic content on the band gap of CH3NH3PbI3 were studied. The methylammonium lead iodide (CH3NH3PbI3) films were fabricated with different molar ratios of CH3NH3I to PbI2. We found that the films become compact and the crystalline size decreased from 6.0 to 0.2 μm and the optical band gap of CH3NH3PbI3 could be transferred from direct to indirect with increasing CH3NH3I content in the precursor. The experimental results demonstrated that the existence of the indirect band gap in CH3NH3PbI3 film and the CH3NH3I content plays a key role in adjusting the film morphology and optical band. The investigation of the optical band transition induced by changing organic content could provide a different view on studying CH3NH3PbI3 materials.

  7. AES, XPS, and TDS study of the adsorption and desorption of NH 3 on ultra-thin chromium oxide films formed on chromium single crystal surfaces

    NASA Astrophysics Data System (ADS)

    Ma, H.; Berthier, Y.; Marcus, P.

    1999-12-01

    Ultra-thin films of Cr 2O 3 have been produced by oxidation of Cr(110) surfaces in O 2 (pO 2=3×10 -8 mbar) at 190°C. The adsorption and desorption of NH 3 on the thin Cr 2O 3 films have been studied by LEED, AES, XPS, and TDS. The kinetics of ammonia adsorption was investigated by AES and adsorbed NH 3 states on chromium oxide surfaces were identified by XPS. After exposure to NH 3, N 1s signals were observed at 398.6 and 400.7 eV. These results were interpreted by the existence of two types of adsorbed species resulting from the interaction of NH 3 with acid sites of the chromium oxide surface. Accordingly, two desorption peaks corresponding to NH 2 and NH 3 were observed by TDS (at 150°C).

  8. Ft-Ir Measurements of NH_3 Line Intensities in the 60 - 550 CM-1 Using Soleil/ailes Beamline

    NASA Astrophysics Data System (ADS)

    Sung, Keeyoon; Yu, Shanshan; Pearson, John; Manceron, Laurent; Kwabia Tchana, F.; Pirali, Olivier

    2015-06-01

    Ammonia (NH_3) has been found ubiquitous, e.g., in the interstellar medium, low-mass stars, Jovian planets of our solar system, and possibly in the low temperature exoplanets. Their spectroscopic line parameters are essential in the accurate interpretation of the planetary and astrophysical spectra observed with Herschel, SOFIA, ALMA, and JWST. In our previous paper, the NH_3 line positions in the far-IR region were studied for the ground state and ν_2 in an unprecedented accuracy, which revealed significant deficiencies in the NH_3 intensities, for instance, some weak ΔK = 3 lines were predicted to be ~100 times stronger. Measurement of line intensity for these lines in a consistent manner is demanded because the ΔK = 3 forbidden lines are only way other than collisions and l-doubled states to excite NH_3 to K > 0 levels. Recalling that NH_3 transition lines in the high J and K up to 18 were detected toward the galactic center in the star forming region of Sgr B_2, their accurate intensity measurements are critical in explaining the observed high K excitation, which will provide insights into radiative-transfer vs.levels. The interaction between a large amplitude torsional motion and the hyperfine coupling may also lead to a less known hyperfine effect, the so-called magnetic spin-torsion coupling, which was first studied by Heuvel and Dymanus and which has not yet been conclusively evidenced. In this talk, the magnetic hyperfine structure of the non-rigid methanol molecule will be investigated experimentally and theoretically. 13 hyperfine patterns were recorded using two molecular beam microwave spectrometers. These patterns, along with previously recorded ones,^c were analyzed in an attempt to evidence the effects of the magnetic spin-torsion coupling. The theoretical approach setup to analyze the observed data accounts for the spin-torsion coupling, in addition to the familiar magnetic spin-rotation and spin-spin couplings, and relies on symmetry

  9. Optical-integrated NH3 sensor design using WO3 thin tllms: influence of gas adsorption and chromic effects

    NASA Astrophysics Data System (ADS)

    Hernández, Hugo E. Lazcano; Pérez, Celia Sánchez; Valenzuela, Augusto García

    2008-04-01

    We propose a new model for the design of optical-integrated (OI) sensor, composed of a surface waveguide covered with a sensitive material (SM) deposited at the surface in the form of thin films. Commonly these last are metallic oxides which becomes highly absorbent in the presence of the gas to be detected. In this way, the optical signal propagating in the waveguide will be attenuated proportionally to the amount of the gas in the surrounding environment. When the sensing is carried out, commonly it is supposed that completely all the volume of the SM increase its absorbance, however this assumption causes that the transmission losses be overestimated; our model, according to the adsorption kinetics of gases, considers the growth of the adsorber layer over the SM as a fourth layer where the optical changes happen. We use this model to design an ammonia NH3 sensor considering tungsten trioxide WO3 as SM. Our model approaches in 102 dB/cm the calculus of the losses, in agreement with that observed in experiments. The refractive index η'(λ) and the absorbance of η″(λ) were calculated under inert and NH3 gas conditions, through the analysis of the UV-VIS-NIR transmittance spectra, and the numerical method of Swanepoel, in order to be incorporated in the simulation of the OI proposed structure with a multilayer method software. Experimentally we analyse the influence of thermochromism and photochromism in the response of gasochromism. We tested WO3 samples elaborated by sputtering method with a combination of monoclinic-triclinic crystalline structure, measuring as minimum 200 ppm of NH3 at λ = 1000 nm and at 100 °C. The best sample was tested to NH3 detection, using monochromatic sources: λ = 830 nm, λ = 980 nm and λ = 1550 nm; obtaining intensity attenuations of 10%, 16% and 29%, respectively to 5000 ppm of NH3 at 100 °C. This is a new proposal that can predicts better the interaction between the material and the optical field in optical sensing

  10. Device simulation of lead-free CH3NH3SnI3 perovskite solar cells with high efficiency

    NASA Astrophysics Data System (ADS)

    Du, Hui-Jing; Wang, Wei-Chao; Zhu, Jian-Zhuo

    2016-10-01

    The lead-free perovskite solar cells (PSCs) have drawn a great deal of research interest due to the Pb toxicity of the lead halide perovskite. CH3NH3SnI3 is a viable alternative to CH3NH3PbX3, because it has a narrower band gap of 1.3 eV and a wider visible absorption spectrum than the lead halide perovskite. The progress of fabricating tin iodide PSCs with good stability has stimulated the studies of these CH3NH3SnI3 based cells greatly. In the paper, we study the influences of various parameters on the solar cell performance through theoretical analysis and device simulation. It is found in the simulation that the solar cell performance can be improved to some extent by adjusting the doping concentration of the perovskite absorption layer and the electron affinity of the buffer and HTM, while the reduction of the defect density of the perovskite absorption layer significantly improves the cell performance. By further optimizing the parameters of the doping concentration (1.3× 1016 cm-3) and the defect density (1× 1015 cm-3) of perovskite absorption layer, and the electron affinity of buffer (4.0 eV) and HTM (2.6 eV), we finally obtain some encouraging results of the J sc of 31.59 mA/cm2, V oc of 0.92 V, FF of 79.99%, and PCE of 23.36%. The results show that the lead-free CH3NH3SnI3 PSC is a potential environmentally friendly solar cell with high efficiency. Improving the Sn2 + stability and reducing the defect density of CH3NH3SnI3 are key issues for the future research, which can be solved by improving the fabrication and encapsulation process of the cell. Project supported by the Graduate Student Education Teaching Reform Project, China (Grant No. JG201512) and the Young Teachers Research Project of Yanshan University, China (Grant No. 13LGB028).

  11. Metal-Borohydride-Modified Zr(BH4 )4 ⋅8 NH3 : Low-Temperature Dehydrogenation Yielding Highly Pure Hydrogen.

    PubMed

    Huang, Jianmei; Ouyang, Liuzhang; Gu, Qinfen; Yu, Xuebin; Zhu, Min

    2015-10-12

    Due to its high hydrogen density (14.8 wt %) and low dehydrogenation peak temperature (130 °C), Zr(BH4 )4 ⋅8 NH3 is considered to be one of the most promising hydrogen-storage materials. To further decrease its dehydrogenation temperature and suppress its ammonia release, a strategy of introducing LiBH4 and Mg(BH4 )2 was applied to this system. Zr(BH4 )4 ⋅8 NH3 -4 LiBH4 and Zr(BH4 )4 ⋅8 NH3 -2 Mg(BH4 )2 composites showed main dehydrogenation peaks centered at 81 and 106 °C as well as high hydrogen purities of 99.3 and 99.8 mol % H2 , respectively. Isothermal measurements showed that 6.6 wt % (within 60 min) and 5.5 wt % (within 360 min) of hydrogen were released at 100 °C from Zr(BH4 )4 ⋅8 NH3 -4 LiBH4 and Zr(BH4 )4 ⋅8 NH3 -2 Mg(BH4 )2 , respectively. The lower dehydrogenation temperatures and improved hydrogen purities could be attributed to the formation of the diammoniate of diborane for Zr(BH4 )4 ⋅8 NH3 -4 LiBH4 , and the partial transfer of NH3 groups from Zr(BH4 )4 ⋅8 NH3 to Mg(BH4 )2 for Zr(BH4 )4 ⋅8 NH3 -2 Mg(BH4 )2 , which result in balanced numbers of BH4 and NH3 groups and a more active H(δ+) ⋅⋅⋅(-δ) H interaction. These advanced dehydrogenation properties make these two composites promising candidates as hydrogen-storage materials.

  12. Estimating NH3 emissions from agricultural fertilizer application in China using the bi-directional CMAQ model coupled to an agro-ecosystem model

    NASA Astrophysics Data System (ADS)

    Fu, X.; Wang, S. X.; Ran, L. M.; Pleim, J. E.; Cooter, E.; Bash, J. O.; Benson, V.; Hao, J. M.

    2015-06-01

    Atmospheric ammonia (NH3) plays an important role in atmospheric aerosol chemistry. China is one of the largest NH3 emitting countries with the majority of NH3 emissions coming from agricultural practices, such as fertilizer application and livestock production. The current NH3 emission estimates in China are mainly based on pre-defined emission factors that lack temporal or spatial details, which are needed to accurately predict NH3 emissions. This study provides the first online estimate of NH3 emissions from agricultural fertilizer application in China, using an agricultural fertilizer modeling system which couples a regional air quality model (the Community Multi-scale Air Quality model, or CMAQ) and an agro-ecosystem model (the Environmental Policy Integrated Climate model, or EPIC). This method improves the spatial and temporal resolution of NH3 emissions from this sector. We combined the cropland area data of 14 crops from 2710 counties with the Moderate Resolution Imaging Spectroradiometer (MODIS) land use data to determine the crop distribution. The fertilizer application rates and methods for different crops were collected at provincial or agricultural region levels. The EPIC outputs of daily fertilizer application and soil characteristics were input into the CMAQ model and the hourly NH3 emissions were calculated online with CMAQ running. The estimated agricultural fertilizer NH3 emissions in this study were approximately 3 Tg in 2011. The regions with the highest modeled emission rates are located in the North China Plain. Seasonally, peak ammonia emissions occur from April to July. Compared with previous researches, this study considers an increased number of influencing factors, such as meteorological fields, soil and fertilizer application, and provides improved NH3 emissions with higher spatial and temporal resolution.

  13. Estimating NH3 emissions from agricultural fertilizer application in China using the bi-directional CMAQ model coupled to an agro-ecosystem model

    NASA Astrophysics Data System (ADS)

    Fu, X.; Wang, S. X.; Ran, L. M.; Pleim, J. E.; Cooter, E.; Bash, J. O.; Benson, V.; Hao, J. M.

    2015-01-01

    Atmospheric ammonia (NH3) plays an important role in atmospheric chemistry. China is one of the largest NH3 emitting countries with the majority of NH3 emissions coming from the agricultural practices, such as fertilizer application and livestock. The current NH3 emission estimates in China are mainly based on pre-defined emission factors that lack the temporal or spatial details, which are needed to accurately predict NH3 emissions. In this study, we estimate, for the first time, the NH3 emission from the agricultural fertilizer application in China online using an agricultural fertilizer modeling system coupling a regional air quality model (the Community Multi-Scale Air Quality model, CMAQ) and an agro-ecosystem model (the Environmental Policy Integrated Climate model, EPIC), which improves the spatial and temporal resolution of NH3 emission from this sector. Cropland area data of 14 crops from 2710 counties and the Moderate Resolution Imaging Spectroradiometer (MODIS) land use data are combined to determine the crop distribution. The fertilizer application rate and method for different crop are collected at provincial or agriculture-regional level. The EPIC outputs of daily fertilizer application and soil characteristics are inputed into the CMAQ model and the hourly NH3 emission are calculated online with CMAQ running. The estimated agricultural fertilizer NH3 emission in this study is about 3 Tg in 2011. The regions with the highest modeled emission rates are located in the North China Plain. Seasonally, the peak ammonia emissions occur from April to July.Compared with previous researches, this method considers more influencing factors, such as meteorological fields, soil and the fertilizer application, and provides improved NH3 emission with higher spatial and temporal resolution.

  14. New VISTA on ammonia in the 1.5 μm region: Assignments for the ν3 + 2 ν4 bands of 14NH 3 and 15NH 3 by isotopic shift labeling

    NASA Astrophysics Data System (ADS)

    Lees, R. M.; Li, Li; Xu, Li-Hong

    2008-09-01

    Further insight into the manifold of vibrational combination and overtone bands in the 1.5 μm infrared spectrum of ammonia has been obtained using a vibrational isotopic shift technique for assignment (VISTA), a simple stratagem for classifying spectral lines into their respective absorption bands from their fingerprint isotopic shifts. In a comparison of spectra of 14NH 3 and 15NH 3 recorded from 6400 to 6808 cm -1 with a tunable diode laser spectrometer, we have exploited isotopic shift labeling to identify lines of the ν3 + 2 ν4 asymmetric stretch-bend combination band for both species. Line positions, inversion and l-doublet splittings, and ν3 + 2 ν4 parameter estimates from isolated-state fits are reported for the two isotopologues. This band accounts for the majority of strong ammonia lines with unreported assignments in the important 1.5 μm spectral window for environmental monitoring and remote sensing. An interesting coincidence is that the pP(6, 6) inversion doublet for each of the ν3 + 2 ν4, ν1 + ν3, ν1 + 2 ν4 and ν3 + ν4 bands turns out to have been involved in previous 14NH 3 monitoring studies, most notably for the much-studied ν1 + ν3 feature at 1.5317 μm or 6528.77 cm -1 which we now find to be a close blend of a pP(6, 6) component with the known pP(5, 3) a line.

  15. Low-temperature high-resolution absorption spectrum of 14NH3 in the ν1+ν3 band region (1.51 μm)

    NASA Astrophysics Data System (ADS)

    Földes, T.; Golebiowski, D.; Herman, M.; Softley, T. P.; Di Lonardo, G.; Fusina, L.

    2014-09-01

    Jet-cooled spectra of 14NH3 and 15NH3 in natural abundance were recorded using cavity ring-down (CRDS, 6584-6670 cm-1) and cavity enhanced absorption (CEAS, 6530-6700 cm-1) spectroscopy. Line broadening effects in the CRDS spectrum allowed lines with J″-values between 0 and 3 to be identified. Intensity ratios in 14NH3 between the jet-cooled CRDS and literature room-temperature data from Sung et al. (J. Quant. Spectrosc. Radiat. Transfer, 113 (2012), 1066) further assisted the line assignments. Ground state combination differences were extensively used to support the assignments, providing reliable values for J, K and inversion symmetry of the ground state vibrational levels. CEAS data helped in this respect for the lowest J lines, some of which are saturated in the CRDS spectrum. Further information on a/s doublets arose from the observed spectral structures. Thirty-two transitions of 14NH3 were assigned in this way and a limited but significant number (19) of changes in the assignments results, compared to Sung et al. or to Cacciani et al. (J. Quant. Spectrosc. Radiat. Transfer, 113 (2012), 1084). Sixteen known and 25 new low-J transitions were identified for 15NH3 in the CRDS spectrum but the much scarcer literature information did not allow for any more refined assignment. The present line position measurements improve on literature values published for 15NH3 and on some line positions for 14NH3.

  16. Lattice potential energy and standard molar enthalpy in the formation of 1—dodecylamine hydrobromide (1-C12H25NH3·Br)(s)

    NASA Astrophysics Data System (ADS)

    Liu, Yu-Pu; Di, You-Ying; Dan, Wen-Yan; He, Dong-Hua; Kong, Yu-Xia; Yang, Wei-Wei

    2011-02-01

    This paper reports that 1-dodecylamine hydrobromide (1-C12H25NH3·Br)(s) has been synthesized using the liquid phase reaction method. The lattice potential energy of the compound 1-C12H25NH3·Br and the ionic volume and radius of the 1-C12H25NH3+ cation are obtained from the crystallographic data and other auxiliary thermodynamic data. The constant-volume energy of combustion of 1-C12H25NH3·Br(s) is measured to be ΔcUmo(1-C12H25NH3·Br, s) = -(7369.03±3.28) kJ·mol-1 by means of an RBC-II precision rotating-bomb combustion calorimeter at T = (298.15±0.001) K. The standard molar enthalpy of combustion of the compound is derived to be ΔcHmo(1-C12H25NH3·Br, s) = -(7384.52±3.28) kJ·mol-1 from the constant-volume energy of combustion. The standard molar enthalpy of formation of the compound is calculated to be ΔfHmo(1-C12H25NH3·Br, s)=-(1317.86±3.67) kJ·mol-1 from the standard molar enthalpy of combustion of the title compound and other auxiliary thermodynamic quantities through a thermochemical cycle.

  17. APEX-CHAMP+ high-J CO observations of low-mass young stellar objects. IV. Mechanical and radiative feedback

    NASA Astrophysics Data System (ADS)

    Yıldız, U. A.; Kristensen, L. E.; van Dishoeck, E. F.; Hogerheijde, M. R.; Karska, A.; Belloche, A.; Endo, A.; Frieswijk, W.; Güsten, R.; van Kempen, T. A.; Leurini, S.; Nagy, Z.; Pérez-Beaupuits, J. P.; Risacher, C.; van der Marel, N.; van Weeren, R. J.; Wyrowski, F.

    2015-04-01

    Context. During the embedded stage of star formation, bipolar molecular outflows and UV radiation from the protostar are important feedback processes. Both processes reflect the accretion onto the forming star and affect subsequent collapse or fragmentation of the cloud. Aims: Our aim is to quantify the feedback, mechanical and radiative, for a large sample of low-mass sources in a consistent manner. The outflow activity is compared to radiative feedback in the form of UV heating by the accreting protostar to search for correlations and evolutionary trends. Methods: Large-scale maps of 26 young stellar objects, which are part of the Herschel WISH key program are obtained using the CHAMP+ instrument on the Atacama Pathfinder EXperiment (12CO and 13CO 6-5; Eup ~ 100 K), and the HARP-B instrument on the James Clerk Maxwell Telescope (12CO and 13CO 3-2; Eup ~ 30 K). The maps have high spatial resolution, particularly the CO 6-5 maps taken with a 9″ beam, resolving the morphology of the outflows. The maps are used to determine outflow parameters and the results are compared with higher-J CO lines obtained with Herschel. Envelope models are used to quantify the amount of UV-heated gas and its temperature from 13CO 6-5 observations. Results: All sources in our sample show outflow activity, with the spatial extent decreasing from the Class 0 to the Class I stage. Consistent with previous studies, the outflow force, FCO, is larger for Class 0 sources than for Class I sources, even if their luminosities are comparable. The outflowing gas typically extends to much greater distances than the power-law envelope and therefore influences the surrounding cloud material directly. Comparison of the CO 6-5 results with HIFI H2O and PACS high-J CO lines, both tracing currently shocked gas, shows that the two components are linked, even though the transitions do not probe the same gas. The link does not extend down to CO 3-2. The conclusion is that CO 6-5 depends on the shock

  18. Modeling impacts of NH3 on uptake of H2SO4 by charged nucleating nanoparticles in the Earth's atmosphere

    NASA Astrophysics Data System (ADS)

    Nadykto, A. B.; Nazarenko, K. M.; Markov, P. N.; Yu, F.

    2016-06-01

    The understanding of the role of ammonia, a well-known stabilizer of binary sulfuric acid-water clusters, in the gas-to-nanoparticle conversion in the Earth atmosphere is critically important for the assessment of aerosol radiative forcing associated with the climate changes. The sulfuric acid H2SO4 is present in the atmosphere in the form of the gas-phase hydrates (H2SO4)(H2O)n, whose interaction with NH3 leads to the formation of more stable bisulfate clusters (NH3)(H2SO4)(H2O)n. Although the impact of NH3 on the thermochemical stability of binary clusters nucleating homogeneously has been studied in some detail in the past, the effect of ammonia on other microphysical properties relevant to nucleation remains insufficiently well understood. In the present study, the effect of ammonia on the electrical dipole moment controlling the nucleation of airborne ions via the dipole-charge interaction has been investigated using the Density Functional Theory (DFT), ab initio MP2 and model chemistry G3 methods. The presence of ammonia in (H2SO4)(H2O)n is found to lead to very large enhancement in the dipole moment, which exceeds 2.0-2.5 Debyes (˜60-80%), 3.7-5.0 Debyes (˜90-180%), 1.4-4.5 Debyes (˜50-150%) and 2.1-5.5 Debyes (˜60-700%) for n = 0, n = 1, n = 2 and n = 3, respectively. The implications of this include the significantly increased uptake of the sulfuric acid, the key atmospheric nucleation precursor, by airborne ions and neutrals (due to dipole-dipole interaction), enhanced nucleation rates and the elevated production of ultrafine particles, which cause adverse health impacts.

  19. Mobile Column Measurements of HCHO, NO2, NH3, and C2H6 in Colorado during FRAPPE

    NASA Astrophysics Data System (ADS)

    Kille, N.; Volkamer, R. M.; Baidar, S.; Ortega, I.; Sinreich, R.; Hannigan, J. W.; Cooper, O. R.; Nussbaumer, E.; Pfister, G.

    2015-12-01

    Gases from anthropogenic sources have the potential to have a profound impact on air quality. Emissions from large cattle feedlots and ONG (Oil and Natural Gas) sites are comprised of NH3 (ammonia) and C2H6 (ethane) as pollutants. C2H6 contributes to photochemical ozone (O3) production and oxidation production of HCHO (formaldehyde). NH3 is a major source for reactive nitrogen to form particulate matter 2.5, which negatively affects human health. NO2 (nitrogen dioxide), emitted during combustion, is considered a large-scale pollutant and contributes to the formation of O3. Deploying an innovative suite of remote sensing instruments in a mobile laboratory, a Multi Axis Differential Optical Absorption Spectrometer (MAX-DOAS), a UV-Vis Spectrometer, and a Fourier Transform Infrared Spectrometer, we obtain mobile column measurements at high spatial and temporal resolution, 2 seconds for the UV-Vis and IR spectrometers and 20 seconds for the MAX-DOAS. Within the scope of the Front Range Air Pollution and Photochemistry Experiment (FRAPPE) we measure total columns of HCHO, NO2, NH3, and C2H6 using the University of Colorado mobile laboratory. Emissions of urban areas, agriculture, and ONG sites were studied. For the measurement of total columns the solar occultation flux method has been applied. We measured significant variability in the columns. The measurement of total columns allows one to determine the emission flux and source strength when driving a closed box around or upwind and downwind of a source with the mobile laboratory. We present results from select research drives.

  20. Theoretical NH{_3} Spectra in 5800-7000 CM-1 Region and CO{_2} IR Intensity: Updates

    NASA Astrophysics Data System (ADS)

    Huang, Xinchuan; Schwenke, David W.; Lee, Timothy J.; Sung, Keeyoon; Brown, Linda R.; Tashkun, Sergey A.

    2012-06-01

    Recently we have successfully applied the "Best Theory + High-resolution Experimental Data" strategy to NH{_3} and CO{_2}. The essential strategy is to refine a high quality, purely ab initio potential energy surface (PES) with reliable high resolution experimental data, so the IR line lists computed on the refined PES and dipole moment surface (DMS) can go beyond simple data reproduction. The goal is to make reliable predictions for higher J/K/energy rovibrational transitions with similar accuracies, i.e. 0.01-0.03 cm-1. The reliability and accuracy of data included in the refinement largely determines the quality of predictions and the ultimate merit of our work. With recent 14NH{_3} experiments in 5800 - 7000 cm-1, the effective coverage (with 0.01-0.03 cm-1 accuracy) of our NH{_3} PES has extended to this complex spectral region. Excellent agreement between current experiment analysis and our primitive HSL-3 PES refinement will be presented, and source of discrepancies will be discussed. The synergy between the experiments and theory is of great value. For CO{_2}, we have updated the theoretical IR intensity of the 12C16O{_2} line list with a more reliable DMS, then carried out very detailed comparisons with both pure experimental data and HITRAN/CDSD models. Results suggest that our line lists should be useful for the astronomical or earth-based detection of CO{_2} isotopologues. X. Huang, D.W. Schwenke, and T.J. Lee, J. Chem. Phys. 129, 214304 (2008); J. Chem. Phys. 134, 044320/044321 (2011). X. Huang, D.W. Schwenke, S.A. Tashkun, and T.J. Lee J. Chem. Phys. 136, submitted (2012).

  1. 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.

  2. Fe/SSZ-13 as an NH3-SCR Catalyst: A Reaction Kinetics and FTIR/Mössbauer Spectroscopic Study

    SciTech Connect

    Gao, Feng; Kollar, Marton; Kukkadapu, Ravi K.; Washton, Nancy M.; Wang, Yilin; Szanyi, Janos; Peden, Charles H.F.

    2015-03-01

    Using a traditional aqueous solution ion-exchange method under a protecting atmosphere of N2, an Fe/SSZ-13 catalyst active in NH3-SCR was synthesized. Mössbauer and FTIR spectroscopies were used to probe the nature of the Fe sites. In the fresh sample, the majority of Fe species are extra-framework cations. The likely monomeric and dimeric ferric ions in hydrated form are [Fe(OH)2]+ and [HO-Fe-O-Fe-OH]2+, based on Mössbauer measurements. During the severe hydrothermal aging (HTA) applied in this study, a majority of cationic Fe species convert to FeAlOx and clustered FeOx species, accompanied by severe dealumination of the SSZ-13 framework. The clustered FeOx species do not give a sextet Mössbauer spectrum, indicating that these are highly disordered. However, some Fe species in cationic positions remain after aging as determined from Mössbauer measurements and CO/NO FTIR titrations. NO/NH3 oxidation reaction tests reveal that dehydrated cationic Fe are substantially more active in catalyzing oxidation reactions than the hydrated ones. For NH3-SCR, enhancement of NO oxidation under ‘dry’ conditions promotes SCR rates below ~300 • C. This is due mainly to contribution from the “fast” SCR channel. Above ~300 • C, enhancement of NH3 oxidation under ‘dry’ conditions, however, becomes detrimental to NOx conversions. The HTA sample loses much of the SCR activity below ~300 • C; however, above ~400 • C much of the activity remains. This may suggest that the FeAlOx and FeOx species become active at such elevated temperatures. Alternatively, the high-temperature activity may be maintained by the remaining extra-framework cationic species. For potential practical applications, Fe/SSZ-13 may be used as a co-catalyst for Cu/CHA as integral aftertreatment SCR catalysts on the basis of the stable high temperature activity after hydrothermal aging. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy

  3. CO2-dominated Atmosphere in Equilibrium with NH3-H2O Ocean: Application to Early Titan and Ocean Planets

    NASA Astrophysics Data System (ADS)

    Marounina, N.; Grasset, O.; Tobie, G.; Carpy, S.

    2015-12-01

    During the accretion of Titan, impact heating may have been sufficient to allow the global melting of water ice (Monteux et al. 2014) and the release of volatile compounds, with CO2 and NH3 as main constituents (Tobie et al. 2012). Thus, on primitive Titan, it is thought that a massive atmosphere was in contact with a global water ocean. Similar configurations may occur on temperate water-rich planets called ocean planets (Léger et al. 2004, Kitzmann et al. 2015).Due to its rather low solubility in liquid water, carbon dioxide is expected to be one of the major components in the atmosphere. The atmospheric amount of CO2 is a key parameter for assessing the thermal evolution of the planetary surface because of its strong greenhouse effect. However, ammonia significantly affects the solubility of CO2 in water and hence the atmosphere-ocean thermo-chemical equilibrium. For primitive Titan, estimating the mass, temperature and composition of the primitive atmosphere is important to determine mechanisms that led to the present-day N2-CH4 dominated atmosphere. Similarly, for ocean planets, the influence of ammonia on the atmospheric abundance in CO2 has consequences for the definition of the habitable zone.To investigate the atmospheric composition of the water-rich worlds for a wide range of initial compositions, we have developed a vapor-liquid equilibrium model of the NH3-CO2-H2O system, where we account for the non-ideal comportment of both vapor and liquid phases and the ion speciation of volatiles dissolved in the aqueous phase. We show that adding NH3 to the CO2-H2O binary system induces an efficient absorption of the CO2 in the liquid phase and thus a lower CO2 partial pressure in the vapor phase. Indeed, the CO2 partial pressure remains low for the CO2/NH3 ratio of liquid concentrations lower than 0.5.Assuming various initial compositions of Titan's global water ocean, we explore the thermal and compositional evolution of a massive primitive atmosphere using

  4. Adsorption and dissociation of NH3 on clean and hydroxylated TiO2 rutile (110) surfaces: a computational study.

    PubMed

    Chang, Jee-Gong; Chen, Hsin-Tsung; Ju, Shin-Pon; Chang, Ching-Sheng; Weng, Meng-Hsiung

    2011-04-30

    The adsorption and dissociation of NH(3) on the clean and hydroxylated TiO(2) rutile (110) surfaces have been investigated by the first-principles calculations. The monodentate adsorbates such as H(3)N-Ti(a), H(2)N-Ti(a), N-Ti(a), H(2)N-O(a), HN-O(a), N-O(a) and H-O(a), as well as the bidentate adsorbate, Ti-N-Ti(a) can be formed on the clean surface. It is found that the hydroxyl group enhances the adsorption of certain adsorbates on the five-fold-coordinated Ti atoms (5c-Ti), namely H(2)N-Ti(a), HN-Ti(a), N-Ti(a) and Ti-N-Ti(a). In addition, the adsorption energy increases as the number of hydroxyl groups increases. On the contrary, the opposite effect is found for those on the two-fold-coordinated O atoms (2c-O). The enhanced adsorption of NH(x) (x = 1-2) on the 5c-Ti is due to the large electronegativity of the OH group, increasing the acidity of the Ti center. This also contributes to diminish the adsorption of NH(x) (x = 1-2) on the two-fold-coordinated O atoms (2c-O) decreasing its basicity. According to potential energy profile, the NH(3) dissociation on the TiO(2) surface is endothermic and the hydroxyl group is found to lower the energetics of H(2)N-Ti(a)+H-O(a) and HN-Ti(a)+2{H-O(a)}, but slightly raise the energetic of Ti-N-Ti(a)+3{H-O(a)} compare to those on the clean surface. However, the dissociation of NH(3) is found to occur on the hydroxylated surface with an overall endothermic by 31.8 kcal/mol and requires a barrier of 37.5 kcal/mol. A comparison of NH(3) on anatase surface has been discussed. The detailed electronic analysis is also carried out to gain insights into the interaction nature between adsorbate and surface.

  5. Measurements of Line Positions and Intensities of 14NH_3 in the 1.5 μm Region

    NASA Astrophysics Data System (ADS)

    Sung, Keeyoon; Brown, Linda R.; Huang, Xinchuan; Schwenke, David W.; Lee, Timothy J.

    2011-06-01

    In the atmosphere of outer planets, low mass brown dwarfs, and possibly extrasolar planets, ammonia (NH_3) is one of the major opacity sources particularly in the 1.5 μm region (the H-band). However, the spectroscopic information of NH_3 in the region is completely missing in the HITRAN database. NH_3 has four infrared active fundamental modes, with the well-known inversion doubling for {ν_2} band, in addition to the usual vibrational degeneracies. Its strong bands, {ν_1}, {ν_3} and 2{ν_4}, dominate the spectrum at 3 μm, while their corresponding overtone and combination bands (e.g., 2{ν_1}, 2{ν_3}, {ν_1}+{ν_3}, {ν_1}+2{ν_4} and {ν_3}+2{ν_4}) are prominent in the 1.5 μm region. As part of an effort to provide a complete set of NH_3 spectroscopic information in the 1.5 μm region, we are analyzing the laboratory spectra recorded at various temperatures (200 - 299 K) with the McMath-Pierce Fourier transform spectrometer (FTS) on Kitt Peak Observatory in Arizona. Line positions and strengths have been measured from the laboratory spectra, from which lower state energies and quantum assignments are being determined by adopting intensity ratios at two different temperatures and combination differnces. A theoretical IR linelist built upon the recent HSL-2 potential energy surface (nonadiabatic corrections included) is complementarily used for the quantum assignments. Preliminary results are presented for {ν_1}+{ν_3}, 2{ν_3}, {ν_1}+2{ν_4} and {ν_3}+{2ν_4} bands and compared with those from early work available. X. Huang, D.W. Schwenke, and T.J. Lee J. Chem. Phys. 134, (2011) 044320/044321 The research described in this paper was performed at the Jet Propulsion Laboratory, California Institute of Technology and the Ames Research Center under contracts with National Aeronautics and Space Administration.

  6. Synthesis, structural characterization, electrical properties and antioxidant activity of [p-(NH3)C6H4NH3]3P6O18·6H2O

    NASA Astrophysics Data System (ADS)

    Fezai, Ramzi; Mezni, Ali; Kahlaoui, Messaoud; Rzaigui, Mohamed

    2016-09-01

    Single crystals of a novel organic cyclohexaphosphate, [p-(NH3)C6H4NH3]3P6O18.6H2O, have been prepared in aqueous solution. Its crystal structure can be described by a three-dimensional framework where the P6O186- rings are interconnected by hydrogen bonds to form anionic layers between which organic cations are located. Hydrogen bonding network connecting the different components is given. The thermal stability and spectroscopic properties of this material are given too. Its DC and AC electrical conductivities, modulus analysis and dielectric constants have been investigated. The AC conductivity is found to obey the universal power law. The DC electrical conductivity indicates a semiconductor behavior. The kind of the observed conduction is protonic by translocation. X-rays structural and electrical results are correlated. This compound has also been screened for its antioxidant activity, determined in vitro, using 1,1-diphenyl-2-picrylhydrazyl, reducing power, hydroxyl scavenging ability and ferrous ion chelating (FIC) methods and with ascorbic acid as reference.

  7. The C(3P) + NH3 Reaction in Interstellar Chemistry. II. Low Temperature Rate Constants and Modeling of NH, NH2, and NH3 Abundances in Dense Interstellar Clouds

    NASA Astrophysics Data System (ADS)

    Hickson, Kevin M.; Loison, Jean-Christophe; Bourgalais, Jérémy; Capron, Michael; Le Picard, Sébastien D.; Goulay, Fabien; Wakelam, Valentine

    2015-10-01

    A continuous supersonic flow reactor has been used to measure rate constants for the C(3P) + NH3 reaction over the temperature range 50-296 K. C(3P) atoms were created by the pulsed laser photolysis of CBr4. The kinetics of the title reaction were followed directly by vacuum ultra-violet laser induced fluorescence of C(3P) loss and through H(2S) formation. The experiments show unambiguously that the reaction is rapid at 296 K, becoming faster at lower temperatures, reaching a value of (1.8 ± 0.2) × 10-10 cm3 molecule-1 s-1 at 50 K. As this reaction is not currently included in astrochemical networks, its influence on interstellar nitrogen hydride abundances is tested through a dense cloud model including gas-grain interactions. In particular, the effect of the ortho-to-para ratio of H2, which plays a crucial role in interstellar NH3 synthesis, is examined.

  8. Questioning Antiferromagnetic Ordering in the Expanded Metal, Li(NH3)4: A Lack of Evidence from μSR.

    PubMed

    Seel, Andrew G; Baker, Peter J; Cottrell, Stephen P; Howard, Christopher A; Skipper, Neal T; Edwards, Peter P

    2015-10-01

    We present the results of a muon spin relaxation study of the solid phases of the expanded metal, Li(NH3)4. No discernible change in muon depolarization dynamics is witnessed in the lowest temperature phase (≤25 K) of Li(NH3)4, thus suggesting that the prevailing view of antiferromagnetic ordering is incorrect. This is consistent with the most recent neutron diffraction data. Discernible differences in muon behavior are reported for the highest temperature phase of Li(NH3)4 (82-89 K), attributed to the onset of structural dynamics prior to melting. PMID:26722900

  9. Mobile mapping and eddy covariance flux measurements of NH3 emissions from cattle feedlots with a portable laser-based open-path sensor

    NASA Astrophysics Data System (ADS)

    Tao, L.; Sun, K.; Pan, D.; Golston, L.; Stanton, L. G.; Ham, J. M.; Shonkwiler, K. B.; Nash, C.; Zondlo, M. A.

    2014-12-01

    Ammonia (NH3) is the dominant alkaline species in the atmosphere and an important compound in the global nitrogen cycle. There is a large uncertainty in NH3 emission inventory from agriculture, which is the largest source of NH3, including livestock farming and fertilizer applications. In recent years, a quantum cascade laser (QCL)-based open-path sensor has been developed to provide high-resolution, fast-response and high-sensitivity NH3 measurements. It has a detection limit of 150 pptv with a sample rate up to 20 Hz. This sensor has been integrated into a mobile platform mounted on the roof of a car to perform measurement of multiple trace gases. We have also used the sensor for eddy covariance (EC) flux measurements. The mobile sensing method provides high spatial resolution and fast mapping of measured gases. Meanwhile, the EC flux method offers accurate flux measurements and resolves the diurnal variability of NH3emissions. During the DISCOVER-AQ and FRAPPÉ field campaigns in 2014, this mobile platform was used to study NH3 emissions from cattle feedlot near Fort Morgan, Colorado. This specific feedlot was mapped multiple times in different days to study the variability of its plume characteristics. At the same time, we set up another open-path NH3 sensor with LICOR open-path sensors to perform EC flux measurements of NH3, CH4 and CO2 simultaneously in the same cattle feedlot as shown in Fig. 1. NH3/CH4 emission flux ratio show a strong temperature dependence from EC flux measurements. The median value of measured NH3 and CH4 emission flux ratio is 0.60 ppmv/ppmv. In contrast, the median value of ΔNH3/ΔCH4 ratios measured from mobile platform is 0.53 ppmv/ppmv for the same farm. The combination of mobile mapping and EC flux measurements with the same open-path sensors greatly improves understanding of NH3 emissions both spatially and temporally.

  10. Significant Promotion Effect of Mo Additive on a Novel Ce-Zr Mixed Oxide Catalyst for the Selective Catalytic Reduction of NO(x) with NH3.

    PubMed

    Ding, Shipeng; Liu, Fudong; Shi, Xiaoyan; Liu, Kuo; Lian, Zhihua; Xie, Lijuan; He, Hong

    2015-05-13

    A novel Mo-promoted Ce-Zr mixed oxide catalyst prepared by a homogeneous precipitation method was used for the selective catalytic reduction (SCR) of NO(x) with NH3. The optimal catalyst showed high NH3-SCR activity, SO2/H2O durability, and thermal stability under test conditions. The addition of Mo inhibited growth of the CeO2 particle size, improved the redox ability, and increased the amount of surface acidity, especially the Lewis acidity, all of which were favorable for the excellent NH3-SCR performance. It is believed that the catalyst is promising for the removal of NO(x) from diesel engine exhaust.

  11. A new list of line positions and strengths of 15NH3 in the range 6369-6578 cm-1 at room temperature

    NASA Astrophysics Data System (ADS)

    El Romh, J.; Cacciani, P.; Taher, F.; Čermák, P.; Cosléou, J.; Khelkhal, M.

    2016-08-01

    The spectrum of 15NH3 has been investigated at room temperature in the 6367-6578 cm-1 region using an external cavity tunable diode laser spectrometer. Particular care was taken to discriminate 15NH3 from the main species 14NH3 present as an impurity in the spectra. As a result, a new list of line positions and line strengths has been proposed for this isotopologue. Together 3002 transitions have been observed, and their line strengths extending on four orders of magnitudes were derived.

  12. EMRP JRP MetNH3: Towards a Consistent Metrological Infrastructure for Ammonia Measurements in Ambient Air

    NASA Astrophysics Data System (ADS)

    Leuenberger, Daiana; Balslev-Harder, David; Braban, Christine F.; Ebert, Volker; Ferracci, Valerio; Gieseking, Bjoern; Hieta, Tuomas; Martin, Nicholas A.; Pascale, Céline; Pogány, Andrea; Tiebe, Carlo; Twigg, Marsailidh M.; Vaittinen, Olavi; van Wijk, Janneke; Wirtz, Klaus; Niederhauser, Bernhard

    2016-04-01

    Measuring ammonia in ambient air is a sensitive and priority issue due to its harmful effects on human health and ecosystems. In addition to its acidifying effect on natural waters and soils and to the additional nitrogen input to ecosystems, ammonia is an important precursor for secondary aerosol formation in the atmosphere. 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 regarding certified reference material (CRM), applicable analytical methods, measurement uncertainty, quality assurance and quality control (QC/QA) procedures as well as in the infrastructure to attain metrological traceability. As shown in a key comparison in 2007, there are even discrepancies between reference materials provided by European National Metrology Institutes (NMIs) at amount fraction levels up to three orders of magnitude higher than ambient air levels. MetNH3 (Metrology for ammonia in ambient air), a three-year project that started in June 2014 in the framework of the European Metrology Research Programme (EMRP), aims to reduce the gap between requirements set by the European emission regulations and state-of-the-art of analytical methods and reference materials. The overarching objective of the JRP is to achieve metrological traceability for ammonia measurements in ambient air from primary certified reference material CRM and instrumental standards to the field level. This requires the successful completion of the three main goals, which have been assigned to three technical work packages: To develop improved reference gas mixtures by static and dynamic gravimetric generation methods Realisation and characterisation of traceable preparative calibration standards (in pressurised cylinders as well as mobile generators) of ammonia amount fractions similar to those in ambient air based on existing methods for other reactive analytes. The

  13. Computational study of Al- or P-doped single-walled carbon nanotubes as NH3 and NO2 sensors

    NASA Astrophysics Data System (ADS)

    Azizi, Khaled; Karimpanah, Mohammad

    2013-11-01

    Density functional theory (DFT) calculations were carried out to analyze the electronic and structural properties of pristine and aluminum or phosphorus doped (8,0) single walled carbon nanotube (SWCNT) as a sensor for the detection of nitrogen dioxide (NO2) and ammonia (NH3). The binding energies, equilibrium gas-nanotube distances, the amounts of charge transfer and molecular orbital schemes as well as the density of states have been calculated and used to interpret the mechanism of gas adsorption on the surface of nanotubes. In agreement with the experimental data, our results show considerable binding energy and energy gap alteration due to the adsorption of NO2 on pristine SWCNT. The results reveal that the doping of both Al and P atoms increase the capability of the nanotube for the adsorption of NO2, and the effect is more significant for the Al-doped nanotube. The Al-doped nanotube can also be considered as a good sensor for NH3 due to its high binding energy, considerable amount of charge transfer and energy band gap alteration.

  14. Magnetic ordering-induced multiferroic behavior in [CH3NH3][Co(HCOO)3] metal-organic framework.

    DOE PAGES

    Gomez-Aguirre, Lilian Claudia; Zapf, Vivien S.; Pato-Doldan, Breogan; Mira, Jorge; Castro-Garcia, Socorro; Senaris-Rodriguez, Maria Antonia; Sanchez-Andujara, Manuel; Singleton, John

    2015-12-30

    Here, we present the first example of magnetic ordering-induced multiferroic behavior in a metal–organic framework magnet. This compound is [CH3NH3][Co(HCOO)3] with a perovskite-like structure. The A-site [CH3NH3]+ cation strongly distorts the framework, allowing anisotropic magnetic and electric behavior and coupling between them to occur. This material is a spin canted antiferromagnet below 15.9 K with a weak ferromagnetic component attributable to Dzyaloshinskii–Moriya (DM) interactions and experiences a discontinuous hysteretic magnetic-field-induced switching along [010] and a more continuous hysteresis along [101]. Coupling between the magnetic and electric order is resolved when the field is applied along this [101]: a spin rearrangementmore » occurs at a critical magnetic field in the ac plane that induces a change in the electric polarization along [101] and [10-1]. The electric polarization exhibits an unusual memory effect, as it remembers the direction of the previous two magnetic-field pulses applied. The data are consistent with an inverse-DM mechanism for multiferroic behavior.« less

  15. Detection of interstellar NH3 in the far-infrared - Warm and dense gas in Orion-KL

    NASA Technical Reports Server (NTRS)

    Townes, C. H.; Genzel, R.; Watson, D. M.; Storey, J. W. V.

    1983-01-01

    Results of an investigation are presented which show the detection of the (J,K) = a(4,3)-s(3,3) rotation-inversion transition of ammonia at 124.6 microns toward the center of the Orion-KL region. The line is found to be in emission and has a FWHM greater than or equal to 30 km/s, while the far-IR ammonia line emission probably comes mainly from the 'hot core', a compact region of warm, very dense gas previously identified by the radio inversion lines of NH3. The a(4,3)-s(3,3) line is very optically thick and it is determined that radiative excitation of the (4,3) NH3 level by far-IR emission from dust within the source can be ruled out. It is concluded that the (4,3) level is probably collisionally excited and the gas in the hot core region is warmer than the dust. Densities of approximately 10 to the 7th/cu cm are high enough to explain the observations, while shock heating by the mass outflow from IRc2 may account for the high gas temperatures in the hot core region.

  16. The C(3P) + NH3 Reaction in Interstellar Chemistry. I. Investigation of the Product Formation Channels

    NASA Astrophysics Data System (ADS)

    Bourgalais, Jérémy; Capron, Michael; Abhinavam Kailasanathan, Ranjith Kumar; Osborn, David L.; Hickson, Kevin M.; Loison, Jean-Christophe; Wakelam, Valentine; Goulay, Fabien; Le Picard, Sébastien D.

    2015-10-01

    The product formation channels of ground state carbon atoms, C(3P), reacting with ammonia, NH3, have been investigated using two complementary experiments and electronic structure calculations. Reaction products are detected in a gas flow tube experiment (330 K, 4 Torr) using tunable vacuum-ultraviolet (VUV) photoionization coupled with time of flight mass spectrometry. Temporal profiles of the species formed and photoionization spectra are used to identify primary products of the C + NH3 reaction. In addition, H-atom formation is monitored by VUV laser induced fluorescence (LIF) from room temperature to 50 K in a supersonic gas flow generated by the Laval nozzle technique. Electronic structure calculations are performed to derive intermediates, transition states, and complexes formed along the reaction coordinate. The combination of photoionization and LIF experiments supported by theoretical calculations indicate that in the temperature and pressure range investigated, the H + H2CN production channel represents 100% of the product yield for this reaction. Kinetics measurements of the title reaction down to 50 K and the effect of the new rate constants on interstellar nitrogen hydride abundances using a model of dense interstellar clouds are reported in Paper II.

  17. TiO2 particles on a 3D network of single-walled nanotubes for NH3 gas sensors.

    PubMed

    Jo, Yong Deok; Lee, Sooken; Seo, Jeongeun; Lee, Soobum; Ann, Doyeon; Lee, Haiwon

    2014-12-01

    Ammonia (NH3) gas is one of the gases which causes damage to environment such as acidification and climate change. In this study, a gas sensor based on the three-dimensional (3D) network of single-walled nanotubes (SWNTs) was fabricated for the detection of NH3 gas in dry air. The sensor showed enhanced performance due to the fast gas diffusion rate and weak interactions between the carbon nanotubes and the substrate. Metal oxide particles were introduced to enhance the performance of the gas sensor. Atomic layer deposition (ALD) was employed to deposit the metal oxide in the complex structure, and good control over thickness was achieved. The hybrid gas sensor consisting of the 3D network of SWNTs with anatase TiO2 particles showed stable, repeatable, and enhanced gas sensor performance. The phase of TiO2 particles was characterized by Raman and the morphology of the TiO2 particles on the 3D network of SWNTs was analyzed by transmission electron microscope.

  18. Characterization of an Fe≡N-NH2 Intermediate Relevant to Catalytic N2 Reduction to NH3

    PubMed Central

    Connor, Bridget A.; Gunderson, William A.; Zhang, Limei; Hoffman, Brian M.; Peters, Jonas C.

    2015-01-01

    The ability of certain transition metals to mediate the reduction of N2 to NH3 has attracted broad interest in the biological and inorganic chemistry communities. Early transition metals such as Mo and W readily bind N2 and mediate its protonation at one or more N atoms to furnish M(NxHy) species that can be characterized and, in turn, extrude NH3. By contrast, the direct protonation of Fe-N2 species to Fe(NxHy) products that can be characterized has been elusive. Herein we show that addition of acid at low temperature to [(TPB)Fe(N2)][Na(12-crown-4)] results in a new S = 1/2 Fe species. EPR, ENDOR, Mössbauer, and EXAFS analysis, coupled with a DFT study, unequivocally assign this new species as [(TPB)Fe≡N-NH2]+, a doubly protonated hydrazido(2-) complex featuring an Fe-to-N triple bond. This unstable species offers strong evidence that the first steps in Fe-mediated nitrogen reduction by [(TPB)Fe(N2)][Na(12-crown-4)] can proceed along a distal or `Chatt-type' pathway. A brief discussion of whether subsequent catalytic steps may involve early or late stage cleavage of the N-N bond, as would be found in limiting distal or alternating mechanisms, respectively, is also provided. PMID:26000443

  19. The C(3P) + NH3 reaction in interstellar chemistry. I. Investigation of the product formation channels

    DOE PAGES

    Bourgalais, Jeremy; Capron, Michael; Kailasanathan, Ranjith Kumar Abhinavam; Osborn, David L.; Hickson, Kevin M.; Loison, Jean -Christophe; Wakelam, Valentine; Goulay, Fabien; Picard, Sebastien D. Le

    2015-10-13

    The product formation channels of ground state carbon atoms, C(3P), reacting with ammonia, NH3, have been investigated using two complementary experiments and electronic structure calculations. Reaction products are detected in a gas flow tube experiment (330 K, 4 Torr) using tunable vacuum-ultraviolet (VUV) photoionization coupled with time of flight mass spectrometry. Temporal profiles of the species formed and photoionization spectra are used to identify primary products of the C + NH3 reaction. In addition, H-atom formation is monitored by VUV laser induced fluorescence (LIF) from room temperature to 50 K in a supersonic gas flow generated by the Laval nozzlemore » technique. Electronic structure calculations are performed to derive intermediates, transition states, and complexes formed along the reaction coordinate. The combination of photoionization and LIF experiments supported by theoretical calculations indicate that in the temperature and pressure range investigated, the H + H2CN production channel represents 100% of the product yield for this reaction. As a result, kinetics measurements of the title reaction down to 50 K and the effect of the new rate constants on interstellar nitrogen hydride abundances using a model of dense interstellar clouds are reported in Paper II.« less

  20. Extended line positions, intensities, empirical lower state energies and quantum assignments of NH3 from 6300 to 7000 cm-1

    NASA Astrophysics Data System (ADS)

    Sung, Keeyoon; Brown, Linda R.; Huang, Xinchuan; Schwenke, David W.; Lee, Timothy J.; Coy, Stephen L.; Lehmann, Kevin K.

    2012-07-01

    Nearly 4800 features of ammonia between 6300 and 7000 cm-1 with intensities ≥4×10-24 cm-1/(molecule·cm-2) at 296 K were measured using 16 pure NH3 spectra recorded at various temperatures (296-185 K) with the McMath-Pierce Fourier Transform Spectrometer at Kitt Peak National Observatory, AZ. The line positions and intensities were retrieved by fitting individual spectra based on a Voigt line shape profile and then averaging the values to form the experimental linelist. The integrated intensity of the region was 4.68×10-19 cm-1/(molecule·cm-2) at 296 K. Empirical lower state energies were also estimated for 3567 absorption line features using line intensities retrieved from 10 spectra recorded at gas temperature between 185 and 233 K. Finally, using Ground State Combination Differences (GSCDs) and the empirical lower state energy estimates, the quantum assignments were determined for 1096 transitions in the room temperature linelist, along with empirical upper state energies for 434 levels. The assignments correspond to seven vibrational states, as confirmed from recent ab initio calculations. The resulting composite database of 14NH3 line parameters will provide experimental constraints to ab initio calculations and support remote sensing of gaseous bodies including the atmospheres of Earth, (exo)planets, brown dwarfs, and other astrophysical environments.

  1. ZnO nanoplates surfaced-decorated by WO3 nanorods for NH3 gas sensing application

    NASA Astrophysics Data System (ADS)

    Dien Nguyen, Dac; Do, Duc Tho; Hien Vu, Xuan; Vuong Dang, Duc; Chien Nguyen, Duc

    2016-03-01

    Zinc oxide (ZnO) nanoplates and tungsten trioxide (WO3) nanorods were synthesized by hydrothermal treatment from zinc nitrate/potassium hydroxide and sodium tungstate/hydrochloric acid, respectively. The structure, morphology and compositions of the as-prepared WO3/ZnO nano-composites were characterized by x-ray diffraction, field emission scanning electron microscopy and energy dispersive spectroscopy. The obtained ZnO nanoplates have regular shape, single-crystal wurtzite structure with the thickness of 40 nm and 200 versus 400 nm in lateral dimensions. The WO3 nanorods possess the average diameter of 20 nm and the length of approximately 120 nm which were distributed on the surfaces of ZnO nanoplates. The WO3/ZnO nano-composites were prepared by grinding WO3 nanorods powder with ZnO nanoplates powder in various weight ratios (1:2, 1:1 and 2:1). The NH3 gas sensing properties of WO3/ZnO nano-composites were examined through the electrical resistance measurement. The gas sensing performance of the WO3/ZnO composite with weight ratio of 1:1 was better compared with that of other samples. For this sample, the maximum response to 300 ppm NH3 was 24 at the operating temperature of 250 °C. In addition, the gas sensing mechanism of the WO3/ZnO composites was discussed.

  2. 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.

  3. Strong covalency-induced recombination centers in perovskite solar cell material CH3NH3PbI3.

    PubMed

    Agiorgousis, Michael L; Sun, Yi-Yang; Zeng, Hao; Zhang, Shengbai

    2014-10-15

    Inorganic-organic hybrid perovskites are a new family of solar cell materials, which have recently been used to make solar cells with efficiency approaching 20%. Here, we report the unique defect chemistry of the prototype material, CH3NH3PbI3, based on first-principles calculation. We found that both the Pb cations and I anions in this material exhibit strong covalency as characterized by the formation of Pb dimers and I trimers with strong covalent bonds at some of the intrinsic defects. The Pb dimers and I trimers are only stabilized in a particular charge state with significantly lowered energy, which leads to deep charge-state transition levels within the band gap, in contradiction to a recent proposal that this system has only shallow intrinsic defects. Our results show that, in order to prevent the deep-level defects from being effective recombination centers, the equilibrium carrier concentrations should be controlled so that the Fermi energy is about 0.3 eV away from the band edges. Beyond this range, according to a Shockley-Read-Hall analysis, the non-equilibrium carrier lifetime will be strongly affected by the concentration of I vacancies and the anti-site defects with I occupying a CH3NH3 site.

  4. Depletion region effect of highly efficient hole conductor free CH3NH3PbI3 perovskite solar cells.

    PubMed

    Aharon, Sigalit; Gamliel, Shany; El Cohen, Bat; Etgar, Lioz

    2014-06-14

    The inorganic-organic perovskite is currently attracting a lot of attention due to its use as a light harvester in solar cells. The large absorption coefficients, high carrier mobility and good stability of organo-lead halide perovskites present good potential for their use as light harvesters in mesoscopic heterojunction solar cells. This work concentrated on a unique property of the lead halide perovskite, its function simultaneously as a light harvester and a hole conductor in the solar cell. A two-step deposition technique was used to optimize the perovskite deposition and to enhance the solar cell efficiency. It was revealed that the photovoltaic performance of the hole conductor free perovskite solar cell is strongly dependent on the depletion layer width which was created at the TiO2-CH3NH3PbI3 junction. X-ray diffraction measurements indicate that there were no changes in the crystallographic structure of the CH3NH3PbI3 perovskite over time, which supports the high stability of these hole conductor free perovskite solar cells. Furthermore, the power conversion efficiency of the best cells reached 10.85% with a fill factor of 68%, a Voc of 0.84 V, and a Jsc of 19 mA cm(-2), the highest efficiency to date of a hole conductor free perovskite solar cell.

  5. Low Threshold Two-Photon-Pumped Amplified Spontaneous Emission in CH3NH3PbBr3 Microdisks.

    PubMed

    Yang, Bin; Mao, Xin; Yang, Songqiu; Li, Yajuan; Wang, Yanqiu; Wang, Meishan; Deng, Weiqiao; Han, Keli

    2016-08-01

    Two-photon-pumped amplified spontaneous emission (ASE) of CH3NH3PbBr3 microdisks (MDs) were investigated by using femtosecond laser system. Low threshold at 2.2 mJ cm(-2) was obtained. Also, emission spectral tunability from 500 to 570 nm was demonstrated by synthesis the mixed halide perovskite MDs. The spatial effect of photoluminescence (PL) properties under one-photon and two-photon excitation were also studied by means of two-photon laser scanning microscope (TPLSM) and time-resolved PL spectroscopy. It was found that the band to band emission of near-surface regions and photocarriers' diffusion from near-surface regions to interior regions is significant for one-photon excitation. By contrast, reabsorption of emission under two-photon excitation plays a major role in the emission properties of the MDs. These results will give a more comprehensive understanding of the nonlinear effect of CH3NH3PbBr3 single crystals.

  6. Dynamic Growth of Pinhole-Free Conformal CH3NH3PbI3 Film for Perovskite Solar Cells.

    PubMed

    Li, Bo; Tian, Jianjun; Guo, Lixue; Fei, Chengbin; Shen, Ting; Qu, Xuanhui; Cao, Guozhong

    2016-02-01

    Two-step dipping is one of the popular low temperature solution methods to prepare organic-inorganic halide perovskite (CH3NH3PbI3) films for solar cells. However, pinholes in perovskite films fabricated by the static growth method (SGM) result in low power conversion efficiency (PCE) in the resulting solar cells. In this work, the static dipping process is changed into a dynamic dipping process by controlled stirring PbI2 substrates in CH3NH3I isopropanol solution. The dynamic growth method (DGM) produces more nuclei and decreases the pinholes during the nucleation and growth of perovskite crystals. The compact perovskite films with free pinholes are obtained by DGM, which present that the big perovskite particles with a size of 350 nm are surrounded by small perovskite particles with a size of 50 nm. The surface coverage of the perovskite film is up to nearly 100%. Such high quality perovskite film not only eliminated pinholes, resulting in reduced charge recombination of the solar cells, but also improves the light harvesting efficiency. As a result, the PCE of the perovskite solar cells is increased from 11% for SGM to 13% for DGM.

  7. [Rb(18-crown-6)][Rb([2.2.2]-cryptand)]Rb(2)Sn(9)·5NH(3).

    PubMed

    Gaertner, Stefanie; Korber, Nikolaus

    2011-05-01

    The crystal structure of the title compound, poly[[(4,7,13,16,21,24-hexa-oxa-1,10-diaza-bicyclo-[8.8.8]hexa-cosa-ne)rubidium] [[(1,4,7,10,13,16-hexa-oxacyclo-octa-deca-ne)rubidium]di-μ-rubidium-μ-nona-stannide] penta-ammonia], {[Rb(C(18)H(36)N(2)O(6))][Rb(3)Sn(9)(C(12)H(24)O(6))C(12)H(24)O(6))]·5NH(3)}(n) represents the first ammoniate of a Zintl anion together with two different chelating substances, namely 18-crown-6 and [2.2.2]-cryptand. The involvement of these large mol-ecules in the crystal structure of [Rb(18-crown-6)][Rb([2.2.2]-cryptand)]Rb(2)Sn(9)·5NH(3) leads to the formation of a new structural motif, namely one-dimensionally extended double strands running parallel to [100] and built by Sn(9) (4-) cages and Rb(+) cations. The double strands are shielded by 18-crown-6 and [2.2.2]-cryptand. The cations are additionally coordin-ated by ammonia mol-ecules. One of the four independent Rb(+) cations is disordered over two sets of sites in a 0.74 (2):0.26 (2) ratio. PMID:21754329

  8. Measurements of NO2, SO2, NH3, HNO3 and O3 in West African urban environments

    NASA Astrophysics Data System (ADS)

    Adon, Marcellin; Yoboué, Véronique; Galy-Lacaux, Corinne; Liousse, Catherine; Diop, Babakar; Doumbia, El Hadji Thierno; Gardrat, Eric; Ndiaye, Seydi Ababacar; Jarnot, Christian

    2016-06-01

    In this paper, we present the measurements of atmospheric gas concentrations of NO2, SO2, NH3, HNO3, and O3 performed at two traffic sites in the context of the POLCA (Pollution of African Capitals) program. These gases were measured using a passive sampling technique from Jan. 2008 to Dec. 2009 at Dakar and from Jun. 2008 to Dec. 2009 at Bamako. In addition, during these periods there were two intensive measurement campaigns (from 19 Jan. to 2 Feb. 2009 at Bamako and from 30 Nov. to 13 Dec. 2009 at Dakar) where real-time active analysers were used to measure NO2 and SO2. Results show that Dakar has a pollution level for NO2 and SO2 higher than that of Bamako, whereas it is lower for NH3 concentrations. Monthly values of NO2 range between 21.1 and 43.5 ppb in Dakar with an annual mean concentration of 31.7 ppb (59.6 μg/m3). NO2 values in Bamako are 9.4-22.6 ppb with a mean of 16.2 ppb. At Dakar, the mean annual NO2 limit value (21.3 ppb or 40 μg/m3) recommended by the World Health Organization (WHO) is widely exceeded. The mean annual concentration of SO2 is 15.9 ppb in Dakar and 3.6 ppb in Bamako. These differences may be explained by different sources of traffic between Bamako (with mainly gasoline vehicles) and Dakar (with mainly diesel vehicles). The annual mean NH3 concentration is about two times higher in Bamako (46.7 ppb) than in Dakar (21.1 ppb). In addition to other possible sources, we assume that the ammonia from domestic fires and uncontrolled garbage incineration may have more influence at Bamako than at Dakar. The mean annual concentrations of HNO3 and O3 are 1.3 ppb and 7.7 ppb in Dakar and 0.6 ppb and 5.1 ppb in Bamako, respectively. Seasonal variation in measured gas concentrations are low in Bamako and more pronounced in Dakar, except for HNO3 and NH3. At Dakar, NO2 and SO2 daily mean concentrations are higher during the weekdays than on weekends, when urban activities are reduced, whereas at Bamako, no significant difference was observed

  9. 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

  10. 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.

  11. 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.

  12. Development and uncertainty analysis of a high-resolution NH3 emissions inventory and its implications with precipitation over the Pearl River Delta region, China

    NASA Astrophysics Data System (ADS)

    Zheng, J. Y.; Yin, S. S.; Kang, D. W.; Che, W. W.; Zhong, L. J.

    2012-08-01

    Detailed NH3 emission inventories are important to understand various atmospheric processes, air quality modeling studies, air pollution management, and related environmental and ecological issues. A high-resolution NH3 emission inventory was developed based on state-of-the-science techniques, up-to-date information, and advanced expert knowledge for the Pearl River Delta region, China. To provide model-ready emissions input, this NH3 emissions inventory was spatially allocated to 3 km × 3 km grid cells using source-based spatial surrogates with geographical information system (GIS) technology. For NH3 emissions, 9 source categories and 45 subcategories were identified in this region, and detailed spatial and temporal characteristics were investigated. Results show that livestock is by far the most important NH3 emission source by contributing about 61.7% of the total NH3 emissions in this region, followed by nitrogen fertilizer applications (~23.7%) and non-agricultural sources (~14.6%). Uncertainty analysis reveals that the uncertainties associated with different sources vary from source to source and the magnitude of the uncertainty associated with a specific source mainly depends on the degree of accuracy of the emission factors and activity data as well as the technique used to perform the estimate. Further studies should give priority to the hog, broiler, goose subsectors of the livestock source and N fertilizer application source in order to reduce uncertainties of ammonia emission estimates in this region. The validity of the NH3 emissions inventory is justified by the trend analysis of local precipitation compositions, such as pH values, the Ca2++NH4+/SO42-+ NO3- ratios, and NH4+ concentrations which are directly or indirectly related to NH3 emissions.

  13. H-bonding of an NH3 gas molecule to H2O/Pt(111) — A barrier-free path

    NASA Astrophysics Data System (ADS)

    Henkelman, Graeme; Feibelman, Peter J.

    2016-02-01

    Does an OH-flipping barrier hinder H-bond formation between a gas phase molecule and a water monolayer whose free OH ligands point toward a substrate? According to density functional theory calculations for water on Pt(111) the answer is yes, when the molecule is CO or N2, but no when it is NH3. The difference is the relatively strong attraction of the NH3 lone pair to free OH ligands.

  14. Growth of CH3NH3PbI3 cuboids with controlled size for high-efficiency perovskite solar cells.

    PubMed

    Im, Jeong-Hyeok; Jang, In-Hyuk; Pellet, Norman; Grätzel, Michael; Park, Nam-Gyu

    2014-11-01

    Perovskite solar cells with submicrometre-thick CH(3)NH(3)PbI(3) or CH(3)NH(3)PbI(3-x)Cl(x) active layers show a power conversion efficiency as high as 15%. However, compared to the best-performing device, the average efficiency was as low as 12%, with a large standard deviation (s.d.). Here, we report perovskite solar cells with an average efficiency exceeding 16% and best efficiency of 17%. This was enabled by the growth of CH(3)NH(3)PbI(3) cuboids with a controlled size via a two-step spin-coating procedure. Spin-coating of a solution of CH(3)NH(3)I with different concentrations follows the spin-coating of PbI(2), and the cuboid size of CH(3)NH(3)PbI(3) is found to strongly depend on the concentration of CH(3)NH(3)I. Light-harvesting efficiency and charge-carrier extraction are significantly affected by the cuboid size. Under simulated one-sun illumination, average efficiencies of 16.4% (s.d. ± 0.35), 16.3% (s.d. ± 0.44) and 13.5% (s.d. ± 0.34) are obtained from solutions of CH(3)NH(3)I with concentrations of 0.038 M, 0.050 M and 0.063 M, respectively. By controlling the size of the cuboids of CH(3)NH(3)PbI(3) during their growth, we achieved the best efficiency of 17.01% with a photocurrent density of 21.64 mA cm(-2), open-circuit photovoltage of 1.056 V and fill factor of 0.741.

  15. The influence of leaf-atmosphere NH3(g ) exchange on the isotopic composition of nitrogen in plants and the atmosphere.

    PubMed

    Johnson, Jennifer E; Berry, Joseph A

    2013-10-01

    The distribution of nitrogen isotopes in the biosphere has the potential to offer insights into the past, present and future of the nitrogen cycle, but it is challenging to unravel the processes controlling patterns of mixing and fractionation. We present a mathematical model describing a previously overlooked process: nitrogen isotope fractionation during leaf-atmosphere NH3(g ) exchange. The model predicts that when leaf-atmosphere exchange of NH3(g ) occurs in a closed system, the atmospheric reservoir of NH3(g ) equilibrates at a concentration equal to the ammonia compensation point and an isotopic composition 8.1‰ lighter than nitrogen in protein. In an open system, when atmospheric concentrations of NH3(g ) fall below or rise above the compensation point, protein can be isotopically enriched by net efflux of NH3(g ) or depleted by net uptake. Comparison of model output with existing measurements in the literature suggests that this process contributes to variation in the isotopic composition of nitrogen in plants as well as NH3(g ) in the atmosphere, and should be considered in future analyses of nitrogen isotope circulation. The matrix-based modelling approach that is introduced may be useful for quantifying isotope dynamics in other complex systems that can be described by first-order kinetics. PMID:23452149

  16. A facile, solvent vapor-fumigation-induced, self-repair recrystallization of CH3NH3PbI3 films for high-performance perovskite solar cells.

    PubMed

    Zhu, Weidong; Yu, Tao; Li, Faming; Bao, Chunxiong; Gao, Hao; Yi, Yong; Yang, Jie; Fu, Gao; Zhou, Xiaoxin; Zou, Zhigang

    2015-03-12

    A high-quality CH3NH3PbI3 film is crucial in the manufacture of a high-performance perovskite solar cell. Here, a recrystallization process via facile fumigation with DMF vapor has been successfully introduced to self-repair of CH3NH3PbI3 films with poor coverage and low crystallinity prepared by the commonly used one-step spin-coating method. We found that the CH3NH3PbI3 films with dendritic structures can spontaneously transform to the uniform ones with full coverage and high crystallinity by adjusting the cycles of the recrystallization process. The mesostructured perovskite solar cells based on these repaired CH3NH3PbI3 films showed reproducible optimal power conversion efficiency (PCE) of 11.15% and average PCE of 10.25±0.90%, which are much better than that of devices based on the non-repaired CH3NH3PbI3 films. In addition, the hysteresis phenomenon in the current-voltage test can also be effectively alleviated due to the quality of the films being improved in the optimized devices. Our work proved that the fumigation of solvent vapor can modify metal organic perovskite films such as CH3NH3PbI3. It offers a novel and attractive way to fabricate high-performance perovskite solar cells.

  17. B40 fullerene as a highly sensitive molecular device for NH3 detection at low bias: a first-principles study

    NASA Astrophysics Data System (ADS)

    Lin, Bin; Dong, Huilong; Du, Chunmiao; Hou, Tingjun; Lin, Haiping; Li, Youyong

    2016-02-01

    The adsorption of small molecules (NH3, N2, H2 and CH4) on all-boron fullerene B40 is investigated by density functional theory (DFT) and the non-equilibrium Green’s function (NEGF) for its potential application in the field of single-molecular gas sensors. The high adsorption energies (-1.09 to -0.75 eV) of NH3 on different adsorption sites of the B40 surface indicate that NH3 strongly chemisorbs to B40. The charge transfer induced by the NH3 adsorption results in a modification of the density of states (DOS) of B40 near the Fermi level, and therefore changes its electronic transport properties. For all possible adsorption sites, the adsorption of NH3 exclusively leads to a decrease of the conductance of B40. Taking into consideration that the non-polar gas molecules (e.g. N2, H2 and CH4) are only physisorbed and show negligible effect on the conductance properties of B40, we would expect that B40 can be used as a single-molecular gas sensor to distinguish NH3 from non-polar gas molecules at low bias.

  18. Reaction pathway investigation on the selective catalytic reduction of NO with NH3 over Cu/SSZ-13 at low temperatures.

    PubMed

    Su, Wenkang; Chang, Huazhen; Peng, Yue; Zhang, Chaozhi; Li, Junhua

    2015-01-01

    The mechanism of the selective catalytic reduction of NO with NH3 was studied using Cu/SSZ-13. The adspecies of NO and NH3 as well as the active intermediates were investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy and temperature-programmed surface reaction. The results revealed that three reactions were possible between adsorbed NH3 and NOx. NO2(-) could be generated by direct formation or NO3(-) reduction via NO. In a standard selective catalytic reduction (SCR) reaction, NO3(-) was hard to form, because NO2(-) was consumed by ammonia before it could be further oxidized to nitrates. Additionally, adsorbed NH3 on the Lewis acid site was more active than NH4(+). Thus, SCR mainly followed the reaction between Lewis acid site-adsorbed NH3 and directly formed NO2(-). Higher Cu loading could favor the formation of active Cu-NH3, Cu-NO2(-), and Cu-NO3(-), improving the SCR activity at low temperature. PMID:25485842

  19. Reaction pathway investigation on the selective catalytic reduction of NO with NH3 over Cu/SSZ-13 at low temperatures.

    PubMed

    Su, Wenkang; Chang, Huazhen; Peng, Yue; Zhang, Chaozhi; Li, Junhua

    2015-01-01

    The mechanism of the selective catalytic reduction of NO with NH3 was studied using Cu/SSZ-13. The adspecies of NO and NH3 as well as the active intermediates were investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy and temperature-programmed surface reaction. The results revealed that three reactions were possible between adsorbed NH3 and NOx. NO2(-) could be generated by direct formation or NO3(-) reduction via NO. In a standard selective catalytic reduction (SCR) reaction, NO3(-) was hard to form, because NO2(-) was consumed by ammonia before it could be further oxidized to nitrates. Additionally, adsorbed NH3 on the Lewis acid site was more active than NH4(+). Thus, SCR mainly followed the reaction between Lewis acid site-adsorbed NH3 and directly formed NO2(-). Higher Cu loading could favor the formation of active Cu-NH3, Cu-NO2(-), and Cu-NO3(-), improving the SCR activity at low temperature.

  20. Study on the mechanism of NH3-selective catalytic reduction over CuCexZr1-x/TiO2

    NASA Astrophysics Data System (ADS)

    Chen, Xujuan; Sun, Xiaoliang; Gong, Cairong; Lv, Gang; Song, Chonglin

    2016-06-01

    Copper-cerium-zirconium catalysts loaded on TiO2 prepared by a wet impregnation method were investigated for NH3-selective catalytic reduction (SCR) of NOx. The reaction mechanism was proposed on the basis of results from in situ diffuse reflectance infrared transform spectroscopy (DRIFT). When NH3 is introduced, ammonia bonded to Lewis acid sites is more stable over CuCe0.25Zr0.75/TiO2 at high temperature, while Brønsted acid sites are more important than Lewis acid sites at low temperature. For the NH3+NO+O2 co-adsorption, NH3 species occupy most of activity sites on CuCe0.25Zr0.75/TiO2 catalyst, and mainly exist in the forms of NH4 + (at low temperature) and NH3 coordinated (at high temperature), playing a crucial role in the NH3-SCR process. Two different reaction routes, the L-H mechanism at low temperature (< 200°C) and the E-R mechanism at high temperature (> 200°C), are presented for the SCR reaction over CuCe0.25Zr0.75/TiO2 catalyst.

  1. In situ IR studies of Co and Ce doped Mn/TiO2 catalyst for low-temperature selective catalytic reduction of NO with NH3

    NASA Astrophysics Data System (ADS)

    Qiu, Lu; Pang, Dandan; Zhang, Changliang; Meng, Jiaojiao; Zhu, Rongshu; Ouyang, Feng

    2015-12-01

    The Mn-Co-Ce/TiO2 catalyst was prepared by wet co-impregnation method for selective catalytic reduction of NO by NH3 in the presence of oxygen. The adsorption and co-adsorption of NH3, NO and O2 on catalysts were investigated by in situ FTIR spectroscopy. The results suggested that addition of cobalt and cerium oxides increased the numbers of acid and redox sites. Especially, the cobalt oxide produced lots of Brønsted acid sites, which favor to the adsorption of coordinated NH3 through NH3 migration. Ce addition improved amide ions formation to reach best NO reduction selectivity. A mechanistic pathway over Mn-Co-Ce/TiO2 was proposed. At low-temperature SCR reaction, coordinated NH3 reacted with NO2-, and amide reacted with NO (ad) or NO (g) to form N2. NO2 was related to the formation of nitrite on Co-contained catalysts and the generation of sbnd NH2- on Ce-contained catalysts. At high temperature, the other branch reaction also occurred between the coordinated NH3 and nitrate species, resulting in N2O yield increase.

  2. The influence of leaf-atmosphere NH3(g ) exchange on the isotopic composition of nitrogen in plants and the atmosphere.

    PubMed

    Johnson, Jennifer E; Berry, Joseph A

    2013-10-01

    The distribution of nitrogen isotopes in the biosphere has the potential to offer insights into the past, present and future of the nitrogen cycle, but it is challenging to unravel the processes controlling patterns of mixing and fractionation. We present a mathematical model describing a previously overlooked process: nitrogen isotope fractionation during leaf-atmosphere NH3(g ) exchange. The model predicts that when leaf-atmosphere exchange of NH3(g ) occurs in a closed system, the atmospheric reservoir of NH3(g ) equilibrates at a concentration equal to the ammonia compensation point and an isotopic composition 8.1‰ lighter than nitrogen in protein. In an open system, when atmospheric concentrations of NH3(g ) fall below or rise above the compensation point, protein can be isotopically enriched by net efflux of NH3(g ) or depleted by net uptake. Comparison of model output with existing measurements in the literature suggests that this process contributes to variation in the isotopic composition of nitrogen in plants as well as NH3(g ) in the atmosphere, and should be considered in future analyses of nitrogen isotope circulation. The matrix-based modelling approach that is introduced may be useful for quantifying isotope dynamics in other complex systems that can be described by first-order kinetics.

  3. DRIFT study on cerium-tungsten/titania catalyst for selective catalytic reduction of NOx with NH3.

    PubMed

    Chen, Liang; Li, Junhua; Ge, Maofa

    2010-12-15

    CeO(2)/TiO(2) and CeO(2)-WO(3)/TiO(2) catalysts prepared by impregnation method assisted with ultrasonic energy were investigated on the selective catalytic reduction (SCR) of NO(x) (NO and NO(2)) by NH(3). The catalytic activity of 10% CeO(2)/TiO(2) (CeTi) was greatly enhanced by the addition of 6% WO(3) in the broad temperature range of 200-500 °C, the promotion mechanism was proposed on basis of the results of in situ diffuse reflectance infrared transform spectroscopy (DRIFT). When NH(3) was introduced into both catalysts preadsorbed with NO + O(2), SCR would not proceed except for the reaction between NO(2) and ammonia. For CeO(2)/TiO(2) catalysts, coordinated NH(3) linked to Lewis acid sites were the main adsorbed ammonia species. When NO + O(2) was introduced, all the ammonia species consumed rapidly, indicating that these species could react with NO(x) effectively. Two different reaction routes, L-H mechanism at low temperature (<200 °C) and E-R mechanism at high temperatures (>200 °C), were presented for SCR reaction over CeO(2)/TiO(2) catalyst. For CeO(2)-WO(3)/TiO(2) catalysts, the Lewis acid sites on Ce(4+) state could be converted to Brønsted acid sites due to the unsaturated coordination of Ce(n+) and W(n+) ions. When NO + O(2) was introduced, the reaction proceeded more quickly than that on CeO(2)/TiO(2). The reaction route mainly followed E-R mechanism in the temperature range investigated (150-350 °C) over CeO(2)-WO(3)/TiO(2) catalysts. Tungstation was beneficial for the formation of Ce(3+), which would influence the active sites of the catalyst and further change the mechanisms of SCR reaction. In this way, the cooperation of tungstation and the presence of Ce(3+) state resulted in the better activity of CeO(2)-WO(3)/TiO(2) compared to that of CeO(2)/TiO(2).

  4. Low surface recombination velocity in solution-grown CH3NH3PbBr3 perovskite single crystal

    NASA Astrophysics Data System (ADS)

    Yang, Ye; Yan, Yong; Yang, Mengjin; Choi, Sukgeun; Zhu, Kai; Luther, Joseph M.; Beard, Matthew C.

    2015-08-01

    Organic-inorganic hybrid perovskites are attracting intense research effort due to their impressive performance in solar cells. While the carrier transport parameters such as mobility and bulk carrier lifetime shows sufficient characteristics, the surface recombination, which can have major impact on the solar cell performance, has not been studied. Here we measure surface recombination dynamics in CH3NH3PbBr3 perovskite single crystals using broadband transient reflectance spectroscopy. The surface recombination velocity is found to be 3.4+/-0.1 × 103 cm s-1, ~2-3 orders of magnitude lower than that in many important unpassivated semiconductors employed in solar cells. Our result suggests that the planar grain size for the perovskite thin films should be larger than ~30 μm to avoid the influence of surface recombination on the effective carrier lifetime.

  5. NH3 Trace Detection Using a Tunable Lead-Salt Diode Laser Near 10 μm

    NASA Astrophysics Data System (ADS)

    Dallah, M.; Salloum, A.

    2015-11-01

    We demonstrate a closed path ammonia gas sensor based on a tunable lead-salt diode laser. In order to measure NH3 concentrations, the laser is scanned over two absorption lines 992.68 and 992.45 cm-1 of the ν2 vibrational band. These lines have free interference patterns with other species in the atmosphere. The experiments are performed with an ammonia mixture in the air at room temperature in an optical multi-path White cell. In our preliminary experiments, a detection limit of ~4 ppb is achieved using direct absorption at 100 mbar pressure and 15 m path length. A detection limit of 0.2 ppb can be reached.

  6. Toward a chemiresistive ammonia (NH3) gas sensor based on viral-templated gold nanoparticles embedded in polypyrrole nanowires

    NASA Astrophysics Data System (ADS)

    Yan, Yiran; Zhang, Miluo; Su, Heng Chia; Myung, Nosang V.; Haberer, Elaine D.

    2014-08-01

    Preliminary studies toward the assembly of a gold-polypyrrole (PPy) peapod-like chemiresistive ammonia (NH3) gas sensors are presented. The proposed synthesis process will use electropolymerization to embed gold nanoparticles in polypyrrole nanowires. Viral-templating of gold nanoparticles and PPy electrodeposition via cyclic voltammetry are the focus of this investigation. A gold-binding M13 bacteriophage was used as a bio-template to assemble continuous chains of gold nanoparticles on interdigitated Pt working electrodes. The dimensions of the resulting nanowire-like structures were examined and the electrical resistance measured. PPy films were electropolymerized using an interdigitated planar, Pt electrode integrated counter and reference electrode. Morphological characterization of the polymer films was completed.

  7. Vibrational signatures of hydrogen bonding in the protonated ammonia clusters NH4+(NH3)1-4

    NASA Astrophysics Data System (ADS)

    Yang, Y.; Kühn, O.; Santambrogio, G.; Goebbert, D. J.; Asmis, K. R.

    2008-12-01

    The gas phase vibrational spectroscopy of the protonated ammonia dimer N2H7+, a prototypical system for strong hydrogen bonding, is studied in the spectral region from 330 to 1650 cm-1 by combining infrared multiple photon dissociation and multidimensional quantum mechanical simulations. The fundamental transition of the antisymmetric proton stretching vibration is observed at 374 cm-1 and assigned on the basis of a six-dimensional model Hamiltonian, which predicts this transition at 471 cm-1. Photodissociation spectra of the larger protonated ammonia clusters NH4+(NH3)n with n =2-4 are also reported for the range from 1050 to 1575 cm-1. The main absorption features can be assigned within the harmonic approximation, supporting earlier evidence that hydrogen bonding in these clusters is considerably weaker than for n =1.

  8. Controlled growth of CH3NH3PbI3 nanowires in arrays of open nanofluidic channels

    NASA Astrophysics Data System (ADS)

    Spina, Massimo; Bonvin, Eric; Sienkiewicz, Andrzej; Forró, László; Horváth, Endre

    2016-01-01

    Spatial positioning of nanocrystal building blocks on a solid surface is a prerequisite for assembling individual nanoparticles into functional devices. Here, we report on the graphoepitaxial liquid-solid growth of nanowires of the photovoltaic compound CH3NH3PbI3 in open nanofluidic channels. The guided growth, visualized in real-time with a simple optical microscope, undergoes through a metastable solvatomorph formation in polar aprotic solvents. The presently discovered crystallization leads to the fabrication of mm2-sized surfaces composed of perovskite nanowires having controlled sizes, cross-sectional shapes, aspect ratios and orientation which have not been achieved thus far by other deposition methods. The automation of this general strategy paves the way towards fabrication of wafer-scale perovskite nanowire thin films well-suited for various optoelectronic devices, e.g. solar cells, lasers, light-emitting diodes and photodetectors.

  9. Controlled growth of CH3NH3PbI3 nanowires in arrays of open nanofluidic channels.

    PubMed

    Spina, Massimo; Bonvin, Eric; Sienkiewicz, Andrzej; Náfrádi, Bálint; Forró, László; Horváth, Endre

    2016-01-01

    Spatial positioning of nanocrystal building blocks on a solid surface is a prerequisite for assembling individual nanoparticles into functional devices. Here, we report on the graphoepitaxial liquid-solid growth of nanowires of the photovoltaic compound CH3NH3PbI3 in open nanofluidic channels. The guided growth, visualized in real-time with a simple optical microscope, undergoes through a metastable solvatomorph formation in polar aprotic solvents. The presently discovered crystallization leads to the fabrication of mm(2)-sized surfaces composed of perovskite nanowires having controlled sizes, cross-sectional shapes, aspect ratios and orientation which have not been achieved thus far by other deposition methods. The automation of this general strategy paves the way towards fabrication of wafer-scale perovskite nanowire thin films well-suited for various optoelectronic devices, e.g. solar cells, lasers, light-emitting diodes and photodetectors. PMID:26806213

  10. Low Surface Recombination Velocity in Solution-Grown CH3NH3PbBr3 Perovskite Single Crystal

    DOE PAGES

    Yang, Ye; Yan, Yong; Yang, Mengjin; Choi, Sukgeun; Zhu, Kai; Luter, Joseph M.; Beard, Matthew C.

    2015-08-06

    Organic-inorganic hybrid perovskites are attracting intense research effort due to their impressive performance in solar cells. While the carrier transport parameters such as mobility and bulk carrier lifetime shows sufficient characteristics, the surface recombination, which can have major impact on the solar cell performance, has not been studied. Here we measure surface recombination dynamics in CH3NH3PbBr3 perovskite single crystals using broadband transient reflectance spectroscopy. The surface recombination velocity is found to be 3.4±0.1 103 cm s-1, B2–3 orders of magnitude lower than that in many important unpassivated semiconductors employed in solar cells. Our result suggests that the planar grain sizemore » for the perovskite thin films should be larger thanB30 mm to avoid the influence of surface recombination on the effective carrier lifetime.« less

  11. Controlled growth of CH3NH3PbI3 nanowires in arrays of open nanofluidic channels

    PubMed Central

    Spina, Massimo; Bonvin, Eric; Sienkiewicz, Andrzej; Forró, László; Horváth, Endre

    2016-01-01

    Spatial positioning of nanocrystal building blocks on a solid surface is a prerequisite for assembling individual nanoparticles into functional devices. Here, we report on the graphoepitaxial liquid-solid growth of nanowires of the photovoltaic compound CH3NH3PbI3 in open nanofluidic channels. The guided growth, visualized in real-time with a simple optical microscope, undergoes through a metastable solvatomorph formation in polar aprotic solvents. The presently discovered crystallization leads to the fabrication of mm2-sized surfaces composed of perovskite nanowires having controlled sizes, cross-sectional shapes, aspect ratios and orientation which have not been achieved thus far by other deposition methods. The automation of this general strategy paves the way towards fabrication of wafer-scale perovskite nanowire thin films well-suited for various optoelectronic devices, e.g. solar cells, lasers, light-emitting diodes and photodetectors. PMID:26806213

  12. The optoelectronic role of chlorine in CH3NH3PbI3(Cl)-based perovskite solar cells

    PubMed Central

    Chen, Qi; Zhou, Huanping; Fang, Yihao; Stieg, Adam Z.; Song, Tze-Bin; Wang, Hsin-Hua; Xu, Xiaobao; Liu, Yongsheng; Lu, Shirong; You, Jingbi; Sun, Pengyu; McKay, Jeff; Goorsky, Mark S.; Yang, Yang

    2015-01-01

    Perovskite photovoltaics offer a compelling combination of extremely low-cost, ease of processing and high device performance. The optoelectronic properties of the prototypical CH3NH3PbI3 can be further adjusted by introducing other extrinsic ions. Specifically, chlorine incorporation has been shown to affect the morphological development of perovksite films, which results in improved optoelectronic characteristics for high efficiency. However, it requires a deep understanding to the role of extrinsic halide, especially in the absence of unpredictable morphological influence during film growth. Here we report an effective strategy to investigate the role of the extrinsic ion in the context of optoelectronic properties, in which the morphological factors that closely correlate to device performance are mostly decoupled. The chlorine incorporation is found to mainly improve the carrier transport across the heterojunction interfaces, rather than within the perovskite crystals. Further optimization according this protocol leads to solar cells achieving power conversion efficiency of 17.91%. PMID:26068804

  13. Electron-Temperature Dependence of the Recombination of NH4(+)((NH3)(sub n) Ions with Electrons

    NASA Technical Reports Server (NTRS)

    Skrzypkowski, M. P.; Johnson, R.

    1997-01-01

    The two-body recombination of NH4(+)(NH3)(sub 2,3) cluster-ions with electrons has been studied in an afterglow experiment in which the electron temperature T, was elevated by radio-frequency heating from 300 K up to 900 K. The recombination coefficients for the n = 2 and n = 3 cluster ions were found to be equal, alpha(sub 2, sup(2)) = alpha(sub 3, sup(2)) = (4.8 +/- 0.5) x 10(exp - 6)cu cm/s, and to vary with electron temperature as T(sub c, sup -0.65) rather than to be nearly temperature-independent as had been inferred from measurements in microwave-heated plasmas.

  14. Low surface recombination velocity in solution-grown CH3NH3PbBr3 perovskite single crystal

    PubMed Central

    Yang, Ye; Yan, Yong; Yang, Mengjin; Choi, Sukgeun; Zhu, Kai; Luther, Joseph M.; Beard, Matthew C.

    2015-01-01

    Organic-inorganic hybrid perovskites are attracting intense research effort due to their impressive performance in solar cells. While the carrier transport parameters such as mobility and bulk carrier lifetime shows sufficient characteristics, the surface recombination, which can have major impact on the solar cell performance, has not been studied. Here we measure surface recombination dynamics in CH3NH3PbBr3 perovskite single crystals using broadband transient reflectance spectroscopy. The surface recombination velocity is found to be 3.4±0.1 × 103 cm s−1, ∼2–3 orders of magnitude lower than that in many important unpassivated semiconductors employed in solar cells. Our result suggests that the planar grain size for the perovskite thin films should be larger than ∼30 μm to avoid the influence of surface recombination on the effective carrier lifetime. PMID:26245855

  15. A theoretical investigation of gaseous absorption by water droplets from SO2-HNO3-NH3-CO2-HCl mixtures

    NASA Technical Reports Server (NTRS)

    Adewuyi, Y. G.; Carmichael, G. R.

    1982-01-01

    A physical-chemical model is developed and used to investigate gaseous absorption by water droplets from trace gas mixtures. The model is an extension of that of Carmichael and Peters (1979) and includes the simultaneous absorption of SO2, NH3, HNO3, CO2, and HCl. Gas phase depletion is also considered. Presented results demonstrate that the absorption behavior of raindrops is strongly dependent on drop size, fall distance, trace gas concentrations, and the chemical and physical properties of the constituents of the mixture. In addition, when gas phase depletion is considered, the absorption rates and equilibrium values are also dependent on the precipitation rate itself. Also, the trace constituents liquid phase concentrations may be a factor of six or more lower when gas depletion is considered then when the depletion is ignored. However, the hydrogen ion concentration may be insensitive to the gas phase depletion.

  16. Photolysis products of CO, NH3 aND H2O and their significance to reactions on interstellar grains

    NASA Technical Reports Server (NTRS)

    Ferris, J. P.

    1986-01-01

    With the increase in evidence that interstellar grains are the basic building blocks of comets and with the realization that comet collisions with the earth have probably occured at a much higher frequency than earlier assumed it may be presumed that interstellar dust chemistry played an important role in the early chemistry of the earth. As a part of the study of the photochemical processes taking place on interstellar grains the photolysis of mixtures of CO, NH3 and H2O was performed at 10 K, 77K and 298K. The reaction products were determined by GC/MS and HPLC analysis to be lactic acid, glycolic acid, hydroxyacetamide, urea, biuret, oxamic acid, oxamide, glyceric acid and glyceramide. Ethylene glycol and glycerol were also detected but is is not clear at present whether these are true photoproducts or contaminants. The mechanism of formation of these molecules are discussed as well as their possible significance to the origins of life.

  17. A near infrared line list for NH3: Analysis of a Kitt Peak spectrum after 35 years

    NASA Astrophysics Data System (ADS)

    Barton, Emma J.; Yurchenko, Sergei N.; Tennyson, Jonathan; Béguier, Serge; Campargue, Alain

    2016-07-01

    A Fourier Transform (FT) absorption spectrum of room temperature NH3 in the region 7400-8640 cm-1 is analysed using a variational line list and ground state energies determined using the MARVEL procedure. The spectrum was measured by Dr. Catherine de Bergh in 1980 and is available from the Kitt Peak data center. The centers and intensities of 8468 ammonia lines were retrieved using a multiline fitting procedure. 2474 lines are assigned to 21 bands providing 1692 experimental energies in the range 7500-9200 cm-1. The spectrum was assigned by the joint use of the BYTe variational line list and combination differences. The assignments and experimental energies presented in this work are the first for ammonia in the region 7400-8640 cm-1, considerably extending the range of known vibrational-excited states.

  18. Quantum chemical study and infrared spectroscopy of hydrogen-bonded CHCl3-NH3 in the gas phase

    NASA Astrophysics Data System (ADS)

    Hippler, Michael

    2007-08-01

    Molecular association of chloroform with ammonia is studied by high-level quantum chemical calculations including correlated MP2 and CCSD(T) calculations with basis sets up to6-311++G(d,p) and counterpoise corrected energies, geometries, and frequencies. The calculations predict an eclipsed hydrogen-bonded complex of C3v symmetry (ΔE0=-15.07kJmol-1) with 225.4pm intermolecular CH⋯N distance. Intermolecular interactions are analysed by Kitaura-Morokuma [Int. J. Quantum Chem. 10, 325 (1976)] interaction energy decomposition. Compared to the monomer, the C-H bond is elongated, and the CH-stretching fundamental shifts to lower wave numbers and has a marked ˜340-fold increase of its intensity. Based on these predictions, the complex is observed by infrared spectroscopy in the gas phase at room temperature. A subtraction procedure isolates its spectrum, and a dilution series confirms the presence of a 1:1 complex. The CHCl3⋯NH3 complex has an experimental -17.5cm-1 shift of its CH-stretching vibration, and CDCl3⋯NH3 a -12.5cm-1 shift of the CD-stretching vibration. After a deperturbation of the CH-stretching/bending mode Fermi resonance system, this indicates a "redshifting" or more appropriately, a "C-H elongating" hydrogen bond in agreement with the ab initio calculations. An estimate of the complex concentration gives the equilibrium constant Kp=0.024 (pθ=105Pa ) at 295K for the dimerization, providing one of the few examples where a hydrogen-bonded gas phase complex at room temperature could be quantitatively studied by infrared spectroscopy.

  19. VizieR Online Data Catalog: W51 Main NH3 and CH3OH data cubes

    NASA Astrophysics Data System (ADS)

    Goddi, C.; Ginsburg, A.; Zhang, Q.

    2016-04-01

    Observations of NH3 toward the W51 complex were conducted usi Karl G. Jansky Very Large Array (JVLA) of the National Radio Astronomy Observatory (NRAO)1 in the B configuration. By using the broadband JVLA K- and Ka-band receivers, we observed a total of five metastable inversion transitions of NH3: (J,K) = (6, 6), (7, 7), (9, 9), (10, 10), and (13, 13) at the 1cm band with frequencies ranging from ~25GHz for the (6, 6) line to ~33GHz for the (13, 13) line. Transitions were observed in pairs of independently tunable basebands during 6h tracks (two targets per track: W51 - this paper; NGC 7538 IRS1 - Paper I, Goddi et al., 2015A&A...573A.108G) on three different dates in 2012: the (6, 6) and (7, 7) lines on May 31 at K-band, the (9, 9) and (13, 13) lines on June 21, and the (10, 10) transition on August 7, both at Ka-band. Each baseband had eight sub-bands with a 4MHz bandwidth (~40km/s at 30GHz), providing a total coverage of 32MHz (~320km/s at 30GHz). Each sub-band consisted of 128 channels with a separation of 31.25kHz (~0.3km/s at 30GHz). The typical on-source integration time was about 80min. Each transition was observed with fast switching, where 80s scans on target were alternated with 40s scans on the nearby (1.2° on the sky) QSO J1924+1540 (measured flux density 0.6-0.7Jy, depending on frequency). We derived absolute flux calibration from observations of 3C 48 (Sν=0.5-0.7Jy, depending on frequency), and bandpass calibration from observations of 3C 84 (Sν=27-29Jy, depending on frequency). (2 data files).

  20. Passive SCR for lean gasoline NOX control: Engine-based strategies to minimize fuel penalty associated with catalytic NH3 generation

    DOE PAGES

    Prikhodko, Vitaly Y.; Parks, James E.; Pihl, Josh A.; Toops, Todd J.

    2016-02-18

    Lean gasoline engines offer greater fuel economy than common stoichiometric gasoline engines. However, excess oxygen prevents the use of the current three-way catalyst (TWC) to control nitrogen oxide (NOX) emissions in lean exhaust. A passive SCR concept, introduced by General Motors Global R&D, makes use of a TWC that is already onboard to generate NH3 under slightly rich conditions, which is stored on the downstream SCR. The stored NH3 is then used to reduce NOX emissions when the engine switches to lean operation. In this work, the effect of engine parameters, such as air-fuel equivalence ratio and spark timing, onmore » NH3 generation over a commercial Pd-only TWC with no dedicated oxygen storage component was evaluated on a 2.0-liter BMW lean burn gasoline direct injection engine. NOX reduction, NH3 formation, and reductant utilization processes were evaluated, and fuel efficiency was assessed and compared to the stoichiometric engine operation case. We found air-fuel equivalence ratio to be one of the most important parameters in controlling the NH3 production; however, the rich operation necessary for NH3 production results in a fuel consumption penalty. The fuel penalty can be minimized by adjusting spark timing to increase rich-phase engine out NOX emissions and, thereby, NH3 levels. Additionally, higher engine out NOX during engine load increase to simulate acceleration resulted in additional fuel savings. Ultimately, a 10% fuel consumption benefit was achieved with the passive SCR approach by optimizing rich air-fuel equivalence ratio and spark timing while also utilizing acceleration load conditions.« less

  1. Emissions of NO and NH3 from a Typical Vegetable-Land Soil after the Application of Chemical N Fertilizers in the Pearl River Delta

    PubMed Central

    Li, Dejun

    2013-01-01

    Cropland soil is an important source of atmospheric nitric oxide (NO) and ammonia (NH3). Chinese croplands are characterized by intensive management, but limited information is available with regard to NO emissions from croplands in China and NH3 emissions in south China. In this study, a mesocosm experiment was conducted to measure NO and NH3 emissions from a typical vegetable-land soil in the Pearl River Delta following the applications of 150 kg N ha−1 as urea, ammonium nitrate (AN) and ammonium bicarbonate (ABC), respectively. Over the sampling period after fertilization (72 days for NO and 39 days for NH3), mean NO fluxes (± standard error of three replicates) in the control and urea, AN and ABC fertilized mesocosms were 10.9±0.9, 73.1±2.9, 63.9±1.8 and 66.0±4.0 ng N m−2 s−1, respectively; mean NH3 fluxes were 8.9±0.2, 493.6±4.4, 144.8±0.1 and 684.7±8.4 ng N m−2 s−1, respectively. The fertilizer-induced NO emission factors for urea, AN and ABC were 2.6±0.1%, 2.2±0.1% and 2.3±0.2%, respectively. The fertilizer-induced NH3 emission factors for the three fertilizers were 10.9±0.2%, 3.1±0.1% and 15.2±0.4%, respectively. From the perspective of air quality protection, it would be better to increase the proportion of AN application due to its lower emission factors for both NO and NH3. PMID:23527173

  2. Optical Transitions in Hybrid Perovskite Solar Cells: Ellipsometry, Density Functional Theory, and Quantum Efficiency Analyses for CH3NH3PbI3

    NASA Astrophysics Data System (ADS)

    Shirayama, Masaki; Kadowaki, Hideyuki; Miyadera, Tetsuhiko; Sugita, Takeshi; Tamakoshi, Masato; Kato, Masato; Fujiseki, Takemasa; Murata, Daisuke; Hara, Shota; Murakami, Takurou N.; Fujimoto, Shohei; Chikamatsu, Masayuki; Fujiwara, Hiroyuki

    2016-01-01

    Light-induced photocarrier generation is an essential process in all solar cells, including organic-inorganic hybrid (CH3NH3PbI3 ) solar cells, which exhibit a high short-circuit current density (Jsc ) of approximately 20 mA /cm2 . Although the high Jsc observed in the hybrid solar cells relies on strong electron-photon interaction, the optical transitions in the perovskite material remain unclear. Here, we report artifact-free CH3NH3PbI3 optical constants extracted from ultrasmooth perovskite layers without air exposure and assign all of the optical transitions in the visible and ultraviolet region unambiguously, based on density-functional theory (DFT) analysis that assumes a simple pseudocubic crystal structure. From the self-consistent spectroscopic ellipsometry analysis of the ultrasmooth CH3NH3PbI3 layers, we find that the absorption coefficients of CH3NH3PbI3 (α =3.8 ×104 cm-1 at 2.0 eV) are comparable to those of CuInGaSe2 and CdTe, and high α values reported in earlier studies are overestimated seriously by the extensive surface roughness of CH3NH3PbI3 layers. The polarization-dependent DFT calculations show that CH3NH3 + interacts strongly with the PbI3 - cage, modifying the CH3NH3PbI3 dielectric function in the visible region rather significantly. In particular, the transition matrix element of CH3NH3PbI3 varies, depending on the position of CH3NH3 + within the Pb—I network. When the effect of CH3NH3 + on the optical transition is eliminated in the DFT calculation, the CH3NH3PbI3 dielectric function deduced from DFT shows an excellent agreement with the experimental result. As a result, distinct optical transitions observed at E0(Eg)=1.61 eV , E1=2.53 eV , and E2=3.24 eV in CH3NH3PbI3 are attributed to the direct semiconductor-type transitions at the R , M , and X points in the pseudocubic Brillouin zone, respectively. We further perform the quantum efficiency (QE) analysis for a standard hybrid-perovskite solar cell incorporating a mesoporous TiO2

  3. Insight into the CH3NH3PbI3/C interface in hole-conductor-free mesoscopic perovskite solar cells.

    PubMed

    Li, Jiangwei; Niu, Guangda; Li, Wenzhe; Cao, Kun; Wang, Mingkui; Wang, Liduo

    2016-08-01

    Perovskite solar cells (PSCs) with hole-conductor-free mesoscopic architecture have shown superb stability and great potential in practical application. The printable carbon counter electrodes take full responsibility of extracting holes from the active CH3NH3PbI3 absorbers. However, an in depth study of the CH3NH3PbI3/C interface properties, such as the structural formation process and the effect of interfacial conditions on hole extraction, is still lacking. Herein, we present, for the first time, an insight into the spatial confinement induced CH3NH3PbI3/C interface formation by in situ photoluminescence observations during the crystallization process of CH3NH3PbI3. The derived reaction kinetics allows a quantitative description of the perovskite formation process. In addition, we found that the interfacial contact between carbon and perovskite was dominant for hole extraction efficiency and associated with the photovoltaic parameter of short circuit current density (JSC). Consequently, we conducted a solvent vapor assisted process of PbI2 diffusion to carefully control the CH3NH3PbI3/C interface with less unreacted PbI2 barrier. The improvement of interface conditions thereby contributes to a high hole extraction proved by the charge extraction resistance and PL lifetime change, resulting in the increased JSC valve.

  4. Insight into the CH3NH3PbI3/C interface in hole-conductor-free mesoscopic perovskite solar cells.

    PubMed

    Li, Jiangwei; Niu, Guangda; Li, Wenzhe; Cao, Kun; Wang, Mingkui; Wang, Liduo

    2016-08-01

    Perovskite solar cells (PSCs) with hole-conductor-free mesoscopic architecture have shown superb stability and great potential in practical application. The printable carbon counter electrodes take full responsibility of extracting holes from the active CH3NH3PbI3 absorbers. However, an in depth study of the CH3NH3PbI3/C interface properties, such as the structural formation process and the effect of interfacial conditions on hole extraction, is still lacking. Herein, we present, for the first time, an insight into the spatial confinement induced CH3NH3PbI3/C interface formation by in situ photoluminescence observations during the crystallization process of CH3NH3PbI3. The derived reaction kinetics allows a quantitative description of the perovskite formation process. In addition, we found that the interfacial contact between carbon and perovskite was dominant for hole extraction efficiency and associated with the photovoltaic parameter of short circuit current density (JSC). Consequently, we conducted a solvent vapor assisted process of PbI2 diffusion to carefully control the CH3NH3PbI3/C interface with less unreacted PbI2 barrier. The improvement of interface conditions thereby contributes to a high hole extraction proved by the charge extraction resistance and PL lifetime change, resulting in the increased JSC valve. PMID:27385565

  5. All solid-state solar cells based on CH3NH3PbI3-sensitized TiO2 nanotube arrays

    NASA Astrophysics Data System (ADS)

    Yang, Xiuchun; Liu, Wei; Ren, Peng

    2016-09-01

    TiO2 nanotube arrays (TiO2 NTAs) were firstly used as photoanode in methylammonium lead iodide (CH3NH3PbI3) perovskite/TiO2 NTAs heterojunction solar cell, where CH3NH3PbI3 functions as both light absorber and hole conductor. The composition, structure and photoelectrochemical properties of the as-prepared samples were characterized by x-ray diffractometer (XRD), field-emission scanning electron microscope (FE-SEM), ultraviolet-visible (UV-vis) spectrophotometer and electrochemical workstation. The results indicate that the as-prepared CH3NH3PbI3 belongs to the cubic crystal system, and TiO2 NTAs sensitized by 0.3 M CH3NH3I and PbI2 exhibit the best photoelectrochemical properties with an open-circuit voltage of 0.422 V and a short-circuit current density of 173.4 μA cm-2. The EIS result shows that the extremely large resistance at CH3NH3PbI3/FTO interface contributes to the low current density of the perovskite solar cell.

  6. A photoelectrochemical biosensor for fibroblast-like synoviocyte cell using visible light-activated NCQDs sensitized-ZnO/CH3NH3PbI3 heterojunction.

    PubMed

    Pang, Xuehui; Zhang, Yong; Pan, Jihong; Zhao, Yanxia; Chen, Yao; Ren, Xiang; Ma, Hongmin; Wei, Qin; Du, Bin

    2016-03-15

    Based on ZnO nanorods (NRs)/CH3NH3PbI3/nitrogen-doped carbon quantum dots (NCQDs) nanocomposites, the highly sensitive detection of fibroblast-like synoviocyte (FLS) cell was realized by a photoelectrochemical (PEC) biosensor. ZnO/CH3NH3PbI3/NCQDs nanocomposites were exploited as the photo-to-electron generator to produce the signal. CH3NH3PbI3 was spin-coated on ZnO surface after ZnO NRs grew on ITO electrode then by dropping on the modified electrode, NCQDs were diffused and adhered to the surface of ZnO and CH3NH3PbI3. In the presence of EDC/NHS, the combination of CH3NH3PbI3 and NCQDs was achieved by the carboxyl groups (-COOH) and amino groups (-NH2) in the preparation process. Furthermore, the capture probe of FLS cell, CD95 antibody, can be anchored by -COOH and -NH2 groups through EDC/NHS. The specific recognition between the antibody capture probes and cell targets gained high-sensitive detection for FLS cell for the first time. The developed biosensor showed a wide linear range from 1.0 × 10(4)cell/mL to 10 cell/mL and a low detection limit of 2 cell/mL. This kind of biosensor would provide a novel detection strategy for FLS cell.

  7. Influence of bulking agents on CH4, N2O, and NH3 emissions during rapid composting of pig manure from the Chinese Ganqinfen system*

    PubMed Central

    Sun, Xiang-ping; Lu, Peng; Jiang, Tao; Schuchardt, Frank; Li, Guo-xue

    2014-01-01

    Mismanagement of the composting process can result in emissions of CH4, N2O, and NH3, which have caused severe environmental problems. This study was aimed at determining whether CH4, N2O, and NH3 emissions from composting are affected by bulking agents during rapid composting of pig manure from the Chinese Ganqinfen system. Three bulking agents, corn stalks, spent mushroom compost, and sawdust, were used in composting with pig manure in 60 L reactors with forced aeration for more than a month. Gas emissions were measured continuously, and detailed gas emission patterns were obtained. Concentrations of NH3 and N2O from the composting pig manure mixed with corn stalks or sawdust were higher than those from the spent mushroom compost treatment, especially the sawdust treatment, which had the highest total nitrogen loss among the three runs. Most of the nitrogen was lost in the form of NH3, which accounts for 11.16% to 35.69% of the initial nitrogen. One-way analysis of variance for NH3 emission showed no significant differences between the corn stalk and sawdust treatments, but a significant difference was noted between the spent mushroom compost and sawdust treatments. The introduction of sawdust reduced CH4 emission more than the corn stalks and spent mushroom compost. However, there were no significant differences among the three runs for total carbon loss. All treatments were matured after 30 d. PMID:24711356

  8. Effect of water vapor on NH3-NO/NO2 SCR performance of fresh and aged MnOx-NbOx-CeO2 catalysts.

    PubMed

    Chen, Lei; Si, Zhichun; Wu, Xiaodong; Weng, Duan; Wu, Zhenwei

    2015-05-01

    A MnOx-NbOx-CeO2 catalyst for low temperature selective catalytic reduction (SCR) of NOx with NH3 was prepared by a sol-gel method, and characterized by NH3-NO/NO2 SCR catalytic activity, NO/NH3 oxidation activity, NOx/NH3 TPD, XRD, BET, H2-TPR and in-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). The results indicate that the MnOx-NbOx-CeO2 catalyst shows excellent low temperature NH3-SCR activity in the temperature range of 150-300°C. Water vapor inhibits the low temperature activity of the catalyst in standard SCR due to the inhibition of NOx adsorption. As the NO2 content increases in the feed, water vapor does not affect the activity in NO2 SCR. Meanwhile, water vapor significantly enhances the N2 selectivity of the fresh and the aged catalysts due to its inhibition of the decomposition of NH4NO3 into N2O.

  9. Synthesis and molecular structure of [Cu(NH3)4][Ni(CN)4]: A missing piece in the [Cu(NH3)n][Ni(CN)4] story

    NASA Astrophysics Data System (ADS)

    Solanki, Dina; Hogarth, Graeme

    2015-11-01

    Reaction of CuCl2·2H2O and K2[Ni(CN)4]·2H2O in aqueous ammonia gave blue rod-like crystals of [Cu(NH3)4][Ni(CN)4]. An X-ray crystallographic reveals that square-planar anions and cations are weakly associated through coordination of a cis pair of cyanide ligands to copper, with one short and one long contact and thus the copper centre is best described as a square-based pyramid. Crystals lose ammonia readily upon removal from the solvent and this has been probed by TGA and DSC measurements. For comparison we have also re-determined the structure of the related ethylenediamine (en) complex [Cu(en)2][Ni(CN)4] at 150 K. This consists of a 1D chain in which a trans pair of cyanide ligands bind to copper such that the latter has an overall tetragonally distorted octahedral coordination geometry.

  10. Facile fabrication of large-grain CH3NH3PbI3-xBrx films for high-efficiency solar cells via CH3NH3Br-selective Ostwald ripening

    DOE PAGES

    Yang, Mengjin; Zhang, Taiyang; Schulz, Philip; Li, Zhen; Li, Ge; Kim, Dong Hoe; Guo, Nanjie; Berry, Joseph J.; Zhu, Kai; Zhao, Yixin

    2016-08-01

    Organometallic halide perovskite solar cells (PSCs) have shown great promise as a low-cost, high-efficiency photovoltaic technology. Structural and electro-optical properties of the perovskite absorber layer are most critical to device operation characteristics. Here we present a facile fabrication of high-efficiency PSCs based on compact, large-grain, pinhole-free CH3NH3PbI3-xBrx (MAPbI3-xBrx) thin films with high reproducibility. A simple methylammonium bromide (MABr) treatment via spin-coating with a proper MABr concentration converts MAPbI3 thin films with different initial film qualities (for example, grain size and pinholes) to high-quality MAPbI3-xBrx thin films following an Ostwald ripening process, which is strongly affected by MABr concentration and ismore » ineffective when replacing MABr with methylammonium iodide. A higher MABr concentration enhances I-Br anion exchange reaction, yielding poorer device performance. Lastly, this MABr-selective Ostwald ripening process improves cell efficiency but also enhances device stability and thus represents a simple, promising strategy for further improving PSC performance with higher reproducibility and reliability.« less

  11. The reaction NH2 + PH3 yields NH3 + PH2: Absolute rate constant measurement and implication for NH3 and PH3 photochemistry in the atmosphere of Jupiter

    NASA Technical Reports Server (NTRS)

    Bosco, S. R.; Brobst, W. D.; Nava, D. F.; Stief, L. J.

    1983-01-01

    The rate constant is measured over the temperature interval 218-456 K using the technique of flash photolysis-laser-induced fluorescence. NH2 radicals are produced by the flash photolysis of ammonia highly diluted in argon, and the decay of fluorescent NH2 photons is measured by multiscaling techniques. For each of the five temperatures employed in the study, the results are shown to be independent of variations in PH3 concentration, total pressure (argon), and flash intensity. It is found that the rate constant results are best represented for T between 218 and 456 K by the expression k = (1.52 + or - 0.16) x 10 to the -12th exp(-928 + or - 56/T) cu cm per molecule per sec; the error quoted is 1 standard deviation. This is the first determination of the rate constant for the reaction NH2 + PH3. The data are compared with an estimate made in order to explain results of the radiolysis of NH3-PH3 mixtures. The Arrhenius parameters determined here for NH2 + PH3 are then constrasted with those for the corresponding reactions of H and OH with PH3.

  12. Facile fabrication of large-grain CH3NH3PbI3−xBrx films for high-efficiency solar cells via CH3NH3Br-selective Ostwald ripening

    PubMed Central

    Yang, Mengjin; Zhang, Taiyang; Schulz, Philip; Li, Zhen; Li, Ge; Kim, Dong Hoe; Guo, Nanjie; Berry, Joseph J.; Zhu, Kai; Zhao, Yixin

    2016-01-01

    Organometallic halide perovskite solar cells (PSCs) have shown great promise as a low-cost, high-efficiency photovoltaic technology. Structural and electro-optical properties of the perovskite absorber layer are most critical to device operation characteristics. Here we present a facile fabrication of high-efficiency PSCs based on compact, large-grain, pinhole-free CH3NH3PbI3−xBrx (MAPbI3−xBrx) thin films with high reproducibility. A simple methylammonium bromide (MABr) treatment via spin-coating with a proper MABr concentration converts MAPbI3 thin films with different initial film qualities (for example, grain size and pinholes) to high-quality MAPbI3−xBrx thin films following an Ostwald ripening process, which is strongly affected by MABr concentration and is ineffective when replacing MABr with methylammonium iodide. A higher MABr concentration enhances I–Br anion exchange reaction, yielding poorer device performance. This MABr-selective Ostwald ripening process improves cell efficiency but also enhances device stability and thus represents a simple, promising strategy for further improving PSC performance with higher reproducibility and reliability. PMID:27477212

  13. Facile fabrication of large-grain CH3NH3PbI3-xBrx films for high-efficiency solar cells via CH3NH3Br-selective Ostwald ripening

    NASA Astrophysics Data System (ADS)

    Yang, Mengjin; Zhang, Taiyang; Schulz, Philip; Li, Zhen; Li, Ge; Kim, Dong Hoe; Guo, Nanjie; Berry, Joseph J.; Zhu, Kai; Zhao, Yixin

    2016-08-01

    Organometallic halide perovskite solar cells (PSCs) have shown great promise as a low-cost, high-efficiency photovoltaic technology. Structural and electro-optical properties of the perovskite absorber layer are most critical to device operation characteristics. Here we present a facile fabrication of high-efficiency PSCs based on compact, large-grain, pinhole-free CH3NH3PbI3-xBrx (MAPbI3-xBrx) thin films with high reproducibility. A simple methylammonium bromide (MABr) treatment via spin-coating with a proper MABr concentration converts MAPbI3 thin films with different initial film qualities (for example, grain size and pinholes) to high-quality MAPbI3-xBrx thin films following an Ostwald ripening process, which is strongly affected by MABr concentration and is ineffective when replacing MABr with methylammonium iodide. A higher MABr concentration enhances I-Br anion exchange reaction, yielding poorer device performance. This MABr-selective Ostwald ripening process improves cell efficiency but also enhances device stability and thus represents a simple, promising strategy for further improving PSC performance with higher reproducibility and reliability.

  14. Facile fabrication of large-grain CH3NH3PbI3-xBrx films for high-efficiency solar cells via CH3NH3Br-selective Ostwald ripening.

    PubMed

    Yang, Mengjin; Zhang, Taiyang; Schulz, Philip; Li, Zhen; Li, Ge; Kim, Dong Hoe; Guo, Nanjie; Berry, Joseph J; Zhu, Kai; Zhao, Yixin

    2016-01-01

    Organometallic halide perovskite solar cells (PSCs) have shown great promise as a low-cost, high-efficiency photovoltaic technology. Structural and electro-optical properties of the perovskite absorber layer are most critical to device operation characteristics. Here we present a facile fabrication of high-efficiency PSCs based on compact, large-grain, pinhole-free CH3NH3PbI3-xBrx (MAPbI3-xBrx) thin films with high reproducibility. A simple methylammonium bromide (MABr) treatment via spin-coating with a proper MABr concentration converts MAPbI3 thin films with different initial film qualities (for example, grain size and pinholes) to high-quality MAPbI3-xBrx thin films following an Ostwald ripening process, which is strongly affected by MABr concentration and is ineffective when replacing MABr with methylammonium iodide. A higher MABr concentration enhances I-Br anion exchange reaction, yielding poorer device performance. This MABr-selective Ostwald ripening process improves cell efficiency but also enhances device stability and thus represents a simple, promising strategy for further improving PSC performance with higher reproducibility and reliability. PMID:27477212

  15. The reaction NH2 + PH3 yields NH3 + PH2 - Absolute rate constant measurement and implication for NH3 and PH3 photochemistry in the atmosphere of Jupiter

    NASA Technical Reports Server (NTRS)

    Bosco, S. R.; Brobst, W. D.; Nava, D. F.; Stief, L. J.

    1983-01-01

    The rate constant is measured over the temperature interval 218-456 K using the technique of flash photolysis-laser-induced fluorescence. NH2 radicals are produced by the flash photolysis of ammonia highly diluted in argon, and the decay of fluorescent NH2 photons is measured by multiscaling techniques. For each of the five temperatures employed in the study, the results are shown to be indepenent of variations in PH3 concentration, total pressure (argon), and flash intensity. It is found that the rate constant results are best represented for T between 218 and 456 K by the expression k = (1.52 + or - 0.16) x 10 to the -12th exp(-928 + or - 56/T) cu cm per molecule per sec; the error quoted is 1 standard deviation. This is the first determination of the rate constant for the reaction NH2 + PH3. The data are compared with an estimate made in order to explain results of the radiolysis of NH3-PH3 mixtures. The Arrhenius parameters determined here for NH2 + PH3 are then contrasted with those for the corresponding reactions of H and OH with PH3.

  16. Low-temperature selective catalytic reduction of NO with NH3 over nanoflaky MnOx on carbon nanotubes in situ prepared via a chemical bath deposition route

    NASA Astrophysics Data System (ADS)

    Fang, Cheng; Zhang, Dengsong; Cai, Sixiang; Zhang, Lei; Huang, Lei; Li, Hongrui; Maitarad, Phornphimon; Shi, Liyi; Gao, Ruihua; Zhang, Jianping

    2013-09-01

    Nanoflaky MnOx on carbon nanotubes (nf-MnOx@CNTs) was in situ synthesized by a facile chemical bath deposition route for low-temperature selective catalytic reduction (SCR) of NO with NH3. This catalyst was mainly characterized by the techniques of X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N2 adsorption-desorption analysis, X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR) and NH3 temperature-programmed desorption (NH3-TPD). The SEM, TEM, XRD results and N2 adsorption-desorption analysis indicated that the CNTs were surrounded by nanoflaky MnOx and the obtained catalyst exhibited a large surface area as well. Compared with the MnOx/CNT and MnOx/TiO2 catalysts prepared by an impregnation method, the nf-MnOx@CNTs presented better NH3-SCR activity at low temperature and a more extensive operating temperature window. The XPS results showed that a higher atomic concentration of Mn4+ and more chemisorbed oxygen species existed on the surface of CNTs for nf-MnOx@CNTs. The H2-TPR and NH3-TPD results demonstrated that the nf-MnOx@CNTs possessed stronger reducing ability, more acid sites and stronger acid strength than the other two catalysts. Based on the above mentioned favourable properties, the nf-MnOx@CNT catalyst has an excellent performance in the low-temperature SCR of NO to N2 with NH3. In addition, the nf-MnOx@CNT catalyst also presented favourable stability and H2O resistance.Nanoflaky MnOx on carbon nanotubes (nf-MnOx@CNTs) was in situ synthesized by a facile chemical bath deposition route for low-temperature selective catalytic reduction (SCR) of NO with NH3. This catalyst was mainly characterized by the techniques of X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N2 adsorption-desorption analysis, X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR) and NH3 temperature

  17. Electroluminescence from perovskite LEDs with the structure of Ag/Spiro-OMeTAD/CH3NH3PbI3/TiO2/FTO

    NASA Astrophysics Data System (ADS)

    Wang, Minhuan; Shi, Yantao; Bian, Jiming; Dong, Qingshun; Sun, Hongjun; Liu, Hongzhu; Luo, Yingmin; Zhang, Yuzhi

    2016-10-01

    The perovskite light-emitting diodes (Pe-LEDs) with the structure of Ag/Spiro-OMeTAD/CH3NH3PbI3/TiO2/FTO were synthesized, where the CH3NH3PbI3 perovskite layer was deposited by a two-step spin-coating process. A dominant near-infrared electroluminescence (EL) at 773 nm was detected from the Pe-LEDs under forward bias at room temperature. The origin and mechanism of the EL were discussed in comparison with the photoluminescence (PL) spectra, and it was attributed to the radiative recombination of electrons and holes confined in the CH3NH3PbI3 emissive layer. Moreover, the corresponding energy band diagrams was proposed to illustrate the carrier transport mechanism in the Pe-LED device.

  18. Excellent performance of one-pot synthesized Cu-SSZ-13 catalyst for the selective catalytic reduction of NOx with NH3.

    PubMed

    Xie, Lijuan; Liu, Fudong; Ren, Limin; Shi, Xiaoyan; Xiao, Feng-Shou; He, Hong

    2014-01-01

    Cu-SSZ-13 samples prepared by a novel one-pot synthesis method achieved excellent NH3-SCR performance and high N2 selectivity from 150 to 550 °C after ion exchange treatments. The selected Cu3.8-SSZ-13 catalyst was highly resistant to large space velocity (800 000 h(-1)) and also maintained high NOx conversion in the presence of CO2, H2O, and C3H6 in the simulated diesel exhaust. Isolated Cu(2+) ions located in three different sites were responsible for its excellent NH3-SCR activity. Primary results suggest that the one-pot synthesized Cu-SSZ-13 catalyst is a promising candidate as an NH3-SCR catalyst for the NOx abatement from diesel vehicles.

  19. Rotational excitation of symmetric top molecules by collisions with atoms: Close coupling, coupled states, and effective potential calculations for NH3-He

    NASA Technical Reports Server (NTRS)

    Green, S.

    1976-01-01

    The formalism for describing rotational excitation in collisions between symmetric top rigid rotors and spherical atoms is presented both within the accurate quantum close coupling framework and also the coupled states approximation of McGuire and Kouri and the effective potential approximation of Rabitz. Calculations are reported for thermal energy NH3-He collisions, treating NH3 as a rigid rotor and employing a uniform electron gas (Gordon-Kim) approximation for the intermolecular potential. Coupled states are found to be in nearly quantitative agreement with close coupling results while the effective potential method is found to be at least qualitatively correct. Modifications necessary to treat the inversion motion in NH3 are discussed.

  20. Excellent performance of one-pot synthesized Cu-SSZ-13 catalyst for the selective catalytic reduction of NOx with NH3.

    PubMed

    Xie, Lijuan; Liu, Fudong; Ren, Limin; Shi, Xiaoyan; Xiao, Feng-Shou; He, Hong

    2014-01-01

    Cu-SSZ-13 samples prepared by a novel one-pot synthesis method achieved excellent NH3-SCR performance and high N2 selectivity from 150 to 550 °C after ion exchange treatments. The selected Cu3.8-SSZ-13 catalyst was highly resistant to large space velocity (800 000 h(-1)) and also maintained high NOx conversion in the presence of CO2, H2O, and C3H6 in the simulated diesel exhaust. Isolated Cu(2+) ions located in three different sites were responsible for its excellent NH3-SCR activity. Primary results suggest that the one-pot synthesized Cu-SSZ-13 catalyst is a promising candidate as an NH3-SCR catalyst for the NOx abatement from diesel vehicles. PMID:24295053

  1. Diffusion length of photo-generated charge carriers in layers and powders of CH3NH3PbI3 perovskite

    NASA Astrophysics Data System (ADS)

    Dittrich, Th.; Lang, F.; Shargaieva, O.; Rappich, J.; Nickel, N. H.; Unger, E.; Rech, B.

    2016-08-01

    The diffusion or transport lengths of photo-generated charge carriers in CH3NH3PbI3 layers (thickness up to 1 μm) and powders have been directly measured with high accuracy by modulated surface photovoltage after Goodman. The values of the diffusion lengths of photo-generated charge carriers ranged from 200 nm to tenths of μm. In thin CH3NH3PbI3 layers, the transport lengths corresponded to the layer thickness whereas in thicker layers and in crystallites of CH3NH3PbI3 powders the grain size limited the diffusion length. For grains, the diffusion length of photo-generated charge carriers depended on the measurement conditions.

  2. The enhancement for SCR of NO by NH3 over the H2 or CO pretreated Ag/γ-Al2O3 catalyst.

    PubMed

    Yu, Lemeng; Zhong, Qin; Zhang, Shule

    2014-06-28

    H2 or CO pretreatment had been processed on the Ag/γ-Al2O3 catalyst which significantly enhanced its NH3-SCR activity. The main purpose of this study was to prove that the impacts of pretreatment on silver species caused the enhancement. XRD, UV-vis, XPS, in situ FTIR and NO-TPD results showed the relationship between pretreatment, Ag species, NOX adsorption and NOX conversion. Extra nitrates were adsorbed on the Ag clusters which were produced by the pretreatment, thereby enhancing the activity. The reactivities between NO and NH3 had been studied. The difference between CO-pretreatment and H2-pretreatment had also been discussed. Furthermore, the durability and stability of the pretreated sample were tested. Therefore, a modified Ag2O/Al2O3 catalyst for NH3-SCR was researched.

  3. Calibrated Passive Sampling--Multi-plot Field Measurements of NH3 Emissions with a Combination of Dynamic Tube Method and Passive Samplers.

    PubMed

    Pacholski, Andreas

    2016-01-01

    Agricultural ammonia (NH3) emissions (90% of total EU emissions) are responsible for about 45% airborne eutrophication, 31% soil acidification and 12% fine dust formation within the EU15. But NH3 emissions also mean a considerable loss of nutrients. Many studies on NH3 emission from organic and mineral fertilizer application have been performed in recent decades. Nevertheless, research related to NH3 emissions after application fertilizers is still limited in particular with respect to relationships to emissions, fertilizer type, site conditions and crop growth. Due to the variable response of crops to treatments, effects can only be validated in experimental designs including field replication for statistical testing. The dominating ammonia loss methods yielding quantitative emissions require large field areas, expensive equipment or current supply, which restricts their application in replicated field trials. This protocol describes a new methodology for the measurement of NH3 emissions on many plots linking a simple semi-quantitative measuring method used in all plots, with a quantitative method by simultaneous measurements using both methods on selected plots. As a semi-quantitative measurement method passive samplers are used. The second method is a dynamic chamber method (Dynamic Tube Method) to obtain a transfer quotient, which converts the semi-quantitative losses of the passive sampler to quantitative losses (kg nitrogen ha(-1)). The principle underlying this approach is that passive samplers placed in a homogeneous experimental field have the same NH3 absorption behavior under identical environmental conditions. Therefore, a transfer co-efficient obtained from single passive samplers can be used to scale the values of all passive samplers used in the same field trial. The method proved valid under a wide range of experimental conditions and is recommended to be used under conditions with bare soil or small canopies (<0.3 m). Results obtained from

  4. Calibrated Passive Sampling--Multi-plot Field Measurements of NH3 Emissions with a Combination of Dynamic Tube Method and Passive Samplers.

    PubMed

    Pacholski, Andreas

    2016-03-21

    Agricultural ammonia (NH3) emissions (90% of total EU emissions) are responsible for about 45% airborne eutrophication, 31% soil acidification and 12% fine dust formation within the EU15. But NH3 emissions also mean a considerable loss of nutrients. Many studies on NH3 emission from organic and mineral fertilizer application have been performed in recent decades. Nevertheless, research related to NH3 emissions after application fertilizers is still limited in particular with respect to relationships to emissions, fertilizer type, site conditions and crop growth. Due to the variable response of crops to treatments, effects can only be validated in experimental designs including field replication for statistical testing. The dominating ammonia loss methods yielding quantitative emissions require large field areas, expensive equipment or current supply, which restricts their application in replicated field trials. This protocol describes a new methodology for the measurement of NH3 emissions on many plots linking a simple semi-quantitative measuring method used in all plots, with a quantitative method by simultaneous measurements using both methods on selected plots. As a semi-quantitative measurement method passive samplers are used. The second method is a dynamic chamber method (Dynamic Tube Method) to obtain a transfer quotient, which converts the semi-quantitative losses of the passive sampler to quantitative losses (kg nitrogen ha(-1)). The principle underlying this approach is that passive samplers placed in a homogeneous experimental field have the same NH3 absorption behavior under identical environmental conditions. Therefore, a transfer co-efficient obtained from single passive samplers can be used to scale the values of all passive samplers used in the same field trial. The method proved valid under a wide range of experimental conditions and is recommended to be used under conditions with bare soil or small canopies (<0.3 m). Results obtained from

  5. Supramolecular cation assemblies of hydrogen-bonded (NH4+/NH2NH3+)(crown ether) in [Ni(dmit)2]-based molecular conductors and magnets.

    PubMed

    Akutagawa, Tomoyuki; Hasegawa, Tatsuo; Nakamura, Takayoshi; Inabe, Tamotsu

    2002-07-31

    Hydrogen-bonded supramolecular cation assemblies of (NH4+/NH2-NH3+)(crown ether), where the crown ether is [12]crown-4, [15]crown-5, or [18]crown-6, were incorporated into electrically conducting [Ni(dmit)2] salts (dmit2- = 2-thioxo-1,3-dithiole-4,5-dithiolate). (NH4+)([12]crown-4)[Ni(dmit)2]3(CH3CN)2 had a pyramidal shape, while ionic channels were observed in (NH4+)(0.88)([15]crown-5)[Ni(dmit)(2)]2 and (NH4+)(0.70)([18]crown-6)[Ni(dmit)(2)]2. Both (NH4+)(0.88)([15]crown-5) and (NH4+)(0.70)([18]crown-6) contained regularly spaced [Ni(dmit)(2)] stacks formed by N-H.O hydrogen bonding between the oxygen atoms in crown ethers and the NH4+ ion. NH4+ occurred nonstoichiometrically; there were vacant ionic sites in the ionic channels. The ionic radius of NH4+ is larger than the cavity radius of [15]crown-5 and [18]crown-6. Therefore, NH4+ ions could not pass through the cavity and were distributed randomly in the ionic channels. The static disorder caused the conduction electrons to be randomly localized to the [Ni(dmit)2] stacks. Hydrazinium (NH2-NH3+) formed the supramolecular cations in (NH2-NH3+)([12]crown-4)2[Ni(dmit)2]4 and (NH2-NH3+)2([15]crown-5)3[Ni(dmit)2]6, possessing a sandwich and club-sandwich structure, respectively. To the best of our knowledge, these represent the first hydrazinium-crown ether assemblies to be identified in the solid. In the supramolecular cations, hydrogen bonding was detected between the ammonium or the amino protons of NH2-NH3+ and the oxygen atoms of crown ethers. The sandwich-type cations coexisted with the [Ni(dmit)2] dimer stacks. Although the assemblies were typically semiconducting, ferromagnetic interaction (Weiss temperature = +1 K) was detected in the case of (NH2-NH3+)2([15]crown-5)3[Ni(dmit)2]6. The (NH2-NH3+)0.8([18]crown-6)[Ni(dmit)2]2 and (NH4+)0.76([18]crown-6)[Ni(dmit)2]2 crystals were isomorphous. The large and flexible [18]crown-6 allowed for maintaining the same ionic channel structure through replacement of the NH

  6. Partial pressures and nature of products. Application to the photolysis of PH3 and NH3 in the atmosphere of Jupiter and Saturn.

    PubMed

    Guillemin, J C; El Chaouch, S; Bouayad, A; Janati, T

    2001-01-01

    The photolysis of mixtures of gases containing NH3 or PH3 presents important differences mainly due to the strength of the X-H bond. On some examples, these differences are evidenced and the consequences for mixtures of gases containing these two compounds are shown: the photolysis of ammonia and ethylene mainly gives ethyl-, butyl- and hexylamine whereas the photolysis of phosphine and ethylene leads to ethyl- and vinylphosphine. When gaseous mixtures of NH3, PH3 and ethylene are photolyzed together, the presence of phosphine dramatically decreases the formation of nitrogen derivatives. The relevance of such lab studies to the atmospheres of Jupiter and Saturn is discussed.

  7. The use of NH3 to promote the production of large-diameter single-walled carbon nanotubes with a narrow (n,m) distribution.

    PubMed

    Zhu, Zhen; Jiang, Hua; Susi, Toma; Nasibulin, Albert G; Kauppinen, Esko I

    2011-02-01

    We demonstrate here a simple and effective (n,m)-selective growth of single-walled carbon nanotubes (SWCNTs) in an aerosol floating catalyst chemical vapor deposition (CVD) process by introducing a certain amount of ammonia (NH(3)). Chiralities of carbon nanotubes produced in the presence of 500 ppm NH(3) at 880 °C are narrowly distributed around the major semiconducting (13,12) nanotube with over 90% of SWCNTs having large chiral angles in the range 20°-30°, and nearly 50% in the range 27°-29°. The developed synthesis process enables chiral-selective growth at high temperature for structurally stable carbon nanotubes with large diameters.

  8. Impedance Spectroscopic Indication for Solid State Electrochemical Reaction in (CH3NH3)PbI3 Films.

    PubMed

    Zohar, Arava; Kedem, Nir; Levine, Igal; Zohar, Dorin; Vilan, Ayelet; Ehre, David; Hodes, Gary; Cahen, David

    2016-01-01

    Halide perovskite-based solar cells still have limited reproducibility, stability, and incomplete understanding of how they work. We track electronic processes in [CH3NH3]PbI3(Cl) ("perovskite") films in vacuo, and in N2, air, and O2, using impedance spectroscopy (IS), contact potential difference, and surface photovoltage measurements, providing direct evidence for perovskite sensitivity to the ambient environment. Two major characteristics of the perovskite IS response change with ambient environment, viz. -1- appearance of negative capacitance in vacuo or post-vacuo N2 exposure, indicating for the first time an electrochemical process in the perovskite, and -2- orders of magnitude decrease in the film resistance upon transferring the film from O2-rich ambient atmosphere to vacuum. The same change in ambient conditions also results in a 0.5 V decrease in the material work function. We suggest that facile adsorption of oxygen onto the film dedopes it from n-type toward intrinsic. These effects influence any material characterization, i.e., results may be ambient-dependent due to changes in the material's electrical properties and electrochemical reactivity, which can also affect material stability.

  9. Direct Observation of Ferroelectric Domains in Solution-Processed CH3NH3PbI3 Perovskite Thin Films.

    PubMed

    Kutes, Yasemin; Ye, Linghan; Zhou, Yuanyuan; Pang, Shuping; Huey, Bryan D; Padture, Nitin P

    2014-10-01

    A new generation of solid-state photovoltaics is being made possible by the use of organometal-trihalide perovskite materials. While some of these materials are expected to be ferroelectric, almost nothing is known about their ferroelectric properties experimentally. Using piezoforce microscopy (PFM), here we show unambiguously, for the first time, the presence of ferroelectric domains in high-quality β-CH3NH3PbI3 perovskite thin films that have been synthesized using a new solution-processing method. The size of the ferroelectric domains is found to be about the size of the grains (∼100 nm). We also present evidence for the reversible switching of the ferroelectric domains by poling with DC biases. This suggests the importance of further PFM investigations into the local ferroelectric behavior of hybrid perovskites, in particular in situ photoeffects. Such investigations could contribute toward the basic understanding of photovoltaic mechanisms in perovskite-based solar cells, which is essential for the further enhancement of the performance of these promising photovoltaics.

  10. Thermal Assisted Oxygen Annealing for High Efficiency Planar CH3NH3PbI3 Perovskite Solar Cells

    PubMed Central

    Ren, Zhiwei; Ng, Annie; Shen, Qian; Gokkaya, Huseyin Cem; Wang, Jingchuan; Yang, Lijun; Yiu, Wai-Kin; Bai, Gongxun; Djurišić, Aleksandra B.; Leung, Wallace Woon-fong; Hao, Jianhua; Chan, Wai Kin; Surya, Charles

    2014-01-01

    We report investigations on the influences of post-deposition treatments on the performance of solution-processed methylammonium lead triiodide (CH3NH3PbI3)-based planar solar cells. The prepared films were stored in pure N2 at room temperature or annealed in pure O2 at room temperature, 45°C, 65°C and 85°C for 12 hours prior to the deposition of the metal electrodes. It is found that annealing in O2 leads to substantial increase in the power conversion efficiencies (PCEs) of the devices. Furthermore, strong dependence on the annealing temperature for the PCEs of the devices suggests that a thermally activated process may underlie the observed phenomenon. It is believed that the annealing process may facilitate the diffusion of O2 into the spiro-MeOTAD for inducing p-doping of the hole transport material. Furthermore, the process can result in lowering the localized state density at the grain boundaries as well as the bulk of perovskite. Utilizing thermal assisted O2 annealing, high efficiency devices with good reproducibility were attained. A PCE of 15.4% with an open circuit voltage (VOC) 1.04 V, short circuit current density (JSC) 23 mA/cm2, and fill factor 0.64 had been achieved for our champion device. PMID:25341527

  11. Kinetics and Mechanisms of the Acid-base Reaction Between NH3 and HCOOH in Interstellar Ice Analogs

    NASA Astrophysics Data System (ADS)

    Bergner, Jennifer B.; Öberg, Karin I.; Rajappan, Mahesh; Fayolle, Edith C.

    2016-10-01

    Interstellar complex organic molecules are commonly observed during star formation, and are proposed to form through radical chemistry in icy grain mantles. Reactions between ions and neutral molecules in ices may provide an alternative cold channel to complexity, as ion-neutral reactions are thought to have low or even no-energy barriers. Here we present a study of the kinetics and mechanisms of a potential ion-generating, acid-base reaction between NH3 and HCOOH to form the salt NH{}4+HCOO-. We observe salt growth at temperatures as low as 15 K, indicating that this reaction is feasible in cold environments. The kinetics of salt growth are best fit by a two-step model involving a slow “pre-reaction” step followed by a fast reaction step. The reaction energy barrier is determined to be 70 ± 30 K with a pre-exponential factor 1.4 ± 0.4 × 10-3 s-1. The pre-reaction rate varies under different experimental conditions and likely represents a combination of diffusion and orientation of reactant molecules. For a diffusion-limited case, the pre-reaction barrier is 770 ± 110 K with a pre-exponential factor of ˜7.6 × 10-3 s-1. Acid-base chemistry of common ice constituents is thus a potential cold pathway to generating ions in interstellar ices.

  12. Nonvolatile Bipolar Resistive Switching Behavior in the Perovskite-like (CH3NH3)2FeCl4.

    PubMed

    Lv, Fengzhen; Gao, Cunxu; Zhou, Heng-An; Zhang, Peng; Mi, Kui; Liu, Xiaoxing

    2016-07-27

    The bipolar resistive switching behavior in a device based on an crystalline iron-based organic-inorganic, perovskite-like material of (CH3NH3)2FeCl4 (MAFC), was examined and studied. Both high and low resistance states appeared to have no obvious degradation during a measurement period of 600 s with 400 cycles in a Ag/MAFC/Cu device, which also exhibited good thermal stability over a wide temperature range of 290 to 340 K. The conductivity-state switching behavior was derived from the competition between the ionic current within the MAFC and the Faradaic current that originated from oxidative reactions at the Ag/MAFC/Cu interface. A model explaining the oxidative reaction process was established to describe the symmetric resistive switching behavior in the Ag/MAFC/Cu cell. With an applied bias voltage sweeping, the oxidative layers passivated and dissipated at the Ag/MAFC/Cu interface that resulted in the competition between the induced current and the ionic current, and thus caused a symmetric resistance change. On the basis of this interfacial effect, the MAFC crystals can be used as memristor elements in devices for write-read-erase-rewrite process. PMID:27414403

  13. Stable and durable CH3NH3PbI3 perovskite solar cells at ambient conditions

    NASA Astrophysics Data System (ADS)

    Rajamanickam, Nagalingam; Kumari, Sudesh; Kalyan Vendra, Venkat; Lavery, Brandon W.; Spurgeon, Joshua; Druffel, Thad; Sunkara, Mahendra K.

    2016-06-01

    Degradation of metal‑organic halide perovskites when exposed to ambient conditions is a crucial issue that needs to be addressed for commercial viability of perovskite solar cells (PSCs). Here, a concept of encapsulating CH3NH3PbI3 perovskite crystals with a multi-functional graphene–polyaniline (PANI) composite coating to protect the perovskite against degradation from moisture, oxygen and UV light is presented. Hole-conducting polymers containing 2D layered sheet materials are presented here as multi-functional materials with oxygen and moisture impermeability. Specific studies involving PANI and graphene composites as coatings for perovskite crystals exhibited resistance to moisture and oxygen under continued exposure to UV and visible light. Most importantly, no perovskite degradation was observed even after 96 h of exposure of the PSCs to extremely high humidity (99% relative humidity). Our observations and results on perovskite protection with graphene/conducting polymer composites open up opportunities for glove-box-free and atmospheric processing of PSCs.

  14. Stable and durable CH3NH3PbI3 perovskite solar cells at ambient conditions

    NASA Astrophysics Data System (ADS)

    Rajamanickam, Nagalingam; Kumari, Sudesh; Kalyan Vendra, Venkat; Lavery, Brandon W.; Spurgeon, Joshua; Druffel, Thad; Sunkara, Mahendra K.

    2016-06-01

    Degradation of metal-organic halide perovskites when exposed to ambient conditions is a crucial issue that needs to be addressed for commercial viability of perovskite solar cells (PSCs). Here, a concept of encapsulating CH3NH3PbI3 perovskite crystals with a multi-functional graphene-polyaniline (PANI) composite coating to protect the perovskite against degradation from moisture, oxygen and UV light is presented. Hole-conducting polymers containing 2D layered sheet materials are presented here as multi-functional materials with oxygen and moisture impermeability. Specific studies involving PANI and graphene composites as coatings for perovskite crystals exhibited resistance to moisture and oxygen under continued exposure to UV and visible light. Most importantly, no perovskite degradation was observed even after 96 h of exposure of the PSCs to extremely high humidity (99% relative humidity). Our observations and results on perovskite protection with graphene/conducting polymer composites open up opportunities for glove-box-free and atmospheric processing of PSCs.

  15. Ab initio simulation of ammonia monohydrate (NH3ṡH2O) and ammonium hydroxide (NH4OH)

    NASA Astrophysics Data System (ADS)

    Fortes, A. D.; Brodholt, J. P.; Wood, I. G.; Vočadlo, L.; Jenkins, H. D. B.

    2001-10-01

    We report the results of the first pseudopotential plane-wave simulations of the static properties of ammonia monohydrate phase I (AMH I) and ammonium hydroxide. Our calculated fourth-order logarithmic equation of state, at zero pressure and temperature, has molar volume, V0=36.38(3) cm3 mol-1, bulk modulus, K0=9.59(9) GPa, and the first derivative of the bulk modulus with respect to pressure, K0'=5.73(21). Both this and the lattice parameters are in very good agreement with experimental values. The monohydrate transforms, via a solid-state proton transfer reaction, to ammonium hydroxide (NH4OH) at 5.0(4) GPa. The equation of state of ammonium hydroxide is, V0=31.82(5) cm3 mol-1, K0=14.78(62) GPa, K0'=2.69(48). We calculate the reaction enthalpy, ΔH(NH4OH,s→NH3ṡH2O,s)=-14.8(5) kJ mol-1 at absolute zero, and thus estimate the enthalpy of formation, ΔfH⊖(NH4OH,s)=-356 kJ mol-1 at 298 K. This result places an upper limit of 84 kJ mol-1 on the barrier to rotation of the ammonium cation, and yields an average hydrogen bond enthalpy of ˜23 kJ mol-1.

  16. High intrinsic carrier mobility and photon absorption in the perovskite CH3NH3PbI3.

    PubMed

    Wang, Youwei; Zhang, Yubo; Zhang, Peihong; Zhang, Wenqing

    2015-05-01

    The carrier transport and optical properties of the hybrid organic-inorganic perovskite CH3NH3PbI3 are investigated using first-principles approaches. We found that the electron and hole mobilities could reach surprisingly high values of 7-30 × 10(3) and 1.5-5.5 × 10(3) cm(2) V(-1) s(-1), respectively, and both are estimated to be much higher than the current experimental measurements. The high carrier mobility is ascribed to the intrinsically small effective masses of anti-bonding band-edge states. The above results imply that there is still space to improve the performance of related solar cells. This material also has a sharp photon absorption edge and an absorption coefficient as high as 10(5) cm(-1), both of which contribute to effective utilization of solar radiation. Although band-edge states are mainly derived from the inorganic ions of Pb and I, thermal movement of the organic base has indirect influences on the bandgap and carrier effective masses, resulting in the temperature-dependent solar cell efficiencies. PMID:25855411

  17. Dynamics study of the OH + NH3 hydrogen abstraction reaction using QCT calculations based on an analytical potential energy surface

    NASA Astrophysics Data System (ADS)

    Monge-Palacios, M.; Corchado, J. C.; Espinosa-Garcia, J.

    2013-06-01

    To understand the reactivity and mechanism of the OH + NH3 → H2O + NH2 gas-phase reaction, which evolves through wells in the entrance and exit channels, a detailed dynamics study was carried out using quasi-classical trajectory calculations. The calculations were performed on an analytical potential energy surface (PES) recently developed by our group, PES-2012 [Monge-Palacios et al. J. Chem. Phys. 138, 084305 (2013)], 10.1063/1.4792719. Most of the available energy appeared as H2O product vibrational energy (54%), reproducing the only experimental evidence, while only the 21% of this energy appeared as NH2 co-product vibrational energy. Both products appeared with cold and broad rotational distributions. The excitation function (constant collision energy in the range 1.0-14.0 kcal mol-1) increases smoothly with energy, contrasting with the only theoretical information (reduced-dimensional quantum scattering calculations based on a simplified PES), which presented a peak at low collision energies, related to quantized states. Analysis of the individual reactive trajectories showed that different mechanisms operate depending on the collision energy. Thus, while at high energies (Ecoll ≥ 6 kcal mol-1) all trajectories are direct, at low energies about 20%-30% of trajectories are indirect, i.e., with the mediation of a trapping complex, mainly in the product well. Finally, the effect of the zero-point energy constraint on the dynamics properties was analyzed.

  18. A cation trap for anodic stripping voltammetry: NH3-plasma treated carbon nanotubes for adsorption and detection of metal ions.

    PubMed

    Wei, Yan; Yang, Ran; Chen, Xing; Wang, Lun; Liu, Jin-Huai; Huang, Xing-Jiu

    2012-11-28

    NH(3)-plasma treated multi-walled carbon nanotubes (pn-MWCNTs) with cation traps for the detection of ultratrace quantities of Zn(II), Cd(II), Cu(II), and Hg(II) using square wave anodic stripping voltammetry (SWASV) is described. The pn-MWCNTs use their adsorption performance to enhance the sensitivity. It is found that under optimized conditions Zn(II), Cd(II), Cu(II) and Hg(II) were individually detected at potentials of -1.16, -0.78, -0.268 and 0.108 V, respectively. The detection limit (3σ method) of 0.314, 0.0272, 0.2263, and 0.1439 nM toward Zn(II), Cd(II), Cu(II), and Hg(II) is achievable, respectively. No interference could be seen during the simultaneous detection of Zn(II), Cd(II), Cu(II), and Hg(II). The pn-MWCNTs exhibit excellent selectivity owing to the different ability of adsorption. A study of the ability of pn-MWCNTs in practical application is carried out using a sample of water collected from Dongpu Reservoir in Hefei City, Anhui, China. It is found that the results were favorable when compared against inductively coupled plasma atomic emission spectrometry (ICP-AES) analysis.

  19. Emissions of Volatile Inorganic Halogens, Carboxylic Acids, NH3, and SO2 From Experimental Burns of Southern African Biofuels

    NASA Astrophysics Data System (ADS)

    Keene, W. C.; Lobert, J. M.; Lobert, J. M.; Maben, J. R.; Scharffe, D. H.; Crutzen, P. J.; Crutzen, P. J.

    2001-12-01

    As part of SAFARI 2000, biofuels (savanna grasses, shrubs, woody plants, litter, agricultural waste, and charcoal) were sampled during late summer and early autumn in the savannah of Kruger National Park, the Kalahari of Etosha National Park, and the Miombo woodlands in Zambia and Malawi. Sixty subsamples were experimentally burned under semi-controlled conditions at the Max Planck Institute for Chemistry in Mainz, Germany. Emissions were sampled with tandem mist chambers to quantify HCl, CH3COOH, HCOOH, NH3, and SO2 and with a high-volume filter pack to quantify volatile inorganic Cl, Br, and I. The elemental compositions of the fuel and ash from each burn were also analyzed. Molar emission ratios of these species relative to CO, CO2, and the elemental composition of the fuel will be calculated and used to estimate regional emissions from biomass burning over southern Africa. The relative contributions of each species to elemental mass balances during burns will also be assessed. >http://jurgenlobert.org/projects/mpi_safari/ and

  20. TiO2 nanotube-supported cu as the catalyst for selective NO reduction with NH3.

    PubMed

    Chen, Shin-An; Nian, Jun-Nan; Tsai, Chien-Cheng; Teng, Hsisheng

    2007-05-01

    Catalyst supports composed of titanate nanotubes were prepared from hydrothermal treatment on TiO2 nanoparticles in NaOH followed by HCl washing. The nanotubes exhibited well-defined TiO2 anatase phase after calcination at 400 degrees C. The nanotube aggregates and other commercially available TiO2 nanoparticles, all with surface areas >300 m(2)/g, were impregnated with Cu and examined in selective catalytic reduction of NO with NH3. In catalyst preparation, the nanotubes were found to be more thermally stable than nanoparticles, withstanding agglomeration at elevated temperatures. The Cu species supported on the nanotubes showed a higher catalytic activity than those supported on the nanoparticles. Analysis with temperature programmed reduction, X-ray photoelectron spectroscopy, and NO adsorption reflected that the layered-titanate feature of the tube wall was advantageous for even distribution of the Cu species, thus leading to the high-catalytic activity of the tubular Cu/TiO2 catalyst.

  1. Mn-CeOx/Ti-PILCs for selective catalytic reduction of NO with NH3 at low temperature.

    PubMed

    Shen, Boxiong; Ma, Hongqing; Yao, Yan

    2012-01-01

    Titanium-pillared clays (Ti-PILCs) were obtained by different ways from TiCl4, Ti(OC3H7)4 and TiOSO4, respectively. Mn-CeO(x)/)Ti-PILCs were then prepared and their activities of selective catalytic reduction (SCR) of NO with NH3 at low-temperature were evaluated. Mn-CeO(x)/Ti-PILCs were characterized by X-ray diffraction, N2 adsorption, Fourier transform infrared spectroscopy, thermal analysis, temperature-programmed desorption of ammonia and H2-temperature-programmed reduction. It was found that Ti-pillar tend to be helpful for the enlargement of surface area, pore volume, acidity and the enhancement of thermal stability for Mn-CeO(x)/Ti-PILCs. Mn-CeO(x)/Ti-PILCs catalysts were active for the SCR of NO. Among three resultant Mn-CeO(x)/Ti-PILCs, the catalyst from TiOSO4 showed the highest activity with 98% NO conversion at 220 degrees C, it also exhibited good resistance to H2O and SO2 in flue gas. The catalyst from TiCl4 exhibited the lowest activity due to the unsuccessful pillaring process.

  2. Density Functional Studies of Stoichiometric Surfaces of Orthorhombic Hybrid Perovskite CH3NH3PbI3

    DOE PAGES

    Wang, Yun; Huang, Jingsong; Sumpter, Bobby G.; Zhang, Haimin; Liu, Porun; Yang, Huagui; Zhao, Huijun

    2014-12-19

    Organic/inorganic hybrid perovskite materials are highly attractive for dye-sensitized solar cells as demonstrated by their rapid advances in energy conversion efficiency. In this work, the structures, energetics, and electronic properties for a range of stoichiometric surfaces of the orthorhombic perovskite CH3NH3PbI3 are theoretically studied using density functional theory. Various possible spatially and constitutionally isomeric surfaces are considered by diversifying the spatial orientations and connectivities of surface Pb-I bonds. The comparison of the surface energies for the most stable configurations identified for various surfaces shows that the stabilities of stoichiometric surfaces are mainly dictated by the coordination numbers of surface atoms,more » which are directly correlated with the numbers of broken bonds. Additionally, Coulombic interactions between I anions and organic countercations on the surface also contribute to the stabilization. Electronic properties are compared between the most stable (100) surface and the bulk phase, showing generally similar features except for the lifted band degeneracy and the enhanced bandgap energy for the surface. These studies on the stoichiometric surfaces serve as the first step toward gaining a fundamental understanding of the interfacial properties in the current structural design of perovskite based solar cells, in order to achieve further breakthroughs in solar conversion efficiencies.« less

  3. Density Functional Studies of Stoichiometric Surfaces of Orthorhombic Hybrid Perovskite CH3NH3PbI3

    SciTech Connect

    Wang, Yun; Huang, Jingsong; Sumpter, Bobby G.; Zhang, Haimin; Liu, Porun; Yang, Huagui; Zhao, Huijun

    2014-12-19

    Organic/inorganic hybrid perovskite materials are highly attractive for dye-sensitized solar cells as demonstrated by their rapid advances in energy conversion efficiency. In this work, the structures, energetics, and electronic properties for a range of stoichiometric surfaces of the orthorhombic perovskite CH3NH3PbI3 are theoretically studied using density functional theory. Various possible spatially and constitutionally isomeric surfaces are considered by diversifying the spatial orientations and connectivities of surface Pb-I bonds. The comparison of the surface energies for the most stable configurations identified for various surfaces shows that the stabilities of stoichiometric surfaces are mainly dictated by the coordination numbers of surface atoms, which are directly correlated with the numbers of broken bonds. Additionally, Coulombic interactions between I anions and organic countercations on the surface also contribute to the stabilization. Electronic properties are compared between the most stable (100) surface and the bulk phase, showing generally similar features except for the lifted band degeneracy and the enhanced bandgap energy for the surface. These studies on the stoichiometric surfaces serve as the first step toward gaining a fundamental understanding of the interfacial properties in the current structural design of perovskite based solar cells, in order to achieve further breakthroughs in solar conversion efficiencies.

  4. Ionic polarization-induced current-voltage hysteresis in CH3NH3PbX3 perovskite solar cells.

    PubMed

    Meloni, Simone; Moehl, Thomas; Tress, Wolfgang; Franckevičius, Marius; Saliba, Michael; Lee, Yong Hui; Gao, Peng; Nazeeruddin, Mohammad Khaja; Zakeeruddin, Shaik Mohammed; Rothlisberger, Ursula; Graetzel, Michael

    2016-02-01

    CH3NH3PbX3 (MAPbX3) perovskites have attracted considerable attention as absorber materials for solar light harvesting, reaching solar to power conversion efficiencies above 20%. In spite of the rapid evolution of the efficiencies, the understanding of basic properties of these semiconductors is still ongoing. One phenomenon with so far unclear origin is the so-called hysteresis in the current-voltage characteristics of these solar cells. Here we investigate the origin of this phenomenon with a combined experimental and computational approach. Experimentally the activation energy for the hysteretic process is determined and compared with the computational results. First-principles simulations show that the timescale for MA(+) rotation excludes a MA-related ferroelectric effect as possible origin for the observed hysteresis. On the other hand, the computationally determined activation energies for halide ion (vacancy) migration are in excellent agreement with the experimentally determined values, suggesting that the migration of this species causes the observed hysteretic behaviour of these solar cells.

  5. Two mixed-NH3/amine platinum (II) anticancer complexes featuring a dichloroacetate moiety in the leaving group

    PubMed Central

    Liu, Weiping; Su, Jia; Jiang, Jing; Li, Xingyao; Ye, Qingsong; Zhou, Hongyu; Chen, Jialin; Li, Yan

    2013-01-01

    Two mixed-NH3/amine platinum (II) complexes of 3-dichoroacetoxylcyclobutane-1, 1-dicarboxylate have been prepared in the present study and characterized by elemental analysis and IR, HPLC-MS and 1H, 13C-NMR. The complexes exist in equilibrium between two position isomeric forms and undergo hydrolysis reaction in aqueous solution, releasing the platinum pharmacophores and dichloroacetate which is a small-molecular cell apoptosis inducer. Both complexes were evaluated for in vitro cytotoxic profile in A549, SGC-7901 and SK-OV-3 caner cells as well as in BEAS-2B normal cells. They exhibit markedly cytoxicity toward cancer cells by selectively inducing the apoptosis of cancer cells, whereas leaving normal cells less affected. They have also the ability to overcome the resistance of SK-OV-3 cancer cells to cisplatin. Our findings offer an alternative novel way to develop platinum drugs which can both overcome the drug resistance and selectively target tumor cells. PMID:23955304

  6. Effects of SO2 on selective catalytic reduction of NO with NH3 over a TiO2 photocatalyst

    NASA Astrophysics Data System (ADS)

    Yamamoto, Akira; Teramura, Kentaro; Hosokawa, Saburo; Tanaka, Tsunehiro

    2015-04-01

    The effect of SO2 gas was investigated on the activity of the photo-assisted selective catalytic reduction of nitrogen monoxide (NO) with ammonia (NH3) over a TiO2 photocatalyst in the presence of excess oxygen (photo-SCR). The introduction of SO2 (300 ppm) greatly decreased the activity of the photo-SCR at 373 K. The increment of the reaction temperature enhanced the resistance to SO2 gas, and at 553 K the conversion of NO was stable for at least 300 min of the reaction. X-ray diffraction, FTIR spectroscopy, thermogravimetry and differential thermal analysis, x-ray photoelectron spectroscopy (XPS), elemental analysis and N2 adsorption measurement revealed that the ammonium sulfate species were generated after the reaction. There was a strong negative correlation between the deposition amount of the ammonium sulfate species and the specific surface area. Based on the above relationship, we concluded that the deposition of the ammonium sulfate species decreased the specific surface area by plugging the pore structure of the catalyst, and the decrease of the specific surface area resulted in the deactivation of the catalyst.

  7. Clumped-isotope signatures at equilibrium of CH4, NH3, H2O, H2S and SO2

    NASA Astrophysics Data System (ADS)

    Liu, Qi; Liu, Yun

    2016-02-01

    High precision Δi values at equilibrium determined by theoretical methods are imperatively needed as references for the development of new clumped-isotope thermometers (or tracers). In this study, quantum chemistry methods with corrections beyond the harmonic approximation are used to obtain the clumped-isotope signatures at equilibrium of several gas-phase molecules (i.e., CH4, NH3, H2O, H2S, and SO2). Here, we consider as many corrections to the traditional Bigeleisen-Mayer equation as possible to obtain accurate Δi values at equilibrium and their temperature dependences. The corrections include anharmonic correction for zero-point energy, anharmonic correction for vibrational excited states, vibration-rotation coupling correction for zero-point energy, vibration-rotation coupling correction for vibrational excited states, quantum mechanical correction to rotation, and centrifugal distortion correction, which are important for theoretical understanding of clumped-isotope signals. Specifically, molecular constants are calculated via second-order perturbative analysis at the MP2/aug-cc-pVTZ level. The CCSD/6-311+G(3df,3pd) and CCSD/aug-cc-pVTZ levels are further employed to ensure the precision of harmonic frequencies of methane. For methane, a polynomial fit of ΔCH133D values over the temperature range of from 273.15 to 1000 K is obtained:

  8. Dynamics study of the OH + NH3 hydrogen abstraction reaction using QCT calculations based on an analytical potential energy surface.

    PubMed

    Monge-Palacios, M; Corchado, J C; Espinosa-Garcia, J

    2013-06-01

    To understand the reactivity and mechanism of the OH + NH3 → H2O + NH2 gas-phase reaction, which evolves through wells in the entrance and exit channels, a detailed dynamics study was carried out using quasi-classical trajectory calculations. The calculations were performed on an analytical potential energy surface (PES) recently developed by our group, PES-2012 [Monge-Palacios et al. J. Chem. Phys. 138, 084305 (2013)]. Most of the available energy appeared as H2O product vibrational energy (54%), reproducing the only experimental evidence, while only the 21% of this energy appeared as NH2 co-product vibrational energy. Both products appeared with cold and broad rotational distributions. The excitation function (constant collision energy in the range 1.0-14.0 kcal mol(-1)) increases smoothly with energy, contrasting with the only theoretical information (reduced-dimensional quantum scattering calculations based on a simplified PES), which presented a peak at low collision energies, related to quantized states. Analysis of the individual reactive trajectories showed that different mechanisms operate depending on the collision energy. Thus, while at high energies (E(coll) ≥ 6 kcal mol(-1)) all trajectories are direct, at low energies about 20%-30% of trajectories are indirect, i.e., with the mediation of a trapping complex, mainly in the product well. Finally, the effect of the zero-point energy constraint on the dynamics properties was analyzed.

  9. Ionic polarization-induced current-voltage hysteresis in CH3NH3PbX3 perovskite solar cells.

    PubMed

    Meloni, Simone; Moehl, Thomas; Tress, Wolfgang; Franckevičius, Marius; Saliba, Michael; Lee, Yong Hui; Gao, Peng; Nazeeruddin, Mohammad Khaja; Zakeeruddin, Shaik Mohammed; Rothlisberger, Ursula; Graetzel, Michael

    2016-01-01

    CH3NH3PbX3 (MAPbX3) perovskites have attracted considerable attention as absorber materials for solar light harvesting, reaching solar to power conversion efficiencies above 20%. In spite of the rapid evolution of the efficiencies, the understanding of basic properties of these semiconductors is still ongoing. One phenomenon with so far unclear origin is the so-called hysteresis in the current-voltage characteristics of these solar cells. Here we investigate the origin of this phenomenon with a combined experimental and computational approach. Experimentally the activation energy for the hysteretic process is determined and compared with the computational results. First-principles simulations show that the timescale for MA(+) rotation excludes a MA-related ferroelectric effect as possible origin for the observed hysteresis. On the other hand, the computationally determined activation energies for halide ion (vacancy) migration are in excellent agreement with the experimentally determined values, suggesting that the migration of this species causes the observed hysteretic behaviour of these solar cells. PMID:26852685

  10. Ionic polarization-induced current–voltage hysteresis in CH3NH3PbX3 perovskite solar cells

    PubMed Central

    Meloni, Simone; Moehl, Thomas; Tress, Wolfgang; Franckevičius, Marius; Saliba, Michael; Lee, Yong Hui; Gao, Peng; Nazeeruddin, Mohammad Khaja; Zakeeruddin, Shaik Mohammed; Rothlisberger, Ursula; Graetzel, Michael

    2016-01-01

    CH3NH3PbX3 (MAPbX3) perovskites have attracted considerable attention as absorber materials for solar light harvesting, reaching solar to power conversion efficiencies above 20%. In spite of the rapid evolution of the efficiencies, the understanding of basic properties of these semiconductors is still ongoing. One phenomenon with so far unclear origin is the so-called hysteresis in the current–voltage characteristics of these solar cells. Here we investigate the origin of this phenomenon with a combined experimental and computational approach. Experimentally the activation energy for the hysteretic process is determined and compared with the computational results. First-principles simulations show that the timescale for MA+ rotation excludes a MA-related ferroelectric effect as possible origin for the observed hysteresis. On the other hand, the computationally determined activation energies for halide ion (vacancy) migration are in excellent agreement with the experimentally determined values, suggesting that the migration of this species causes the observed hysteretic behaviour of these solar cells. PMID:26852685

  11. Photoluminescence characterisations of a dynamic aging process of organic-inorganic CH3NH3PbBr3 perovskite.

    PubMed

    Sheng, R; Wen, X; Huang, S; Hao, X; Chen, S; Jiang, Y; Deng, X; Green, M A; Ho-Baillie, A W Y

    2016-01-28

    After unprecedented development of organic-inorganic lead halide perovskite solar cells over the past few years, one of the biggest barriers towards their commercialization is the stability of the perovskite material. It is thus important to understand the interaction between the perovskite material and oxygen and/or humidity and the associated degradation process in order to improve device and encapsulation design for better durability. Here we characterize the dynamic aging process in vapour-assisted deposited (VASP) CH3NH3PbBr3 perovskite thin films using advanced optical techniques, such as time-resolved photoluminescence and fluorescence lifetime imaging microscopy (FLIM). Our investigation reveals that the perovskite grains grow spontaneously and the larger grains are formed at room temperature in the presence of moisture and oxygen. This crystallization process leads to a higher density of defects and a shorter carrier lifetime, specifically in the larger grains. Excitation-intensity-dependent steady-state photoluminescence shows both N2 stored and aged perovskite exhibit a super-linear increase of photoluminescence intensity with increasing excitation intensity; and the larger slope in aged sample suggests a larger density of defects is generated, consistent with time-resolved PL measurements. PMID:26753563

  12. Structure cristalline et etude par spectrometrie de vibration (IR et Raman) du bis(ethylenediammonium) diphosphate (NH 3(CH 2) 2NH 3) 2 · P 2O 7

    NASA Astrophysics Data System (ADS)

    Kamoun, Slaheddine; Jouini, Amor; Daoud, Abdelaziz

    1992-07-01

    Classical methods extensively known for the synthesis of inorganic condensed phosphates are used to give compounds that are intermediate between inorganic and organic. We prepared the title compound to examine the possibility of using, in this new field, the ion exchange resin and Boullé's methods. Chemical preparation, crystal structure, and vibrational studies are given for a new diphosphate. The bis(ethylenediammonium) diphosphate salt is monoclinic with the unit cell dimensions a = 8.724(1), b = 13.511(2), c = 10.039(1)Å, β = 96.25(1)°, V = 1176.3(5)Å 3, Dm = 1.673Mg m -3, D x = 1.684Mg m -3, μ = 2.163 mm -1, space group C2 c with Z = 4. The structure was solved by the Patterson method and refined to a final R value of 0.059 for 2602 observed independent reflections. The P sbnd O(L) sbnd P bridge is symmetrical with a P sbnd O(L) distance of 1.570(1)Åand a POP angle of 141.94(7)°. The P 2O 4-7 anions are located around the twofold axis. The ethylenediammonium dications have a trans configuration. Half of them, having a crystallographic inversion center, are located in channels delimited by the diphosphate anions. The others, located around the twofold axis, are sandwiched along the c axis between two diphosphate anions. The cohesion and the stability of the atomic arrangement result from the N sbnd H···O hydrogen bonds. The IR and Raman spectra of [NH 3(CH) 2NH 32 · P 2O 7 are recorded and analyzed. From the spectra it is inferred that the P 2O 4-7 anion has a C2 symmetry in the crystal; all the POP modes (stretching and bending) are active in IR and Raman.

  13. Synthesis, crystal structure, thermal analysis, vibrational study dielectric behaviour and Hirshfeld surface analysis of [C6H10(NH3)2)]2 SnCl6 (Cl)2

    NASA Astrophysics Data System (ADS)

    Mkaouar, Imen; Karâa, Najla; Hamdi, Besma; Zouari, Ridha

    2016-07-01

    A new organotin (IV), bis 1-2 diammonium cyclohexane octachlorotin dichloride, have been synthesized. The molecular structures of the complexes have been determined using single crystal X-ray diffraction analysis reveals that complexes crystallizes in orthorhombic space group P4/n with a = 13.014(3)Å, b = 13.014(3), c = 16.822(4)Å, V = 2849.0(11)Å3. The structure consists of three-dimensional tanks framework. They show further that the tin (IV) ion is octahedral surrounded by six atoms with six chloride ligands, tow [C6H10(NH3)2]2+ cations and tow isolated chloride ion Cl-. The new compound has been characterized by differential scanning calorimetric (DSC) technique, 13C MAS-NMR, FT-IR, RAMAN spectroscopic studies and dielectric properties are detected in the frequency interval of 209 Hz-5 MHz and in the temperature interval of 313-373 K, have been carried out in order to characterize the complexes, the Hirschfeld surface analysis have been performed to gain insight into the behavior of these weak interactions.

  14. Surface study and sensing activity of nanotubular indium trioxide to NH3, H2S, NO2 and CO environmental pollutants

    NASA Astrophysics Data System (ADS)

    Zamani, Mehdi

    2016-02-01

    Molecular and electronic structures of nanotubular indium trioxide were studied using B3LYP and CAM-B3LYP density functional methods. Three nanotube models including nanotubes with closed ends (CENT), one opened end (OOENT) and two opened ends (TOENT) were considered. The highest occupied molecular orbital (HOMO) of CENT is distributed over the entire nanotube; while it is distributed on the end cap of OOENT. In both CENT and OOENT, the distribution of the lowest unoccupied molecular orbital (LUMO) is on the end caps. HOMO and LUMO of TOENT are distributed on the center of nanotube. The sensing activity of OOENT to environmental pollutants was evaluated regarding the interaction of nanotube with NH3, H2S, NO2 and CO molecules. Adsorptions over different positions of OOENT are exothermic and the NH3 adsorption is thermodynamically more favorable. The selectivity of OOENT toward gaseous pollutants is investigated as NH3 > H2S > CO > NO2. Interaction of NO2 and CO over the closed end (end cap) of nanotube is preferred; while adsorption of NH3 and H2S on the opened end is more favorable.

  15. Perovskite CH3NH3PbI3(Cl) Single Crystals: Rapid Solution Growth, Unparalleled Crystalline Quality, and Low Trap Density toward 10(8) cm(-3).

    PubMed

    Lian, Zhipeng; Yan, Qingfeng; Gao, Taotao; Ding, Jie; Lv, Qianrui; Ning, Chuangang; Li, Qiang; Sun, Jia-Lin

    2016-08-01

    Single crystal reflects the intrinsic physical properties of a material, and single crystals with high-crystalline quality are highly desired for the acquisition of high-performance devices. We found that large single crystals of perovskite CH3NH3PbI3(Cl) could be grown rapidly from chlorine-containing solutions. Within 5 days, CH3NH3PbI3(Cl) single crystal as large as 20 mm × 18 mm × 6 mm was harvested. As a most important index to evaluate the crystalline quality, the full width at half-maximum (fwhm) in the high-resolution X-ray rocking curve (HR-XRC) of as-grown CH3NH3PbI3(Cl) single crystal was measured as 20 arcsec, which is far superior to so far reported CH3NH3PbI3 single crystals (∼1338 arcsec). The unparalleled crystalline quality delivered a low trap-state density of down to 7.6 × 10(8) cm(-3), high carrier mobility of 167 ± 35 cm(2) V(-1) s(-1), and long transient photovoltaic carrier lifetime of 449 ± 76 μs. The improvement in the crystalline quality, together with the rapid growth rate and excellent carrier transport property, provides state-of-the-art single crystalline hybrid perovskite materials for high-performance optoelectronic devices. PMID:27458057

  16. Tuning superior solar cell performance of carrier mobility and absorption in perovskite CH3NH3GeCl3: A density functional calculations

    NASA Astrophysics Data System (ADS)

    Zhao, Yu-Qing; Wu, Li-Juan; Liu, Biao; Wang, Ling-Zhi; He, Peng-Bin; Cai, Meng-Qiu

    2016-05-01

    The solar cell based on hybrid organic-inorganic halide perovskite has received considerable attention. One of the most important issues in the pursuit of further developments in this area is to obtain both a high carrier mobility and an excellent ability of light adsorption. In this paper, we investigate the electronic structure and electronic effective masses of the new non-toxic material CH3NH3GeCl3 by first-principle calculations. The results show that the absorption efficiency of CH3NH3GeCl3 is more superior to that of CH3NH3PbI3 in short wavelength region. We trace this result to the ferroelectricity caused by the more serious octahedral GeCl6- distortion. We also discover a new relationship between the carrier effective masses anisotropy and the anisotropy of electronic density of states along three principal directions. Moreover, while applied the isotropic compressive pressure, the absorption efficiency and carrier mobility of CH3NH3GeCl3 in orthorhombic phase are improved greatly due to changes of electronic structure. We speculate that these are general results of tuning of the carrier mobility by controlling the band gap and the electronic occupation along different directions, to obtain both a high carrier mobility and an excellent ability of light adsorption.

  17. Substitution Reactions of the Aluminum Chlorogermylenoid H2GeClAlCl2 with HF, H2O, NH3, HCl, H2S, and PH3.

    PubMed

    Yan, Bingfei; Zhang, Mingxia; Li, Wenzuo; Xiao, Cuiping; Li, Qingzhong; Cheng, Jianbo

    2016-01-01

    Quantum chemical calculations have been performed for the substitution reactions of the aluminum chlorogermylenoid H2GeClAlCl2 with HF, H2O, NH3, HCl, H2S, and PH3 to get more insights into the reactivity of H2GeClAlCl2. The theoretical calculated results indicated that the substitution reactions of H2GeClAlCl2 with HF, H2O, NH3, HCl, H2S, and PH3 proceeded in a concerted manner. There were one transition state and one intermediate which connected the reactants and the products along the potential energy surface. The six substitution reactions of H2GeClAlCl2 with HF, H2O, NH3, HCl, H2S, and PH3 are compared with the addition reaction s of H2Ge with these hydrides. And based on the calculated results we concluded that the substitution reactions of H2GeClAlCl2 with these hydrides involve two steps, one is dissociation onto H2Ge with AlCl3, and the other is the addition reactions of H2Ge with HF, H2O, NH3, HCl, H2S, and PH3.

  18. 130 °C CH3NH3I treatment temperature in vapor-assisted solution process for large grain and full-coverage perovskite thin films

    NASA Astrophysics Data System (ADS)

    Li, Nannan; Shi, Chengwu; Zhang, Zhengguo; Wang, Yanqing; Xiao, Guannan; Wang, Ran

    2016-10-01

    In this paper, the self-made setup with excellent controllability and general applicability was developed for the preparation of perovskite thin films using vapor-assisted solution process. The CH3NH3I treatment temperature was 130 °C, 140 °C, 150 °C in vapor-assisted solution process, the grain size of the corresponding perovskite thin films was ∼600 nm, ∼400 nm, ∼200 nm, and the best photoelectric conversion efficiency of the corresponding perovskite solar cells was 12.62%, 11.72% and 11.50%, respectively. The result demonstrated that the CH3NH3I treatment temperature can be decreased from 150 °C to 130 °C and the large grain and full-coverage perovskite thin film was obtained using the self-made setup at the CH3NH3I treatment temperature of 130 °C in ambient atmosphere because the CH3NH3I treatment temperature was usually 150 °C.

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

    PubMed

    Nourry, Sendres; Krim, Lahouari

    2016-07-21

    Although NH3 molecules interacting with ground state nitrogen atoms N((4)S) seem not to be a very reactive system without providing additional energy to initiate the chemical process, we show through this study that, in the solid phase, at very low temperature, NH3 + N((4)S) reaction leads to the formation of the amidogen radical NH2. Such a dissociation reaction previously thought to occur exclusively through UV photon or energetic particle irradiation is in this work readily occurring just by stimulating the mobility of N((4)S)-atoms in the 3-10 K temperature range in the solid sample. The N((4)S)-N((4)S) recombination may be the source of metastable molecular nitrogen N2(A), a reactive species which might trigger the NH3 dissociation or react with ground state nitrogen atoms N((4)S) to form excited nitrogen atoms N((4)P/(2)D) through energy transfer processes. Based on our obtained results, it is possible to propose reaction pathways to explain the NH2 radical formation which is the first step in the activation of stable species such as NH3, a chemical induction process that, in addition to playing an important role in the origin of molecular complexity in interstellar space, is known to require external energy supplies to occur in the gas phase. PMID:27340010

  20. WO3/CeO2/TiO2 Catalysts for Selective Catalytic Reduction of NO(x) by NH3: Effect of the Synthesis Method.

    PubMed

    Michalow-Mauke, Katarzyna A; Lu, Ye; Ferri, Davide; Graule, Thomas; Kowalski, Kazimierz; Elsener, Martin; Kröcher, Oliver

    2015-01-01

    WO3/CeO2/TiO2, CeO2/TiO2 and WO3/TiO2 catalysts were prepared by wet impregnation. CeO2/TiO2 and WO3/TiO2 showed activity towards the selective catalytic reduction (SCR) of NO(x) by NH3, which was significantly improved by subsequent impregnation of CeO/TiO2 with WO3. Catalytic performance, NH3 oxidation and NH3 temperature programmed desorption of wet-impregnated WO3/CeO2/TiO2 were compared to those of a flame-made counterpart. The flame-made catalyst exhibits a peculiar arrangement of W-Ce-Ti-oxides that makes it very active for NH3-SCR. Catalysts prepared by wet impregnation with the aim to mimic the structure of the flame-made catalyst were not able to fully reproduce its activity. The differences in the catalytic performance between the investigated catalysts were related to their structural properties and the different interaction of the catalyst components.

  1. Structures and Electronic Properties of Different CH3NH3PbI3/TiO2 Interface: A First-Principles Study

    PubMed Central

    Geng, Wei; Tong, Chuan-Jia; Liu, Jiang; Zhu, Wenjun; Lau, Woon-Ming; Liu, Li-Min

    2016-01-01

    Methylammonium lead iodide perovskite, CH3NH3PbI3, has attracted particular attention due to its fast increase in efficiency in dye sensitization TiO2 solid-state solar cells. We performed first-principles calculations to investigate several different types of CH3NH3PbI3/TiO2 interfaces. The interfacial structures between the different terminated CH3NH3PbI3 and phase TiO2 are thoroughly explored, and the calculated results suggest that the interfacial Pb atoms play important roles in the structure stability and electronic properties. A charge transfer from Pb atoms to the O atoms of TiO2 lead to the band edge alignment of Pb-p above Ti-d about 0.4 eV, suggesting a better carries separation. On the other hand, for TiO2, rutile (001) is the better candidate due to the better lattice and atoms arrangement match with CH3NH3PbI3. PMID:26846401

  2. A study of the OMVPE growth mechanisms using internal reflectance spectroscopy to examine adsorption of TMGa and NH3 and surface reactions between them

    NASA Astrophysics Data System (ADS)

    Tripathi, A.; Mazzarese, D.; Conner, W. C.; Jones, K. A.

    1989-01-01

    Internal reflection spectroscopy spectra show that NH3 and ND3 chemisorb onto (100) and (111)A GaAs surfaces. Adsorption occurs by the formation of Ga—N bonds via Lewis acid-base reactions which are identified by an absorption band between 1325 and 1100 cm-1 with peaks near 1285, 1220 and 1150 cm-1. No NH3 absorption bands are detected when the (111)B surface is exposed. TMGa also chemisorbs onto the (100) GaAs surface. The adsorption spectra of NH3 + TMGa is a function of the order in which the reactants are introduced. When NH3 is introduced first, the reactivity is much greater as is evidenced by the almost total elimination of absorption peaks associated with N—H and CH3 peaks which suggests that the reactions are surface catalyzed methane elimination reactions. Implications of the requirement that the hydride be adsorbed and the methyls react with the hydrogen atoms from the hydride to ALE and MOMBE growth are discussed. Also, consistent explanations are presented for why growth on the (111)B surface is difficult, the growth rate is independent of the hydride partial pressure under normal growth conditions, the incorporation of C into GaAs has an orientational dependence, and As is more preferentially incorporated into GaAsP at the lower growth temperatures.

  3. In situ supported MnO(x)-CeO(x) on carbon nanotubes for the low-temperature selective catalytic reduction of NO with NH3.

    PubMed

    Zhang, Dengsong; Zhang, Lei; Shi, Liyi; Fang, Cheng; Li, Hongrui; Gao, Ruihua; Huang, Lei; Zhang, Jianping

    2013-02-01

    The MnO(x) and CeO(x) were in situ supported on carbon nanotubes (CNTs) by a poly(sodium 4-styrenesulfonate) assisted reflux route for the low-temperature selective catalytic reduction (SCR) of NO with NH(3). X-Ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS), H(2) temperature-programmed reduction (H(2)-TPR) and NH(3) temperature-programmed desorption (NH(3)-TPD) have been used to elucidate the structure and surface properties of the obtained catalysts. It was found that the in situ prepared catalyst exhibited the highest activity and the most extensive operating-temperature window, compared to the catalysts prepared by impregnation or mechanically mixed methods. The XRD and TEM results indicated that the manganese oxide and cerium oxide species had a good dispersion on the CNT surface. The XPS results demonstrated that the higher atomic concentration of Mn existed on the surface of CNTs and the more chemisorbed oxygen species exist. The H(2)-TPR results suggested that there was a strong interaction between the manganese oxide and cerium oxide on the surface of CNTs. The NH(3)-TPD results demonstrated that the catalysts presented a larger acid amount and stronger acid strength. In addition, the obtained catalysts exhibited much higher SO(2)-tolerance and improved the water-resistance as compared to that prepared by impregnation or mechanically mixed methods.

  4. High-performance perovskite CH3NH3PbI3 thin films for solar cells prepared by single-source physical vapour deposition

    PubMed Central

    Fan, Ping; Gu, Di; Liang, Guang-Xing; Luo, Jing-Ting; Chen, Ju-Long; Zheng, Zhuang-Hao; Zhang, Dong-Ping

    2016-01-01

    In this work, an alternative route to fabricating high-quality CH3NH3PbI3 thin films is proposed. Single-source physical vapour deposition (SSPVD) without a post-heat-treating process was used to prepare CH3NH3PbI3 thin films at room temperature. This new process enabled complete surface coverage and moisture stability in a non-vacuum solution. Moreover, the challenges of simultaneously controlling evaporation processes of the organic and inorganic sources via dual-source vapour evaporation and the heating process required to obtain high crystallization were avoided. Excellent composition with stoichiometry transferred from the powder material, a high level of tetragonal phase-purity, full surface coverage, well-defined grain structure, high crystallization and reproducibility were obtained. A PCE of approximately 10.90% was obtained with a device based on SSPVD CH3NH3PbI3. These initial results suggest that SSPVD is a promising method to significantly optimize perovskite CH3NH3PbI3 solar cell efficiency. PMID:27426686

  5. Study of the structure, energetics, and vibrational properties of small ammonia clusters (NH3)n (n = 2-5) using correlated ab initio methods.

    PubMed

    Janeiro-Barral, Paula E; Mella, Massimo

    2006-10-01

    Equilibrium geometries, interaction energies, and harmonic frequencies of (NH3)n isomers (n = 2-5) have been computed using correlated calculations (MP2) in conjunction with Dunning's aug-cc-pVXZ (X = D, T, Q) basis sets and the Counterpoise procedure. Whenever available, literature values for the binding energy and geometry of dimers and trimers agree well with our data. Low lying isomers for (NH3)4 and (NH3)5 have been found to have similar binding energies (roughly 16 and 20 kcal/mol for the tetramer and pentamer, respectively), perhaps suggesting the presence of a very smooth energy landscape. Using BSSE corrected forces or freezing the monomer structure to its gas phase geometry have been found to have only a weak impact on the energetic and structural properties of the clusters. The effect of zero-point energy (ZPE) on the relative stability of the clusters has been estimated using harmonic frequencies. The latter also highlighted the presence of vibrational fingerprints for the presence of double acceptor ammonia molecules. Many-body effects for (NH3)n isomers (n = 2-4) have been investigated to explore the possibility of building a pairwise interaction model for ammonia. In the frame of the work presented, we have found the 3-body effect to account for 10-15% of the total interaction energy, whereas the 4-body effects may be neglected as first approximation.

  6. Structure-Activity Relationships in NH3-SCR over Cu-SSZ-13 as Probed by Reaction Kinetics and EPR Studies

    SciTech Connect

    Gao, Feng; Walter, Eric D.; Karp, Eric M.; Luo, Jin-Yong; Tonkyn, Russell G.; Kwak, Ja Hun; Szanyi, Janos; Peden, Charles HF

    2013-04-01

    Cu-SSZ-13 catalysts with various Cu loadings were prepared via solution ion exchange. The hydrated samples were studied with Electron Paramagnetic Resonance (EPR). Cu2+ ion coordination numbers were obtained by analyzing the hyperfine structures while Cu-Cu distances were estimated from line broadening of the EPR features. By coupling EPR and temperature-programmed reduction (TPR) results, two Cu2+ ion locations were suggested. Standard and fast NH3-SCR, as well as non-selective NH3 oxidation reactions were carried out over these catalysts at high space velocities. For the SCR reaction, intra-particle diffusion limitation was found throughout the reaction temperatures investigated. Although clear structure-activity relationships cannot be derived, the reaction results allow for reactant diffusivities and Cu2+ ion locations to be estimated. The slower NH3 oxidation reaction, on the other hand, is kinetically limited at low temperatures, and, therefore, allows for a correlation between Cu2+ ion location and reaction kinetics to be made. Furthermore, the dynamic Cu2+ ion motion as a function of temperature could also be derived from the NH3 oxidation kinetics.

  7. [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

  8. Lead free CH3NH3SnI3 perovskite thin-film with p-type semiconducting nature and metal-like conductivity

    NASA Astrophysics Data System (ADS)

    Iefanova, Anastasiia; Adhikari, Nirmal; Dubey, Ashish; Khatiwada, Devendra; Qiao, Qiquan

    2016-08-01

    Lead free CH3NH3SnI3 perovskite thin film was prepared by low temperature solution processing and characterized using current sensing atomic force microscopy (CS-AFM). Analysis of electrical, optical, and optoelectrical properties reveals unique p-type semiconducting nature and metal like conductivity of this material. CH3NH3SnI3 film also showed a strong absorption in visible and near infrared spectrum with absorption onset of 1.3 eV. X-ray Diffraction analysis and scanning electron microscopy (SEM) confirmed a structure of this compound and uniform film formation. The morphology, film uniformity, light harvesting and electrical properties strongly depend on preparation method and precursor solution. CH3NH3SnI3 films prepared based on dimethylformamide (DMF) showed higher crystallinity and light harvesting capability compared to the film based on combination of dimethyl sulfoxide (DMSO) with gamma-butyrolactone (GBL). Local photocurrent mapping analysis showed that CH3NH3SnI3 can be used as an active layer and have a potential to fabricate lead free photovoltaic devices.

  9. High-performance perovskite CH3NH3PbI3 thin films for solar cells prepared by single-source physical vapour deposition

    NASA Astrophysics Data System (ADS)

    Fan, Ping; Gu, Di; Liang, Guang-Xing; Luo, Jing-Ting; Chen, Ju-Long; Zheng, Zhuang-Hao; Zhang, Dong-Ping

    2016-07-01

    In this work, an alternative route to fabricating high-quality CH3NH3PbI3 thin films is proposed. Single-source physical vapour deposition (SSPVD) without a post-heat-treating process was used to prepare CH3NH3PbI3 thin films at room temperature. This new process enabled complete surface coverage and moisture stability in a non-vacuum solution. Moreover, the challenges of simultaneously controlling evaporation processes of the organic and inorganic sources via dual-source vapour evaporation and the heating process required to obtain high crystallization were avoided. Excellent composition with stoichiometry transferred from the powder material, a high level of tetragonal phase-purity, full surface coverage, well-defined grain structure, high crystallization and reproducibility were obtained. A PCE of approximately 10.90% was obtained with a device based on SSPVD CH3NH3PbI3. These initial results suggest that SSPVD is a promising method to significantly optimize perovskite CH3NH3PbI3 solar cell efficiency.

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

    PubMed

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

    2015-04-28

    Organometal halide perovskites are inexpensive materials with desirable characteristics of color-tunable and narrow-band emissions for lighting and display technology, but they suffer from low photoluminescence quantum yields at low excitation fluencies. Here we developed a ligand-assisted reprecipitation strategy to fabricate brightly luminescent and color-tunable colloidal CH3NH3PbX3 (X = Br, I, Cl) quantum dots with absolute quantum yield up to 70% at room temperature and low excitation fluencies. To illustrate the photoluminescence enhancements in these quantum dots, we conducted comprehensive composition and surface characterizations and determined the time- and temperature-dependent photoluminescence spectra. Comparisons between small-sized CH3NH3PbBr3 quantum dots (average diameter 3.3 nm) and corresponding micrometer-sized bulk particles (2-8 μm) suggest that the intense increased photoluminescence quantum yield originates from the increase of exciton binding energy due to size reduction as well as proper chemical passivations of the Br-rich surface. We further demonstrated wide-color gamut white-light-emitting diodes using green emissive CH3NH3PbBr3 quantum dots and red emissive K2SiF6:Mn(4+) as color converters, providing enhanced color quality for display technology. Moreover, colloidal CH3NH3PbX3 quantum dots are expected to exhibit interesting nanoscale excitonic properties and also have other potential applications in lasers, electroluminescence devices, and optical sensors. PMID:25824283

  11. Comparison of π-hole tetrel bonding with σ-hole halogen bonds in complexes of XCN (X = F, Cl, Br, I) and NH3.

    PubMed

    Nziko, Vincent de Paul N; Scheiner, Steve

    2016-02-01

    In addition to the standard halogen bond formed when NH3 approaches XCN (X = F, Cl, Br, I) along its molecular axis, a perpendicular approach is also possible, toward a π-hole that is present above the X-C bond. MP2/aug-cc-pVDZ calculations indicate the latter geometry is favored for X = F, and the σ-hole structure is preferred for the heavier halogens. The π-hole structure is stabilized by charge transfer from the NH3 lone pair into the π*(CN) antibonding orbital, and is characterized by a bond path from the N of NH3 to the C atom of XCN, a form of tetrel bond. The most stable 2 : 1 NH3/XCN heterotrimer for X = F and Cl is cyclic and contains a tetrel bond augmented by a pair of NHN H-bonds. For X = Br and I, the favored trimer is noncyclic, stabilized by a tetrel and a halogen bond.

  12. Thermolysis, nonisothermal decomposition kinetics, specific heat capacity and adiabatic time-to-explosion of [Cu(NH3)4](DNANT)2 (DNANT= dinitroacetonitrile).

    PubMed

    Zhang, Yu; Wu, Hao; Xu, Kangzhen; Zhang, Wantao; Ren, Zhaoyu; Song, Jirong; Zhao, Fengqi

    2014-02-20

    A new energetic copper complex of dinitroacetonitrile (DNANT), [Cu(NH3)4](DNANT)2, was first synthesized through an unexpected reaction. The thermal decomposition of [Cu(NH3)4](DNANT)2 was studied with DSC and TG/DTG methods. The gas products were analyzed through a TG-FTIR-MS method. The nonisothermal kinetic equation of the exothermic process is dα/dT = 10(10.92)/β4(1 - α)[-ln(1 - α)](3/4) exp(-1.298 × 10(5)/RT). The self-accelerating decomposition temperature and critical temperature of thermal explosion are 217.9 and 221.0 °C. The specific heat capacity of [Cu(NH3)4](DNANT)2 was determined with a micro-DSC method, and the molar heat capacity is 512.6 J mol(-1) K(-1) at 25 °C. Adiabatic time-to-explosion of Cu(NH3)4(DNANT)2 was also calculated to be about 137 s.

  13. [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

  14. Negative ion formation in electron-stimulated desorption of CF2Cl2 coadsorbed with polar NH3 on Ru(0001).

    PubMed

    Solovev, S; Kusmierek, D O; Madey, T E

    2004-01-01

    Photon-induced dissociation of CF2Cl2 (freon-12) in the stratosphere contributes substantially to atmospheric ozone depletion. We report recent results on dissociation and negative ion formation in electron-stimulated desorption (ESD) of CF2Cl2 on Ru(0001), when CF2Cl2 is coadsorbed with a polar molecule (NH3), for electron energies ranging from 50 to 300 eV. Two different time-of-flight methods are used in this investigation: (a) an ESD ion angular distribution detector with wide collection angle and (b) a quadrupole mass spectrometer with narrow collection angle and high mass resolution. Many negative ESD fragments are seen (F-, Cl-, FCl-, CF-, F2-, and Cl2-), whose intensities depend on the surface preparation. Using both detectors we observe a giant enhancement of Cl- and F- yields for ESD of CF2Cl2 coadsorbed with approximately 1 ML of NH3; this enhancement (>10(3) for Cl-) is specific to certain ions, and is attributed to an increased probability of dissociative electron attachment due to "trapped" low-energy secondary electrons, i.e., precursor states of the solvated electron in NH3. In further studies, the influence of polar NH3 spacer layers (1-10 ML) on ESD of top-layer CF2Cl2 is determined, and compared with thick films of condensed CF2Cl2. The magnitudes and energy dependences of the Cl- yields are different in these cases, due to several contributing factors.

  15. Efficient and stable CH3NH3PbI3-sensitized ZnO nanorod array solid-state solar cells.

    PubMed

    Bi, Dongqin; Boschloo, Gerrit; Schwarzmüller, Stefan; Yang, Lei; Johansson, Erik M J; Hagfeldt, Anders

    2013-12-01

    We report for the first time the use of a perovskite (CH3NH3PbI3) absorber in combination with ZnO nanorod arrays (NRAs) for solar cell applications. The perovskite material has a higher absorption coefficient than molecular dye sensitizers, gives better solar cell stability, and is therefore more suited as a sensitizer for ZnO NRAs. A solar cell efficiency of 5.0% was achieved under 1000 W m(-2) AM 1.5 G illumination for a solar cell with the structure: ZnO NRA/CH3NH3PbI3/spiro-MeOTAD/Ag. Moreover, the solar cell shows a good long-term stability. Using transient photocurrent and photovoltage measurements it was found that the electron transport time and lifetime vary with the ZnO nanorod length, a trend which is similar to that in dye-sensitized solar cells, DSCs, suggesting a similar charge transfer process in ZnO NRA/CH3NH3PbI3 solar cells as in conventional DSCs. Compared to CH3NH3PbI3/TiO2 solar cells, ZnO shows a lower performance due to more recombination losses.

  16. High-performance perovskite CH3NH3PbI3 thin films for solar cells prepared by single-source physical vapour deposition.

    PubMed

    Fan, Ping; Gu, Di; Liang, Guang-Xing; Luo, Jing-Ting; Chen, Ju-Long; Zheng, Zhuang-Hao; Zhang, Dong-Ping

    2016-01-01

    In this work, an alternative route to fabricating high-quality CH3NH3PbI3 thin films is proposed. Single-source physical vapour deposition (SSPVD) without a post-heat-treating process was used to prepare CH3NH3PbI3 thin films at room temperature. This new process enabled complete surface coverage and moisture stability in a non-vacuum solution. Moreover, the challenges of simultaneously controlling evaporation processes of the organic and inorganic sources via dual-source vapour evaporation and the heating process required to obtain high crystallization were avoided. Excellent composition with stoichiometry transferred from the powder material, a high level of tetragonal phase-purity, full surface coverage, well-defined grain structure, high crystallization and reproducibility were obtained. A PCE of approximately 10.90% was obtained with a device based on SSPVD CH3NH3PbI3. These initial results suggest that SSPVD is a promising method to significantly optimize perovskite CH3NH3PbI3 solar cell efficiency. PMID:27426686

  17. Surface plasmon resonance study on the optical sensing properties of tin oxide (SnO2) films to NH3 gas

    NASA Astrophysics Data System (ADS)

    Paliwal, Ayushi; Sharma, Anjali; Tomar, Monika; Gupta, Vinay

    2016-04-01

    Surface plasmon resonance (SPR) technique is an easy and reliable method for detecting very low concentration of toxic gases at room temperature using a gas sensitive thin film layer. In the present work, a room temperature operated NH3 gas sensor has been developed using a laboratory assembled SPR measurement setup utilising a p-polarized He-Ne laser and prism coupling technique. A semiconducting gas sensitive tin oxide (SnO2) layer has been deposited under varying growth conditions (i.e., by varying deposition pressure) over the gold coated prism (BK-7) to excite the surface plasmon modes in Kretschmann configuration. The SPR reflectance curves for prism/Au/SnO2/air system for SnO2 thin films prepared at different sputtering pressure were measured, and the SnO2 film deposited at 10 mT pressure is found to exhibit a sharp SPR reflectance curve with minimum reflectance (0.32) at the resonance angle of 44.7° which is further used for sensing NH3 gas of different concentration at room temperature. The SPR reflectance curve shows a significant shift in resonance angle from 45.05° to 58.55° on interacting with NH3. The prepared sensor is found to give high sensing response (0.11) with high selectivity towards very low concentration of NH3 (0.5 ppm) and quick response time at room temperature.

  18. Surface modification of graphite-encapsulated iron nanoparticles by RF excited Ar/NH3 gas mixture plasma and their application to Escherichia coli capture

    NASA Astrophysics Data System (ADS)

    Viswan, Anchu; Chou, Han; Sugiura, Kuniaki; Nagatsu, Masaaki

    2016-09-01

    Graphite-encapsulated iron nanoparticles with an average diameter of 20 nm were synthesized using the DC arc discharge method. For biomedical application, the nanoparticles were functionalized with amino groups using an inductively coupled radio-frequency (RF) plasma. The Ar, NH3, and Ar/NH3 plasmas that were used for functionalization were diagnosed using optical emission spectroscopy, confirming the presence of the required elements. The best conditions for functionalization were optimized by changing various parameters. The pretreatment time with Ar plasma was varied from 0 to 12.5 min, the post-treatment time from 30 s to 3 min. The dependence of the RF power and the gas mixture ratio of Ar/NH3 on the amino group population was also analyzed. From Raman spectroscopy, x-ray photoelectron spectroscopy, and determination of absolute number of amino groups through chemical derivatization, it was found that 5 min of Ar pretreatment and 6%NH3/94%Ar plasma post-treatment for 3 min with an RF power of 80 W gives the best result of about 5  ×  104 amino groups per particle. The nanoparticles that were amino functionalized under optimized conditions and immobilized with an Escherichia coli (E.coli) antibody on their surface were incubated with E.coli bacteria to determine the efficiency of collection by direct culture assay.

  19. Structures and Electronic Properties of Different CH3NH3PbI3/TiO2 Interface: A First-Principles Study.

    PubMed

    Geng, Wei; Tong, Chuan-Jia; Liu, Jiang; Zhu, Wenjun; Lau, Woon-Ming; Liu, Li-Min

    2016-01-01

    Methylammonium lead iodide perovskite, CH3NH3PbI3, has attracted particular attention due to its fast increase in efficiency in dye sensitization TiO2 solid-state solar cells. We performed first-principles calculations to investigate several different types of CH3NH3PbI3/TiO2 interfaces. The interfacial structures between the different terminated CH3NH3PbI3 and phase TiO2 are thoroughly explored, and the calculated results suggest that the interfacial Pb atoms play important roles in the structure stability and electronic properties. A charge transfer from Pb atoms to the O atoms of TiO2 lead to the band edge alignment of Pb-p above Ti-d about 0.4 eV, suggesting a better carries separation. On the other hand, for TiO2, rutile (001) is the better candidate due to the better lattice and atoms arrangement match with CH3NH3PbI3. PMID:26846401

  20. CH4/NH3/H2O spark tholin: chemical analysis and interaction with Jovian aqueous clouds.

    PubMed

    McDonald, G D; Khare, B N; Thompson, W R; Sagan, C

    1991-01-01

    The organic solid (tholin) produced by spark discharge in a CH4 + NH3 + H2O atmosphere is investigated, along with the separable components of its water-soluble fraction. The chemistry of this material serves as a provisional model for the interaction of Jovian organic heteropolymers with the deep aqueous clouds of Jupiter. Intact (unhydrolyzed) tholin is resolved into four chemically distinct fractions by high-pressure liquid chromatography (HPLC). Gel filtration chromatography reveals abundant components at molecular weights approximately or equal to 600-700 and 200-300 Da. Gas chromatography/mass spectrometry of derivatized hydrolysis products of unfractionated tholin shows about 10% by mass protein and nonprotein amino acids, chiefly glycine, alanine, aspartic acid, beta-alanine, and beta-aminobutyric acid, and 12% by mass other organic acids and hydroxy acids. The stereospecificity of alanine is investigated and shown to be racemic. The four principal HPLC fractions yield distinctly different proportions of amino acids. Chemical tests show that small peptides or organic molecules containing multiple amino acid precursors are a possibility in the intact tholins, but substantial quantities of large peptides are not indicated. Candidate 700-Da molecules have a central unsaturated, hydrocarbon- and nitrile-rich core, linked by acid-labile (ester or amide) bonds to amino acid and carboxylic acid side groups. The core is probably not HCN "polymer." The concentration of amino acids from tholin hydrolysis in the lower aqueous clouds of Jupiter, about 0.1 micromole, is enough to maintain small populations of terrestrial microorganisms even if the amino acids must serve as the sole carbon source.

  1. Aqueous dispersions of magnetite nanoparticles with NH3+ surfaces for magnetic manipulations of biomolecules and MRI contrast agents.

    PubMed

    Shieh, Dar-Bin; Cheng, Fong-Yu; Su, Chia-Hao; Yeh, Chen-Sheng; Wu, Ming-Ting; Wu, Ya-Na; Tsai, Chiau-Yuang; Wu, Chao-Liang; Chen, Dong-Hwang; Chou, Chen-Hsi

    2005-12-01

    In the current study, amine surface modified iron-oxide nanoparticles of 6 nm diameter without polymer coating were fabricated in an aqueous solution by organic acid modification as an adherent following chemical coprecipitation. Structure and the superparamagnetic property of magnetite nanoparticles were characterized by selected area electron diffraction (SAED) and superconducting quantum interference measurement device (SQUID). X-ray photoelectron spectrometer (XPS) and zeta potential measurements revealed cationic surface mostly decorated with terminal -NH(3)(+). This feature enables them to function as a magnetic carrier for nucleotides via electrostatic interaction. In addition, Fe(3)O(4)/trypsin conjugates with well-preserved functional activity was demonstrated. The nanoparticles displayed excellent in vitro biocompatibility. The NMR and the in vitro MRI measurements showed significantly reduced water proton relaxation times of both T(1) and T(2). Significantly reduced T(2) and T(2)*-weighted signal intensity were observed in a 1.5 T clinical MR imager. In vivo imaging contrast effect showed a fast and prolonged inverse contrast effect in the liver that lasted for more than 1 week. In addition, it was found that the spherical Fe(3)O(4) assembled as rod-like configuration through an aging process in aqueous solution at room temperature. Interestingly, TEM observation of the liver tissue revealed the rod-like shape but not the spherical-type nanoparticles being taken up by the Kupffer cells 120 h after tail vein infusion. Combining these results, we have demonstrated the potential applications of the newly synthesized magnetite nanoparticles in a broad spectrum of biomedical applications.

  2. Insight into the CH3NH3PbI3/C interface in hole-conductor-free mesoscopic perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Li, Jiangwei; Niu, Guangda; Li, Wenzhe; Cao, Kun; Wang, Mingkui; Wang, Liduo

    2016-07-01

    Perovskite solar cells (PSCs) with hole-conductor-free mesoscopic architecture have shown superb stability and great potential in practical application. The printable carbon counter electrodes take full responsibility of extracting holes from the active CH3NH3PbI3 absorbers. However, an in depth study of the CH3NH3PbI3/C interface properties, such as the structural formation process and the effect of interfacial conditions on hole extraction, is still lacking. Herein, we present, for the first time, an insight into the spatial confinement induced CH3NH3PbI3/C interface formation by in situ photoluminescence observations during the crystallization process of CH3NH3PbI3. The derived reaction kinetics allows a quantitative description of the perovskite formation process. In addition, we found that the interfacial contact between carbon and perovskite was dominant for hole extraction efficiency and associated with the photovoltaic parameter of short circuit current density (JSC). Consequently, we conducted a solvent vapor assisted process of PbI2 diffusion to carefully control the CH3NH3PbI3/C interface with less unreacted PbI2 barrier. The improvement of interface conditions thereby contributes to a high hole extraction proved by the charge extraction resistance and PL lifetime change, resulting in the increased JSC valve.Perovskite solar cells (PSCs) with hole-conductor-free mesoscopic architecture have shown superb stability and great potential in practical application. The printable carbon counter electrodes take full responsibility of extracting holes from the active CH3NH3PbI3 absorbers. However, an in depth study of the CH3NH3PbI3/C interface properties, such as the structural formation process and the effect of interfacial conditions on hole extraction, is still lacking. Herein, we present, for the first time, an insight into the spatial confinement induced CH3NH3PbI3/C interface formation by in situ photoluminescence observations during the crystallization

  3. Using stable isotopes of reactive N in dry and wet deposition to investigate the source, transport, and fate of NOx and NH3

    NASA Astrophysics Data System (ADS)

    Felix, J.; Elliott, E. M.

    2011-12-01

    Reactive N emissions (NH3 and NOx) can reach the land surfaces via both wet (NH4+, NO3) and dry (NOx, HNO3, NH3, NH4+) depositional processes. Together, these reactive N compounds are important global contributors to air and water quality degradation. Although nitrate concentrations in wet deposition have decreased in the U.S. during the last two decades due to NOx emission regulations set forth by the Clean Air Act, ammonium concentrations in wet deposition have recently increased. In order to further decrease NOx emissions and decrease NH3 emissions, additional tools for reactive N source apportionment are essential. The stable isotopic composition of reactive N may be one such tool for characterizing source, transport, and fate of reactive N emissions. Here, we present results from a comprehensive inventory of the isotopic composition of reactive N emission sources, focusing mainly on agricultural and fossil fuel sources. We build on these inventory results by tracing reactive N emissions across multiple landscapes including: a dairy operation, a conventionally managed cornfield, a tallgrass prairie, and a concentrated animal feeding operation. We then use two examples to illustrate how reactive N isotopes can be used in a regional context. First, we illustrate how passive NH3 samplers deployed at nine U.S. monitoring sites reflect spatial variations in predominant NH3 sources. Secondly, we reconstruct the regional influence of agricultural NOx emissions to nitrate deposition recorded in an ice core from Summit, Greenland. These results reveal significant evidence that the trend in the N isotopic composition of 20th century nitrate deposition in Greenland was driven by increasing biogenic soil NOx emissions induced by fertilizer application in the US over the last century. Together, these studies demonstrate the isotopic composition of reactive N emissions can be an additional tool for investigators to source and trace reactive N emissions in both historical and

  4. Spontaneous gradual accumulation of hexagonally-aligned nano-silica on gold nanoparticles embedded in stabilized zirconia: a pathway from catalytic to NH3-sensing performance

    NASA Astrophysics Data System (ADS)

    Plashnitsa, Vladimir V.; Elumalai, Perumal; Fujio, Yuki; Kawaguchi, Toshikazu; Miura, Norio

    2011-05-01

    The present study highlights the influence of nano-impurities on the catalytic/sensing performance of nano-structured Au sensing-electrodes (SEs) housed in a quartz reactor and operated at high temperature over a long period of time. The planar sensor, made from a nano-structured Au-SE on a polished-polycrystalline (pp) yttria-stabilized zirconia (YSZ) substrate exhibited initially negligible electromotive force (emf) response to each of the examined gases (CO, CH4, C3H8, C3H6, NOx and NH3; 400 ppm each) at 700 °C in the presence of 5 vol.% oxygen and 5 vol.% water vapor. Such a poor emf response was attributed to the excellent gas-phase oxidation/reduction ability of Au nanoparticles embedded in the YSZ substrate at high temperature. The response of the planar sensor made up of nano-structured Au-SE was monitored for about 75 days at 700 °C. As a result of this long-term monitoring, we detected the appearance of highly sensitive and selective NH3 gas-sensing properties after 45-75 days of sensor operation. Detailed observation of the morphology and composition of the as-fabricated nano-structured Au-SE after 75 days operation at 700 °C revealed the gradual accumulation of hexagonally-aligned SiO2 nano-impurities on the surface of the Au nanoparticles. The NH3 sensing mechanism of the YSZ-based sensor using the spontaneously-formed composite (nano-Au + nano-SiO2)-SE is therefore proposed to be based on a strong acid-base interaction between gaseous NH3 and SiO2 nano-impurities, followed by spillover of adsorbed NH3 towards the nano-Au/pp-YSZ interface.

  5. Comparison study of Cu-Fe-Ti and Co-Fe-Ti oxide catalysts for selective catalytic reduction of NO with NH3 at low temperature.

    PubMed

    Zhu, Lin; Zhong, Zhaoping; Yang, Han; Wang, Chunhua

    2016-09-15

    In this paper, a series of Cu-Fe-Ti and Co-Fe-Ti oxide catalysts were prepared by sol gel method. Cu-Fe-Ti and Co-Fe-Ti oxide catalysts showed the moderate catalytic activity for selective catalytic reduction (SCR) of NO with NH3 at low temperature. The catalysts with the molar ratio as 4:1:10 (M:Fe:Ti) were selected as the representatives for comparison of reaction properties and H2O resistance, which were denoted as Cu-Fe/TiO2 and Co-Fe/TiO2 respectively. The characterization results manifested Co-Fe/TiO2 owned more adsorption capacity of the reactants and Cu-Fe/TiO2 had better redox ability. The in situ DRIFTS experiments indicated that adsorbed NH3 species and nitrate species both exhibited reaction activity for Co-Fe/TiO2, while nitric oxide was only be reduced by adsorbed NH3 species through Eley-Rideal mechanism for Cu-Fe/TiO2 at 150°C. Co-Fe/TiO2 exhibited the better resistance to H2O and its temperature window shifted towards the higher temperature in presence of 10vol% H2O, while the SCR activity of Cu-Fe/TiO2 was inhibited significantly in the whole temperature range investigated. The suppression of adsorption and activation for NH3 and NOx might be the reasons for the reversible inactivation, which was confirmed by the inhibitation of catalytic activities for separation NH3 and NO oxidation under the wet condition. We speculated that different thermal stability of adsorbed species and redox capacity of catalysts leaded to the different SCR behavior in absence and presence of H2O. PMID:27280535

  6. Iron-doped Mn-Ce/TiO2 catalyst for low temperature selective catalytic reduction of NO with NH3.

    PubMed

    Shen, Boxiong; Liu, Ting; Zhao, Ning; Yang, Xiaoyan; Deng, Lidan

    2010-01-01

    The catalysts of iron-doped Mn-Ce/TiO2 (Fe-Mn-Ce/TiO2) prepared by sol-gel method were investigated for low temperature selective catalytic reduction (SCR) of NO with NH3. It was found that the NO conversion over Fe-Mn-Ce/TiO2 was obviously improved after iron doping compared with that over Mn-Ce/TiO2. Fe-Mn-Ce/TiO2 with the molar ratio of Fe/Ti = 0.1 exhibited the highest activity. The results showed that 96.8% NO conversion was obtained over Fe (0.1)-Mn-Ce/TiO2 at 180 degrees C at a space velocity of 50,000 hr(-1). Fe-Mn-Ce/TiO2 exhibited much higher resistance to H2O and SO2 than that of Mn-Ce/TiO2. The properties of the catalysts were characterized using X-ray diffraction (XRD), N2 adsorption, temperature programmed desorption (NH3-TPD and NOx-TPD), and Xray photoelectron spectroscopy (XPS) techniques. BET, NH3-TPD and NOx-TPD results showed that the specific surface area and NH3 and NOx adsorption capacity of the catalysts increased with iron doping. It was known from XPS analysis that iron valence state on the surface of the catalysts were in Fe3+ state. The doping of iron enhanced the dispersion and oxidation state of Mn and Ce on the surface of the catalysts. The oxygen concentrations on the surface of the catalysts were found to increase after iron doping. Fe-Mn-Ce/TiO2 represented a promising catalyst for low temperature SCR of NO with NH3 in the presence of H2O and SO2.

  7. Comparison study of Cu-Fe-Ti and Co-Fe-Ti oxide catalysts for selective catalytic reduction of NO with NH3 at low temperature.

    PubMed

    Zhu, Lin; Zhong, Zhaoping; Yang, Han; Wang, Chunhua

    2016-09-15

    In this paper, a series of Cu-Fe-Ti and Co-Fe-Ti oxide catalysts were prepared by sol gel method. Cu-Fe-Ti and Co-Fe-Ti oxide catalysts showed the moderate catalytic activity for selective catalytic reduction (SCR) of NO with NH3 at low temperature. The catalysts with the molar ratio as 4:1:10 (M:Fe:Ti) were selected as the representatives for comparison of reaction properties and H2O resistance, which were denoted as Cu-Fe/TiO2 and Co-Fe/TiO2 respectively. The characterization results manifested Co-Fe/TiO2 owned more adsorption capacity of the reactants and Cu-Fe/TiO2 had better redox ability. The in situ DRIFTS experiments indicated that adsorbed NH3 species and nitrate species both exhibited reaction activity for Co-Fe/TiO2, while nitric oxide was only be reduced by adsorbed NH3 species through Eley-Rideal mechanism for Cu-Fe/TiO2 at 150°C. Co-Fe/TiO2 exhibited the better resistance to H2O and its temperature window shifted towards the higher temperature in presence of 10vol% H2O, while the SCR activity of Cu-Fe/TiO2 was inhibited significantly in the whole temperature range investigated. The suppression of adsorption and activation for NH3 and NOx might be the reasons for the reversible inactivation, which was confirmed by the inhibitation of catalytic activities for separation NH3 and NO oxidation under the wet condition. We speculated that different thermal stability of adsorbed species and redox capacity of catalysts leaded to the different SCR behavior in absence and presence of H2O.

  8. Spontaneous gradual accumulation of hexagonally-aligned nano-silica on gold nanoparticles embedded in stabilized zirconia: a pathway from catalytic to NH3-sensing performance.

    PubMed

    Plashnitsa, Vladimir V; Elumalai, Perumal; Fujio, Yuki; Kawaguchi, Toshikazu; Miura, Norio

    2011-05-01

    The present study highlights the influence of nano-impurities on the catalytic/sensing performance of nano-structured Au sensing-electrodes (SEs) housed in a quartz reactor and operated at high temperature over a long period of time. The planar sensor, made from a nano-structured Au-SE on a polished-polycrystalline (pp) yttria-stabilized zirconia (YSZ) substrate exhibited initially negligible electromotive force (emf) response to each of the examined gases (CO, CH(4), C(3)H(8), C(3)H(6), NO(x) and NH(3); 400 ppm each) at 700 °C in the presence of 5 vol.% oxygen and 5 vol.% water vapor. Such a poor emf response was attributed to the excellent gas-phase oxidation/reduction ability of Au nanoparticles embedded in the YSZ substrate at high temperature. The response of the planar sensor made up of nano-structured Au-SE was monitored for about 75 days at 700 °C. As a result of this long-term monitoring, we detected the appearance of highly sensitive and selective NH(3) gas-sensing properties after 45-75 days of sensor operation. Detailed observation of the morphology and composition of the as-fabricated nano-structured Au-SE after 75 days operation at 700 °C revealed the gradual accumulation of hexagonally-aligned SiO(2) nano-impurities on the surface of the Au nanoparticles. The NH(3) sensing mechanism of the YSZ-based sensor using the spontaneously-formed composite (nano-Au + nano-SiO(2))-SE is therefore proposed to be based on a strong acid-base interaction between gaseous NH(3) and SiO(2) nano-impurities, followed by spillover of adsorbed NH(3) towards the nano-Au/pp-YSZ interface.

  9. The nature of the AgI...AgI interaction in different Ag(NH3)2 dimers embedded in supramolecular solids.

    PubMed

    Zheng, Shao-Liang; Volkov, Anatoliy; Nygren, Cara L; Coppens, Philip

    2007-01-01

    An isolated silver(I) ammonia monomer, a dimer, and a novel dimer containing an intercalated water molecule have been embedded as guests in supramolecular frameworks, [Ag(NH3)2][(H2thpe)(H3thpe)].MeCN (1), [{Ag(NH3)2}2][(H2thpe)2]4.25 H2O (2), and [{Ag(NH3)2}-H2O-{Ag(NH3)2}][(H2thpe)(2)]benzene (3) (H3THPE=tris(hydroxyphenyl)ethane). The [{Ag(NH3)2}2]2+ dimer is not stable as an isolated entity, but is stabilized by hydrogen bonding in the supramolecular framework. The water-intercalated silver(I) ammonia dimer, which constitutes a novel species, is also subject by hydrogen bonding in concentrated solutions. The destabilization energy of the dimer relative to isolated monomers is calculated to be approximately 300 kJ mol(-1) by both perturbation methods and DFT theory. For the water-intercalated dimer it is calculated to be approximately 200 kJ mol(-1) according to the BSSE-corrected MP2 calculation. The different aggregate states show a dramatic variation of absorption and emission properties, in accordance with the concentration dependent red-shift observed in solutions. Natural-bond-orbital analysis shows that the disilver-ammonium-aquo "sandwich" cation in 3 is stabilized by interaction between the pi lone pair orbital on the oxygen atom of the water molecule and Ag(I)--N sigma antibonding molecular orbital.

  10. Mixed-Halide CH3 NH3 PbI3-x Xx (X=Cl, Br, I) Perovskites: Vapor-Assisted Solution Deposition and Application as Solar Cell Absorbers.

    PubMed

    Sedighi, Rahime; Tajabadi, Fariba; Shahbazi, Saeed; Gholipour, Somayeh; Taghavinia, Nima

    2016-08-01

    There have been recent reports on the formation of single-halide perovskites, CH3 NH3 PbX3 (X=Cl, Br, I), by means of vapor-assisted solution processing. Herein, the successful formation of mixed-halide perovskites (CH3 NH3 PbI3-x Xx ) by means of a vapor-assisted solution method at ambient atmosphere is reported. The perovskite films are synthesized by exposing PbI2 film to CH3 NH3 X (X=I, Br, or Cl) vapor. The prepared perovskite films have uniform surfaces with good coverage, as confirmed by SEM images. The inclusion of chlorine and bromine into the structure leads to a lower temperature and shorter reaction time for optimum perovskite film formation. In the case of CH3 NH3 PbI3-x Clx , the optimum reaction temperature is reduced to 100 °C, and the resulting phases are CH3 NH3 PbI3 (with trace Cl) and CH3 NH3 PbCl3 with a ratio of about 2:1. In the case of CH3 NH3 PbI3-x Brx , single-phase CH3 NH3 PbI2 Br is formed in a considerably shorter reaction time than that of CH3 NH3 PbI3 . The mesostructured perovskite solar cells based on CH3 NH3 PbI3 films show the best optimal power conversion efficiency of 13.5 %, whereas for CH3 NH3 PbI3-x Clx and CH3 NH3 PbI3-x Brx the best recorded efficiencies are 11.6 and 10.5 %, respectively.

  11. Synthesis, Characterization, and Cytotoxicity of Platinum(IV) Carbamate Complexes

    PubMed Central

    Wilson, Justin J.; Lippard, Stephen J.

    2011-01-01

    The synthesis, characterization, and cytotoxicity of eight new platinum(IV) complexes having the general formula, c,c,t-[Pt(NH3)2Cl2(O2CNHR)2], are reported, where R = tert-butyl (4), cyclopentyl (5), cyclohexyl (6), phenyl (7), p-tolyl (8), p-anisole (9), 4-fluorophenyl (10), or 1-naphthyl (11). These compounds were synthesized by reacting organic isocyanates with the platinum(IV) complex, c,c,t-[Pt(NH3)2Cl2(OH)2]. The electrochemistry of the compounds was investigated by cyclic voltammetry. The aryl carbamate complexes 7 – 11 exhibit reduction peak potentials near −720 mV vs. Ag/AgCl, whereas the alkyl carbamate complexes display reduction peak potentials between −820 and −850 mV vs. Ag/AgCl. The cyclic voltammograms of c,c,t-[Pt(NH3)2Cl2(O2CCH3)2] (1), c,c,t-[Pt(NH3)2Cl2(O2CCF3)2] (2), and cis-[Pt(NH3)2Cl4] (3) were measured for comparison. Density functional theory (DFT) studies were undertaken to investigate the electronic structures of 1 – 11 and to determine their adiabatic electron affinities. A linear correlation (R2 = 0.887) between computed adiabatic electron affinities and measured reduction peak potential was discovered. The biological activity of 4 – 11 and, for comparison, cisplatin was evaluated in human lung cancer A549 and normal MRC-5 cells by the MTT assay. The compounds exhibit comparable or slightly better activity than cisplatin against the A549 cells. In MRC-5 cells, all are equally or slightly less cytotoxic than cisplatin, except for 4 and 5, which are more toxic. PMID:21361279

  12. Planar CH3NH3PbBr3 hybrid solar cells with 10.4% power conversion efficiency, fabricated by controlled crystallization in the spin-coating process.

    PubMed

    Heo, Jin Hyuck; Song, Dae Ho; Im, Sang Hyuk

    2014-12-23

    A power conversion efficiency of 10.4% is demonstrated in planar CH3 NH3 PbBr3 hybrid solar cells without hysteresis of the J-V curve, by way of controlled crystallization in the spin-coating process. The high efficiency is attributed to the formation of a dense CH3 NH3 PbBr3 thin film by the introduction of HBr solution because the HBr increases the solubility of the CH3 NH3 PbBr3 and forms a thinner CH3 NH3 PbBr3 layer with full surface coverage.

  13. Efficient hysteresis-less bilayer type CH3NH3PbI3 perovskite hybrid solar cells

    NASA Astrophysics Data System (ADS)

    Park, Jin Kyoung; Hyuck Heo, Jin; Han, Hye Ji; Lee, Min Ho; Song, Dae Ho; You, Myoung Sang; Sung, Shi-Joon; Kim, Dae-Hwan; Im, Sang Hyuk

    2016-01-01

    Bilayer type CH3NH3PbI3 (MAPbI3) perovskite hybrid solar cells were fabricated via a one-step spin-coating process by using solubility controlled MAPbI3 solutions of MAPbI3-DMSO (dimethyl sulfoxide) and MAPbI3-DMF (N, N-dimethylformamide)-HI. The best DMSO-bilayer device showed 1.07 ± 0.02 V V oc (open-circuit voltage), 20.2 ± 0.1 mA cm-2 J sc (short-circuit current density), 68 ± 2% FF (fill factor), and 15.2 ± 0.3% η (overall power conversion efficiency) under the forward scan direction and 1.07 ± 0.02 V V oc, 20.4 ± 0.1 mA cm-2 J sc, 70 ± 3% FF, and 15.9 ± 0.4% η under the reverse scan direction. The best HI-bilayer device had 1.08 ± 0.02 V V oc, 20.6 ± 0.1 mA cm-2 J sc, 75 ± 1% FF, and 17.2 ± 0.2% η under the forward scan direction and 1.08 ± 0.02 V V oc, 20.6 ± 0.1 mA cm-2 J sc, 76 ± 2% FF, and 17.4 ± 0.3% η under the reverse scan direction. The deviation of average device efficiency ({η }{{avg}}) of 20 DMSO samples and 20 HI samples was 14.2 ± 0.95% and 16.2 ± 0.85%, respectively. Therefore, the HI-bilayer devices exhibited better device efficiency and smaller J-V (current density-voltage) hysteresis with respect to the scan direction than the DMSO-bilayer devices due to the reduced recombination and traps by the formation of a purer and larger MAPbI3 perovskite crystalline film.

  14. Estimating the agricultural fertilizer NH3 emission in China based on the bi-directional CMAQ model and an agro-ecosystem model

    NASA Astrophysics Data System (ADS)

    Wang, S.

    2014-12-01

    Atmospheric ammonia (NH3) plays an important role in fine particle formation. Accurate estimates of ammonia can reduce uncertainties in air quality modeling. China is one of the largest countries emitting ammonia with the majority of NH3 emissions coming from the agricultural practices, such as fertilizer applications and animal operations. The current ammonia emission estimates in China are mainly based on pre-defined emission factors. Thus, there are considerable uncertainties in estimating NH3 emissions, especially in time and space distribution. For example, fertilizer applications vary in the date of application and amount by geographical regions and crop types. In this study, the NH3 emission from the agricultural fertilizer use in China of 2011 was estimated online by an agricultural fertilizer modeling system coupling a regional air-quality model and an agro-ecosystem model, which contains three main components 1) the Environmental Policy Integrated Climate (EPIC) model, 2) the meso-scale meteorology Weather Research and Forecasting (WRF) model and 3) the CMAQ air quality model with bi-directional ammonia fluxes. The EPIC output information about daily fertilizer application and soil characteristics would be the input of the CMAQ model. In order to run EPIC model, much Chinese local information is collected and processed. For example, Crop land data are computed from the MODIS land use data at 500-m resolution and crop categories at Chinese county level; the fertilizer use rate for different fertilizer types, crops and provinces are obtained from Chinese statistic materials. The system takes into consideration many influencing factors on agriculture ammonia emission, including weather, the fertilizer application method, timing, amount, and rate for specific pastures and crops. The simulated fertilizer data is compared with the NH3 emissions and fertilizer application data from other sources. The results of CMAQ modeling are also discussed and analyzed with

  15. The relationship between NH3 emissions from a poultry farm and soil NO and N2O fluxes from a downwind forest

    NASA Astrophysics Data System (ADS)

    Skiba, U.; Dick, J.; Storeton-West, R.; Lopez-Fernandez, S.; Woods, C.; Tang, S.; Vandijk, N.

    2006-08-01

    Intensive livestock farms emit large concentrations of NH3, most of which is deposited very close to the source. The presence of trees enhances the deposition. Rates to downwind forests can exceed 40 kg N ha-1 y-1. The steep gradient in large NH3 concentrations of 34.3±20.4, 47.6±24.9, 21.7±16.8 µg NH3 m3 at the edge of a forest 15, 30 and 45 m downwind of the farm to near background concentrations within 270 m downwind (1.15±0.7 µg NH3 m3) provides an ideal site to study the effect of different rates of atmospheric NH3 concentrations and inferred deposition on biological and chemical processes under similar environmental conditions. We have investigated the effect of different NH3 concentrations and implied deposition rates on the flux of NO and N2O from soil in a mixed woodland downwind of a large poultry farm (160 000 birds) in Scotland, which has been operating for about 40 years. Measurements were carried out for a 6 month period, with hourly NO flux measurements, daily N2O fluxes close to the farm and monthly at all sites, and monthly cumulative wet and dry N deposition. The increased NH3 and NH4+ deposition to the woodland increased emissions of NO and N2O and soil available NH4+ and NO3- concentrations. Average NO and N2O fluxes measured 15, 25 and 45 m downwind of the farm were 111.2±41.1, 123.3±40.7, 38.3±28.8 µg NO-N m-2 h-1 and 9.9±7.5, 34.3±33.3 and 21.2±6.1 µg N2O-N m-2 h-1, respectively. At the background site 270 m downwind the N2O flux was reduced to 1.75±2.1 µg N2O-N m-2 h-1. NO emissions were significantly influenced by seasonal and daily changes in soil temperature and followed a diurnal pattern with maximum emissions approximately 3 h after noon. For N2O no consistent diurnal pattern was observed. Changes in soil moisture content had a less clear effect on the NO and N2O flux. In spite of the large NO and N2O emissions accounting for >3% of the N deposited to the woodland downwind of the farm, extrapolation to the entire British

  16. Solution-based mist CVD technique for CH3NH3Pb(Br1- x Cl x )3 inorganic-organic perovskites

    NASA Astrophysics Data System (ADS)

    Nishinaka, Hiroyuki; Yoshimoto, Masahiro

    2016-10-01

    We report the growth of inorganic-organic perovskites using a solution-based mist chemical vapor deposition (mist CVD) technique and the successful growth of the alloying CH3NH3Pb(Br1- x Cl x )3 using mixture solutions of Br and Cl precursors. The formation mechanism of the inorganic-organic perovskite grown by the laminar flow-type mist CVD is suggested to be a vapor phase reaction, although solution precursors are used. The near-band-edge emissions from photoluminescence can be tuned from 500 to 550 nm by considering Br/Cl ratios in the solution without crystal phase segregation by incorporating Cl into crystalline CH3NH3PbBr3 films.

  17. Investigation of the Performance of HEMT-Based NO, NO2 and NH3 Exhaust Gas Sensors for Automotive Antipollution Systems

    PubMed Central

    Halfaya, Yacine; Bishop, Chris; Soltani, Ali; Sundaram, Suresh; Aubry, Vincent; Voss, Paul L.; Salvestrini, Jean-Paul; Ougazzaden, Abdallah

    2016-01-01

    We report improved sensitivity to NO, NO2 and NH3 gas with specially-designed AlGaN/GaN high electron mobility transistors (HEMT) that are suitable for operation in the harsh environment of diesel exhaust systems. The gate of the HEMT device is functionalized using a Pt catalyst for gas detection. We found that the performance of the sensors is enhanced at a temperature of 600 °C, and the measured sensitivity to 900 ppm-NO, 900 ppm-NO2 and 15 ppm-NH3 is 24%, 38.5% and 33%, respectively, at 600 °C. We also report dynamic response times as fast as 1 s for these three gases. Together, these results indicate that HEMT sensors could be used in a harsh environment with the ability to control an anti-pollution system in real time. PMID:26907298

  18. Thermodynamic Origin of Photoinstability in the CH3NH3Pb(I1-xBrx)3 Hybrid Halide Perovskite Alloy.

    PubMed

    Brivio, Federico; Caetano, Clovis; Walsh, Aron

    2016-03-17

    The formation of solid-solutions of iodide, bromide, and chloride provides the means to control the structure, band gap, and stability of hybrid halide perovskite semiconductors for photovoltaic applications. We report a computational investigation of the CH3NH3PbI3/CH3NH3PbBr3 alloy from density functional theory with a thermodynamic analysis performed within the generalized quasi-chemical approximation. We construct the phase diagram and identify a large miscibility gap, with a critical temperature of 343 K. The observed photoinstability in some mixed-halide solar cells is explained by the thermodynamics of alloy formation, where an initially homogeneous solution is subject to spinodal decomposition with I and Br-rich phases, which is further complicated by a wide metastable region defined by the binodal line. PMID:26952337

  19. van der Waals forces and confinement in carbon nanopores: Interaction between CH4, COOH, NH3, OH, SH and single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Weck, Philippe F.; Kim, Eunja; Wang, Yifeng

    2016-05-01

    Interactions between CH4, COOH, NH3, OH, SH and armchair (n, n) (n = 4, 7, 14) and zigzag (n, 0) (n = 7, 12, 25) single-walled carbon nanotubes (SWCNTs) have been systematically investigated within the framework of dispersion-corrected density functional theory (DFT-D2). Endohedral and exohedral molecular adsorption on SWCNT walls is energetically unfavorable or weak, despite the use of C6 /r6 pairwise London-dispersion corrections. The effects of pore size and chirality on the molecule/SWCNTs interaction were also assessed. Chemisorption of COOH, NH3, OH and SH at SWCNT edge sites was examined using a H-capped (7, 0) SWCNT fragment and its impact on electrophilic, nucleophilic and radical attacks was predicted by means of Fukui functions.

  20. The polythiophene molecular segment as a sensor model for H2O, HCN, NH3, SO3, and H2S: a density functional theory study.

    PubMed

    Shokuhi Rad, Ali; Esfahanian, Mehri; Ganjian, Etesam; Tayebi, Habib-Allah; Novir, Samaneh Bagheri

    2016-06-01

    Studying the interaction of some atmospheric gases (H2O, HCN, NH3, SO3 and H2S) with 3PT oligomers is important in the development of polymeric sensors for gas detection. In the present study, we studied the relaxed geometries, interaction energies, charge analysis, HOMO-LUMO orbital analysis, and UV-vis spectra of all interacted systems using first-principles density functional theory (DFT). All these analyses indicated the potential of polythiophene as an inexpensive polymeric sensor for the analytes mentioned. Interaction energy values of -19.90, -19.66, -14.01, -8.70, and -4.76 kJ mol(-1) were achieved for adsorption of SO3, H2O, NH3, HCN, and H2S on 3PT, respectively. Consequently, clarification of their physical parameters became the major focus of this study.

  1. CeO2 doped anatase TiO2 with exposed (001) high energy facets and its performance in selective catalytic reduction of NO by NH3

    NASA Astrophysics Data System (ADS)

    Wang, Haiqiang; Cao, Shuang; Fang, Zheng; Yu, Feixiang; Liu, Yue; Weng, Xiaole; Wu, Zhongbiao

    2015-03-01

    Ceria doped on anatase TiO2 with high energy (001) facets was synthesized in this paper, which was subsequently utilized for selective catalytic reduction (SCR) of NO by NH3. After subjected to a range of analytical techniques, such as XRD, BET, TEM, XPS ESR, H2-TPR and NH3-TPD, it was found that compared with Ce/P25 catalyst, the presence of (001) facets over the TiO2 support had yielded a remarkably high activity at 390-490 °C for NO removal. The unique feature of active-energy (001) facets had enhanced the thermal stability of CeO2 whilst the presence of Ti3+ over the TiO2 surface had effectively facilitated the SCR process, both of which resulted in the remarkable catalytic performance for the catalyst.

  2. Regulatory band gap of vacancy at the B sites in CH3NH3Pb1-xI3 perovskite

    NASA Astrophysics Data System (ADS)

    Ji, D. H.; Xiao, X. J.; Zhang, C. M.; Li, X. L.; Hu, M. Z.; Yin, Y.

    2016-08-01

    The structure, electronic structure, states density and optics properties of the orthorhombic CH3NH3Pb1-xI3 perovskite with vacancy at the B sites are calculated by the CASTEP program. The calculated results indicate that the cell volume shrinks with the content of vacancy at the B sites increasing, and the structure has the large degree of distortion from the cubic structure. The band gaps are 1.656, 1.750, 3.077, 3.256 and 4.76 eV, corresponding to x = 0.00, 0.25, 0.50, 0.75 and 1.00, respectively. As an application, the additional absorption peak can be obtained by CH3NH3Pb1-xI3 perovskite doped vacancy at the B sites.

  3. Direct Evidence for Ammonium Ion Formation in Ice through Ultraviolet-induced Acid-Base Reaction of NH3 with H3O+

    NASA Astrophysics Data System (ADS)

    Moon, Eui-Seong; Kang, Heon; Oba, Yasuhiro; Watanabe, Naoki; Kouchi, Akira

    2010-04-01

    We present direct evidence for ammonium ion (NH4 +) formation through ultraviolet (UV) photolysis of NH3-H2O mixture ice that does not contain acids. NH4 + forms by the reaction of NH3 with protonic defects (H3O+) in the UV-photolyzed ice. Our observations may explain the deficient counter-anions in interstellar ice relative to the abundance of NH4 +. Also, H3O+ may play an important role in the acid-base chemistry of interstellar ice in UV-irradiating environments. IR absorption results suggest that NH4 + is a potential contributor to the interstellar 6.85 μm band but is not a dominant component.

  4. Methyl Acetate Synthesis by Esterification on the Modified Ferrierite: Correlation of Acid Sites Measured by Pyridine IR and NH3-TPD for Steady-State Activity.

    PubMed

    Park, Jae Hyun; Pang, Changhyun; Chung, Chan-Hwa; Bae, Jong Wook

    2016-05-01

    The amounts of Brønsted acid sites on K, P, and Zr-modified microporous Ferrierite zeolite were investigated through pyridine FT-IR and NH3-TPD analyses. P-modified Ferrierite showed a superior catalytic activity for methyl acetate synthesis by esterification of methanol and acetic acid. The catalytic activity at steady-state with the acidic properties of as-prepared catalysts was well correlated with the results of pyridine FT-IR (intensity ratio of Brønsted acid sites to total acid sites) compared with that of NH3-TPD. The results can suggest the proper and simple method to estimate the esterification activity at steady-state using the measured acid sites on the as-prepared zeolites. PMID:27483801

  5. Direct Conversion of CH3NH3PbI3 from Electrodeposited PbO for Highly Efficient Planar Perovskite Solar Cells

    PubMed Central

    Huang, Jin-hua; Jiang, Ke-jian; Cui, Xue-ping; Zhang, Qian-qian; Gao, Meng; Su, Mei-ju; Yang, Lian-ming; Song, Yanlin

    2015-01-01

    Organic-inorganic hybrid perovskite materials have recently been identified as a promising light absorber for solar cells. In the efficient solar cells, the perovskite active layer has generally been fabricated by either vapor deposition or two-step sequential deposition process. Herein, electrochemically deposited PbO film is in situ converted into CH3NH3PbI3 through solid-state reaction with adjacent CH3NH3I layer, exhibiting a large-scale flat and uniform thin film with fully substrate coverage. The resultant planar heterojunction photovoltaic device yields a best power conversion efficiency of 14.59% and an average power conversion efficiency of 13.12 ± 1.08% under standard AM 1.5 conditions. This technique affords a facile and environment-friendly method for the fabrication of the perovskite based solar cells with high reproducibility, paving the way for the practical application. PMID:26510520

  6. Beam maser investigation of inelastic scattering of NH3. III. Cross sections for rotational transitions induced by CO2, N2, and H2

    NASA Astrophysics Data System (ADS)

    Klaassen, D. B. M.; ter Meulen, J. J.; Dymanus, A.

    1983-01-01

    Cross sections for rotational transitions between various low-lying inversion doublets of NH3 in collisions with CO2, N2, and H2 are measured in a double-resonance beam maser setup. A modification of Anderson's theory [D. B. M. Klaassen, J. J. ter Meulen, and A. Dymanus, J. Chem. Phys. 77, 4972 (1982)] yields values for the cross sections that are in good agreement with the experimental results for CO2 and N2. For the system NH3-H2, transition probabilities are evaluated in Anderson's theory using ``bent'' trajectories. Induction and dispersion terms up to R-7 are considered in the long-range intermolecular potential. For the short-range repulsive part, two empirical potentials are proposed with parameters that are fitted to the experimental results. Integral cross sections for rotational transitions calculated with these potentials are also presented.

  7. Thermodynamic Origin of Photoinstability in the CH3NH3Pb(I1–xBrx)3 Hybrid Halide Perovskite Alloy

    PubMed Central

    2016-01-01

    The formation of solid-solutions of iodide, bromide, and chloride provides the means to control the structure, band gap, and stability of hybrid halide perovskite semiconductors for photovoltaic applications. We report a computational investigation of the CH3NH3PbI3/CH3NH3PbBr3 alloy from density functional theory with a thermodynamic analysis performed within the generalized quasi-chemical approximation. We construct the phase diagram and identify a large miscibility gap, with a critical temperature of 343 K. The observed photoinstability in some mixed-halide solar cells is explained by the thermodynamics of alloy formation, where an initially homogeneous solution is subject to spinodal decomposition with I and Br-rich phases, which is further complicated by a wide metastable region defined by the binodal line. PMID:26952337

  8. Photoabsorption and photoionization cross sections of NH3, PH3, H2S, C2H2, and C2H4 in the VUV region

    NASA Technical Reports Server (NTRS)

    Xia, T. J.; Chien, T. S.; Wu, C. Y. Robert; Judge, D. L.

    1991-01-01

    Using synchrotron radiation as a continuum light source, the photoabsorption and photoionization cross sections of NH3, PH3, H2S, C2H2, and C2H4 have been measured from their respective ionization thresholds to 1060 A. The vibrational constants associated with the nu(2) totally symmetric, out-of-plane bending vibration of the ground electronic state of PH3(+) have been obtained. The cross sections and quantum yields for producing neutral products through photoexcitation of these molecules in the given spectral regions have also been determined. In the present work, autoionization processes were found to be less important than dissociation and predissociation processes in NH3, PH3, and C2H4. Several experimental techniques have been employed in order to examine the various possible systematic errors critically.

  9. van der Waals forces and confinement in carbon nanopores: Interaction between CH4, COOH, NH3, OH, SH and single-walled carbon nanotubes

    DOE PAGES

    Weck, Philippe F.; Kim, Eunja; Wang, Yifeng

    2016-04-13

    Interactions between CH4, COOH, NH3, OH, SH and armchair (n,n)(n=4,7,14) and zigzag (n,0)(n=7,12,25) single-walled carbon nanotubes (SWCNTs) have been systematically investigated within the framework of dispersion-corrected density functional theory (DFT-D2). Endohedral and exohedral molecular adsorption on SWCNT walls is energetically unfavorable or weak, despite the use of C6/r6 pairwise London-dispersion corrections. The effects of pore size and chirality on the molecule/SWCNTs interaction were also assessed. Furthermore, chemisorption of COOH, NH3, OH and SH at SWCNT edge sites was examined using a H-capped (7,0) SWCNT fragment and its impact on electrophilic, nucleophilic and radical attacks was predicted by means of Fukuimore » functions.« less

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

    DOE PAGES

    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

  11. Full Printable Processed Mesoscopic CH3NH3PbI3/TiO2 Heterojunction Solar Cells with Carbon Counter Electrode

    PubMed Central

    Ku, Zhiliang; Rong, Yaoguang; Xu, Mi; Liu, Tongfa; Han, Hongwei

    2013-01-01

    A mesoscopic methylammonium lead iodide (CH3NH3PbI3) perovskite/TiO2 heterojunction solar cell is developed with low-cost carbon counter electrode (CE) and full printable process. With carbon black/spheroidal graphite CE, this mesoscopic heterojunction solar cell presents high stability and power conversion efficiency of 6.64%, which is higher than that of the flaky graphite based device and comparable to the conventional Au version. PMID:24185501

  12. Aerodynamic gradient measurements of the NH3-HNO3-NH4NO3 triad using a wet chemical instrument: an analysis of precision requirements and flux errors

    NASA Astrophysics Data System (ADS)

    Wolff, V.; Trebs, I.; Ammann, C.; Meixner, F. X.

    2010-02-01

    The aerodynamic gradient method is widely used for flux measurements of ammonia, nitric acid, particulate ammonium nitrate (the NH3-HNO3-NH4NO3 triad) and other water-soluble reactive trace compounds. The surface exchange flux is derived from a measured concentration difference and micrometeorological quantities (turbulent exchange coefficient). The significance of the measured concentration difference is crucial for the significant determination of surface exchange fluxes. Additionally, measurements of surface exchange fluxes of ammonia, nitric acid and ammonium nitrate are often strongly affected by phase changes between gaseous and particulate compounds of the triad, which make measurements of the four individual species (NH3, HNO3, NH4+, NO3- necessary for a correct interpretation of the measured concentration differences. We present here a rigorous analysis of results obtained with a multi-component, wet-chemical instrument, able to simultaneously measure gradients of both gaseous and particulate trace substances. Basis for our analysis are two field experiments, conducted above contrasting ecosystems (grassland, forest). Precision requirements of the instrument as well as errors of concentration differences and micrometeorological exchange parameters have been estimated, which, in turn, allows the establishment of thorough error estimates of the derived fluxes of NH3, HNO3, NH4+, and NO3-. Derived median flux errors for the grassland and forest field experiments were: 39% and 50% (NH3), 31% and 38% (HNO3), 62% and 57% (NH4+), and 47% and 68% (NO3-), respectively. Additionally, we provide the basis for using field data to characterize the instrument performance, as well as subsequent quantification of surface exchange fluxes and underlying mechanistic processes under realistic ambient measurement conditions.

  13. Aerodynamic gradient measurements of the NH3-HNO3-NH4NO3 triad using a wet chemical instrument: an analysis of precision requirements and flux errors

    NASA Astrophysics Data System (ADS)

    Wolff, V.; Trebs, I.; Ammann, C.; Meixner, F. X.

    2009-10-01

    The aerodynamic gradient method is widely used for flux measurements of ammonia, nitric acid, particulate ammonium nitrate (the NH3-HNO3-NH4NO3 triad) and other water-soluble reactive trace compounds. The surface exchange flux is derived from a measured concentration difference and micrometeorological quantities (turbulent exchange coefficient). The significance of the measured concentration difference is crucial for the significant determination of surface exchange fluxes. Additionally, measurements of surface exchange fluxes of ammonia, nitric acid and ammonium nitrate are often strongly affected by phase changes between gaseous and particulate compounds of the triad, which make measurements of the four individual species (NH3, HNO3, NH4+, NO3-) necessary for a correct interpretation of the measured concentration differences. We present here a rigorous analysis of results obtained with a multi-component, wet-chemical instrument, able to simultaneously measure gradients of both gaseous and particulate trace substances. Basis for our analysis are two field experiments, conducted above contrasting ecosystems (grassland, forest). Precision requirements of the instrument as well as errors of concentration differences and micrometeorological exchange parameters have been estimated, which, in turn, allows the establishment of thorough error estimates of the derived fluxes of NH3, HNO3, NH4+, and NO3-. Derived median flux errors for the grassland and forest field experiments were: 39 and 50% (NH3), 31 and 38% (HNO3), 62 and 57% (NH4+), and 47 and 68% (NO3-), respectively. Additionally, we provide the basis for using field data to characterize the instrument performance, as well as subsequent quantification of surface exchange fluxes and underlying mechanistic processes under realistic ambient measurement conditions.

  14. Correlation between Cu ion migration behaviour and deNOx activity in Cu-SSZ-13 for the standard NH3-SCR reaction.

    PubMed

    Beale, A M; Lezcano-Gonzalez, I; Slawinksi, W A; Wragg, D S

    2016-05-01

    Here we present the results of a synchrotron-based in situ, time-resolved PXRD study during activation of two Cu-SSZ-13 catalysts under O2/He and one during standard NH3-SCR reaction conditions to obtain insight into the behaviour of Cu ions. The results obtained indicate that deNOx activity is inexorably linked with occupancy of the zeolite 6r. PMID:27075517

  15. Efficient CH3 NH3 PbI3 Perovskite Solar Cells Employing Nanostructured p-Type NiO Electrode Formed by a Pulsed Laser Deposition.

    PubMed

    Park, Jong Hoon; Seo, Jangwon; Park, Sangman; Shin, Seong Sik; Kim, Young Chan; Jeon, Nam Joong; Shin, Hee-Won; Ahn, Tae Kyu; Noh, Jun Hong; Yoon, Sung Cheol; Hwang, Cheol Seong; Seok, Sang Il

    2015-07-15

    Highly transparent and nanostructured nickel oxide (NiO) films through pulsed laser deposition are introduced for efficient CH3 NH3 PbI3 perovskite solar cells. The (111)-oriented nanostructured NiO film plays a key role in extracting holes and preventing electron leakage as hole transporting material. The champion device exhibits a power conversion efficiency of 17.3% with a very high fill factor of 0.813. PMID:26038099

  16. Correlation between Cu ion migration behaviour and deNOx activity in Cu-SSZ-13 for the standard NH3-SCR reaction.

    PubMed

    Beale, A M; Lezcano-Gonzalez, I; Slawinksi, W A; Wragg, D S

    2016-05-01

    Here we present the results of a synchrotron-based in situ, time-resolved PXRD study during activation of two Cu-SSZ-13 catalysts under O2/He and one during standard NH3-SCR reaction conditions to obtain insight into the behaviour of Cu ions. The results obtained indicate that deNOx activity is inexorably linked with occupancy of the zeolite 6r.

  17. Self-formed grain boundary healing layer for highly efficient CH3 NH3 PbI3 perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Son, Dae-Yong; Lee, Jin-Wook; Choi, Yung Ji; Jang, In-Hyuk; Lee, Seonhee; Yoo, Pil J.; Shin, Hyunjung; Ahn, Namyoung; Choi, Mansoo; Kim, Dongho; Park, Nam-Gyu

    2016-07-01

    Perovskite solar cells have attracted significant research efforts due to their remarkable performance, with certified power conversion efficiency now reaching 22%. Solution-processed perovskite thin films are polycrystalline, and grain boundaries are thought to be responsible for causing recombination and trapping of charge carriers. Here we report an effective and reproducible way of treating grain boundaries in CH3NH3PbI3 films deposited by means of a Lewis acid-base adduct approach. We show by high-resolution transmission electron microscopy lattice images that adding 6 mol% excess CH3NH3I to the precursor solution resulted in a CH3NH3I layer forming at the grain boundaries. This layer is responsible for suppressing non-radiative recombination and improving hole and electron extraction at the grain boundaries by forming highly ionic-conducting pathways. We report an average power conversion efficiency of 20.1% over 50 cells (best cell at 20.4%) together with significantly reduced current-voltage hysteresis achieved by this grain boundary healing process.

  18. First-principles study of photovoltaics and carrier mobility for non-toxic halide perovskite CH3NH3SnCl3: theoretical prediction.

    PubMed

    Wang, Lin-Zhi; Zhao, Yu-Qing; Liu, Biao; Wu, Li-Juan; Cai, Meng-Qiu

    2016-08-10

    Promising candidates in this respect are organometal perovskites ABX3, which have been intensely investigated during the last years. In this paper, we calculate the crystal structures, optical properties and carrier mobility for three phases of non-toxic perovskite halide CH3NH3SnCl3 by applying density functional theory with the nonlocal van der Waals (vdW) correlation. The results show that CH3NH3SnCl3 has superior performance in terms of its optical absorption coefficient, which reaches as high as 10(5) cm(-1) and has proven itself to be a perfect solar light harvester. Most importantly, the results of intrinsic carrier mobility of CH3NH3SnCl3 show that the electron mobility of the triclinic phase can achieve a large magnitude of 1700 cm(2) V(-1) s(-1), which is mainly due to the small effective mass. We ascribe the superior photoelectric property to the ferroelectricity, which may be caused by the distorted octahedral SnCl6(-).

  19. Electron-hole diffusion lengths >175 μm in solution-grown CH3NH3PbI3 single crystals

    DOE PAGES

    Dong, Qingfeng; Fang, Yanjun; Shao, Yuchuan; Mulligan, Padhraic; Qiu, Jie; Cao, Lei; Huang, Jinsong

    2015-02-27

    Long, balanced electron and hole diffusion lengths greater than 100 nanometers in the polycrystalline organolead trihalide compound CH3NH3PbI3 are critical for highly efficient perovskite solar cells. We found that the diffusion lengths in CH3NH3PbI3 single crystals grown by a solution-growth method can exceed 175 micrometers under 1 sun (100 mW cm–2) illumination and exceed 3 millimeters under weak light for both electrons and holes. The internal quantum efficiencies approach 100% in 3-millimeter-thick single-crystal perovskite solar cells under weak light. These long diffusion lengths result from greater carrier mobility, longer lifetime, and much smaller trap densities in the single crystals thanmore » in polycrystalline thin films. As a result, the long carrier diffusion lengths enabled the use of CH3NH3PbI3 in radiation sensing and energy harvesting through the gammavoltaic effect, with an efficiency of 3.9% measured with an intense cesium-137 source.« less

  20. DRIFT studies on promotion mechanism of H3PW12O40 in selective catalytic reduction of NO with NH3.

    PubMed

    Weng, Xiaole; Dai, Xiaoxia; Zeng, Qingshan; Liu, Yue; Wu, Zhongbiao

    2016-01-01

    Heteropoly acids (HPAs) have been effectively utilized in selective catalytic reduction (SCR) of NO to improve the NH3 absorption capacity and alkaline/alkali metal resistance for SCR catalysts. However, despite the promise on super-acidities, their other properties that would work on SCR process are still lack of exploration. In this study, a 12-tungstaphosphoric acid (H3PW12O40, HPW) was selected to modify a well-reported CeO2 catalyst. The resulted CeO2/HPW catalyst was subsequently utilized for SCR of NO with excess NH3, which revealed a significantly promoted performance in SCR reaction. DRIFT analyses showed that the unique NO2 absorption capacity of HPW could prevent the NO2 being further oxidized into nitrate species and the abundant Brønsted acid sites could effectively retain the NH3, avoiding them being over-oxidized at evaluated temperatures. The presence of NO2 was demonstrated able to induce a so called "fast SCR" reaction over the CeO2/HPW catalyst, which effectively facilitated the SCR reaction. Furthermore, we have also constructed a CeO2@HPW catalyst, which showed an enhanced SO2 poisoning resistance in SCR reaction. PMID:26397902

  1. 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.

  2. Factors Affecting the Sealing Efficiency of Low-k Dielectric Surface Pores Using Successive He and Ar/NH3 Plasma Treatment

    NASA Astrophysics Data System (ADS)

    Shoeb, Juline; Kushner, Mark

    2009-10-01

    Sequential treatment of porous SiCOH by He and NH3 plasmas is effective at sealing pores while maintaining the low-k of the dielectric. He plasmas activate surface sites to accelerate the reactions responsible for pore sealing. Additional NH3 plasma treatment completes the sealing through formation of Si-N, C-N and N-N bonds resulting from the adsorption of NHx. To seal pores, sufficient He plasma exposure time is required to break Si-O bonds at SiO2 sites and to activate pore lining CHn groups by removal of H atoms. Sealing efficiency degrades if the pore radius is too large to link the sites of opposite pore walls by Si-N-N-C, Si-N-N-Si or C-N-N-C chains. In this talk, we discuss results from a computational investigation of the sealing efficiency of a porous carbon doped silica films (SiOCH). The Hybrid Plasma Equipment Model provided the fluxes of ions, neutrals and photons onto the surface from He and NH3/Ar ICPs. The sealing mechanism was implemented in the Monte Carlo Feature Profile Model with which profiles of the low-k pores are predicted. Factors affecting the sealing efficiency, such as treatment time, bias, average pore radius and pore radius standard deviation will be discussed.

  3. Achieving Ultrafast Hole Transfer at the Monolayer MoS2 and CH3NH3PbI3 Perovskite Interface by Defect Engineering.

    PubMed

    Peng, Bo; Yu, Guannan; Zhao, Yawen; Xu, Qiang; Xing, Guichuan; Liu, Xinfeng; Fu, Deyi; Liu, Bo; Tan, Jun Rong Sherman; Tang, Wei; Lu, Haipeng; Xie, Jianliang; Deng, Longjiang; Sum, Tze Chien; Loh, Kian Ping

    2016-06-28

    The performance of a photovoltaic device is strongly dependent on the light harvesting properties of the absorber layer as well as the charge separation at the donor/acceptor interfaces. Atomically thin two-dimensional transition metal dichalcogenides (2-D TMDCs) exhibit strong light-matter interaction, large optical conductivity, and high electron mobility; thus they can be highly promising materials for next-generation ultrathin solar cells and optoelectronics. However, the short optical absorption path inherent in such atomically thin layers limits practical applications. A heterostructure geometry comprising 2-D TMDCs (e.g., MoS2) and a strongly absorbing material with long electron-hole diffusion lengths such as methylammonium lead halide perovskites (CH3NH3PbI3) may overcome this constraint to some extent, provided the charge transfer at the heterostructure interface is not hampered by their band offsets. Herein, we demonstrate that the intrinsic band offset at the CH3NH3PbI3/MoS2 interface can be overcome by creating sulfur vacancies in MoS2 using a mild plasma treatment; ultrafast hole transfer from CH3NH3PbI3 to MoS2 occurs within 320 fs with 83% efficiency following photoexcitation. Importantly, our work highlights the feasibility of applying defect-engineered 2-D TMDCs as charge-extraction layers in perovskite-based optoelectronic devices. PMID:27243103

  4. Triggering N(2) uptake via redox-induced expulsion of coordinated NH(