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Sample records for catalytic chemical vapour

  1. Fabrication of multiwalled carbon nanotubes in the channels of iron loaded three dimensional mesoporous material by catalytic chemical vapour deposition technique

    NASA Astrophysics Data System (ADS)

    Somanathan, T.; Gokulakrishnan, N.; Chandrasekar, G.; Pandurangan, A.

    2011-01-01

    The growth of multiwalled carbon nanotubes (MWNTs) was successfully achieved in the channels of three dimensional (3D) iron loaded mesoporous matrices (KIT-6) by employing catalytic chemical vapour deposition (CCVD) technique. The synthesised MWNTs, which were characterised by SEM, TEM and Raman spectroscopy, consist of thick graphene layers of about 10 nm composed of 29 graphene sheets with inner and outer diameter of ∼17 nm and ∼37 nm, respectively. The Raman spectrum showed the formation of well-graphitised MWNTs with significantly higher IG/ID ratio of 1.47 compared to commercial MWNTs. Comparatively, 2 wt% Fe loaded KIT-6 material produced a better yield of 91%, which is also highest compared with the report of MWNTs synthesis using mesoporous materials reported so far.

  2. Fine-tuning of catalytic tin nanoparticles by the reverse micelle method for direct deposition of silicon nanowires by a plasma-enhanced chemical vapour technique.

    PubMed

    Poinern, Gérrard E J; Ng, Yan-Jing; Fawcett, Derek

    2010-12-15

    The reverse micelle method was used for the reduction of a tin (Sn) salt solution to produce metallic Sn nanoparticles ranging from 85 nm to 140 nm in diameter. The reverse micellar system used in this process was hexane-butanol-cetyl trimethylammonium bromide (CTAB). The diameters of the Sn nanoparticles were proportional to the concentration of the aqueous Sn salt solution. Thus, the size of the Sn nanoparticles can easily be controlled, enabling a simple, reproducible mechanism for the growth of silicon nanowires (SiNWs) using plasma-enhanced chemical vapour deposition (PECVD). Both the Sn nanoparticles and silicon nanowires were characterised using field-emission scanning electron microscopy (FE-SEM). Further characterisations of the SiNW's were made using transmission electron microscopy (TEM), atomic force microscopy (AFM) and Raman spectroscopy. In addition, dynamic light scattering (DLS) was used to investigate particle size distributions. This procedure demonstrates an economical route for manufacturing reproducible silicon nanowires using fine-tuned Sn nanoparticles for possible solar cell applications.

  3. Biocompatibility of chemical-vapour-deposited diamond.

    PubMed

    Tang, L; Tsai, C; Gerberich, W W; Kruckeberg, L; Kania, D R

    1995-04-01

    The biocompatibility of chemical-vapour-deposited (CVD) diamond surfaces has been assessed. Our results indicate that CVD diamond is as biocompatible as titanium (Ti) and 316 stainless steel (SS). First, the amount of adsorbed and 'denatured' fibrinogen on CVD diamond was very close to that of Ti and SS. Second, both in vitro and in vivo there appears to be less cellular adhesion and activation on the surface of CVD diamond surfaces compared to Ti and SS. This evident biocompatibility, coupled with the corrosion resistance and notable mechanical integrity of CVD diamond, suggests that diamond-coated surfaces may be highly desirable in a number of biomedical applications. PMID:7654876

  4. Speciation of mercury in fish samples by flow injection catalytic cold vapour atomic absorption spectrometry.

    PubMed

    Zhang, Yanlin; Adeloju, Samuel B

    2012-04-01

    A rapid flow injection catalytic cold vapour atomic absorption spectrometric (FI-CCV-AAS) method is described for speciation and determination of mercury in biological samples. Varying concentrations of NaBH(4) were employed for mercury vapour generation from inorganic and mixture of inorganic and organic (total) Hg. The presence of Fe(3+), Cu(2+) and thiourea had catalytic effect on mercury vapour generation from methylmercury (MeHg) and, when together, Cu(2+) and thiourea had synergistic catalytic effect on the vapour generation. Of the two metal ions, Fe(3+) gave the best sensitivity enhancement, achieving the same sensitivity for MeHg and inorganic Hg(2+). Due to similarity of resulting sensitivity, Hg(2+) was used successfully as a primary standard for quantification of inorganic and total Hg. The catalysis was homogeneous in nature, and it was assumed that the breaking of the C-Hg bond was facilitated by the delocalization of the 5d electron pairs in Hg atom. The extraction of MeHg and inorganic mercury (In-Hg) in fish samples were achieved quantitatively with hydrochloric acid in the presence of thiourea and determined by FI-CCV-AAS. The application of the method to the quantification of mercury species in a fish liver reference material DOLT-4 gave 91.5% and 102.3% recoveries for total and methyl mercury, respectively. The use of flow injection enabled rapid analysis with a sample throughput of 180 h(-1).

  5. Chemical vapour deposition of zeolitic imidazolate framework thin films

    NASA Astrophysics Data System (ADS)

    Stassen, Ivo; Styles, Mark; Grenci, Gianluca; Gorp, Hans Van; Vanderlinden, Willem; Feyter, Steven De; Falcaro, Paolo; Vos, Dirk De; Vereecken, Philippe; Ameloot, Rob

    2016-03-01

    Integrating metal-organic frameworks (MOFs) in microelectronics has disruptive potential because of the unique properties of these microporous crystalline materials. Suitable film deposition methods are crucial to leverage MOFs in this field. Conventional solvent-based procedures, typically adapted from powder preparation routes, are incompatible with nanofabrication because of corrosion and contamination risks. We demonstrate a chemical vapour deposition process (MOF-CVD) that enables high-quality films of ZIF-8, a prototypical MOF material, with a uniform and controlled thickness, even on high-aspect-ratio features. Furthermore, we demonstrate how MOF-CVD enables previously inaccessible routes such as lift-off patterning and depositing MOF films on fragile features. The compatibility of MOF-CVD with existing infrastructure, both in research and production facilities, will greatly facilitate MOF integration in microelectronics. MOF-CVD is the first vapour-phase deposition method for any type of microporous crystalline network solid and marks a milestone in processing such materials.

  6. Nano structured carbon nitrides prepared by chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Karuppannan, Ramesh; Prashantha, M.

    2010-08-01

    Nanostructured carbon nitride films were prepared by pyrolysis assisted chemical vapour deposition(CVD). A two zone furnace with a temperature profile having a uniform temperature over a length of 20 cm length has been designed and developed. The precursor Azabenzimidazole was taken in a quartz tube and evaporated at 400 0C. The dense vapours enter the pyrolysis zone kept at a desired temperature and deposit on the quartz substrates. The FTIR spectrum of the prepared samples shows peaks at 1272 cm-1 (C.N stretching) and 1600 cm-1 (C=N) confirms the bonding of nitrogen with carbon. Raman D and G peaks, are observed at 1360 cm-1 and 1576 cm-1 respectively. XPS core level spectra of C 1s and N 1s show the formation of π bonding between carbon and nitrogen atoms. The size of the nano crystals estimated from the SEM images and XRD is ~100 nm. In some regions of the sample a maximum of 57 atom % of nitrogen has been observed.

  7. Light-induced chemical vapour deposition painting with titanium dioxide

    NASA Astrophysics Data System (ADS)

    Halary-Wagner, E.; Bret, T.; Hoffmann, P.

    2003-03-01

    Light-induced chemical vapour deposits of titanium dioxide are obtained from titanium tetra-isopropoxide (TTIP) in an oxygen and nitrogen atmosphere with a long pulse (250 ns) 308 nm XeCl excimer laser using a mask projection set-up. The demonstrated advantages of this technique are: (i) selective area deposition, (ii) precise control of the deposited thickness and (iii) low temperature deposition, enabling to use a wide range of substrates. A revolving mask system enables, in a single reactor load, to deposit shapes of controlled heights, which overlap to build up a complex pattern. Interferential multi-coloured deposits are achieved, and the process limitations (available colours and resolution) are discussed.

  8. Photo Initiated Chemical Vapour Deposition To Increase Polymer Hydrophobicity.

    PubMed

    Bérard, Ariane; Patience, Gregory S; Chouinard, Gérald; Tavares, Jason R

    2016-01-01

    Apple growers face new challenges to produce organic apples and now many cover orchards with high-density polyethylene (HDPE) nets to exclude insects, rather than spraying insecticides. However, rainwater- associated wetness favours the development of apple scabs, Venturia inaequalis, whose lesions accumulate on the leaves and fruit causing unsightly spots. Treating the nets with a superhydrophobic coating should reduce the amount of water that passes through the net. Here we treat HDPE and polyethylene terephthalate using photo-initiated chemical vapour deposition (PICVD). We placed polymer samples in a quartz tube and passed a mixture of H2 and CO through it while a UVC lamp (254 nm) illuminated the surface. After the treatment, the contact angle between water droplets and the surface increased by an average of 20°. The contact angle of samples placed 70 cm from the entrance of the tube was higher than those at 45 cm and 20 cm. The PICVD-treated HDPE achieved a contact angle of 124°. Nets spray coated with a solvent-based commercial product achieved 180° but water ingress was, surprisingly, higher than that for nets with a lower contact angle. PMID:27531048

  9. High crystalline quality single crystal chemical vapour deposition diamond

    NASA Astrophysics Data System (ADS)

    Martineau, P. M.; Gaukroger, M. P.; Guy, K. B.; Lawson, S. C.; Twitchen, D. J.; Friel, I.; Hansen, J. O.; Summerton, G. C.; Addison, T. P. G.; Burns, R.

    2009-09-01

    Homoepitaxial chemical vapour deposition (CVD) on high pressure, high temperature (HPHT) synthetic diamond substrates allows the production of diamond material with controlled point defect content. In order to minimize the extended defect content, however, it is necessary to minimize the number of substrate extended defects that reach the initial growth surface and the nucleation of dislocations at the interface between the CVD layer and its substrate. X-ray topography has indicated that when type IIa HPHT synthetic substrates are used, the density of dislocations nucleating at the interface can be less than 400 cm-2. X-ray topography, photoluminescence imaging and birefringence microscopy of HPHT grown synthetic type IIa diamond clearly show that the extended defect content is growth sector dependent. lang111rang sectors contain the highest concentration of both stacking faults and dislocations but lang100rang sectors are relatively free of both. It has been shown that HPHT treatment of such material can significantly reduce the area of stacking faults and cause dislocations to move. This knowledge, coupled with an understanding of how growth sectors develop during HPHT synthesis, has been used to guide selection and processing of substrates suitable for CVD synthesis of material with high crystalline perfection and controlled point defect content.

  10. Photo Initiated Chemical Vapour Deposition To Increase Polymer Hydrophobicity

    PubMed Central

    Bérard, Ariane; Patience, Gregory S.; Chouinard, Gérald; Tavares, Jason R.

    2016-01-01

    Apple growers face new challenges to produce organic apples and now many cover orchards with high-density polyethylene (HDPE) nets to exclude insects, rather than spraying insecticides. However, rainwater- associated wetness favours the development of apple scabs, Venturia inaequalis, whose lesions accumulate on the leaves and fruit causing unsightly spots. Treating the nets with a superhydrophobic coating should reduce the amount of water that passes through the net. Here we treat HDPE and polyethylene terephthalate using photo-initiated chemical vapour deposition (PICVD). We placed polymer samples in a quartz tube and passed a mixture of H2 and CO through it while a UVC lamp (254 nm) illuminated the surface. After the treatment, the contact angle between water droplets and the surface increased by an average of 20°. The contact angle of samples placed 70 cm from the entrance of the tube was higher than those at 45 cm and 20 cm. The PICVD-treated HDPE achieved a contact angle of 124°. Nets spray coated with a solvent-based commercial product achieved 180° but water ingress was, surprisingly, higher than that for nets with a lower contact angle. PMID:27531048

  11. Photo Initiated Chemical Vapour Deposition To Increase Polymer Hydrophobicity

    NASA Astrophysics Data System (ADS)

    Bérard, Ariane; Patience, Gregory S.; Chouinard, Gérald; Tavares, Jason R.

    2016-08-01

    Apple growers face new challenges to produce organic apples and now many cover orchards with high-density polyethylene (HDPE) nets to exclude insects, rather than spraying insecticides. However, rainwater- associated wetness favours the development of apple scabs, Venturia inaequalis, whose lesions accumulate on the leaves and fruit causing unsightly spots. Treating the nets with a superhydrophobic coating should reduce the amount of water that passes through the net. Here we treat HDPE and polyethylene terephthalate using photo-initiated chemical vapour deposition (PICVD). We placed polymer samples in a quartz tube and passed a mixture of H2 and CO through it while a UVC lamp (254 nm) illuminated the surface. After the treatment, the contact angle between water droplets and the surface increased by an average of 20°. The contact angle of samples placed 70 cm from the entrance of the tube was higher than those at 45 cm and 20 cm. The PICVD-treated HDPE achieved a contact angle of 124°. Nets spray coated with a solvent-based commercial product achieved 180° but water ingress was, surprisingly, higher than that for nets with a lower contact angle.

  12. Long distance spin communication in chemical vapour deposited graphene

    PubMed Central

    Kamalakar, M. Venkata; Groenveld, Christiaan; Dankert, André; Dash, Saroj P.

    2015-01-01

    Graphene is an ideal medium for long-distance spin communication in future spintronic technologies. So far, the prospect is limited by the smaller sizes of exfoliated graphene flakes and lower spin transport properties of large-area chemical vapour-deposited (CVD) graphene. Here we demonstrate a high spintronic performance in CVD graphene on SiO2/Si substrate at room temperature. We show pure spin transport and precession over long channel lengths extending up to 16 μm with a spin lifetime of 1.2 ns and a spin diffusion length ∼6 μm at room temperature. These spin parameters are up to six times higher than previous reports and highest at room temperature for any form of pristine graphene on industrial standard SiO2/Si substrates. Our detailed investigation reinforces the observed performance in CVD graphene over wafer scale and opens up new prospects for the development of lateral spin-based memory and logic applications. PMID:25857650

  13. Carbon Nanotubes/Nanofibers by Plasma Enhanced Chemical Vapour Deposition

    NASA Technical Reports Server (NTRS)

    Teo, K. B. K.; Hash, D. B.; Bell, M. S.; Chhowalla, M.; Cruden, B. A.; Amaratunga, G. A. J.; Meyyappan, M.; Milne, W. I.

    2005-01-01

    Plasma enhanced chemical vapour deposition (PECVD) has been recently used for the production of vertically aligned carbon nanotubedfibers (CN) directly on substrates. These structures are potentially important technologically as electron field emitters (e.g. microguns, microwave amplifiers, displays), nanoelectrodes for sensors, filter media, superhydrophobic surfaces and thermal interface materials for microelectronics. A parametric study on the growth of CN grown by glow discharge dc-PECVD is presented. In this technique, a substrate containing thin film Ni catalyst is exposed to C2H2 and NH3 gases at 700 C. Without plasma, this process is essentially thermal CVD which produces curly spaghetti-like CN as seen in Fig. 1 (a). With the plasma generated by biasing the substrate at -6OOV, we observed that the CN align vertically during growth as shown in Fig. l(b), and that the magnitude of the applied substrate bias affects the degree of alignment. The thickness of the thin film Ni catalyst was found to determine the average diameter and inversely the length of the CN. The yield and density of the CN were controlled by the use of different diffusion barrier materials under the Ni catalyst. Patterned CN growth [Fig. l(c)], with la variation in CN diameter of 4.1% and 6.3% respectively, is achieved by lithographically defining the Ni thin film prior to growth. The shape of the structures could be varied from very straight nanotube-like to conical tip-like nanofibers by increasing the ratio of C2H2 in the gas flow. Due to the plasma decomposition of C2H2, amorphous carbon (a-C) is an undesirable byproduct which could coat the substrate during CN growth. Using a combination of depth profiled Auger electron spectroscopy to study the substrate and in-situ mass spectroscopy to examine gas phase neutrals and ions, the optimal conditions for a-C free growth of CN is determined.

  14. Chemical and catalytic properties of elemental carbon

    SciTech Connect

    Chang, S.G.; Brodzinsky, R.; Gundel, L.A.; Novakov, T.

    1980-10-01

    Elemental carbon particles resulting from incomplete combustion of fossil fuel are one of the major constituents of airborne particulate matter. These particles are a chemically and catalytically active material and can be an effective carrier for other toxic air pollutants through their adsorptive capability. The chemical, adsorptive, and catalytic behaviors of carbon particles depend very much on their crystalline structure, surface composition, and electronic properties. This paper discusses these properties and examines their relevance to atmospheric chemistry.

  15. Crystal growth of HfS 2 by chemical vapour transport with halogen (Cl, Br, I)

    NASA Astrophysics Data System (ADS)

    Fiechter, S.; Eckert, K.

    1988-05-01

    Single crystals of HfS 2 have been prepared by chemical vapour transport (CVT) with halogen. Depending on the transporting agent added, exergonic or endergonic transport was observed. Employing 0.5 mg/cm 3 chlorine or bromine in evacuated and sealed quartz ampoules, exergonic transport occurs. In a temperature gradient from 850 to 870 K transparent reddish-orange crystal platelets of pseudohexagonal shape (10×10×0.05 mm3) were obtained. Endergonic transport, found with iodine as transporting agent, first starts at higher temperatures (1270-1220 K). A thermochemical study of the vapour phase composition revealed that gaseous HfHal 4 and HfHal 3 ( Hal = Cl, Br) are responsible for the exergonic transport observed. Because of the higher stability of HfS 2 against iodine, CVT first starts at elevated temperatures. In the vapour phase Hfl and Hfl 2 dominate and effect a reversal of the transport direction.

  16. Chemical vapour deposition of thermochromic vanadium dioxide thin films for energy efficient glazing

    SciTech Connect

    Warwick, Michael E.A.; Binions, Russell

    2014-06-01

    Vanadium dioxide is a thermochromic material that undergoes a semiconductor to metal transitions at a critical temperature of 68 °C. This phase change from a low temperature monoclinic structure to a higher temperature rutile structure is accompanied by a marked change in infrared reflectivity and change in resistivity. This ability to have a temperature-modulated film that can limit solar heat gain makes vanadium dioxide an ideal candidate for thermochromic energy efficient glazing. In this review we detail the current challenges to such glazing becoming a commercial reality and describe the key chemical vapour deposition technologies being employed in the latest research. - Graphical abstract: Schematic demonstration of the effect of thermochromic glazing on solar radiation (red arrow represents IR radiation, black arrow represents all other solar radiation). - Highlights: • Vanadium dioxide thin films for energy efficient glazing. • Reviews chemical vapour deposition techniques. • Latest results for thin film deposition for vanadium dioxide.

  17. Chemical vapour deposition growth and Raman characterization of graphene layers and carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Lai, Y.-C.; Rafailov, P. M.; Vlaikova, E.; Marinova, V.; Lin, S. H.; Yu, P.; Yu, S.-C.; Chi, G. C.; Dimitrov, D.; Sveshtarov, P.; Mehandjiev, V.; Gospodinov, M. M.

    2016-02-01

    Single-layer graphene films were grown by chemical vapour deposition (CVD) on Cu foil. The CVD process was complemented by plasma enhancement to grow also vertically aligned multiwalled carbon nanotubes using Ni nanoparticles as catalyst. The obtained samples were characterized by Raman spectroscopy analysis. Nature of defects in the samples and optimal growth conditions leading to achieve high quality of graphene and carbon nanotubes are discussed.

  18. Light induced chemical vapour deposition of titanium oxide thin films at room temperature

    NASA Astrophysics Data System (ADS)

    Halary, E.; Benvenuti, G.; Wagner, F.; Hoffmann, P.

    2000-02-01

    High resolution patterned deposition of titania is achieved by light induced chemical vapour deposition (LICVD), by imaging a mask onto a glass substrate. A long pulse XeCl Excimer laser (308 nm) provides, by perpendicular irradiation, the energy to convert titanium tetraisopropoxide (TTIP) vapour into titanium dioxide films, in an oxygen atmosphere, on unheated glass substrates. The amorphous titania deposits contain about 6% carbon contamination according to X-ray photoelectron spectroscopy (XPS) measurements. The deposition rate increases with increasing laser fluence until a maximum value is reached, then remains constant over a wide range, and finally decreases with further fluence increase due to titania ablation or thermal effects. The film thickness increases linearly with the number of pulses after a nucleation period. The strong influence of the laser pulse repetition rate on the growth rate and the thickness profile are reported.

  19. Concurrent growth of InSe wires and In2O3 tulip-like structures in the Au-catalytic vapour-liquid-solid process

    NASA Astrophysics Data System (ADS)

    Taurino, A.; Signore, M. A.

    2015-06-01

    In this work, the concurrent growth of InSe and In2O3 nanostructures, obtained by thermal evaporation of InSe powders on Au-covered Si substrates, has been investigated by scanning and transmission electron microscopy techniques. The vapour-solid and Au catalytic vapour-liquid-solid growth mechanisms, responsible of the simultaneous development of the two different types of nanostructures, i.e. InSe wires and In2O3 tulip-like structures respectively, are discussed in detail. The thermodynamic processes giving rise to the obtained morphologies and materials are explained.

  20. Aerosol assisted chemical vapour deposition control parameters for selective deposition of tungsten oxide nanostructures.

    PubMed

    Vallejos, S; Umek, P; Blackman, C

    2011-09-01

    Tungsten oxide films were deposited via Aerosol Assisted Chemical Vapour Deposition (AACVD) from the single-source precursor W(OPh)6. Film morphology and optimum deposition temperatures for formation of quasi-one-dimensional structures is influenced by the solvent 'carrier' used for deposition of the films with bulk porous films and nanostructured needles, hollow tubes and fibres obtained dependent on the solvent used and the deposition temperature. This influence of solvent could be exploited for the synthesis of other nanomaterials, and so provide a new and versatile route to develop and integrate nanostructured materials for device applications. PMID:22097557

  1. TOPICAL REVIEW: A review of plasma enhanced chemical vapour deposition of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Meyyappan, M.

    2009-11-01

    Plasma enhanced chemical vapour deposition (PECVD) has been widely discussed in the literature for the growth of carbon nanotubes (CNTs) and carbon nanofibres (CNFs) in recent years. Advantages claimed include lower growth temperatures relative to thermal CVD and the ability to grow individual, free-standing, vertical CNFs instead of tower-like structures or ensembles. This paper reviews the current status of the technology including equipment, plasma chemistry, diagnostics and modelling, and mechanisms. Recent accomplishments include PECVD of single-walled CNTs and growth at low temperatures for handling delicate substrates such as glass.

  2. Comparison of laser-ablation and hot-wall chemical vapour deposition techniques for nanowire fabrication

    NASA Astrophysics Data System (ADS)

    Stern, E.; Cheng, G.; Guthrie, S.; Turner-Evans, D.; Broomfield, E.; Lei, B.; Li, C.; Zhang, D.; Zhou, C.; Reed, M. A.

    2006-06-01

    A comparison of the transport properties of populations of single-crystal, In2O3 nanowires (NWs) grown by unassisted hot-wall chemical vapour deposition (CVD) versus NWs grown by laser-ablation-assisted chemical vapour deposition (LA-CVD) is presented. For nominally identical growth conditions across the two systems, NWs fabricated at 850 °C with laser-ablation had significantly higher average mobilities at the 99.9% confidence level, 53.3 ± 5.8 cm2 V-1 s-1 versus 10.2 ± 1.9 cm2 V-1 s-1. It is also observed that increasing growth temperature decreases mobility for LA-CVD NWs. Transmission electron microscopy studies of CVD-fabricated samples indicate the presence of an amorphous In2O3 region surrounding the single-crystal core. Further, low-temperature measurements verify the presence of ionized impurity scattering in low-mobility CVD-grown NWs.

  3. Strain and structure heterogeneity in MoS2 atomic layers grown by chemical vapour deposition.

    PubMed

    Liu, Zheng; Amani, Matin; Najmaei, Sina; Xu, Quan; Zou, Xiaolong; Zhou, Wu; Yu, Ting; Qiu, Caiyu; Birdwell, A Glen; Crowne, Frank J; Vajtai, Robert; Yakobson, Boris I; Xia, Zhenhai; Dubey, Madan; Ajayan, Pulickel M; Lou, Jun

    2014-11-18

    Monolayer molybdenum disulfide (MoS2) has attracted tremendous attention due to its promising applications in high-performance field-effect transistors, phototransistors, spintronic devices and nonlinear optics. The enhanced photoluminescence effect in monolayer MoS2 was discovered and, as a strong tool, was employed for strain and defect analysis in MoS2. Recently, large-size monolayer MoS2 has been produced by chemical vapour deposition, but has not yet been fully explored. Here we systematically characterize chemical vapour deposition-grown MoS2 by photoluminescence spectroscopy and mapping and demonstrate non-uniform strain in single-crystalline monolayer MoS2 and strain-induced bandgap engineering. We also evaluate the effective strain transferred from polymer substrates to MoS2 by three-dimensional finite element analysis. Furthermore, our work demonstrates that photoluminescence mapping can be used as a non-contact approach for quick identification of grain boundaries in MoS2.

  4. Aerosol-assisted delivery of precursors for chemical vapour deposition: expanding the scope of CVD for materials fabrication.

    PubMed

    Marchand, Peter; Hassan, Iman A; Parkin, Ivan P; Carmalt, Claire J

    2013-07-14

    The production of thin films of materials has become the attention of a great deal of research throughout academia and industry worldwide owing to the array of applications which utilise them, including electronic devices, gas sensors, solar cells, window coatings and catalytic systems. Whilst a number of deposition techniques are in common use, chemical vapour deposition (CVD) is an attractive process for the production of a wide range of materials due to the control it offers over film composition, coverage and uniformity, even on large scales. Conventional CVD processes can be limited, however, by the need for suitably volatile precursors. Aerosol-assisted (AA)CVD is a solution-based process which relies on the solubility of the precursor, rather than its volatility and thus vastly extends the range of potentially applicable precursors. In addition, AACVD offers extra means to control film morphology and concurrently the properties of the deposited materials. In this perspective we discuss the AACVD process, the influence of deposition conditions on film characteristics and a number of materials and applications to which AACVD has been found beneficial. PMID:23629474

  5. Single-source precursor for chemical vapour deposition of collapsed boron nitride nanotubes

    NASA Astrophysics Data System (ADS)

    Tang, Chengchun; Bando, Yoshio; Shen, Guozhen; Zhi, Chunyi; Golberg, Dmitri

    2006-12-01

    Ammonium tetrafluoroborate, a cheap and commonly used chemical, was successfully utilized in this study to synthesize BN-coated MgF2 nanowires and collapsed BN nanotubes, although previous investigations have indicated that the compound cannot be used as a chemical vapour deposition (CVD) reaction precursor of amorphous or crystalline BN. Our study reveals that when MgCl2 is used as a promoter a crystalline BN phase can be obtained on a large scale. The MgCl2 also controls the product morphology, resulting in collapsed BN-coated MgF2 nanowires at the first stage of CVD. The detailed morphology of the composite nanowires also depends on the reaction temperature. Increase in temperature stimulates the nanowire formation. The MgF2 inclusions can be fully removed via a simple high-temperature evaporation procedure, forming collapsed BN nanotubes of high purity and yield.

  6. Synthesis of Tin Nitride SnxNyNanowires by Chemical Vapour Deposition

    PubMed Central

    2009-01-01

    Tin nitride (SnxNy) nanowires have been grown for the first time by chemical vapour deposition on n-type Si(111) and in particular by nitridation of Sn containing NH4Cl at 450 °C under a steady flow of NH3. The SnxNynanowires have an average diameter of 200 nm and lengths ≥5 μm and were grown on Si(111) coated with a few nm’s of Au. Nitridation of Sn alone, under a flow of NH3is not effective and leads to the deposition of Sn droplets on the Au/Si(111) surface which impedes one-dimensional growth over a wide temperature range i.e. 300–800 °C. This was overcome by the addition of ammonium chloride (NH4Cl) which undergoes sublimation at 338 °C thereby releasing NH3and HCl which act as dispersants thereby enhancing the vapour pressure of Sn and the one-dimensional growth of SnxNynanowires. In addition to the action of dispersion, Sn reacts with HCl giving SnCl2which in turn reacts with NH3leading to the formation of SnxNyNWs. A first estimate of the band-gap of the SnxNynanowires grown on Si(111) was obtained from optical reflection measurements and found to be ≈2.6 eV. Finally, intricate assemblies of nanowires were also obtained at lower growth temperatures. PMID:20596341

  7. Chemical vapour deposition of zeolitic imidazolate framework thin films.

    PubMed

    Stassen, Ivo; Styles, Mark; Grenci, Gianluca; Gorp, Hans Van; Vanderlinden, Willem; Feyter, Steven De; Falcaro, Paolo; Vos, Dirk De; Vereecken, Philippe; Ameloot, Rob

    2016-03-01

    Integrating metal-organic frameworks (MOFs) in microelectronics has disruptive potential because of the unique properties of these microporous crystalline materials. Suitable film deposition methods are crucial to leverage MOFs in this field. Conventional solvent-based procedures, typically adapted from powder preparation routes, are incompatible with nanofabrication because of corrosion and contamination risks. We demonstrate a chemical vapour deposition process (MOF-CVD) that enables high-quality films of ZIF-8, a prototypical MOF material, with a uniform and controlled thickness, even on high-aspect-ratio features. Furthermore, we demonstrate how MOF-CVD enables previously inaccessible routes such as lift-off patterning and depositing MOF films on fragile features. The compatibility of MOF-CVD with existing infrastructure, both in research and production facilities, will greatly facilitate MOF integration in microelectronics. MOF-CVD is the first vapour-phase deposition method for any type of microporous crystalline network solid and marks a milestone in processing such materials. PMID:26657328

  8. Hot-wire chemical vapour deposition at low substrate temperatures for optoelectronic applications

    NASA Astrophysics Data System (ADS)

    Bakker, R.

    2010-09-01

    The need for large quantities of rapidly and cheaply produced electronic devices has increased rapidly over the past decades. The transistors and diodes that are used to build these devices are predominantly made of crystalline silicon. Since crystalline silicon is very expensive to produce on a large scale and cannot be directly deposited on plastic substrates, much research is being done on thin film amorphous or nanocrystalline semiconductors and insulators. Hot-wire chemical vapour deposition (HWCVD) is a novel, low cost, and convenient way to deposit these materials. The process can be controlled in such a way that specific chemical reactions take place and unwanted side reactions are minimized. It can easily be scaled up to produce large-area thin film electronics. Conventionally, plasma enhanced chemical vapour deposition (PECVD) is used to deposit semiconductors and inorganic dielectrics. Recently, HWCVD has been explored for fast deposition of such materials. An adaptation of HWCVD, initiated chemical vapour deposition (iCVD), offers the unique possibility of producing organic materials and polymers in a vacuum reactor, without the use of solvents. This technique was originally proposed at the Massachusetts institute of technology (MIT) by Prof. Karen Gleason. The iCVD process involves the creation of radicals by dissociation of a peroxide (a molecule with a ~O-O~ bond) by a heated wire in a vacuum reactor. This radical initiates a polymerization reaction of a vinyl (a molecule with a double carbon-carbon bond, ~C=C~) monomer at a substrate held at room temperature. This thesis describes a dedicated iCVD reactor for polymer deposition, installed at Utrecht University, along with a reactor with a cooled substrate holder in an existing HWCVD multi-chamber setup for low-temperature silicon nitride (SiNx) depositions. The most important features of these reactors are described and the characterization techniques are explained. This thesis contains four new

  9. Photoluminescent Si/SiOx nanoparticle network by near atmospheric plasma-enhanced chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Yang, Q. Y.; Wang, D. X.; Guo, Y.; Ding, K.; Xu, J. Z.; Shi, J. J.; Zhang, J.

    2011-11-01

    A very fast and simple near atmospheric plasma-enhanced chemical vapour deposition method modulated by a pulsed negative bias voltage is newly developed to yield a Si/SiOx nanoparticle-linked network structure, which emitted enhanced 410 nm photoluminescence (PL) at room temperature. Hydrogen dissociation, oxidation and polarization of the silane plasma-generated active particles could be tuned by the magnitude of bias voltage. The porosity and oxidation of this network structure and the intensity of its PL spectrum at 410 nm were observed to increase with the bias voltage. The large surface area of the Si/SiOx nanoparticle-linked network intensified the radiative recombination centre effect and caused the PL emission enhancement.

  10. Graphene growth from reduced graphene oxide by chemical vapour deposition: seeded growth accompanied by restoration

    PubMed Central

    Chang, Sung-Jin; Hyun, Moon Seop; Myung, Sung; Kang, Min-A; Yoo, Jung Ho; Lee, Kyoung G.; Choi, Bong Gill; Cho, Youngji; Lee, Gaehang; Park, Tae Jung

    2016-01-01

    Understanding the underlying mechanisms involved in graphene growth via chemical vapour deposition (CVD) is critical for precise control of the characteristics of graphene. Despite much effort, the actual processes behind graphene synthesis still remain to be elucidated in a large number of aspects. Herein, we report the evolution of graphene properties during in-plane growth of graphene from reduced graphene oxide (RGO) on copper (Cu) via methane CVD. While graphene is laterally grown from RGO flakes on Cu foils up to a few hundred nanometres during CVD process, it shows appreciable improvement in structural quality. The monotonous enhancement of the structural quality of the graphene with increasing length of the graphene growth from RGO suggests that seeded CVD growth of graphene from RGO on Cu surface is accompanied by the restoration of graphitic structure. The finding provides insight into graphene growth and defect reconstruction useful for the production of tailored carbon nanostructures with required properties. PMID:26961409

  11. Methyldichloroborane evidenced as an intermediate in the chemical vapour deposition synthesis of boron carbide.

    PubMed

    Reinisch, G; Patel, S; Chollon, G; Leyssale, J-M; Alotta, D; Bertrand, N; Vignoles, G L

    2011-09-01

    The most recent ceramic-matrix composites (CMC) considered for long-life applications as thermostructural parts in aerospace propulsion contain, among others, boron-rich phases like boron carbide. This compound is prepared by thermal Chemical Vapour Infiltration (CVI), starting from precursors like boron halides and hydrocarbons. We present a study aiming at a precise knowledge of the gas-phase composition in a hot-zone LPCVD reactor fed with BCl3, CH4 and H2, which combines experimental and theoretical approaches. This work has brought strong evidences of the presence of Methydichloroborane (MDB, BCl2CH3) in the process. It is demonstrated that this intermediate, the presence of which had never been formally proved before, appears for processing temperatures slightly lower than the deposition temperature of boron carbide. The study features quantum chemical computations, which provide several pieces of information like thermochemical and kinetic data, as well as vibration and rotation frequencies, reaction kinetics computations, and experimental gas-phase characterization of several species by FTIR, for several processing parameter sets. The main results are presented, and the place of MDB in the reaction scheme is discussed.

  12. Quantum Hall resistance standards from graphene grown by chemical vapour deposition on silicon carbide

    PubMed Central

    Lafont, F.; Ribeiro-Palau, R.; Kazazis, D.; Michon, A.; Couturaud, O.; Consejo, C.; Chassagne, T.; Zielinski, M.; Portail, M.; Jouault, B.; Schopfer, F.; Poirier, W.

    2015-01-01

    Replacing GaAs by graphene to realize more practical quantum Hall resistance standards (QHRS), accurate to within 10−9 in relative value, but operating at lower magnetic fields than 10 T, is an ongoing goal in metrology. To date, the required accuracy has been reported, only few times, in graphene grown on SiC by Si sublimation, under higher magnetic fields. Here, we report on a graphene device grown by chemical vapour deposition on SiC, which demonstrates such accuracies of the Hall resistance from 10 T up to 19 T at 1.4 K. This is explained by a quantum Hall effect with low dissipation, resulting from strongly localized bulk states at the magnetic length scale, over a wide magnetic field range. Our results show that graphene-based QHRS can replace their GaAs counterparts by operating in as-convenient cryomagnetic conditions, but over an extended magnetic field range. They rely on a promising hybrid and scalable growth method and a fabrication process achieving low-electron-density devices. PMID:25891533

  13. Interface study between nanostructured tantalum nitride films and carbon nanotubes grown by chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Bouchet-Fabre, B.; Pinault, M.; Foy, E.; Hugon, M. C.; Minéa, T.; Mayne-L'Hermite, M.

    2014-10-01

    We present the role of nitrogen content in tantalum nitride ultra-thin buffers, on the carbon nanotubes (CNTs) growth by chemical vapour deposition at 850 °C, assisted by ferrocene as catalyst source. Tantalum nitride (TaNx) films with a very large range of concentration x = [0, 1.8] and various nanostructures, from amorphous Ta(N) to Ta3N5, were deposited by Highly Pulsed Plasma Magnetron Sputtering. The buffer films are characterized after heat treatment at 850 °C, and after the CNT growth, by wide angle X-ray scattering in grazing incidence and scanning electron microscopy. The CNT diameter explored by transition electron microscopy shows an all-out value for under stoichiometric thin films (Ta1-N1-δ, Ta3-N5-δ) and a minimum value just above the stoichiometric phases (Ta1-N1+δ, Ta3-N5+δ). Firstly one shows that the buffer films under the heat treatment present surface modification highly dependent on their initial state, which influences the catalyst particles diffusion. Secondly at the stoichiometric TaN phase we show that a specific ternary phase FeTa2O6 is formed at the interface CNT/buffer, not present in the other cases, leading to a special CNT growth condition.

  14. Nano sized bismuth oxy chloride by metal organic chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Jagdale, Pravin; Castellino, Micaela; Marrec, Françoise; Rodil, Sandra E.; Tagliaferro, Alberto

    2014-06-01

    Metal organic chemical vapour deposition (MOCVD) method was used to prepare thin films of bismuth based nano particles starting from bismuth salts. Nano sized bismuth oxy chloride (BiOCl) crystals were synthesized from solution containing bismuth chloride (BiCl3) in acetone (CH3sbnd COsbnd CH3). Self-assembly of nano sized BiOCl crystals were observed on the surface of silicon, fused silica, copper, carbon nanotubes and aluminium substrates. Various synthesis parameters and their significant impact onto the formation of self-assembled nano-crystalline BiOCl were investigated. BiOCl nano particles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy and Micro-Raman spectroscopy. These analyses confirm that bismuth nanometer-sized crystal structures showing a single tetragonal phase were indeed bismuth oxy chloride (BiOCl) square platelets 18-250 nm thick and a few micrometres wide.

  15. Chemical Vapour Deposition of Graphene with Re-useable Pt and Cu substrates for Flexible Electronics

    NASA Astrophysics Data System (ADS)

    Karamat, Shumaila; Sonusen, Selda; Celik, Umit; Uysalli, Yigit; Oral, Ahmet

    2015-03-01

    Graphene has gained the attention of scientific world due to its outstanding physical properties. The future demand of flexible electronics such as solar cells, light emitting diodes, photo-detectors and touch screen technology requires more exploration of graphene properties on flexible substrates. The most interesting application of graphene is in organic light emitting diodes (OLED) where efforts are in progress to replace brittle indium tin oxide (ITO) electrode with a flexible graphene electrode because ITO raw materials are becoming increasingly expensive, and its brittle nature makes it unsuitable for flexible devices. In this work, we grow graphene on Pt and Cu substrates using chemical vapour deposition (CVD) and transferred it to a polymer material (PVA) using lamination technique. We used hydrogen bubbling method for separating graphene from Pt and Cu catalyst to reuse the substrates many times. After successful transfer of graphene on polymer samples, we checked the resistivity values of the graphene sheet which varies with growth conditions. Furthermore, Raman, atomic force microscopy (AFM), I-V and Force-displacement measurements will be presented for these samples.

  16. Characterisation of TiO 2 deposited by photo-induced chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Kaliwoh, Never; Zhang, Jun-Ying; Boyd, Ian W.

    2002-01-01

    We report the deposition of thin TiO 2 films on crystalline Si and quartz by photo-induced chemical vapour deposition (CVD) using UV excimer lamps employing a dielectric barrier discharge in krypton chloride (KrCl ∗) to provide intense narrow band radiation at λ=222 nm. The precursor used was titanium isopropoxide (TTIP). Films from around 20-510 nm in thickness with refractive indices from 2.20 to 2.54 were grown at temperatures between 50 and 350 °C. The higher refractive index values compare favourably with the value of 2.58 recorded for the bulk material. The measured deposition rate was around 50 nm/min at 350 °C. Fourier transform infrared spectroscopy (FTIR) revealed the presence of TiO 2 through the observation of a Ti-O absorption peak and the absence of OH in films deposited at 250-350 °C indicated relatively good quality films. The phase of films deposited at 200-350 °C was anatase as determined by X-ray diffraction.

  17. The augmented saddle field discharge characteristics and its applications for plasma enhanced chemical vapour deposition

    SciTech Connect

    Wong, Johnson; Yeghikyan, Davit; Kherani, Nazir P.

    2013-04-07

    A high ion flux parallel electrode plasma is proposed and studied in its DC configuration. By cascading a diode source region which supplies electrons and a saddle field region where these seed electrons are energized and amplified, the energy of ion bombardment on the substrate can be decoupled from the plasma density. The sufficiently large density of electrons and holes in the vicinity of the substrate raises the possibility to perform plasma enhanced chemical vapour deposition on insulating materials, at low sheath voltages (around 40 V in the configuration studied), at low temperatures in which the surface mobility of film growth species may be provided by the bombardment of moderate energy ions. As a benchmarking exercise, experiments are carried out on silane discharge characteristics and deposition of hydrogenated amorphous silicon (a-Si:H) on both silicon wafer and glass. The films grown at low anode voltages have excellent microstructures with predominantly monohydride bonds, sharp band tails, but relatively high integrated defect density in the mid 10{sup 16}/cm{sup 3} range for the particular substrate temperature of 180 Degree-Sign C, indicating that further optimizations are necessary if the electrode configuration is to be used to create a-Si:H devices.

  18. In-line silicon epitaxy for photovoltaics using a continous chemical vapour deposition reactor.

    PubMed

    Keller, Martin; Reber, Stefan; Schillinger, Norbert; Pocza, David; Arnold, Martin

    2011-09-01

    Thin film solar cell techniques can effectively reduce the costs for photovoltaic solar power. However, most of these techniques still have the disadvantage of a comparatively low efficiency. One way to realize a thin film solar cell concept with high efficiency potential is the crystalline silicon thin-film (cSiTF) concept. Following the high-temperature approach, this concept is based on a silicon epitaxy process. This paper reports the current status of the development of a high throughput epitaxy tool at Fraunhofer ISE and presents first results. Also presented is the development of a simulation tool which is a virtual image of the real setup in order to forecast save deposition conditions. The presented epitaxy tool is the ConCVD (Continuous Chemical Vapour Deposition), in which an improved reactor setup has been installed, based on the experience gained so far. To provide insight into upcoming further advances, the industrial scale epitaxy tool ProConCVD is presented as well.

  19. Chemically-modified cellulose paper as a microstructured catalytic reactor.

    PubMed

    Koga, Hirotaka; Kitaoka, Takuya; Isogai, Akira

    2015-01-15

    We discuss the successful use of chemically-modified cellulose paper as a microstructured catalytic reactor for the production of useful chemicals. The chemical modification of cellulose paper was achieved using a silane-coupling technique. Amine-modified paper was directly used as a base catalyst for the Knoevenagel condensation reaction. Methacrylate-modified paper was used for the immobilization of lipase and then in nonaqueous transesterification processes. These catalytic paper materials offer high reaction efficiencies and have excellent practical properties. We suggest that the paper-specific interconnected microstructure with pulp fiber networks provides fast mixing of the reactants and efficient transport of the reactants to the catalytically-active sites. This concept is expected to be a promising route to green and sustainable chemistry.

  20. Mathematical and numerical models of CdTe deposition in a pre-cracking metalorganic chemical vapour deposition reactor

    NASA Astrophysics Data System (ADS)

    Davis, T. J.; McAllister, T.; Maslen, V.; Wilkins, S. W.; Faith, M.; Leech, P.

    1993-10-01

    A mathematical model is used to calculate the deposition profile of CdTe in a horizontal pre-cracker metalorganic chemical vapour deposition (MOCVD) reactor. The model is solved numerically in two dimensions, yielding the temperature profile in the reactor and the concentrations of chemical species. The calculated deposition profiles are compared with growths of CdTe on glass. With appropriate approximations, the model is reduced to a simple form which is solved analytically. This model has enabled us to identify the cause of the non-uniformity in the deposition profile as a variation in the rate of supply of metal vapour. By optimizing the reactor temperature and the gas flow rates, high-uniformity CdTe films have been grown on GaAs substrates.

  1. Guiding Catalytically Active Particles with Chemically Patterned Surfaces

    NASA Astrophysics Data System (ADS)

    Uspal, W. E.; Popescu, M. N.; Dietrich, S.; Tasinkevych, M.

    2016-07-01

    Catalytically active Janus particles suspended in solution create gradients in the chemical composition of the solution along their surfaces, as well as along any nearby container walls. The former leads to self-phoresis, while the latter gives rise to chemiosmosis, providing an additional contribution to self-motility. Chemiosmosis strongly depends on the molecular interactions between the diffusing chemical species and the wall. We show analytically, using an approximate "point-particle" approach, that by chemically patterning a planar substrate one can direct the motion of Janus particles: the induced chemiosmotic flows can cause particles to either "dock" at the chemical step between the two materials or follow a chemical stripe. These theoretical predictions are confirmed by full numerical calculations. Generically, docking occurs for particles which tend to move away from their catalytic caps, while stripe following occurs in the opposite case. Our analysis reveals the physical mechanisms governing this behavior.

  2. Alumina coating on dense tungsten powder by fluidized bed metal organic chemical vapour deposition.

    PubMed

    Rodriguez, Philippe; Caussat, Brigitte; Ablitzer, Carine; Iltis, Xavière; Brothier, Meryl

    2011-09-01

    In order to study the feasibility of coating very dense powders by alumina using Fluidized Bed Metal Organic Chemical Vapour Deposition (FB-MOCVD), experiments were performed on a commercial tungsten powder, 75 microm in median volume diameter and 19,300 kg/m3 in grain density. The first part of the work was dedicated to the experimental study of the tungsten powder fluidization using argon as carrier gas at room temperature and at 400 degrees C. Due to the very high density of the tungsten powder, leading to low initial fixed bed heights and low bed expansions, different weights of powder were tested in order to reach satisfactory temperature profiles along the fluidized bed. Then, using argon as a fluidized bed former and aluminium acetylacetonate Al(C5O2H7)3 as a single source precursor, alumina thin films were deposited on tungsten particles at a low temperature range (e.g., 370-420 degrees C) by FB-MOCVD. The influence of the weight of powder, bed temperature and run duration was studied. Characterizations of the obtained samples were performed by various techniques including scanning electron microscopy (SEM) coupled with Energy Dispersive X-ray Spectroscopy (EDS) analyses, Field Emission Gun SEM (FEG-SEM) and Fourier Transform InfraRed (FT-IR) spectroscopy. The different analyses indicated that tungsten particles were uniformly coated by a continuous alumina thin film. The thickness of the film ranged between 25 and 80 nm, depending on the coating conditions. The alumina thin films were amorphous and contained carbon contamination. This latter may correspond to the adsorption of species resulting from incomplete decomposition of the precursor at so low deposition temperature. PMID:22097534

  3. The Role of Plasma in Plasma Enhanced Chemical Vapour Deposition of Nanostructure Growth

    NASA Technical Reports Server (NTRS)

    Hash, David B.; Meyyappan, M.; Teo, Kenneth B. K.; Lacerda, Rodrigo G.; Rupesinghe, Nalin L.

    2004-01-01

    Chemical vapour deposition (CVD) has become the preferred process for high yield growth of carbon nanotubes and nanofibres because of its ability to pattern growth through lithographic positioning of transition metal catalysts on substrates. Many potential applications of nanotubes such as field emitters [1] require not only patterned growth but also vertical alignment. Some degree of ali,ment in thermal CVD processes can be obtained when carbon nanotubes are grown closely together as a result of van der Waals interactions. The ali,onment however is marginal, and the van der Waals prerequisite makes growth of freestanding nanofibres with thermal CVD unrealizable. The application of electric fields as a means of ali,onment has been shown to overcome this limitation [2-5], and highly aligned nanostructures can be grown if electric fields on the order of 0.5 V/microns are employed. Plasma enhanced CVD in various configurations including dc, rf, microwave, inductive and electron cyclotron resonance has been pursued as a means of enabling alignment in the CVD process. However, the sheath fields for the non-dc sources are in general not sufficient for a high degree of ali,pment and an additional dc bias is usually applied to the growth substrate. This begs the question as to the actual role of the plasma. It is clear that the plasma itself is not required for aligned growth as references [3] and [4] employed fields through small applied voltages (3-20 V) across very small electrode spacings (10-100 microns) and thus avoided striking a discharge.

  4. Catalytic upgrading of butyric acid towards fine chemicals and biofuels

    PubMed Central

    Sjöblom, Magnus; Matsakas, Leonidas; Christakopoulos, Paul; Rova, Ulrika

    2016-01-01

    Fermentation-based production of butyric acid is robust and efficient. Modern catalytic technologies make it possible to convert butyric acid to important fine chemicals and biofuels. Here, current chemocatalytic and biocatalytic conversion methods are reviewed with a focus on upgrading butyric acid to 1-butanol or butyl-butyrate. Supported Ruthenium- and Platinum-based catalyst and lipase exhibit important activities which can pave the way for more sustainable process concepts for the production of green fuels and chemicals. PMID:26994015

  5. Aerosol assisted chemical vapour deposition of gas sensitive SnO2 and Au-functionalised SnO2 nanorods via a non-catalysed vapour solid (VS) mechanism.

    PubMed

    Vallejos, Stella; Selina, Soultana; Annanouch, Fatima Ezahra; Gràcia, Isabel; Llobet, Eduard; Blackman, Chris

    2016-01-01

    Tin oxide nanorods (NRs) are vapour synthesised at relatively lower temperatures than previously reported and without the need for substrate pre-treatment, via a vapour-solid mechanism enabled using an aerosol-assisted chemical vapour deposition method. Results demonstrate that the growth of SnO2 NRs is promoted by a compression of the nucleation rate parallel to the substrate and a decrease of the energy barrier for growth perpendicular to the substrate, which are controlled via the deposition conditions. This method provides both single-step formation of the SnO2 NRs and their integration with silicon micromachined platforms, but also allows for in-situ functionalization of the NRs with gold nanoparticles via co-deposition with a gold precursor. The functional properties are demonstrated for gas sensing, with microsensors using functionalised NRs demonstrating enhanced sensing properties towards H2 compared to those based on non-functionalised NRs. PMID:27334232

  6. Aerosol assisted chemical vapour deposition of gas sensitive SnO2 and Au-functionalised SnO2 nanorods via a non-catalysed vapour solid (VS) mechanism.

    PubMed

    Vallejos, Stella; Selina, Soultana; Annanouch, Fatima Ezahra; Gràcia, Isabel; Llobet, Eduard; Blackman, Chris

    2016-06-23

    Tin oxide nanorods (NRs) are vapour synthesised at relatively lower temperatures than previously reported and without the need for substrate pre-treatment, via a vapour-solid mechanism enabled using an aerosol-assisted chemical vapour deposition method. Results demonstrate that the growth of SnO2 NRs is promoted by a compression of the nucleation rate parallel to the substrate and a decrease of the energy barrier for growth perpendicular to the substrate, which are controlled via the deposition conditions. This method provides both single-step formation of the SnO2 NRs and their integration with silicon micromachined platforms, but also allows for in-situ functionalization of the NRs with gold nanoparticles via co-deposition with a gold precursor. The functional properties are demonstrated for gas sensing, with microsensors using functionalised NRs demonstrating enhanced sensing properties towards H2 compared to those based on non-functionalised NRs.

  7. Aerosol assisted chemical vapour deposition of gas sensitive SnO2 and Au-functionalised SnO2 nanorods via a non-catalysed vapour solid (VS) mechanism

    PubMed Central

    Vallejos, Stella; Selina, Soultana; Annanouch, Fatima Ezahra; Gràcia, Isabel; Llobet, Eduard; Blackman, Chris

    2016-01-01

    Tin oxide nanorods (NRs) are vapour synthesised at relatively lower temperatures than previously reported and without the need for substrate pre-treatment, via a vapour-solid mechanism enabled using an aerosol-assisted chemical vapour deposition method. Results demonstrate that the growth of SnO2 NRs is promoted by a compression of the nucleation rate parallel to the substrate and a decrease of the energy barrier for growth perpendicular to the substrate, which are controlled via the deposition conditions. This method provides both single-step formation of the SnO2 NRs and their integration with silicon micromachined platforms, but also allows for in-situ functionalization of the NRs with gold nanoparticles via co-deposition with a gold precursor. The functional properties are demonstrated for gas sensing, with microsensors using functionalised NRs demonstrating enhanced sensing properties towards H2 compared to those based on non-functionalised NRs. PMID:27334232

  8. Aerosol assisted chemical vapour deposition of gas sensitive SnO2 and Au-functionalised SnO2 nanorods via a non-catalysed vapour solid (VS) mechanism

    NASA Astrophysics Data System (ADS)

    Vallejos, Stella; Selina, Soultana; Annanouch, Fatima Ezahra; Gràcia, Isabel; Llobet, Eduard; Blackman, Chris

    2016-06-01

    Tin oxide nanorods (NRs) are vapour synthesised at relatively lower temperatures than previously reported and without the need for substrate pre-treatment, via a vapour-solid mechanism enabled using an aerosol-assisted chemical vapour deposition method. Results demonstrate that the growth of SnO2 NRs is promoted by a compression of the nucleation rate parallel to the substrate and a decrease of the energy barrier for growth perpendicular to the substrate, which are controlled via the deposition conditions. This method provides both single-step formation of the SnO2 NRs and their integration with silicon micromachined platforms, but also allows for in-situ functionalization of the NRs with gold nanoparticles via co-deposition with a gold precursor. The functional properties are demonstrated for gas sensing, with microsensors using functionalised NRs demonstrating enhanced sensing properties towards H2 compared to those based on non-functionalised NRs.

  9. Fabrication of high density, adherent films of five-fold symmetric diamond crystals by hot filament chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Wei, Qiuping; Ashfold, M. N. R.; Yu, Z. M.; Ma, Li; Yin, D. F.

    2011-12-01

    Five-fold symmetric diamond crystals (FSDCs) have been grown on a large variety of substrates by hot filament chemical vapour deposition (CVD) methods. High density, adherent films of FSDCs have been prepared on carbon steel with a thermal sprayed WC-Co interlayer, and their quality, adhesion and tribological behaviour were investigated. The diamond films show excellent adhesion under Rockwell indentation testing and when subjected to high-speed, high-load, long-time reciprocating dry sliding ball-on-flat wear tests against a Si 3N 4 counter-face in ambient air.

  10. Nanoparticulate cerium dioxide and cerium dioxide-titanium dioxide composite thin films on glass by aerosol assisted chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Qureshi, Uzma; Dunnill, Charles W.; Parkin, Ivan P.

    2009-11-01

    Two series of composite thin films were deposited on glass by aerosol assisted chemical vapour deposition (AACVD)—nanoparticulate cerium dioxide and nanoparticulate cerium dioxide embedded in a titanium dioxide matrix. The films were analysed by a range of techniques including UV-visible absorption spectroscopy, X-ray diffraction, scanning electron microscopy and energy dispersive analysis by X-rays. The AACVD prepared films showed the functional properties of photocatalysis and super-hydrophilicity. The CeO 2 nanoparticle thin films displaying photocatalysis and photo-induced hydrophilicity almost comparable to that of anatase titania.

  11. Recent Advances in Catalytic Conversion of Ethanol to Chemicals

    SciTech Connect

    Sun, Junming; Wang, Yong

    2014-04-30

    With increased availability and decreased cost, ethanol is potentially a promising platform molecule for the production of a variety of value-added chemicals. In this review, we provide a detailed summary of recent advances in catalytic conversion of ethanol to a wide range of chemicals and fuels. We particularly focus on catalyst advances and fundamental understanding of reaction mechanisms involved in ethanol steam reforming (ESR) to produce hydrogen, ethanol conversion to hydrocarbons ranging from light olefins to longer chain alkenes/alkanes and aromatics, and ethanol conversion to other oxygenates including 1-butanol, acetaldehyde, acetone, diethyl ether, and ethyl acetate.

  12. Chemical vapour deposition of tungsten oxide thin films from single-source precursors

    NASA Astrophysics Data System (ADS)

    Cross, Warren Bradley

    This thesis describes the chemical vapour deposition (CVD) of tungsten oxide thin films on glass from a wide range of single-source precursors. Chapter 1 describes previous work that has motivated this research. Chapter 2 discusses the synthesis of conventional style candidates for single-source precursors. Reactions of WOCl4 with 3-methyl salicylic acid (MesaliH2) and 3,5-di-iso-propyl salicylic acid (di-i-PrsaliH2) yielded the ditungsten complexes [WO(Mesali)(MesaliH)2(mu-O)], 1, and [WO(di-i-Prsali)(di-i-PrsaliH)2(mu-O)], 2, and the monotungsten complex [WO(di-i-Pr sali)(di-i-PrsaliH)Cl], 3. Tungsten(VI) dioxo complexes were prepared by ligand exchange reactions of [WO2(acac)2], 4, yielding [WO2(catH)2], 5, and [WO2(malt)2], 6, (catH2 = 3,5-di-tert-butyl-catechol; maltH = maltol). Chapter 3 describes thermal analyses of the complexes 1 - 6 and tungsten hexaphenoxide, and consequently their suitability for CVD. The use of [W(OPh)6] and 2 - 6 in aerosol assisted CVD is reported in Chapter 4. Brown tungsten oxide was deposited from 2 and 3 at 600 °C; blue partially-reduced WO3-x thin films were deposited from [W(OPh)6] from 300 to 500 °C, from 4 at 600 °C and 6 at 620 °C. Sintering all of the coatings in air at 550 °C afforded yellow films of stoichiometric WO3. Raman spectroscopy and glancing angle XRD showed that coatings deposited from [W(OPh)6] at 300 °C were amorphous, whereas all the other films were the monoclinic phase gamma-tungsten oxide. Taking full advantage of the aerosol vaporisation technique led to the CVD of tungsten oxide films from polyoxometalate single-source precursors, as described in Chapter 5. The isopolyanion [nBu4N]2[W6O19], 7, afforded WO3 at 410 °C; the heteropolyanions [nBu4N]4H3[PW11O39], 8, and [nBu4N]4[PNbW11O40], 9, were used to deposit doped WO3 thin films in a highly-controlled manner at 480 °C. Thus, the unprecedented use of large, charged clusters for CVD was demonstrated. Chapter 6 describes investigations of the

  13. Guiding catalytically active particles with chemically patterned surfaces

    NASA Astrophysics Data System (ADS)

    Uspal, William; Popescu, Mihail; Dietrich, Siegfried; Tasinkevych, Mykola

    Catalytically active Janus particles in solution create gradients in the chemical composition of the solution along their surfaces, as well as along any nearby container walls. The former leads to self-phoresis, while the latter gives rise to chemi-osmosis, providing an additional contribution to self-motility. Chemi-osmosis strongly depends on the molecular interactions between the diffusing chemical species and the wall. We show analytically, using an approximate ``point-particle'' approach, that by chemically patterning a planar substrate (e.g., by adsorbing two different materials) one can direct the motion of Janus particles: the induced chemi-osmotic flows can cause particles to either ``dock'' at a chemical step between the two materials, or to follow a chemical stripe. These theoretical predictions are confirmed by full numerical calculations. Generically, docking occurs for particles which tend to move away from their catalytic caps, while stripe-following occurs in the opposite case. Our analysis reveals the physical mechanisms governing this behavior.

  14. Hair analysis as a useful procedure for detection of vapour exposure to chemical warfare agents: simulation of sulphur mustard with methyl salicylate.

    PubMed

    Spiandore, Marie; Piram, Anne; Lacoste, Alexandre; Josse, Denis; Doumenq, Pierre

    2014-06-01

    Chemical warfare agents (CWA) are highly toxic compounds which have been produced to kill or hurt people during conflicts or terrorist attacks. Despite the fact that their use is strictly prohibited according to international convention, populations' exposure still recently occurred. Development of markers of exposure to CWA is necessary to distinguish exposed victims from unexposed ones. We present the first study of hair usage as passive sampler to assess contamination by chemicals in vapour form. This work presents more particularly the hair adsorption capacity for methyl salicylate used as a surrogate of the vesicant sulphur mustard. Chemical vapours toxicity through the respiratory route has historically been defined through Haber's law's concentration-time (Ct) product, and vapour exposure of hair to methyl salicylate was conducted with various times or doses of exposure in the range of incapacitating and lethal Ct products corresponding to sulphur mustard. Following exposure, extraction of methyl salicylate from hair was conducted by simple soaking in dichloromethane. Methyl salicylate could be detected on hair for vapour concentration corresponding to about one fifth of the sulphur mustard concentration that would kill 50% of exposed individuals (LCt50). The amount of methyl salicylate recovered from hair increased with time or dose of exposure. It showed a good correlation with the concentration-time product, suggesting that hair could be used like a passive sampler to assess vapour exposure to chemical compounds. It introduces great perspectives concerning the use of hair as a marker of exposure to CWA.

  15. Durability of silver nanoparticulate films within a silica matrix by flame assisted chemical vapour deposition for biocidal applications.

    PubMed

    Cook, Ian; Shee, David W; Foster, Howard A; Varghese, Sajnu

    2011-09-01

    Healthcare acquired infection (HCAI) rates have come under increasing scrutiny in recent years and been a major priority for health professionals in the UK and elsewhere. Of particular concern is the rise of so called 'superbugs', or those resistant to conventional antibiotics, such as Escherichia coli, Clostridium difficile and methicillin resistant Staphylococcus aureus (MRSA). The reasons for this rise are many and complex, but one important factor is bacterial survival rates on wards and other hospital areas. In this respect, nanostructured biocidal surfaces offer a potentially powerful weapon in the fight against HCAI. In addition to providing a toxic environment to a range of infectious disease-causing bacteria (while remaining harmless to human health), any potential bioactive coated surface is required to be durable enough to withstand regular hospital cleaning methods without a reduction in biocidal activity over time and be economically viable to mass produce. The flame assisted chemical vapour deposition (FACVD) of silver and silver/silica films offer a means of producing such surfaces. In this work, we report investigations into a wide range of experimental factors and parameters affecting film durability, including burner head design and relative water vapour content in the flame environment. The produced films were assessed in terms of durability (by scratch testing) and relative silver content using glow discharge optical emission spectroscopy (GDOES). PMID:22097580

  16. Growth of ZnO Nanorods on Stainless Steel Wire Using Chemical Vapour Deposition and Their Photocatalytic Activity

    PubMed Central

    Abd Aziz, Siti Nor Qurratu Aini; Pung, Swee-Yong; Ramli, Nurul Najiah; Lockman, Zainovia

    2014-01-01

    The photodegradation efficiency of ZnO nanoparticles in removal of organic pollutants deteriorates over time as a high percentage of the nanoparticles can be drained away by water during the wastewater treatment. This problem can be solved by growing the ZnO nanorods on stainless steel wire. In this work, ZnO nanorods were successfully grown on stainless steel wire by chemical vapour deposition. The SAED analysis indicates that ZnO nanorod is a single crystal and is preferentially grown in [0001] direction. The deconvoluted O 1s peak at 531.5 eV in XPS analysis is associated with oxygen deficient, revealing that the ZnO nanorods contain many oxygen vacancies. This observation is further supported by the finding of the small Iuv/Ivis ratio, that is, ~1 in the photoluminescence analysis. The growth of ZnO nanorods on stainless steel wire was governed by vapour-solid mechanism as there were no Fe particles observed at the tips of the nanorods. The photodegradation of Rhodamine B solution by ZnO nanorods followed the first-order kinetics. PMID:24587716

  17. Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels.

    PubMed

    Zhou, Chun-Hui; Xia, Xi; Lin, Chun-Xiang; Tong, Dong-Shen; Beltramini, Jorge

    2011-11-01

    Lignocellulosic biomass is the most abundant and bio-renewable resource with great potential for sustainable production of chemicals and fuels. This critical review provides insights into the state-of the-art accomplishments in the chemocatalytic technologies to generate fuels and value-added chemicals from lignocellulosic biomass, with an emphasis on its major component, cellulose. Catalytic hydrolysis, solvolysis, liquefaction, pyrolysis, gasification, hydrogenolysis and hydrogenation are the major processes presently studied. Regarding catalytic hydrolysis, the acid catalysts cover inorganic or organic acids and various solid acids such as sulfonated carbon, zeolites, heteropolyacids and oxides. Liquefaction and fast pyrolysis of cellulose are primarily conducted over catalysts with proper acidity/basicity. Gasification is typically conducted over supported noble metal catalysts. Reaction conditions, solvents and catalysts are the prime factors that affect the yield and composition of the target products. Most of processes yield a complex mixture, leading to problematic upgrading and separation. An emerging technique is to integrate hydrolysis, liquefaction or pyrolysis with hydrogenation over multifunctional solid catalysts to convert lignocellulosic biomass to value-added fine chemicals and bio-hydrocarbon fuels. And the promising catalysts might be supported transition metal catalysts and zeolite-related materials. There still exist technological barriers that need to be overcome (229 references). PMID:21863197

  18. Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels.

    PubMed

    Zhou, Chun-Hui; Xia, Xi; Lin, Chun-Xiang; Tong, Dong-Shen; Beltramini, Jorge

    2011-11-01

    Lignocellulosic biomass is the most abundant and bio-renewable resource with great potential for sustainable production of chemicals and fuels. This critical review provides insights into the state-of the-art accomplishments in the chemocatalytic technologies to generate fuels and value-added chemicals from lignocellulosic biomass, with an emphasis on its major component, cellulose. Catalytic hydrolysis, solvolysis, liquefaction, pyrolysis, gasification, hydrogenolysis and hydrogenation are the major processes presently studied. Regarding catalytic hydrolysis, the acid catalysts cover inorganic or organic acids and various solid acids such as sulfonated carbon, zeolites, heteropolyacids and oxides. Liquefaction and fast pyrolysis of cellulose are primarily conducted over catalysts with proper acidity/basicity. Gasification is typically conducted over supported noble metal catalysts. Reaction conditions, solvents and catalysts are the prime factors that affect the yield and composition of the target products. Most of processes yield a complex mixture, leading to problematic upgrading and separation. An emerging technique is to integrate hydrolysis, liquefaction or pyrolysis with hydrogenation over multifunctional solid catalysts to convert lignocellulosic biomass to value-added fine chemicals and bio-hydrocarbon fuels. And the promising catalysts might be supported transition metal catalysts and zeolite-related materials. There still exist technological barriers that need to be overcome (229 references).

  19. Catalytic conversion of cellulose to chemicals in ionic liquid.

    PubMed

    Tao, Furong; Song, Huanling; Chou, Lingjun

    2011-01-01

    A simple and effective route for the production of 5-hydroxymethyl furfural (HMF) and furfural from microcrystalline cellulose (MCC) has been developed. CoSO(4) in an ionic liquid, 1-(4-sulfonic acid) butyl-3-methylimidazolium hydrogen sulfate (IL-1), was found to be an efficient catalyst for the hydrolysis of cellulose at 150°C, which led to 84% conversion of MCC after 300min reaction time. In the presence of a catalytic amount of CoSO(4), the yields of HMF and furfural were up to 24% and 17%, respectively; a small amount of levulinic acid (LA) and reducing sugars (8% and 4%, respectively) were also generated. Dimers of furan compounds were detected as the main by-products through HPLC-MS, and with the help of mass spectrometric analysis, the components of gas products were methane, ethane, CO, CO(2,) and H(2). A mechanism for the CoSO(4)-IL-1 hydrolysis system was proposed and IL-1 was recycled for the first time, which exhibited favorable catalytic activity over five repeated runs. This catalytic system may be valuable to facilitate energy-efficient and cost-effective conversion of biomass into biofuels and platform chemicals. PMID:21092940

  20. Liquid and vapour-phase antifungal activities of selected essential oils against candida albicans: microscopic observations and chemical characterization of cymbopogon citratus

    PubMed Central

    2010-01-01

    Background Use of essential oils for controlling Candida albicans growth has gained significance due to the resistance acquired by pathogens towards a number of widely-used drugs. The aim of this study was to test the antifungal activity of selected essential oils against Candida albicans in liquid and vapour phase and to determine the chemical composition and mechanism of action of most potent essential oil. Methods Minimum Inhibitory concentration (MIC) of different essential oils in liquid phase, assayed through agar plate dilution, broth dilution & 96-well micro plate dilution method and vapour phase activity evaluated through disc volatilization method. Reduction of C. albicans cells with vapour exposure was estimated by kill time assay. Morphological alteration in treated/untreated C. albicans cells was observed by the Scanning electron microscopy (SEM)/Atomic force microscopy (AFM) and chemical analysis of the strongest antifungal agent/essential oil has been done by GC, GC-MS. Results Lemon grass (Cymbopogon citratus) essential oil exhibited the strongest antifungal effect followed by mentha (Mentha piperita) and eucalyptus (Eucalyptus globulus) essential oil. The MIC of lemon grass essential oil in liquid phase (288 mg/l) was significantly higher than that in the vapour phase (32.7 mg/l) and a 4 h exposure was sufficient to cause 100% loss in viability of C. albicans cells. SEM/AFM of C. albicans cells treated with lemon grass essential oil at MIC level in liquid and vapour phase showed prominent shrinkage and partial degradation, respectively, confirming higher efficacy of vapour phase. GC-MS analysis revealed that lemon grass essential oil was dominated by oxygenated monoterpenes (78.2%); α-citral or geranial (36.2%) and β-citral or neral (26.5%), monoterpene hydrocarbons (7.9%) and sesquiterpene hydrocarbons (3.8%). Conclusion Lemon grass essential oil is highly effective in vapour phase against C. albicans, leading to deleterious morphological

  1. Perfluorodecyltrichlorosilane-based seed-layer for improved chemical vapour deposition of ultrathin hafnium dioxide films on graphene.

    PubMed

    Kitzmann, Julia; Göritz, Alexander; Fraschke, Mirko; Lukosius, Mindaugas; Wenger, Christian; Wolff, Andre; Lupina, Grzegorz

    2016-07-06

    We investigate the use of perfluorodecyltrichlorosilane-based self-assembled monolayer as seeding layer for chemical vapour deposition of HfO2 on large area CVD graphene. The deposition and evolution of the FDTS-based seed layer is investigated by X-ray photoelectron spectroscopy, Auger electron spectroscopy, and transmission electron microscopy. Crystalline quality of graphene transferred from Cu is monitored during formation of the seed layer as well as the HfO2 growth using Raman spectroscopy. We demonstrate that FDTS-based seed layer significantly improves nucleation of HfO2 layers so that graphene can be coated in a conformal way with HfO2 layers as thin as 10 nm. Proof-of-concept experiments on 200 mm wafers presented here validate applicability of the proposed approach to wafer scale graphene device fabrication.

  2. Palm Oil as the Carbon Source for the Synthesis of Carbon Nanotubes using Floating Catalyst—Chemical Vapour Deposition Method

    NASA Astrophysics Data System (ADS)

    Zobir, S. A. M.; Suriani, A. B.; Khusaimi, Z.; Mamat, H.; Zainal, Z.; Sarijo, S. H.; Rusop, M.

    2011-03-01

    CNTs were synthesized using floating catalyst by dual-furnace thermal chemical vapour deposition method at 800-1000° C. Cooking oil made of palm oil was used as the carbon precursor. Ferrocene in the presence of 0.05 M zinc nitrate and a p-type silicon wafer was used as a catalyst precursor and a sample target, respectively. The deposition temperature was varied from 800-1000° C. Nitrogen gas was used as a gas carrier with a constant flow rate of 150 sccm/min. Field emission scanning electron micrographs show the formation of CNTs together with other carbons formed on the silicon substrate. Raman spectroscopy studies were also supported the formation of CNTs.

  3. Perfluorodecyltrichlorosilane-based seed-layer for improved chemical vapour deposition of ultrathin hafnium dioxide films on graphene

    PubMed Central

    Kitzmann, Julia; Göritz, Alexander; Fraschke, Mirko; Lukosius, Mindaugas; Wenger, Christian; Wolff, Andre; Lupina, Grzegorz

    2016-01-01

    We investigate the use of perfluorodecyltrichlorosilane-based self-assembled monolayer as seeding layer for chemical vapour deposition of HfO2 on large area CVD graphene. The deposition and evolution of the FDTS-based seed layer is investigated by X-ray photoelectron spectroscopy, Auger electron spectroscopy, and transmission electron microscopy. Crystalline quality of graphene transferred from Cu is monitored during formation of the seed layer as well as the HfO2 growth using Raman spectroscopy. We demonstrate that FDTS-based seed layer significantly improves nucleation of HfO2 layers so that graphene can be coated in a conformal way with HfO2 layers as thin as 10 nm. Proof-of-concept experiments on 200 mm wafers presented here validate applicability of the proposed approach to wafer scale graphene device fabrication. PMID:27381715

  4. Perfluorodecyltrichlorosilane-based seed-layer for improved chemical vapour deposition of ultrathin hafnium dioxide films on graphene

    NASA Astrophysics Data System (ADS)

    Kitzmann, Julia; Göritz, Alexander; Fraschke, Mirko; Lukosius, Mindaugas; Wenger, Christian; Wolff, Andre; Lupina, Grzegorz

    2016-07-01

    We investigate the use of perfluorodecyltrichlorosilane-based self-assembled monolayer as seeding layer for chemical vapour deposition of HfO2 on large area CVD graphene. The deposition and evolution of the FDTS-based seed layer is investigated by X-ray photoelectron spectroscopy, Auger electron spectroscopy, and transmission electron microscopy. Crystalline quality of graphene transferred from Cu is monitored during formation of the seed layer as well as the HfO2 growth using Raman spectroscopy. We demonstrate that FDTS-based seed layer significantly improves nucleation of HfO2 layers so that graphene can be coated in a conformal way with HfO2 layers as thin as 10 nm. Proof-of-concept experiments on 200 mm wafers presented here validate applicability of the proposed approach to wafer scale graphene device fabrication.

  5. Electron field emission characteristics of nano-catkin carbon films deposited by electron cyclotron resonance microwave plasma chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Gu, Guang-Rui; Wu, Bao-Jia; Jin, Zhe; Ito, Toshimichi

    2008-02-01

    This paper reported that the nano-catkin carbon films were prepared on Si substrates by means of electron cyclotron resonance microwave plasma chemical vapour deposition in a hydrogen and methane mixture. The surface morphology and the structure of the fabricated films were characterized by using scanning electron microscopes and Raman spectroscopy, respectively. The stable field emission properties with a low threshold field of 5V/μm corresponding to a current density of about 1μA/cm2 and a current density of 3.2mA/cm2 at an electric field of 10V/μm were obtained from the carbon film deposited at CH4 concentration of 8%. The mechanism that the threshold field decreased with the increase of the CH4 concentration and the high emission current appeared at the high CH4 concentration was explained by using the Fowler-Nordheim theory.

  6. Perfluorodecyltrichlorosilane-based seed-layer for improved chemical vapour deposition of ultrathin hafnium dioxide films on graphene.

    PubMed

    Kitzmann, Julia; Göritz, Alexander; Fraschke, Mirko; Lukosius, Mindaugas; Wenger, Christian; Wolff, Andre; Lupina, Grzegorz

    2016-01-01

    We investigate the use of perfluorodecyltrichlorosilane-based self-assembled monolayer as seeding layer for chemical vapour deposition of HfO2 on large area CVD graphene. The deposition and evolution of the FDTS-based seed layer is investigated by X-ray photoelectron spectroscopy, Auger electron spectroscopy, and transmission electron microscopy. Crystalline quality of graphene transferred from Cu is monitored during formation of the seed layer as well as the HfO2 growth using Raman spectroscopy. We demonstrate that FDTS-based seed layer significantly improves nucleation of HfO2 layers so that graphene can be coated in a conformal way with HfO2 layers as thin as 10 nm. Proof-of-concept experiments on 200 mm wafers presented here validate applicability of the proposed approach to wafer scale graphene device fabrication. PMID:27381715

  7. Increasing the output power of single 808-nm laser diodes using diamond submounts produced by microwave plasma chemical vapour deposition

    SciTech Connect

    Ashkinazi, E E; Bezotosnyi, V V; Bondarev, Vadim Yu; Kovalenko, V I; Konov, Vitalii I; Krokhin, Oleg N; Oleshchenko, V A; Pevtsov, Valerii F; Popov, Yurii M; Popovich, A F; Ral'chenko, Viktor G; Cheshev, E A

    2012-11-30

    We have designed and fabricated submounts from synthetic diamond grown by microwave plasma chemical vapour deposition and developed an economical process for metallising such submounts. Laser diode chips having an 808-nm emission wavelength, 3-mm-long cavity and 130-mm-wide stripe contact were mounted on copper heat sinks with the use of diamond submounts differing in quality. The devices were tested for more than 150 h in continuous mode at an output power of 8 W on diamond with a thermal conductivity of 700 W m{sup -1} K{sup -1}, and no changes in their output power were detected. On diamond with a thermal conductivity of 1600 W m{sup -1} K{sup -1}, stable cw operation for 24 h at an output power of 12 W was demonstrated. (letters)

  8. In situ growth rate measurements during plasma-enhanced chemical vapour deposition of vertically aligned multiwall carbon nanotube films

    NASA Astrophysics Data System (ADS)

    Jönsson, M.; Nerushev, O. A.; Campbell, E. E. B.

    2007-08-01

    In situ laser reflectivity measurements are used to monitor the growth of multiwalled carbon nanotube (MWCNT) films grown by DC plasma-enhanced chemical vapour deposition (PECVD) from an iron catalyst film deposited on a silicon wafer. In contrast to thermal CVD growth, there is no initial increase in the growth rate; instead, the initial growth rate is high (as much as 10 µm min-1) and then drops off rapidly to reach a steady level (2 µm min-1) for times beyond 1 min. We show that a limiting factor for growing thick films of multiwalled nanotubes (MWNTs) using PECVD can be the formation of an amorphous carbon layer at the top of the growing nanotubes. In situ reflectivity measurements provide a convenient technique for detecting the onset of the growth of this layer.

  9. Construction of conductive multilayer films of biogenic triangular gold nanoparticles and their application in chemical vapour sensing

    NASA Astrophysics Data System (ADS)

    Singh, Amit; Chaudhari, Minakshi; Sastry, Murali

    2006-05-01

    Metal nanoparticles are interesting building blocks for realizing films for a number of applications that include bio- and chemical sensing. To date, spherical metal nanoparticles have been used to generate functional electrical coatings. In this paper we demonstrate the synthesis of electrically conductive coatings using biologically prepared gold nanotriangles as the building blocks. The gold nanotriangles are prepared by the reduction of aqueous chloroaurate ions using an extract of the lemongrass plant (Cymbopogon flexuosus) which are thereafter assembled onto a variety of substrates by simple solution casting. The conductivity of the film shows a drastic fall upon mild heat treatment, leading to the formation of electrically conductive thin films of nanoparticles. We have also investigated the possibility of using the gold nanotriangle films in vapour sensing. A large fall in film resistance is observed upon exposure to polar molecules such as methanol, while little change occurs upon exposure to weakly polar molecules such as chloroform.

  10. Rational design of a binary metal alloy for chemical vapour deposition growth of uniform single-layer graphene.

    PubMed

    Dai, Boya; Fu, Lei; Zou, Zhiyu; Wang, Min; Xu, Haitao; Wang, Sheng; Liu, Zhongfan

    2011-01-01

    Controlled growth of high-quality graphene is still the bottleneck of practical applications. The widely used chemical vapour deposition process generally suffers from an uncontrollable carbon precipitation effect that leads to inhomogeneous growth and strong correlation to the growth conditions. Here we report the rational design of a binary metal alloy that effectively suppresses the carbon precipitation process and activates a self-limited growth mechanism for homogeneous monolayer graphene. As demonstrated by an Ni-Mo alloy, the designed binary alloy contains an active catalyst component for carbon source decomposition and graphene growth and a black hole counterpart for trapping the dissolved carbons and forming stable metal carbides. This type of process engineering has been used to grow strictly single-layer graphene with 100% surface coverage and excellent tolerance to variations in growth conditions. With simplicity, scalability and a very large growth window, the presented approach may facilitate graphene research and industrial applications. PMID:22045001

  11. Studies of coupled chemical and catalytic coal conversion methods

    SciTech Connect

    Stock, L.M.

    1990-01-01

    This report concerns our research on base-catalyzed coal solubilization and a new approach for hydrogen addition. The work on base-catalyzed, chemical solubilization is continuing. this report is focused on the hydrogenation research. Specifically it deals with the use of arene chromium carbonyl complexes as reagents for the addition of dideuterium to coal molecules. In one phase of the work, he has established that the aromatic hydrocarbons in a representative coal liquid can be converted in very good yield to arene chromium carbonyl compounds. In a second phase of the work directly related to our objective of improved methods for catalytic hydrogenation, he has established that the aromatic constituents of the same coal liquid add dideuterium in the presence of added napththalene chromium carbonyl.

  12. Catalytic Hydrogenation of Bio-Oil for Chemicals and Fuels

    SciTech Connect

    Elliott, Douglas C.

    2006-02-14

    The scope of work includes optimizing processing conditions and demonstrating catalyst lifetime for catalyst formulations that are readily scaleable to commercial operations. We use a bench-scale, continuous-flow, packed-bed, catalytic, tubular reactor, which can be operated in the range of 100-400 mL/hr., from 50-400 C and up to 20MPa (see Figure 1). With this unit we produce upgraded bio-oil from whole bio-oil or useful bio-oil fractions, specifically pyrolytic lignin. The product oils are fractionated, for example by distillation, for recovery of chemical product streams. Other products from our tests have been used in further testing in petroleum refining technology at UOP and fractionation for product recovery in our own lab. Further scale-up of the technology is envisioned and we will carry out or support process design efforts with industrial partners, such as UOP.

  13. A novel three-jet microreactor for localized metal-organic chemical vapour deposition of gallium arsenide: design and simulation

    NASA Astrophysics Data System (ADS)

    Konakov, S. A.; Krzhizhanovskaya, V. V.

    2016-08-01

    We present a novel three-jet microreactor design for localized deposition of gallium arsenide (GaAs) by low-pressure Metal-Organic Chemical Vapour Deposition (MOCVD) for semiconductor devices, microelectronics and solar cells. Our approach is advantageous compared to the standard lithography and etching technology, since it preserves the nanostructure of the deposited material, it is less time-consuming and less expensive. We designed two versions of reactor geometry with a 10-micron central microchannel for precursor supply and with two side jets of a dilutant to control the deposition area. To aid future experiments, we performed computational modeling of a simplified-geometry (twodimensional axisymmetric) microreactor, based on Navier-Stokes equations for a laminar flow of chemically reacting gas mixture of Ga(CH3)3-AsH3-H2. Simulation results show that we can achieve a high-rate deposition (over 0.3 μm/min) on a small area (less than 30 μm diameter). This technology can be used in material production for microelectronics, optoelectronics, photovoltaics, solar cells, etc.

  14. Detection of chemical substances in water using an oxide nanowire transistor covered with a hydrophobic nanoparticle thin film as a liquid-vapour separation filter

    NASA Astrophysics Data System (ADS)

    Lim, Taekyung; Lee, Jonghun; Ju, Sanghyun

    2016-08-01

    We have developed a method to detect the presence of small amounts of chemical substances in water, using a Al2O3 nanoparticle thin film covered with phosphonic acid (HDF-PA) self-assembled monolayer. The HDF-PA self-assembled Al2O3 nanoparticle thin film acts as a liquid-vapour separation filter, allowing the passage of chemical vapour while blocking liquids. Prevention of the liquid from contacting the SnO2 nanowire and source-drain electrodes is required in order to avoid abnormal operation. Using this characteristic, the concentration of chemical substances in water could be evaluated by measuring the current changes in the SnO2 nanowire transistor covered with the HDF-PA self-assembled Al2O3 nanoparticle thin film.

  15. Surface and Compositional Study of Graphene grown on Lithium Niobate (LiNbO3) substrates by Chemical Vapour Deposition

    NASA Astrophysics Data System (ADS)

    Karamat, Shumaila; Celik, Umit; Oral, Ahmet

    The diversity required in the designing of electronic devices motivated the community to always attempt for new functional materials and device structures. Graphene is considered as one of the most promising candidate materials for future electronics and carbon based devices. It is very exciting to combine graphene with new dielectric materials which exhibit multifunctional properties. Lithium Niobate exhibits ferro-, pyro-, and piezoelectric properties with large electro-optic, acousto-optic, and photoelastic coefficients as well as strong photorefractive and photovoltaic effects which made it one of the most extensively studied materials over the last 50 years. We used ambient pressure chemical vapour deposition to grow graphene on LiNbO3 substrates without any catalyst. The growth was carried out in presence of methane, argon and hydrogen. AFM imaging showed very unique structures on the surface which contains triangular domains. X-ray photoelectron spectroscopy (XPS) was used to get information about the presence of necessary elements, their bonding with LiNbO3 substrates. Detailed characterization is under process which will be presented later.

  16. Plasma enhanced chemical vapour deposition of silica onto Ti: Analysis of surface chemistry, morphology and functional hydroxyl groups

    PubMed Central

    Szili, Endre J.; Kumar, Sunil; Smart, Roger St. C.; Lowe, Rachel; Saiz, Eduardo; Voelcker, Nicolas H.

    2009-01-01

    Previously, we have developed and characterised a procedure for the deposition of thin silica films by a plasma enhanced chemical vapour deposition (PECVD) procedure using tetraethoxysilane (TEOS) as the main precursor. We have used the silica coatings for improving the corrosion resistance of metals and for enhancing the bioactivity of biomedical metallic implants. Recently, we have been fine-tuning the PECVD method for producing high quality and reproducible PECVD-silica (PECVD-Si) coatings on metals, primarily for biomaterial applications. In order to understand the interaction of the PECVD-Si coatings with biological species (such as proteins and cells), it is important to first analyse the properties of the silica films deposited using the optimised parameters. Therefore, this current investigation was carried out to analyse the characteristic features of PECVD-Si deposited on Ti substrates (PECVD-Si-Ti). We determined that the PECVD-Si coatings on Ti were conformal to the substrate surface, strongly adhered to the underlying substrate and were resistant to delamination. The PECVD-Si surface was composed of stoichiometric SiO2, showed a low carbon content (below 10 at.%) and was very hydrophilic (contact angle <10°). Finally, we also showed that the PECVD-Si coatings contain functional hydroxyl groups. PMID:19809536

  17. Osteoconductive Potential of Barrier NanoSiO2 PLGA Membranes Functionalized by Plasma Enhanced Chemical Vapour Deposition

    PubMed Central

    Terriza, Antonia; Vilches-Pérez, Jose I.; de la Orden, Emilio; Yubero, Francisco; Gonzalez-Caballero, Juan L.; González-Elipe, Agustin R.; Vilches, José; Salido, Mercedes

    2014-01-01

    The possibility of tailoring membrane surfaces with osteoconductive potential, in particular in biodegradable devices, to create modified biomaterials that stimulate osteoblast response should make them more suitable for clinical use, hopefully enhancing bone regeneration. Bioactive inorganic materials, such as silica, have been suggested to improve the bioactivity of synthetic biopolymers. An in vitro study on HOB human osteoblasts was performed to assess biocompatibility and bioactivity of SiO2 functionalized poly(lactide-co-glycolide) (PLGA) membranes, prior to clinical use. A 15 nm SiO2 layer was deposited by plasma enhanced chemical vapour deposition (PECVD), onto a resorbable PLGA membrane. Samples were characterized by X-ray photoelectron spectroscopy, atomic force microscopy, scanning electron microscopy, and infrared spectroscopy (FT-IR). HOB cells were seeded on sterilized test surfaces where cell morphology, spreading, actin cytoskeletal organization, and focal adhesion expression were assessed. As proved by the FT-IR analysis of samples, the deposition by PECVD of the SiO2 onto the PLGA membrane did not alter the composition and other characteristics of the organic membrane. A temporal and spatial reorganization of cytoskeleton and focal adhesions and morphological changes in response to SiO2 nanolayer were identified in our model. The novedous SiO2 deposition method is compatible with the standard sterilization protocols and reveals as a valuable tool to increase bioactivity of resorbable PLGA membranes. PMID:24883304

  18. Refractive index dependence on optical gap in amorphous silicon—part II. Si prepared by chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Ravindra, N. M.; Ance, C.; Ferraton, J. P.; Berger, J. M.; De Chelle, F.; Robin, S.

    1983-07-01

    In the present study, we essentially attempt to extrapolate our earlier studies (1) to amorphous silicon films prepared by chemical vapour deposition using a slightly different approach. This work assumes significance especially in view of a rather dangerous trend prevailing today to generalize model calculations without attributing any importance to the method of preparation of the films. (2-4) Here, we adopt a spectroscopic approach to analyse the various properties of the a-Si films. Some of these films are doped with boron and most of them have been subjected to post-hydrogenation. This study leads us to conclude that the Moss formula (5) is again a fairly good representative of the optical gap-refractive index variation. The scheme developed by Ravindra et al.(6) is shown to be valid for these CVD films. In the passing, we attempt to analyse the properties of films prepared at different temperatures and at different rates of deposition. The model of Revesz (7) is utilised to explain the variation in the density. Our study leads us to believe that for the CVD technique (a high temperature technique with temperatures close to that of crystallisation (8), the rate of deposition seems to be very important in determining the surface conditions of the films. Further, it is seen that on post-hydrogenation, the spectroscopic parameters as have been defined in the Wemple-Didomenico model (9) behave randomly. The study has been carried out on a large number of samples.

  19. An investigation of plasma chemistry for dc plasma enhanced chemical vapour deposition of carbon nanotubes and nanofibres

    NASA Astrophysics Data System (ADS)

    Hash, David B.; Bell, Martin S.; Teo, Kenneth B. K.; Cruden, Brett A.; Milne, William I.; Meyyappan, M.

    2005-06-01

    The role of plasma in plasma enhanced chemical vapour deposition of carbon nanotubes and nanofibres is investigated with both experimental and computational diagnostic techniques. A residual gas analysis (RGA) of a 12 mbar dc discharge with a C2H2/NH3 gas mixture is conducted near the Ni catalyst surface employed for carbon nanofibre growth. The results are corroborated with a 1D dc discharge model that solves for species densities, ion momentum, and ion, electron and neutral gas thermal energies. The effect of varying the plasma power from 0 to 200 W on the gas composition is studied. The dissociation efficiency of the plasma is demonstrated where over 50% of the feedstock is converted to a mixture of hydrogen, nitrogen and hydrogen cyanide at 200 W. Finally, the important role that endothermic ion-molecule reactions play in this conversion is, for the first time, established. Of these reactions, dissociative proton abstraction and collision-induced dissociation are of the greatest significance.

  20. Titania Coated Mica via Chemical Vapour Deposition, Post N-doped by Liquid Ammonia Treatment

    NASA Astrophysics Data System (ADS)

    Powell, Michael J.; Parkin, Ivan P.

    TiO2 films were successfully grown on synthetic mica powders via Chemical Vapor Deposition (CVD). The CVD rig is a cold-walled design that allows surface coverage of a powder to be successfully achieved. The TiO2 was produced by the reaction between TiCl4 and Ethyl Acetate. The powder produced could be successfully N-doped using post liquid ammonia treatment. The TiO2 powder produced could have potential applications in self-cleaning surfaces or antimicrobial paints.

  1. Strain and structure heterogeneity in MoS2 atomic layers grown by chemical vapour deposition

    DOE PAGES

    Liu, Zheng; Amani, Matin; Najmaei, Sina; Xu, Quan; Zou, Xiaolong; Zhou, Wu; Yu, Ting; Qiu, Caiyu; Birdwell, A. Glen; Crowne, Frank J.; et al

    2014-11-18

    Monolayer molybdenum disulfide (MoS2) has attracted tremendous attention due to its promising applications in high-performance field-effect transistors, phototransistors, spintronic devices, and nonlinear optics. The enhanced photoluminescence effect in monolayer MoS2 was discovered and, as a strong tool, was employed for strain and defect analysis in MoS2. Recently, large-size monolayer MoS2 has been produced by chemical vapor deposition but has not yet been fully explored. Here we systematically characterize chemical vapor deposition grown MoS2 by PL spectroscopy and mapping, and demonstrate non-uniform strain in single-crystalline monolayer MoS2 and strain-induced band gap engineering. We also evaluate the effective strain transferred from polymermore » substrates to MoS2 by three-dimensional finite element analysis. In addition, our work demonstrates that PL mapping can be used as a non-contact approach for quick identification of grain boundaries in MoS2.« less

  2. Catalytic Hydroprocessing of Chemical Models for Bio-oil

    SciTech Connect

    Elliott, Douglas C.; Hart, Todd R.

    2008-12-12

    Bio-oil (product liquids from fast pyrolysis of biomass) is a complex mixture of oxygenates derived from the thermal breakdown of the bio-polymers in biomass. In the case of lignocellulosic biomass, the structures of three major components, cellulose, hemicellulose and lignin, are well represented by the bio-oil components. In order to study the chemical mechanisms of catalytic hydroprocessing of bio-oil, three model compounds were chosen to represent those components. Guaiacol represents the large number of mono- and di-methoxy phenols found in bio-oil derived from softwood or hardwood, respectively. Furfural represents a major pyrolysis product group from cellulosics. Acetic acid is a major product from biomass pyrolysis, derived from the hemicellulose, which has important impacts on the further processing of the bio-oil because of the acidic character. These three compounds were processed using palladium or ruthenium catalyst over a temperature range from 150°C to 300°C. The batch reactor was sampled during each test over a period of four hours. The samples were analyzed by gas chromatography with both a mass selective detector and a flame ionization detector. The products were determined and the reaction pathways for their formation are suggested based on these results. Both temperature and catalyst metal have significant effects on the product composition.

  3. Nanofabrication using home-made RF plasma coupled chemical vapour deposition system

    NASA Astrophysics Data System (ADS)

    Ong, Si Ci; Ilyas, Usman; Rawat, Rajdeep Singh

    2014-08-01

    Zinc oxide, ZnO, a popular semiconductor material with a wide band gap (3.37 eV) and high binding energy of the exciton (60 meV), has numerous applications such as in optoelectronics, chemical/biological sensors, and drug delivery. This project aims to (i) optimize the operating conditions for growth of ZnO nanostructures using the chemical vapor deposition (CVD) method, and (ii) investigate the effects of coupling radiofrequency (RF) plasma to the CVD method on the quality of ZnO nanostructures. First, ZnO nanowires were synthesized using a home-made reaction setup on gold-coated and non-coated Si (100) substrates at 950 °C. XRD, SEM, EDX, and PL measurements were used for characterizations and it was found that a deposition duration of 10 minutes produced the most well-defined ZnO nanowires. SEM analysis revealed that the nanowires had diameters ranging from 30-100 mm and lengths ranging from 1-4 µm. In addition, PL analysis showed strong UV emission at 380 nm, making it suitable for UV lasing. Next, RF plasma was introduced for 30 minutes. Both remote and in situ RF plasma produced less satisfactory ZnO nanostructures with poorer crystalline structure, surface morphology, and optical properties due to etching effect of energetic ions produced from plasma. However, a reduction in plasma discharge duration to 10 minutes produced thicker and shorter ZnO nanostructures. Based on experimentation conducted, it is insufficient to conclude that RF plasma cannot aid in producing well-defined ZnO nanostructures. It can be deduced that the etching effect of energetic ions outweighed the increased oxygen radical production in RF plasma nanofabrication.

  4. Aerosol assisted chemical vapour deposition of Cu-ZnO composite from single source precursors.

    PubMed

    Shahid, Muhammad; Mazhar, Muhammad; Hamid, Mazhar; O'Brien, Paul; Malik, Mohammad A; Helliwell, Madeleine; Raftery, James

    2009-07-28

    Two heterobimetallic precursors [Zn(TFA)3(micro-OH)Cu3(dmae)3Cl].THF (1) and [Zn(TFA)4Cu3(dmae)4] (2) [dmae=N,N-dimethylaminoethanolate and TFA=trifluoroacetate], have been synthesized and characterized by their melting points, elemental analysis, FT-IR spectroscopy, mass spectrometry, TGA and single crystal X-ray diffraction methods. Both complexes were used to deposit thin films of Cu-ZnO composite on glass substrates by aerosol assisted chemical vapor deposition (AACVD) method. The films were characterized by "scotch tape" test for adhesion, thickness measurement as a function of temperature, EDX for composition, SEM for surface morphology and XRD for crystalline phases. Thin film deposition studies at 250, 325, 400, 475 degrees C indicated the increase in thickness with temperature reaching a maximum at 400 degrees C and then decreasing. EDX and PXRD results showed the uniform distribution of cubic metallic copper and hexagonal zinc oxide phases which make them useful for nanocatalysis on structured surfaces. PMID:19587992

  5. Biological properties of carbon powders synthesized using chemical vapour deposition and detonation methods.

    PubMed

    Batory, M; Batory, D; Grabarczyk, J; Kaczorowski, W; Kupcewicz, B; Mitura, K; Nasti, T H; Yusuf, N; Niedzielski, P

    2012-12-01

    Carbon powders can be synthesized using variety of CVD and detonation methods. Several interesting properties of carbon powder particles make them a very attractive material examined in many laboratories all over the world. However there is a lack of information discussing investigation of carbon powders directed to its application in pharmaceutical-cosmetic industry and medicine. Earlier investigation results proved that diamond powders present properties fighting free radicals. Presented work discusses the influence of carbon powder particles manufactured using MW/RF PACVD, RF PACVD and detonation methods onto hydro-lipid skin coat. Before the biological examinations physicochemical properties of carbon powders were determined. Grain size, shape and chemical composition of carbon powders were determined using the scanning electron microscopy. Surface functional groups were characterized by IR Fourier-transform spectroscopy and X-ray photoelectron spectroscopy. Structure and phase composition were investigated by means of the Raman spectroscopy. Results of allergy tests performed on laboratory mice proved that carbon powder particles synthesized using different methods do not cause allergy. In the following stage, the group of 20 patients applied the formula including carbon powder on their face skin. The influence of carbon powder onto hydro-lipid skin coat was determined by measurement of such parameters as: pH reaction, skin temperature, lipid fotometry and level of hydration. Additionally, macro pictures of places where the cream had been applied were registered. As the result of the investigation it was found that powders synthesized using various methods present different physicochemical properties which may individually affect the face skin parameters. The noticeable improvement of hydro-lipid skin coat kilter was observed. PMID:23447955

  6. Antimicrobial activity of novel nanostructured Cu-SiO2 coatings prepared by chemical vapour deposition against hospital related pathogens

    PubMed Central

    2013-01-01

    There is increasing recognition that the healthcare environment acts as an important reservoir for transmission of healthcare acquired infections (HCAI). One method of reducing environmental contamination would be use of antimicrobial materials. The antimicrobial activity of thin silica-copper films prepared by chemical vapour deposition was evaluated against standard strains of bacteria used for disinfectant testing and bacteria of current interest in HCAI. The structure of the coatings was determined using Scanning Electron Microscopy and their hardness and adhesion to the substrate determined. Antimicrobial activity was tested using a method based on BS ISO 22196:2007. The coatings had a pale green-brown colour and had a similar hardness to steel. SEM showed nano-structured aggregates of Cu within a silica matrix. A log10 reduction in viability of >5 could be obtained within 4 h for the disinfectant test strains and within 6 h for producing Acinetobacter baumannii, Klebsiella pneumoniae and Stenotrophomonas maltophilia. Activity against the other hospital isolates was slower but still gave log10 reduction factors of >5 for extended spectrum β-lactamase producing Escherichia coli and >3 for vancomycin resistant Enterococcus faecium, methicillin resistant Staphylococcus aureus and Pseudomonas aeruginosa within 24 h. The results demonstrate the importance of testing antimicrobial materials destined for healthcare use against isolates of current interest in hospitals as well as standard test strains. The coatings used here can also be applied to substrates such as metals and ceramics and have potential applications where reduction of microbial environmental contamination is desirable. PMID:24007899

  7. Real time chemical imaging of a working catalytic membrane reactor during oxidative coupling of methane.

    PubMed

    Vamvakeros, A; Jacques, S D M; Middelkoop, V; Di Michiel, M; Egan, C K; Ismagilov, I Z; Vaughan, G B M; Gallucci, F; van Sint Annaland, M; Shearing, P R; Cernik, R J; Beale, A M

    2015-08-18

    We report the results from an operando XRD-CT study of a working catalytic membrane reactor for the oxidative coupling of methane. These results reveal the importance of the evolving solid state chemistry during catalytic reaction, particularly the chemical interaction between the catalyst and the oxygen transport membrane.

  8. Poisoning of bubble propelled catalytic micromotors: the chemical environment matters.

    PubMed

    Zhao, Guanjia; Sanchez, Samuel; Schmidt, Oliver G; Pumera, Martin

    2013-04-01

    Self-propelled catalytic microjets have attracted considerable attention in recent years and these devices have exhibited the ability to move in complex media. The mechanism of propulsion is via the Pt catalysed decomposition of H2O2 and it is understood that the Pt surface is highly susceptible to poisoning by sulphur-containing molecules. Here, we show that important extracellular thiols as well as basic organic molecules can significantly hamper the motion of catalytic microjet engines. This is due to two different mechanisms: (i) molecules such as dimethyl sulfoxide can quench the hydroxyl radicals produced at Pt surfaces and reduce the amount of oxygen gas generated and (ii) molecules containing -SH, -SSR, and -SCH3 moieties can poison the catalytically active platinum surface, inhibiting the motion of the jet engines. It is essential that the presence of such molecules in the environment be taken into consideration for future design and operation of catalytic microjet engines. We show this effect on catalytic micromotors prepared by both rolled-up and electrodeposition approaches, demonstrating that such poisoning is universal for Pt catalyzed micromotors. We believe that our findings will contribute significantly to this field to develop alternative systems or catalysts for self-propulsion when practical applications in the real environment are considered. PMID:23450281

  9. Poisoning of bubble propelled catalytic micromotors: the chemical environment matters

    NASA Astrophysics Data System (ADS)

    Zhao, Guanjia; Sanchez, Samuel; Schmidt, Oliver G.; Pumera, Martin

    2013-03-01

    Self-propelled catalytic microjets have attracted considerable attention in recent years and these devices have exhibited the ability to move in complex media. The mechanism of propulsion is via the Pt catalysed decomposition of H2O2 and it is understood that the Pt surface is highly susceptible to poisoning by sulphur-containing molecules. Here, we show that important extracellular thiols as well as basic organic molecules can significantly hamper the motion of catalytic microjet engines. This is due to two different mechanisms: (i) molecules such as dimethyl sulfoxide can quench the hydroxyl radicals produced at Pt surfaces and reduce the amount of oxygen gas generated and (ii) molecules containing -SH, -SSR, and -SCH3 moieties can poison the catalytically active platinum surface, inhibiting the motion of the jet engines. It is essential that the presence of such molecules in the environment be taken into consideration for future design and operation of catalytic microjet engines. We show this effect on catalytic micromotors prepared by both rolled-up and electrodeposition approaches, demonstrating that such poisoning is universal for Pt catalyzed micromotors. We believe that our findings will contribute significantly to this field to develop alternative systems or catalysts for self-propulsion when practical applications in the real environment are considered.

  10. a Study of Volatile Precursors for the Growth of Cadmium Sulphide and Cadmium Selenide by Metal Organic Chemical Vapour Deposition.

    NASA Astrophysics Data System (ADS)

    Beer, Michael P.

    Available from UMI in association with The British Library. The wide-band-gap semiconductors, cadmium sulphide and cadmium selenide, may be grown by Metal Organic Chemical Vapour Deposition (MOCVD). This method typically involves the reaction of gaseous streams of Me_2 Cd and H_2Y (Y = S, Se) over a heated substrate (usually gallium arsenide) on which the desired compound is grown as an epitaxial layer. Unfortunately, the precursors start to react in the cold zone of the reactor, that is before they reach the heated substrate. This problem is known as prereaction. The problem of prereaction is partially reduced by the use of adducts of dimethyl cadmium in place of the free dialkyl compound although the mechanism by which such adducts block prereaction is unknown. Accordingly, a study of adducts of dimethyl cadmium was undertaken with a view to determining their properties in all phases. The adduct of Me_2Cd with 2,2^ '-bipyridyl was found to be monomeric in the solid state while that with 1,4-dioxane, a volatile compound used for prereaction reduction, was found to be polymeric. A study of adducts in the gas phase using mass spectrometry and gas phase Fourier transform infrared spectroscopy gave no evidence to suggest there is any gas phase association between 1,4-dioxane and dimethyl cadmium. With the 2,2 ^'-bipyridyl adduct some evidence for partial retention of coordinate bonds upon sublimation was obtained. The solid adduct of Me _2Cd with N,N,N^' ,N^'-tetramethylethylenediamine (TMEDA) was prepared as it was hoped that the flexibility of the aliphatic Lewis base would permit the formation of an adduct containing strong co-ordinate bonds which would remain intact upon sublimation. Using gas phase electron diffraction, the structure of the adduct of Me_2Cd and TMEDA was determined. It was shown to exist in the gas phase purely as the associated monomeric species. The adduct was then employed for the growth of CdS and CdSe in an industrial MOCVD apparatus. The

  11. Vapour breakthrough behaviour of carbon tetrachloride - A simulant for chemical warfare agent on ASZMT carbon: A comparative study with whetlerite carbon

    NASA Astrophysics Data System (ADS)

    Srivastava, Avanish Kumar; Shah, Dilip K.; Mahato, T. H.; Roy, A.; Yadav, S. S.; Srivas, S. K.; Singh, Beer

    2013-06-01

    ASZMT and whetlerite carbon was prepared by impregnation of active carbon with ammonical salts of Cu (II), Ag (I), Zn (II), Mo (VI), TEDA and Cu (II), Ag (I), Cr (VI), NaOH, C5H5N respectively using incipient wetness technique. Thereafter, impregnated carbon systems were characterized using scanning electron microscopy, energy dispersive X-ray, atomic absorption spectroscopy, thermogravimetry and surface characterization techniques. Impregnated carbon systems were evaluated under dynamic conditions against carbon tetrachloride (CCl4) vapour that was used as a simulant for the persistent chemical warfare agents for testing breakthrough times of filter cartridges and canisters of gas masks in the national approval test of respirators. The protective potential of ASZMT carbon was compared with the whetlerite carbon which is presently used in NBC filtration system. The effect of CCl4 concentration, test flow rate, temperature and relative humidity on the breakthrough behaviour of the impregnated carbon systems has also been studied. The study clearly indicated that the whetlerite carbon possessed breakthrough time greater than ASZMT carbon. However, ASZMT carbon provided adequate protection against CCl4 vapours and can be used as an alternative to whetlerite carbon that contain Cr(VI), which is reported to be carcinogenic and having lesser shelf life. The study indicated the breakthrough time of impregnated carbon systems were found to decrease with the increase of the CCl4 concentration and flow rate. The variation in temperature and relative humidity did not significantly affect the breakthrough behaviour of impregnated carbon systems at high vapour concentration of CCl4 whereasbreak through time of impregnated carbon systems reduced by an increase of relative humidity at low CCl4 vapour concentration.

  12. Chemicals from heavy fuels in millisecond catalytic reactors

    NASA Astrophysics Data System (ADS)

    Krummenacher, Jakob Jose

    The role that millisecond catalytic reactors play on the development of the hydrogen economy is crucial because they have higher throughputs and smaller volumes than their traditional counter parts. Issues with the storage and production of hydrogen give an advantage to these reactors because their compact and small size makes them highly portable. As with the development of any new technology challenges that threaten the operation of the millisecond catalytic reactor with liquid fuels were encountered. First, the autoignition of linear alkanes is higher than their boiling points. This makes it impossible to simply vaporize the fuel and mix it with air. Second, analyzing such a diverse range of products using gas chromatography is not possible with conventional equipment. The first results of the especially engineered reactor show the successful partial oxidation of linear alkanes. Decane and hexadecane over rhodium catalysts produce synthesis gas with selectivities exceeding 80%. Experiments confirmed the highly tunable nature of the reactor. A fuel concentrated feed produces ethylene and alpha-olefins with high selectivities. A proposed mechanism and experimental results obtained suggest that these olefins are formed by homogeneous endothermic cracking. A single fuel, decane, was used to study further the millisecond catalytic reactor versatility. Several operating conditions such as catalyst porosity, effect of wash-coat, addition of steam, and addition of hydrogen were studied. Rhodium, platinum, and platinum-rhodium mixtures were coated on supports of different porosity to determine the differences in metal reactivities. The results show that rhodium is the best catalyst for making hydrogen or synthesis gas and that adding steam improves its performance. The highest yields of ethylene and a-olefins were obtained using a platinum catalyst coated with a small amount of rhodium on the front face. A rough economic analysis gives a sound idea of the potential that

  13. Polycyclic organic material (POM) in urban air. Fractionation, chemical analysis and genotoxicity of particulate and vapour phases in an industrial town in Finland

    NASA Astrophysics Data System (ADS)

    Pyysalo, Heikki; Tuominen, Jari; Wickström, Kim; Skyttä, Eija; Tikkanen, Leena; Salomaa, Sisko; Sorsa, Marja; Nurmela, Tuomo; Mattila, Tiina; Pohjola, Veijo

    Polycyclic organic material (POM) was collected by high-volume sampling on filter and on XAD-2 resin from the air of a small industrial town in Finland. Concurrent chemical analysis and the assays for genotoxic activity were performed on the particulate and the vapour phases of ambient air POM and their chemical fractions. Furthermore, correlations between seasonal meteorological parameters and POM concentrations were studied to reveal characteristic POM profiles for various emission sources. The range of total POM concentrations varied from 115 to 380 ng m -3 in late spring and from 17 to 83 ng m -3 in early winter. No direct correlation of ambient POM was seen with the temperature, but rather with the wind direction from various emission sources. Especially the low molecular weight compounds were associated with wind direction from industrial sources. Genotoxic activity, as detected by the Ames Salmonella/microsome test and the SCE assay in CHO cells, was found not only in the paniculate phase samples but also in the vapour phase. The polar fractions of some of the samples showed genotoxic activity, and also direct mutagenicity was observed with both the assay systems; these facts support the significance of compounds other than conventional polycyclic aromatic hydrocarbons (PAH) in the samples.

  14. Work function shifts of catalytic metals under hydrogen gas visualized by terahertz chemical microscopy.

    PubMed

    Kiwa, Toshihiko; Hagiwara, Takafumi; Shinomiya, Mitsuhiro; Sakai, Kenji; Tsukada, Keiji

    2012-05-21

    Terahertz chemical microscopy (TCM) was applied to visualize the distribution of the work function shift of catalytic metals under hydrogen gas. TCM measures the chemical potential on the surface of a SiO(2)/Si/sapphire sensing plate without any contact with the plate. By controlling the bias voltage between an electrode on the SiO(2)/ surface and the Si layer, the relationship between the voltage and the THz amplitude from the sensing plate can be obtained. As a demonstration, two types of structures were fabricated on the sensing plate, and the work function shifts due to catalytic reactions were visualized.

  15. Studies of coupled chemical and catalytic coal conversion methods

    SciTech Connect

    Stock, L.M.; Chatterjee, K.; Cheng, C.; Ettinger, M.; Flores, F.; Jiralerspong, S.; Miyake, M.; Muntean, J.

    1991-12-01

    The objective of this research was to convert coal into a soluble substance under mild conditions. The strategy involved two steps, first to breakdown the macromolecular network of coal, and second to add hydrogen catalytically. We investigated different basic reagents that could, in priciple, break down coal`s structure and alkylation strategies that might enhance its solubility. We examined O- and C-alkylation, the importance of the strength of the base, the character of the added alkyl groups and other reaction parameters. This work provided new information concerning the way in which hydrogen bonding, polarization interactions between aromatic structures and covalent bonding could be disrupted and solubility enhanced. The objective of our research was to explore new organochromium chemistry that might be feasible for the hydrogenation of coal under mild conditions.

  16. Studies of coupled chemical and catalytic coal conversion methods

    SciTech Connect

    Stock, L.M.; Chatterjee, K.; Cheng, C.; Ettinger, M.; Flores, F.; Jiralerspong, S.; Miyake, M.; Muntean, J.

    1991-12-01

    The objective of this research was to convert coal into a soluble substance under mild conditions. The strategy involved two steps, first to breakdown the macromolecular network of coal, and second to add hydrogen catalytically. We investigated different basic reagents that could, in priciple, break down coal's structure and alkylation strategies that might enhance its solubility. We examined O- and C-alkylation, the importance of the strength of the base, the character of the added alkyl groups and other reaction parameters. This work provided new information concerning the way in which hydrogen bonding, polarization interactions between aromatic structures and covalent bonding could be disrupted and solubility enhanced. The objective of our research was to explore new organochromium chemistry that might be feasible for the hydrogenation of coal under mild conditions.

  17. Prediction of Rate Constants for Catalytic Reactions with Chemical Accuracy.

    PubMed

    Catlow, C Richard A

    2016-08-01

    Ex machina: A computational method for predicting rate constants for reactions within microporous zeolite catalysts with chemical accuracy has recently been reported. A key feature of this method is a stepwise QM/MM approach that allows accuracy to be achieved while using realistic models with accessible computer resources.

  18. A Comparative Study of the Dispersion of Multi-Wall Carbon Nanotubes Made by Arc-Discharge and Chemical Vapour Deposition.

    PubMed

    Frømyr, Tomas-Roll; Bourgeaux-Goget, Marie; Hansen, Finn Knut

    2015-05-01

    A method has been developed to characterize the dispersion of multi-wall carbon nanotubes in water using a disc centrifuge for the detection of individual carbon nanotubes, residual aggregates, and contaminants. Carbon nanotubes produced by arc-discharge have been measured and compared with carbon nanotubes produced by chemical vapour deposition. Studies performed on both pristine (see text) arc-discharge nanotubes is rather strong and that high ultra-sound intensity is required to achieve complete dispersion of carbon nanotube bundles. The logarithm of the mode of the particle size distribution of the arc-discharge carbon nanotubes was found to be a linear function of the logarithm of the total ultrasonic energy input in the dispersion process. PMID:26504969

  19. Ellipsometric and Rutherford Back scattering Spectrometry studies of SiO(X)N(Y) films elaborated by plasma-enhanced chemical vapour deposition technique.

    PubMed

    Mahamdi, R; Boulesbaa, M; Saci, L; Mansour, F; Molliet, C; Collet, M; Temple-Boyer, P

    2011-10-01

    Silicon oxynitride (SiO(X)N(Y)) thin films were deposited by plasma-enhanced chemical vapour deposition technique (PECVD) from silane (SiH4), nitrous oxide (N2O), ammonia (NH3) and nitrogen (N2) mixture. Spectroscopic ellipsometry (SE), in the range of wavelengths 450-900 nm, was used to define the film thickness and therefore the deposition rate, as well as the refractive index as a function of the N2O gaseous flow. While considering the (Si3N4, SiO2, H2 or void) heterogeneous mixture, Maxwell Garnett (MG) theory allows to fit the SE measurements and to define the volume fraction of the different phases. Finally, Rutherford Backscattering Spectrometry (RBS) results showed that x = O/Si ratio increases gradually with increasing the N2O flow, allowing the correlation of the SiO(X)N(Y) films main parameters. PMID:22400311

  20. Thin films of tin(II) sulphide (SnS) by aerosol-assisted chemical vapour deposition (AACVD) using tin(II) dithiocarbamates as single-source precursors

    NASA Astrophysics Data System (ADS)

    Kevin, Punarja; Lewis, David J.; Raftery, James; Azad Malik, M.; O'Brien, Paul

    2015-04-01

    The synthesis of the asymmetric dithiocarbamates of tin(II) with the formula [Sn(S2CNRR')2] (where R=Et, R'=n-Bu (1); R=Me, R'=n-Bu (2); R=R'=Et (3)) and their use for the deposition of SnS thin films by aerosol-assisted chemical vapour deposition (AACVD) is described. The effects of temperature and the concentration of the precursors on deposition were investigated. The stoichiometry of SnS was best at higher concentrations of precursors (250 mM) and at 450 °C. The direct electronic band gap of the SnS produced by this method was estimated from optical absorbance measurements as 1.2 eV. The composition of films was confirmed by powder X-ray diffraction (p-XRD) and energy dispersive analysis of X-rays (EDAX) spectroscopy.

  1. Copper-Assisted Direct Growth of Vertical Graphene Nanosheets on Glass Substrates by Low-Temperature Plasma-Enhanced Chemical Vapour Deposition Process

    NASA Astrophysics Data System (ADS)

    Ma, Yifei; Jang, Haegyu; Kim, Sun Jung; Pang, Changhyun; Chae, Heeyeop

    2015-08-01

    Vertical graphene (VG) nanosheets are directly grown below 500 °C on glass substrates by a one-step copper-assisted plasma-enhanced chemical vapour deposition (PECVD) process. A piece of copper foil is located around a glass substrate as a catalyst in the process. The effect of the copper catalyst on the vertical graphene is evaluated in terms of film morphology, growth rate, carbon density in the plasma and film resistance. The growth rate of the vertical graphene is enhanced by a factor of 5.6 with the copper catalyst with denser vertical graphene. The analysis of optical emission spectra suggests that the carbon radical density is increased with the copper catalyst. Highly conductive VG films having 800 Ω/□ are grown on glass substrates with Cu catalyst at a relatively low temperature.

  2. A Comparative Study of the Dispersion of Multi-Wall Carbon Nanotubes Made by Arc-Discharge and Chemical Vapour Deposition.

    PubMed

    Frømyr, Tomas-Roll; Bourgeaux-Goget, Marie; Hansen, Finn Knut

    2015-05-01

    A method has been developed to characterize the dispersion of multi-wall carbon nanotubes in water using a disc centrifuge for the detection of individual carbon nanotubes, residual aggregates, and contaminants. Carbon nanotubes produced by arc-discharge have been measured and compared with carbon nanotubes produced by chemical vapour deposition. Studies performed on both pristine (see text) arc-discharge nanotubes is rather strong and that high ultra-sound intensity is required to achieve complete dispersion of carbon nanotube bundles. The logarithm of the mode of the particle size distribution of the arc-discharge carbon nanotubes was found to be a linear function of the logarithm of the total ultrasonic energy input in the dispersion process.

  3. Self-propulsion and interactions of catalytic particles in a chemically active medium

    NASA Astrophysics Data System (ADS)

    Banigan, Edward J.; Marko, John F.

    2016-01-01

    Enzymatic "machines," such as catalytic rods or colloids, can self-propel and interact by generating gradients of their substrates. We theoretically investigate the behaviors of such machines in a chemically active environment where their catalytic substrates are continuously synthesized and destroyed, as occurs in living cells. We show how the kinetic properties of the medium modulate self-propulsion and pairwise interactions between machines, with the latter controlled by a tunable characteristic interaction range analogous to the Debye screening length in an electrolytic solution. Finally, we discuss the effective force arising between interacting machines and possible biological applications, such as partitioning of bacterial plasmids.

  4. Determination and characterization of phytochelatins by liquid chromatography coupled with on line chemical vapour generation and atomic fluorescence spectrometric detection.

    PubMed

    Bramanti, Emilia; Toncelli, Daniel; Morelli, Elisabetta; Lampugnani, Leonardo; Zamboni, Roberto; Miller, Keith E; Zemetra, Joseph; D'Ulivo, Alessandro

    2006-11-10

    Liquid chromatography (LC) coupled on line with UV/visible diode array detector (DAD) and cold vapour generation atomic fluorescence spectrometry (CVGAFS) has been developed for the speciation, determination and characterization of phytochelatins (PCs). The method is based on a bidimensional approach, e.g. on the analysis of synthetic PC solutions (apo-PCs and Cd(2+)-complexed PCs) (i) by size exclusion chromatography coupled to UV diode array detector (SEC-DAD); (ii) by the derivatization of PC -SH groups in SEC fractions by p-hydroxymercurybenzoate (PHMB) and the indirect detection of PC-PHMB complexes by reversed phase liquid chromatography coupled to atomic fluorescence detector (RPLC-CVGAFS). MALDI-TOF/MS (matrix assisted laser desorption ionization time of flight mass spectrometry) analysis of underivatized synthetic PC samples was performed in order have a qualitative information of their composition. Quantitative analysis of synthetic PC solutions has been performed on the basis of peak area of PC-PHMB complexes of the mercury specific chromatogram and calibration curve of standard solution of glutathione (GSH) complexed to PHMB (GS-PHMB). The limit of quantitation (LOQ) in terms of GS-PHMB complex was 90 nM (CV 5%) with an injection volume of 35 microL, corresponding to 3.2 pmol (0.97 ng) of GSH. The method has been applied to analysis of extracts of cell cultures from Phaeodactylum tricornutum grown in Cd-containing nutrient solutions, analysed by SEC-DAD-CVGAFS and RPLC-DAD-CVGAFS.

  5. Liquid-phase chemical hydrogen storage: catalytic hydrogen generation under ambient conditions.

    PubMed

    Jiang, Hai-Long; Singh, Sanjay Kumar; Yan, Jun-Min; Zhang, Xin-Bo; Xu, Qiang

    2010-05-25

    There is a demand for a sufficient and sustainable energy supply. Hence, the search for applicable hydrogen storage materials is extremely important owing to the diversified merits of hydrogen energy. Lithium and sodium borohydride, ammonia borane, hydrazine, and formic acid have been extensively investigated as promising hydrogen storage materials based on their relatively high hydrogen content. Significant advances, such as hydrogen generation temperatures and reaction kinetics, have been made in the catalytic hydrolysis of aqueous lithium and sodium borohydride and ammonia borane as well as in the catalytic decomposition of hydrous hydrazine and formic acid. In this Minireview we briefly survey the research progresses in catalytic hydrogen generation from these liquid-phase chemical hydrogen storage materials.

  6. Chemicals from Lignin by Catalytic Fast Pyrolysis, from Product Control to Reaction Mechanism.

    PubMed

    Ma, Zhiqiang; Custodis, Victoria; Hemberger, Patrick; Bährle, Christian; Vogel, Frédéric; Jeschk, Gunnar; van Bokhoven, Jeroen A

    2015-01-01

    Conversion of lignin into renewable and value-added chemicals by thermal processes, especially pyrolysis, receives great attention. The products may serve as feedstock for chemicals and fuels and contribute to the development of a sustainable society. However, the application of lignin conversion is limited by the low selectivity from lignin to the desired products. The opportunities for catalysis to selectively convert lignin into useful chemicals by catalytic fast pyrolysis and our efforts to elucidate the mechanism of lignin pyrolysis are discussed. Possible research directions will be identified. PMID:26598403

  7. Physical and chemical activation of reduced graphene oxide for enhanced adsorption and catalytic oxidation.

    PubMed

    Liu, Shizhen; Peng, Wenchao; Sun, Hongqi; Wang, Shaobin

    2014-01-21

    Physical and chemical activation of reduced graphene oxide (RGO) using different reagents, CO2, ZnCl2 and CO2/ZnCl2, to obtain highly porous and metal-free carbonaceous materials was carried out and their adsorption and catalytic behavior were investigated. Physical activation using CO2 was proved to be much more effective than chemical ZnCl2 activation, and increased the specific surface area (SSA) of RGO from ~200 to higher than 600 m(2) g(-1). Methylene blue (MB) was then used to evaluate the adsorption and catalytic activity of the activated RGO (A-RGO) materials with peroxymonosulfate (PMS) as an oxidant. It was found that the SSA and oxygen containing groups are two important factors determining the adsorptive and catalytic performance of the A-RGO materials. RGO by physicochemical CO2/ZnCl2 activation presented the best adsorption and RGO by physical CO2 activation exhibited the highest catalytic degradation of MB.

  8. Aged nano-structured platinum based catalyst: effect of chemical treatment on adsorption and catalytic activity.

    PubMed

    Shim, Wang Geun; Nahm, Seung Won; Park, Hyuk Ryeol; Yun, Hyung Sun; Seo, Seong Gyu; Kim, Sang Chai

    2011-02-01

    To examine the effect of chemical treatment on the adsorption and catalytic activity of nanostructured platinum based catalyst, the aged commercial Pt/AC catalyst was pretreated with sulfuric acid (H2SO4) and a cleaning agent (Hexane). Several reliable methods such as nitrogen adsorption, X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and inductively coupled plasma (ICP) were employed to characterize the aged Pt/AC catalyst and its chemically pretreated Pt/AC catalysts. The catalytic and adsorption activities of nano-structured heterogeneous Pt/AC catalyst were investigated on the basis of toluene oxidation and adsorption isotherm data. In addition, the adsorption isotherms of toluene were used to calculate the adsorption energy distribution functions for the parent catalyst and its pre-treated nano-structured Pt/AC catalysts. It was found that sulfuric acid aqueous treatment can enhance the catalytic performance of aged Pt/AC catalyst toward catalytic oxidation of toluene. It was also shown that a comparative analysis of the energy distribution functions for nano-structured Pt/AC catalysts as well as the pore size distribution provides valuable information about their structural and energetic heterogeneity.

  9. Heat-Resistant Co-W Catalytic Metals for Multilayer Graphene Chemical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Ueno, Kazuyoshi; Karasawa, Yusuke; Kuwahara, Satoru; Baba, Shotaro; Hanai, Hitoshi; Yamazaki, Yuichi; Sakuma, Naoshi; Kajita, Akihiro; Sakai, Tadashi

    2013-04-01

    Multilayer graphene (MLG) is expected to be a low-resistance and high-reliability interconnect material replacing copper (Cu) in nanoscale interconnects. Chemical vapor deposition (CVD) on catalytic metals is expected as a practical method for MLG deposition. To obtain high-quality MLG films without catalyst agglomeration by CVD, heat-resistant Co-W catalytic metals were investigated. The agglomeration of the Co-W catalytic metals was suppressed by increasing the W composition; however, MLG deposition was suppressed at the same time. The effects of W addition on the MLG growth were discussed from the viewpoints of the crystallographic change of the Co-W catalysts and chemical reactions. It was found that the Co grain size was reduced and the fcc Co formation was suppressed by W addition. In addition, graphite formation was supposed to be suppressed by W addition owing to the formation of phases other than fcc Co according to the Co-W-C phase diagram. With the optimum W concentration, MLG crystallinity was improved by high-temperature CVD using the heat-resistant Co-W catalytic metals (0.7 at. %) without agglomeration, compared with that in the case of using pure-Co catalysts.

  10. Catalytic performance of carbon nanotubes in H2O2 decomposition: experimental and quantum chemical study.

    PubMed

    Voitko, Katerina; Tóth, Ajna; Demianenko, Evgenij; Dobos, Gábor; Berke, Barbara; Bakalinska, Olga; Grebenyuk, Anatolij; Tombácz, Etelka; Kuts, Volodymyr; Tarasenko, Yurij; Kartel, Mykola; László, Krisztina

    2015-01-01

    The catalytic performance of multi-walled carbon nanotubes (MWCNTs) with different surface chemistry was studied in the decomposition reaction of H2O2 at various values of pH and temperature. A comparative analysis of experimental and quantum chemical calculation results is given. It has been shown that both the lowest calculated activation energy (∼18.9 kJ/mol) and the highest rate constant correspond to the N-containing CNT. The calculated chemisorption energy values correlate with the operation stability of MWCNTs. Based on the proposed quantum chemical model it was found that the catalytic activity of carbon materials in electron transfer reactions is controlled by their electron donor capability.

  11. Graphene-Semiconductor Catalytic Nanodiodes for Quantitative Detection of Hot Electrons Induced by a Chemical Reaction.

    PubMed

    Lee, Hyosun; Nedrygailov, Ievgen I; Lee, Young Keun; Lee, Changhwan; Choi, Hongkyw; Choi, Jin Sik; Choi, Choon-Gi; Park, Jeong Young

    2016-03-01

    Direct detection of hot electrons generated by exothermic surface reactions on nanocatalysts is an effective strategy to obtain insight into electronic excitation during chemical reactions. For this purpose, we fabricated a novel catalytic nanodiode based on a Schottky junction between a single layer of graphene and an n-type TiO2 layer that enables the detection of hot electron flows produced by hydrogen oxidation on Pt nanoparticles. By making a comparative analysis of data obtained from measuring the hot electron current (chemicurrent) and turnover frequency, we demonstrate that graphene's unique electronic structure and extraordinary material properties, including its atomically thin nature and ballistic electron transport, allow improved conductivity at the interface between the catalytic Pt nanoparticles and the support. Thereby, graphene-based nanodiodes offer an effective and facile way to approach the study of chemical energy conversion mechanisms in composite catalysts with carbon-based supports.

  12. Solid-phase reduction of Cr2O3 under chemical catalytic conditions

    NASA Astrophysics Data System (ADS)

    Simonov, V. K.; Grishin, A. M.

    2016-06-01

    The kinetics of the solid-phase reduction of Cr2O3 with carbon under chemical catalytic action on the reacting system is studied. A significant intensification of the process in the presence of small amounts of potassium and sodium salts is established. The concepts of the catalyst action mechanism are considered and experimentally substantiated. Manufacture of iron-chromium master alloys with a restricted content of carbon can be organized at low temperatures, and they can be used in steelmaking.

  13. Evaluation of water vapour assimilation in the tropical upper troposphere and lower stratosphere by a chemical transport model

    NASA Astrophysics Data System (ADS)

    Payra, Swagata; Ricaud, Philippe; Abida, Rachid; El Amraoui, Laaziz; Attié, Jean-Luc; Rivière, Emmanuel; Carminati, Fabien; von Clarmann, Thomas

    2016-09-01

    The present analysis deals with one of the most debated aspects of the studies on the upper troposphere/lower stratosphere (UTLS), namely the budget of water vapour (H2O) at the tropical tropopause. Within the French project "Multiscale water budget in the upper troposphere and lower stratosphere in the TROpics" (TRO-pico), a global-scale analysis has been set up based on space-borne observations, models and assimilation techniques. The MOCAGE-VALENTINA assimilation tool has been used to assimilate the Aura Microwave Limb Sounder (MLS) version 3.3 H2O measurements within the 316-5 hPa range from August 2011 to March 2013 with an assimilation window of 1 h. Diagnostics based on observations minus analysis and forecast are developed to assess the quality of the assimilated H2O fields. Comparison with an independent source of H2O measurements in the UTLS based on the space-borne Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) observations and with meteorological ARPEGE analyses is also shown. Sensitivity studies of the analysed fields have been performed by (1) considering periods when no MLS measurements are available and (2) using H2O data from another MLS version (4.2). The studies have been performed within three different spaces in time and space coincidences with MLS (hereafter referred to as MLS space) and MIPAS (MIPAS space) observations and with the model (model space) outputs and at three different levels: 121 hPa (upper troposphere), 100 hPa (tropopause) and 68 hPa (lower stratosphere) in January and February 2012. In the MLS space, the analyses behave consistently with the MLS observations from the upper troposphere to the lower stratosphere. In the model space, the analyses are wetter than the reference atmosphere as represented by ARPEGE and MLS in the upper troposphere (121 hPa) and around the tropopause (100 hPa), but are consistent with MLS and MIPAS in the lower stratosphere (68 hPa). In the MIPAS space, the sensitivity and the

  14. Probing the Catalytic Mechanism of Vibrio harveyi GH20 β-N-Acetylglucosaminidase by Chemical Rescue

    PubMed Central

    Meekrathok, Piyanat; Suginta, Wipa

    2016-01-01

    Background Vibrio harveyi GH20 β-N-acetylglucosaminidase (VhGlcNAcase) is a chitinolytic enzyme responsible for the successive degradation of chitin fragments to GlcNAc monomers, activating the onset of the chitin catabolic cascade in marine Vibrios. Methods Two invariant acidic pairs (Asp303-Asp304 and Asp437-Glu438) of VhGlcNAcase were mutated using a site-directed mutagenesis strategy. The effects of these mutations were examined and the catalytic roles of these active-site residues were elucidated using a chemical rescue approach. Enhancement of the enzymic activity of the VhGlcNAcase mutants was evaluated by a colorimetric assay using pNP-GlcNAc as substrate. Results Substitution of Asp303, Asp304, Asp437 or Glu438 with Ala/Asn/Gln produced a dramatic loss of the GlcNAcase activity. However, the activity of the inactive D437A mutant was recovered in the presence of sodium formate. Our kinetic data suggest that formate ion plays a nucleophilic role by mimicking the β-COO-side chain of Asp437, thereby stabilizing the reaction intermediate during both the glycosylation and the deglycosylation steps. Conclusions Chemical rescue of the inactive D437A mutant of VhGlcNAcase by an added nucleophile helped to identify Asp437 as the catalytic nucleophile/base, and hence its acidic partner Glu438 as the catalytic proton donor/acceptor. General Significance Identification of the catalytic nucleophile of VhGlcNAcases supports the proposal of a substrate-assisted mechanism of GH20 GlcNAcases, requiring the catalytic pair Asp437-Glu438 for catalysis. The results suggest the mechanistic basis of the participation of β-N-acetylglucosaminidase in the chitin catabolic pathway of marine Vibrios. PMID:26870945

  15. Note on the stochastic theory of a self-catalytic chemical reaction. II

    NASA Astrophysics Data System (ADS)

    Dambrine, S.; Moreau, M.

    1981-04-01

    The general results of article I on the stochastic representation of the macroscopic stationary state of a self-catalytic chemical system are applied to a step-by-step chemical reaction. The relaxation times to the quasi-stationary state and to the final stationary state are computed by evaluating the first two non-trivial eigenvalues of the transition matrix. The previous results of Oppenheim, Shuler and Weiss are confirmed, precised and extended. The critical and subcritical cases are treated by the same method.

  16. Converting Light Energy to Chemical Energy: A New Catalytic Approach for Sustainable Environmental Remediation

    PubMed Central

    2016-01-01

    We report a synthetic approach to form cubic Cu2O/Pd composite structures and demonstrate their use as photocatalytic materials for tandem catalysis. Pd nanoparticles were deposited onto Cu2O cubes, and their tandem catalytic reactivity was studied via the reductive dehalogenation of polychlorinated biphenyls. The Pd content of the materials was gradually increased to examine its influence on particle morphology and catalytic performance. Materials were prepared at different Pd amounts and demonstrated a range of tandem catalytic reactivity. H2 was generated via photocatalytic proton reduction initiated by Cu2O, followed by Pd-catalyzed dehalogenation using in situ generated H2. The results indicate that material morphology and composition and substrate steric effects play important roles in controlling the overall reaction rate. Additionally, analysis of the postreacted materials revealed that a small number of the cubes had become hollow during the photodechlorination reaction. Such findings offer important insights regarding photocatalytic active sites and mechanisms, providing a pathway toward converting light-based energy to chemical energy for sustainable catalytic reactions not typically driven via light. PMID:27656687

  17. Converting Light Energy to Chemical Energy: A New Catalytic Approach for Sustainable Environmental Remediation

    PubMed Central

    2016-01-01

    We report a synthetic approach to form cubic Cu2O/Pd composite structures and demonstrate their use as photocatalytic materials for tandem catalysis. Pd nanoparticles were deposited onto Cu2O cubes, and their tandem catalytic reactivity was studied via the reductive dehalogenation of polychlorinated biphenyls. The Pd content of the materials was gradually increased to examine its influence on particle morphology and catalytic performance. Materials were prepared at different Pd amounts and demonstrated a range of tandem catalytic reactivity. H2 was generated via photocatalytic proton reduction initiated by Cu2O, followed by Pd-catalyzed dehalogenation using in situ generated H2. The results indicate that material morphology and composition and substrate steric effects play important roles in controlling the overall reaction rate. Additionally, analysis of the postreacted materials revealed that a small number of the cubes had become hollow during the photodechlorination reaction. Such findings offer important insights regarding photocatalytic active sites and mechanisms, providing a pathway toward converting light-based energy to chemical energy for sustainable catalytic reactions not typically driven via light.

  18. Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions

    NASA Astrophysics Data System (ADS)

    Parlett, Christopher M. A.; Isaacs, Mark A.; Beaumont, Simon K.; Bingham, Laura M.; Hondow, Nicole S.; Wilson, Karen; Lee, Adam F.

    2016-02-01

    The chemical functionality within porous architectures dictates their performance as heterogeneous catalysts; however, synthetic routes to control the spatial distribution of individual functions within porous solids are limited. Here we report the fabrication of spatially orthogonal bifunctional porous catalysts, through the stepwise template removal and chemical functionalization of an interconnected silica framework. Selective removal of polystyrene nanosphere templates from a lyotropic liquid crystal-templated silica sol-gel matrix, followed by extraction of the liquid crystal template, affords a hierarchical macroporous-mesoporous architecture. Decoupling of the individual template extractions allows independent functionalization of macropore and mesopore networks on the basis of chemical and/or size specificity. Spatial compartmentalization of, and directed molecular transport between, chemical functionalities affords control over the reaction sequence in catalytic cascades; herein illustrated by the Pd/Pt-catalysed oxidation of cinnamyl alcohol to cinnamic acid. We anticipate that our methodology will prompt further design of multifunctional materials comprising spatially compartmentalized functions.

  19. Effect of oxygen plasma on field emission characteristics of single-wall carbon nanotubes grown by plasma enhanced chemical vapour deposition system

    NASA Astrophysics Data System (ADS)

    Kumar, Avshish; Parveen, Shama; Husain, Samina; Ali, Javid; Zulfequar, Mohammad; Harsh; Husain, Mushahid

    2014-02-01

    Field emission properties of single wall carbon nanotubes (SWCNTs) grown on iron catalyst film by plasma enhanced chemical vapour deposition system were studied in diode configuration. The results were analysed in the framework of Fowler-Nordheim theory. The grown SWCNTs were found to be excellent field emitters, having emission current density higher than 20 mA/cm2 at a turn-on field of 1.3 V/μm. The as grown SWCNTs were further treated with Oxygen (O2) plasma for 5 min and again field emission characteristics were measured. The O2 plasma treated SWCNTs have shown dramatic improvement in their field emission properties with emission current density of 111 mA/cm2 at a much lower turn on field of 0.8 V/μm. The as grown as well as plasma treated SWCNTs were also characterized by various techniques, such as scanning electron microscopy, high resolution transmission electron microscopy, Raman spectroscopy, and Fourier transform infrared spectroscopy before and after O2 plasma treatment and the findings are being reported in this paper.

  20. Effect of oxygen plasma on field emission characteristics of single-wall carbon nanotubes grown by plasma enhanced chemical vapour deposition system

    SciTech Connect

    Kumar, Avshish; Parveen, Shama; Husain, Samina; Ali, Javid; Zulfequar, Mohammad; Harsh; Husain, Mushahid

    2014-02-28

    Field emission properties of single wall carbon nanotubes (SWCNTs) grown on iron catalyst film by plasma enhanced chemical vapour deposition system were studied in diode configuration. The results were analysed in the framework of Fowler-Nordheim theory. The grown SWCNTs were found to be excellent field emitters, having emission current density higher than 20 mA/cm{sup 2} at a turn-on field of 1.3 V/μm. The as grown SWCNTs were further treated with Oxygen (O{sub 2}) plasma for 5 min and again field emission characteristics were measured. The O{sub 2} plasma treated SWCNTs have shown dramatic improvement in their field emission properties with emission current density of 111 mA/cm{sup 2} at a much lower turn on field of 0.8 V/μm. The as grown as well as plasma treated SWCNTs were also characterized by various techniques, such as scanning electron microscopy, high resolution transmission electron microscopy, Raman spectroscopy, and Fourier transform infrared spectroscopy before and after O{sub 2} plasma treatment and the findings are being reported in this paper.

  1. Effect of gas flow rates on the anatase-rutile transformation temperature of nanocrystalline TiO2 synthesised by chemical vapour synthesis.

    PubMed

    Ahmad, Md Imteyaz; Bhattacharya, S S; Fasel, Claudia; Hahn, Horst

    2009-09-01

    Of the three crystallographic allotropes of nanocrystalline titania (rutile, anatase and brookite), anatase exhibits the greatest potential for a variety of applications, especially in the area of catalysis and sensors. However, with rutile being thermodynamically the most stable phase, anatase tends to transform into rutile on heating to temperatures in the range of 500 degrees C to 700 degrees C. Efforts made to stabilize the anatase phase at higher temperatures by doping with metal oxides suffer from the problems of having a large amorphous content on synthesis as well as the formation of secondary impurity phases on doping. Recent studies have suggested that the as-synthesised phase composition, crystallite size, initial surface area and processing conditions greatly influence the anatase to rutile transformation temperature. In this study nanocrystalline titania was synthesised in the anatase form bya chemical vapour synthesis (CVS) method using titanium tetra iso-propoxide (TTIP) as a precursor under varying flow rates of oxygen and helium. The anatase to rutile transformation was studied using high temperature X-ray diffraction (HTXRD) and simultaneous thermogravimetric analysis (STA), followed by transmission electron microscopy (TEM). It was demonstrated that the anatase-rutile transformation temperatures were dependent on the oxygen to helium flow rate ratio during CVS and the results are presented and discussed. PMID:19928267

  2. Aerosol assisted chemical vapour deposition of ZnO films on glass with noble metal and p-type dopants; use of dopants to influence preferred orientation

    NASA Astrophysics Data System (ADS)

    Walters, G.; Parkin, I. P.

    2009-04-01

    The use of aerosol assisted chemical vapour deposition (AACVD) for the formation of zinc oxide and doped ZnO films with control of preferred orientation on glass is reported. Undoped and doped ZnO host matrix films were highly transparent with visible transmission >85%. The Cu (CuO/Cu 2O) doped ZnO thin films were highly coloured and opaque. Undoped and noble metal doped ZnO films had mainly spherical morphology. Aluminium oxide/ZnO composite films had a range of morphologies from spherical to cubic. The XRD patterns for both doped and undoped ZnO films grown at substrate temperatures less than 500 °C showed strong preferred (0 0 2) crystal lattice orientation. The undoped ZnO film at 500 °C exhibited a random crystal orientation pattern for hexagonal ZnO. The introduction of small amounts of Al 2O 3 within the ZnO to form a composite significantly altered the preferred crystal orientation to (1 0 1).

  3. Heterocyclic dithiocarbamato-iron(III) complexes: single-source precursors for aerosol-assisted chemical vapour deposition (AACVD) of iron sulfide thin films.

    PubMed

    Mlowe, Sixberth; Lewis, David J; Malik, Mohammad Azad; Raftery, James; Mubofu, Egid B; O'Brien, Paul; Revaprasadu, Neerish

    2016-02-14

    Tris-(piperidinedithiocarbamato)iron(III) (1) and tris-(tetrahydroquinolinedithiocarbamato)iron(iii) (2) complexes have been synthesized and their single-crystal X-ray structures were determined. Thermogravimetric analysis (TGA) of the complexes showed decomposition to iron sulfide. Both complexes were then used as single-source precursors for the deposition of iron sulfide thin films by aerosol-assisted chemical vapour deposition (AACVD). Energy-dispersive X-ray (EDX) spectroscopy confirmed the formation of iron sulfide films. The addition of tert-butyl thiol almost doubled the sulfur content in the deposited films. Scanning electron microscopy (SEM) images of the iron sulfide films from both complexes showed flakes/leaves/sheets, spherical granules and nanofibres. The sizes and shapes of these crystallites depended on the nature of the precursor, temperature, solvent and the amount of tert-butyl thiol used. The observed optical properties are dependent upon the variation of reaction parameters such as temperature and solvent. Powder X-ray diffraction (p-XRD) studies revealed that pyrrhotite, hexagonal (Fe0.975S), marcasite and smythite (Fe3S4) phases were differently deposited. PMID:26732865

  4. Surface engineering of artificial heart valve disks using nanostructured thin films deposited by chemical vapour deposition and sol-gel methods.

    PubMed

    Jackson, M J; Robinson, G M; Ali, N; Kousar, Y; Mei, S; Gracio, J; Taylor, H; Ahmed, W

    2006-01-01

    Pyrolytic carbon (PyC) is widely used in manufacturing commercial artificial heart valve disks (HVD). Although PyC is commonly used in HVD, it is not the best material for this application since its blood compatibility is not ideal for prolonged clinical use. As a result thrombosis often occurs and the patients are required to take anti-coagulation drugs on a regular basis in order to minimize the formation of thrombosis. However, anti-coagulation therapy gives rise to some detrimental side effects in patients. Therefore, it is extremely urgent that newer and more technically advanced materials with better surface and bulk properties are developed. In this paper, we report the mechanical properties of PyC-HVD, i.e. strength, wear resistance and coefficient of friction. The strength of the material was assessed using Brinell indentation tests. Furthermore, wear resistance and coefficient of friction values were obtained from pin-on-disk testing. The micro-structural properties of PyC were characterized using XRD, Raman spectroscopy and SEM analysis. Also in this paper we report the preparation of freestanding nanocrystalline diamond films (FSND) using the time-modulated chemical vapour deposition (TMCVD) process. Furthermore, the sol-gel technique was used to uniformly coat PyC-HVD with dense, nanocrystalline-titanium oxide (nc-TiO2) coatings. The as-grown nc-TiO2 coatings were characterized for microstructure using SEM and XRD analysis.

  5. Study of the catalyst evolution during annealing preceding the growth of carbon nanotubes by microwave plasma-enhanced chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Malesevic, Alexander; Chen, Hong; Hauffman, Tom; Vanhulsel, Annick; Terryn, Herman; Van Haesendonck, Chris

    2007-11-01

    A two-step catalyst annealing process is developed in order to control the diameter of nickel catalyst particles for the growth of carbon nanotubes (CNTs) by microwave plasma-enhanced chemical vapour deposition (MW PECVD). Thermal annealing of a continuous nickel film in a hydrogen (H2) environment in a first step is found to be insufficient for the formation of nanometre-size, high-density catalyst particles. In a second step, a H2 MW plasma treatment decreases the catalyst diameter by a factor of two and increases the particle density by a factor of five. An x-ray photoelectron spectroscopy study of the catalyst after each step in the annealing process is presented. It is found that the catalyst particles interact with the substrate during thermal annealing, thereby forming a silicate, even if a buffer layer in between the catalyst and the substrate is intended to prevent silicate formation. The silicate formation and reduction is shown to be directly related to the CNT growth mechanism, determining whether the catalyst particles reside at the base or the tip of the growing CNTs. The catalyst particles are used for the growth of a high-density CNT coating by MW PECVD. CNTs are analysed with electron microscopy and Raman spectroscopy.

  6. Broadband antireflection for a high-index substrate using SiN x /SiO2 by inductively coupled plasma chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Lim, Kim Peng; Ng, Doris K. T.; Wang, Qian

    2016-03-01

    This paper presents the development of broadband antireflection coating for a high-index substrate such as Si using SiN x /SiO2 by inductively coupled plasma chemical vapour deposition (ICP-CVD). The thin-film design employs a simulated annealing method for a minimal average reflectance over the wavelength range and incidence angles involved, which gives the optimized refractive index and thickness of each layer of the thin-film stack under different layer numbers. Using ICP-CVD, the SiN x material system is optimized by tuning the SiH4/N2 gas ratio. The corresponding thin-film characterization shows the precise refractive index/film thickness control in deposition, and the deposited film also has a low absorption coefficient and smooth surface. The double-layer SiN x /SiO2 coating with the optimized refractive index and thickness for broadband antireflection is demonstrated experimentally. The average reflectance of the Si surface is reduced from ~32% to ~3.17% at normal incidence for a wavelength range from 400 to 1100 nm.

  7. Strain and structure heterogeneity in MoS2 atomic layers grown by chemical vapour deposition

    SciTech Connect

    Liu, Zheng; Amani, Matin; Najmaei, Sina; Xu, Quan; Zou, Xiaolong; Zhou, Wu; Yu, Ting; Qiu, Caiyu; Birdwell, A. Glen; Crowne, Frank J.; Vajtai, Robert; Yakobson, Boris I.; Xia, Zhenhai; Dubey, Madan; Ajayan, Pulickel M.; Lou, Jun

    2014-11-18

    Monolayer molybdenum disulfide (MoS2) has attracted tremendous attention due to its promising applications in high-performance field-effect transistors, phototransistors, spintronic devices, and nonlinear optics. The enhanced photoluminescence effect in monolayer MoS2 was discovered and, as a strong tool, was employed for strain and defect analysis in MoS2. Recently, large-size monolayer MoS2 has been produced by chemical vapor deposition but has not yet been fully explored. Here we systematically characterize chemical vapor deposition grown MoS2 by PL spectroscopy and mapping, and demonstrate non-uniform strain in single-crystalline monolayer MoS2 and strain-induced band gap engineering. We also evaluate the effective strain transferred from polymer substrates to MoS2 by three-dimensional finite element analysis. In addition, our work demonstrates that PL mapping can be used as a non-contact approach for quick identification of grain boundaries in MoS2.

  8. Heterogeneous Catalytic Conversion of Biobased Chemicals into Liquid Fuels in the Aqueous Phase.

    PubMed

    Wu, Kejing; Wu, Yulong; Chen, Yu; Chen, Hao; Wang, Jianlong; Yang, Mingde

    2016-06-22

    Different biobased chemicals are produced during the conversion of biomass into fuels through various feasible technologies (e.g., hydrolysis, hydrothermal liquefaction, and pyrolysis). The challenge of transforming these biobased chemicals with high hydrophilicity is ascribed to the high water content of the feedstock and the inevitable formation of water. Therefore, aqueous-phase processing is an interesting technology for the heterogeneous catalytic conversion of biobased chemicals. Different reactions, such as dehydration, isomerization, aldol condensation, ketonization, and hydrogenation, are applied for the conversion of sugars, furfural/hydroxymethylfurfural, acids, phenolics, and so on over heterogeneous catalysts. The activity, stability, and reusability of the heterogeneous catalysts in water are summarized, and deactivation processes and several strategies are introduced to improve the stability of heterogeneous catalysts in the aqueous phase. PMID:27158985

  9. Catalytic chemical vapor deposition of single-wall carbon nanotubes at low temperatures.

    PubMed

    Cantoro, Mirco; Hofmann, Stephan; Pisana, Simone; Scardaci, Vittorio; Parvez, Atlus; Ducati, Caterina; Ferrari, Andrea C; Blackburn, Arthur M; Wang, Kai-You; Robertson, John

    2006-06-01

    We report surface-bound growth of single-wall carbon nanotubes (SWNTs) at temperatures as low as 350 degrees C by catalytic chemical vapor deposition from undiluted C2H2. NH3 or H2 exposure critically facilitates the nanostructuring and activation of sub-nanometer Fe and Al/Fe/Al multilayer catalyst films prior to growth, enabling the SWNT nucleation at lower temperatures. We suggest that carbon nanotube growth is governed by the catalyst surface without the necessity of catalyst liquefaction.

  10. Direct observation of electron emission from the grain boundaries of chemical vapour deposition diamond films by tunneling atomic force microscopy

    SciTech Connect

    Chatterjee, Vijay; Harniman, Robert; May, Paul W.; Barhai, P. K.

    2014-04-28

    The emission of electrons from diamond in vacuum occurs readily as a result of the negative electron affinity of the hydrogenated surface due to features with nanoscale dimensions, which can concentrate electric fields high enough to induce electron emission from them. Electrons can be emitted as a result of an applied electric field (field emission) with possible uses in displays or cold-cathode devices. Alternatively, electrons can be emitted simply by heating the diamond in vacuum to temperatures as low as 350 °C (thermionic emission), and this may find applications in solar energy generation or energy harvesting devices. Electron emission studies usually use doped polycrystalline diamond films deposited onto Si or metallic substrates by chemical vapor deposition, and these films have a rough, faceted morphology on the micron or nanometer scale. Electron emission is often improved by patterning the diamond surface into sharp points or needles, the idea being that the field lines concentrate at the points lowering the barrier for electron emission. However, there is little direct evidence that electrons are emitted from these sharp tips. The few reports in the literature that have studied the emission sites suggested that emission came from the grain boundaries and not the protruding regions. We now present direct observation of the emission sites over a large area of polycrystalline diamond using tunneling atomic force microscopy. We confirm that the emission current comes mostly from the grain boundaries, which is consistent with a model for emission in which the non-diamond phase is the source of electrons with a threshold that is determined by the surrounding hydrogenated diamond surface.

  11. The chemical and catalytic properties of nanocrystalline metal oxides prepared through modified sol-gel synthesis

    NASA Astrophysics Data System (ADS)

    Carnes, Corrie Leigh

    The goal of this research was to synthesize, characterize and study the chemical properties of nanocrystalline metal oxides. Nanocrystalline (NC) ZnO, CuO, NiO, Al2O3, and the binary Al2O 3/MgO and ZnO/CuO were prepared through modified sol gel methods. These NC metal oxides were studied in comparison to the commercial (CM) metal oxides. The samples were characterized by XRD, TGA, FTIR, BET, and TEM. The NC samples were all accompanied by a significant increase in surface area and decrease in crystallite size. Several chemical reactions were studied to compare the NC samples to the CM samples. One of the reactions involved a high temperature reaction between carbon tetrachloride and the oxide to form carbon dioxide and the corresponding metal chloride. A similar high temperature reaction was conducted between the metal oxide and hydrogen sulfide to form water and the corresponding metal sulfide. A room temperature gas phase adsorption was studied where SO2 was adsorbed onto the oxide. A liquid phase adsorption conducted at room temperature was the destructive adsorption of paraoxon (a toxic insecticide). In all reactions the NC samples exhibited greater activity, destroying or adsorbing a larger amount of the toxins compared to the CM samples. To better study surface area effects catalytic reactions were also studied. The catalysis of methanol was studied over the nanocrystalline ZnO, CuO, NiO, and ZnO/CuO samples in comparison to their commercial counterparts. In most cases the NC samples proved to be more active catalysts, having higher percent conversions and turnover numbers. A second catalytic reaction was also studied, this reaction was investigated to look at the support effects. The catalysis of cyclopropane to propane was studied over Pt and Co catalysts. These catalysts were supported onto NC and CM alumina by impregnation. By observing differences in the catalytic behavior, support effects have become apparent.

  12. Very low temperature epitaxy of Ge and Ge rich SiGe alloys with Ge2H6 in a Reduced Pressure - Chemical Vapour Deposition tool

    NASA Astrophysics Data System (ADS)

    Aubin, J.; Hartmann, J. M.; Bauer, M.; Moffatt, S.

    2016-07-01

    We have studied the very low temperature epitaxy of pure Ge and of Ge-rich SiGe alloys in a 200 mm industrial reduced pressure chemical vapour deposition tool. We have, first of all, benchmarked germane (GeH4) and digermane (Ge2H6) for the growth of pure Ge. Used Ge2H6 instead of GeH4 enabled us to dramatically increase the Ge growth rate at temperatures 425 °C and lower (5.6 nm min-1 compared to 0.14 nm min-1 at 350 °C with a Ge2H6 mass-flow one fourth that of GeH4). We have also evaluated at 400 °C, 100 Torr, the impact of the GeH4 or Ge2H6 mass-flow on the Ge growth rate. For a given Ge atomic flow, the higher surface reactivity of digermane yielded roughly five times higher growth rates than with germane. We have then combined digermane with disilane (Si2H6) or dichlorosilane (SiH2Cl2) in order to study the GeSi growth kinetics at 475 °C, 100 Torr. While the SiH2Cl2 mass-flow did not have any clear influence on the GeSi growth rate (with a 14 nm min-1 mean value, then), a Si2H6 mass-flow increase resulted in a slight GeSi growth rate increase (from 11 nm min-1 up to 14 nm min-1). Significantly higher Ge concentrations were otherwise accessed with dichlorosilane than with disilane, in the 77-82% range compared to the 39-53% range, respectively.

  13. A spectrometer on chemical vapour deposition-diamond basis for the measurement of the charge-state distribution of heavy ions in a laser-generated plasma

    SciTech Connect

    Cayzac, Witold; Frank, Alexander; Schumacher, Dennis; Roth, Markus; Blazevic, Abel; Wamers, Felix; Traeger, Michael; Berdermann, Eleni; Voss, Bernd; Hessling, Thomas

    2013-04-15

    This article reports on the development and the first applications of a new spectrometer which enables the precise and time-resolved measurement of both the energy loss and the charge-state distribution of ion beams with 10 < Z < 30 at energies of 4-8 MeV/u after their interaction with a laser-generated plasma. The spectrometer is based on five 20 Multiplication-Sign 7 mm{sup 2} large and 20 {mu}m thick polycrystalline diamond samples produced via the Chemical Vapour Deposition (CVD) process and was designed with the help of ion-optical simulations. First experiments with the spectrometer were successfully carried out at GSI using {sup 48}Ca ions at an energy of 4.8 MeV/u interacting with a carbon plasma generated by the laser irradiation of a thin foil target. Owing to the high rate capability and the short response time of the spectrometer, pulsed ion beams with 10{sup 3}-10{sup 4} ions per bunch at a bunch frequency of 108 MHz could be detected. The temporal evolution of the five main charge states of the calcium ion beams as well as the corresponding energy loss values could be measured simultaneously. Due to the outstanding properties of diamond as a particle detector, a beam energy resolution ({Delta}E/E) Almost-Equal-To 0.1% could be reached using the presented experimental method, while a precision of 10% in the energy loss and charge-state distribution data was obtained.

  14. Comparison of the Er,Cr:YSGG laser with a chemical vapour deposition bur and conventional techniques for cavity preparation: a microleakage study.

    PubMed

    Yazici, A Rüya; Yıldırım, Zeren; Antonson, Sibel A; Kilinc, Evren; Koch, Daniele; Antonson, Donald E; Dayangaç, Berrin; Ozgünaltay, Gül

    2012-01-01

    The aim of this study was to compare the effects of the Er,Cr:YSGG laser using chemical vapour deposition (CVD) bur cavity preparation with conventional preparation methods including a diamond bur and a carbide bur on the microleakage with two different adhesive systems. A total of 40 extracted human premolars were randomly assigned to four experimental groups according to the cavity preparation technique: group I diamond bur (Diatech); group II carbide bur (Diatech); group III Er,Cr:YSGG laser (Biolase Millennium II); and group IV CVD bur (CVDentUS). Using the different preparation techniques, Class V standardized preparations were performed on the buccal and lingual surfaces with gingival margins on the dentin and occlusal margins on the enamel. Each preparation group was randomly assigned to two subgroups (five teeth, ten preparations) according to the type of adhesive: an etch-and-rinse adhesive (Adper Single Bond), and a single-step self-etch adhesive (AdheSE One). All preparations were restored with a nanohybrid composite resin in a single increment. Following thermocycling (×500; 5-55°C), the teeth were immersed in basic fuchsin and sectioned in the orovestibular direction. Dye penetration was evaluated under a light microscope by two blinded examiners. Data were statistically analysed with the Kruskal-Wallis and Wilcoxon tests (p<0.05). There were no statistically significant differences between the preparation techniques with either of the two adhesive systems (p>0.05). Comparing the enamel and dentin leakage scores within each group, no statistically significant differences were found (p>0.05). The Er,Cr:YSGG laser cavity preparation did not differ from preparation with CVD, diamond or carbide bur in terms of microleakage with the different adhesive systems.

  15. Metalorganic chemical vapour deposition of GaN layers on ZnO substrates using α-Al2O3 as a transition layer

    NASA Astrophysics Data System (ADS)

    Wang, Shen-Jie; Li, Nola; Yu, Hong Bo; Feng, Zhe Chuan; Summers, Christopher; Ferguson, Ian

    2009-12-01

    This work addresses the instability of a ZnO substrate during metalorganic chemical vapour deposition (MOCVD) growth of GaN by using Al2O3 films deposited by atomic layer deposition (ALD) as a stabilizing transition layer on the Zn face of ZnO (0 0 0 1) substrates. A systematic study of Al2O3 films of different thicknesses (2-90 nm) under different ALDs and post-annealing conditions was carried out. However, this paper focuses on as-deposited 20 and 50 nm Al2O3 films that were transformed to polycrystalline α-Al2O3 phases after optimal annealing at 1100 °C for 10 min and 20 min, respectively. GaN layers were grown on ZnO substrates with these α-Al2O3 transition layers by MOCVD using NH3 as a nitrogen source. Wurtzite GaN was observed by high resolution x-ray diffraction only on 20 nm Al2O3/ZnO substrates. Field-emission scanning electron microscopy showed a mirror-like surface, no etch pits and no film peeling in these samples. Room temperature photoluminescence showed a red-shift in the near band-edge emission of GaN, which may be related to oxygen incorporation forming a shallow donor-related level in GaN. Raman scattering also indicated the presence of a well-crystallized GaN layer on the 20 nm Al2O3/ZnO substrate.

  16. HRI catalytic two-stage liquefaction (CTSL) process materials: chemical analysis and biological testing

    SciTech Connect

    Wright, C.W.; Later, D.W.

    1985-12-01

    This report presents data from the chemical analysis and biological testing of coal liquefaction materials obtained from the Hydrocarbon Research, Incorporated (HRI) catalytic two-stage liquefaction (CTSL) process. Materials from both an experimental run and a 25-day demonstration run were analyzed. Chemical methods of analysis included adsorption column chromatography, high-resolution gas chromatography, gas chromatography/mass spectrometry, low-voltage probe-inlet mass spectrometry, and proton nuclear magnetic resonance spectroscopy. The biological activity was evaluated using the standard microbial mutagenicity assay and an initiation/promotion assay for mouse-skin tumorigenicity. Where applicable, the results obtained from the analyses of the CTSL materials have been compared to those obtained from the integrated and nonintegrated two-stage coal liquefaction processes. 18 refs., 26 figs., 22 tabs.

  17. Solar photo-thermal catalytic reactions to produce high value chemicals

    SciTech Connect

    Prengle, H.W. Jr.; Wentworth, W.E. )

    1992-04-01

    This report presents a summary of the research work accomplished to date on the utilization of solar photo-thermal energy to convert low cost chemical feedstocks into high $-value chemical products. The rationale is that the solar IR-VIS-UV spectrum is unique, supplying endothermic reaction energy as well as VIS-UV for photochemical activation. Chemical market analysis and product price distribution focused attention on speciality chemicals with prices >$1.00/lb, and a synthesis sequence of n-paraffins to aromatics to partial oxidized products. The experimental work has demonstrated that enhanced reaction effects result from VIS-UV irradiation of catalytically active V2O5/SiO2. Experiments of the past year have been on dehydrogenation and dehydrocyclization of n-paraffins to olefins and aromatics with preference for the latter. Recent results using n-hexane produced 95% conversion with 56% benzene; it is speculated that aromatic yield should reach {approximately}70% by further optimization. Pilot- and commercial-scale reactor configurations have been examined; the odds-on-favorite being a shallow fluid-bed of catalyst with incident radiation from the top. Sequencing for maximum cost effectiveness would be day-time endothermic followed by night-time exothermic reactions to produce the products.

  18. Revealing Monoamine Oxidase B Catalytic Mechanisms by Means of the Quantum Chemical Cluster Approach.

    PubMed

    Zapata-Torres, Gerald; Fierro, Angélica; Barriga-González, German; Salgado, J Cristian; Celis-Barros, Cristian

    2015-07-27

    Two of the possible catalytic mechanisms for neurotransmitter oxidative deamination by monoamine oxidase B (MAO B), namely, polar nucleophilic and hydride transfer, were addressed in order to comprehend the nature of their rate-determining step. The Quantum Chemical Cluster Approach was used to obtain transition states of MAO B complexed with phenylethylamine (PEA), benzylamine (BA), and p-nitrobenzylamine (NBA). The choice of these amines relies on their importance to address MAO B catalytic mechanisms so as to help us to answer questions such as why BA is a better substrate than NBA or how para-substitution affects substrate's reactivity. Transition states were later validated by comparison with the experimental free energy barriers. From a theoretical point of view, and according to the our reported transition states, their calculated barriers and structural and orbital differences obtained by us among these compounds, we propose that good substrates such as BA and PEA might follow the hydride transfer pathway while poor substrates such as NBA prefer the polar nucleophilic mechanism, which might suggest that MAO B can act by both mechanisms. The low free energy barriers for BA and PEA reflect the preference that MAO B has for hydride transfer over the polar nucleophilic mechanism when catalyzing the oxidative deamination of neurotransmitters.

  19. Studies of coupled chemical and catalytic coal conversion methods. Tenth quarterly report, January--March 1990

    SciTech Connect

    Stock, L.M.

    1990-12-31

    This report concerns our research on base-catalyzed coal solubilization and a new approach for hydrogen addition. The work on base-catalyzed, chemical solubilization is continuing. this report is focused on the hydrogenation research. Specifically it deals with the use of arene chromium carbonyl complexes as reagents for the addition of dideuterium to coal molecules. In one phase of the work, he has established that the aromatic hydrocarbons in a representative coal liquid can be converted in very good yield to arene chromium carbonyl compounds. In a second phase of the work directly related to our objective of improved methods for catalytic hydrogenation, he has established that the aromatic constituents of the same coal liquid add dideuterium in the presence of added napththalene chromium carbonyl.

  20. Modification of tubular ceramic membranes with carbon nanotubes using catalytic chemical vapor deposition.

    PubMed

    Tran, Duc Trung; Thieffry, Guillemette; Jacob, Matthieu; Batiot-Dupeyrat, Catherine; Teychene, Benoit

    2015-01-01

    In this study, carbon nanotubes (CNTs) were successfully grown on tubular ceramic membranes using the catalytic chemical vapor deposition (CCVD) method. CNTs were synthesized at 650°C for 3-6 h under a 120 mL min(-1) flow of C2H6 on ceramic membranes impregnated with iron salt. The synthesis procedure was beforehand optimized in terms of catalyst amount, impregnation duration and reaction temperature, using small pieces of tubular ceramic membranes. The yield, size and structure of the CNTs produced were characterized using thermogravimetric analysis and microscopic imaging techniques. Afterwards, preliminary filtration tests with alginate and phenol were performed on two modified tubular membranes. The results indicate that the addition of CNTs on the membrane material increased the permeability of ceramic membrane and its ability to reject alginate and adsorb phenol, yet decreased its fouling resistance. PMID:26465312

  1. High-Quality Amorphous-Crystalline Silicon Heterostructures Using the Grid-Based Triode Radio-Frequency Plasma Enhanced Chemical Vapour Deposition Method

    NASA Astrophysics Data System (ADS)

    Mahtani, Pratish

    The amorphous-crystalline silicon heterojunction (SHJ) represents a new paradigm in crystalline silicon (c-Si) photovoltaics (PV). To achieve the 27% efficiency target for SHJ PV, defects in the silicon heterointerface must be minimized by growing high-quality hydrogenated amorphous silicon (a-Si:H) onto the c-Si surfaces without deposition-related damage. Typically, a-Si:H is deposited using radio-frequency (RF) plasma enhanced chemical vapour deposition (PECVD), which in its conventional configuration directly exposes the c-Si growth surface to the ignited plasma. In this thesis, silicon heterostructures prepared by the grid-based triode RF PECVD method is investigated for the first time. The triode method allows for high-quality a-Si:H growth with the c-Si surfaces shielded from any potential plasma damage. Using a custom-built configurable PECVD facility, a systematic study was conducted and it was demonstrated that the triode method affords the preparation of a-Si:H with excellent bulk film quality and state-of-the-art passivation for c-Si surfaces. Using the triode method, an effective minority carrier lifetime (taueff) of 8.1 ms and an Auger-corrected surface recombination velocity (S) of 2.4 cm/s at an excess carrier density of 1015 cm-3 have been achieved for 1-2 ohm-cm n-type c-Si passivated with intrinsic a-Si:H. Further, using the triode method to deposit thin-layers of intrinsic and doped a-Si:H, a conventional SHJ solar cell structure was prepared and was found to exhibit an excellent implied Voc of 710 mV. Under all conditions scanned, samples prepared in the triode configuration showed improved passivation compared with samples prepared in the conventional diode configuration with the best triode prepared sample showing a nearly threefold increase in taueff and a twofold decrease in S compared with the best diode prepared sample. Furthermore, a-Si:H deposited using the triode method showed significantly improved bulk properties compared to diode

  2. Perovskite tungsten bronze-type crystals of Li{sub x}WO{sub 3} grown by chemical vapour transport and their characterisation

    SciTech Connect

    Ruescher, Claus H. Dey, Kalpana R.; Debnath, Tapas; Horn, Ingo; Glaum, Robert; Hussain, Altaf

    2008-01-15

    Crystals of Li{sub x}WO{sub 3} with nominal compositions, x=0.1, 0.25, 0.3, 0.35, 0.4 and 0.45 were grown by chemical vapour transport method using HgCl{sub 2} as transporting agent. A complete transport was achieved with a temperature gradient T{sub 1}/T{sub 2}=800/700 deg. C revealing bluish-black crystals of sizes up to a few 10th of a millimeter. X-ray powder diffraction and infrared (IR) absorption spectra show Perovskite tungsten bronze of cubic symmetry (PTB{sub c}) for x=0.45 and 0.4, mixed phase of PTB{sub c} and Perovskite tungsten bronze of tetragonal symmetry (PTB{sub t}) for x=0.35, 0.3 and 0.25 and of PTB{sub t} and Perovskite tungsten bronze of orthorhombic symmetry (PTB{sub o}) for x=0.1. The structure of PTB{sub t} is explained by the off centring of the W-ions along c and tilting of the WO{sub 6} octahedra around c. Crystal slices of mixed phase (i.e. PTB{sub c} and PTB{sub t}) reveal bright and dark areas on a sub-millimeter scale which are separated by sharp interfaces. Laser ablation inductively coupled plasma optical emission (LA ICP OES) analysis on small spot sizes show the separation into Li contents of x=0.18 (bright areas) and x=0.38 (dark areas) as threshold compositions of PTB{sub t} and PTB{sub c}, respectively. Polarized reflectivity using a microscope technique in the bright area of the crystals indicates strong anisotropic absorption effects with maximum between 1000 and 6000 cm{sup -1}, which are related to optical excitations of polarons. Crystals of composition x=0.4 and 0.45 appear optically homogeneous and show an effective 'free carrier-type plasma frequency' (w{sub p}) of about 12,900 and 13,700 cm{sup -1}, respectively. - Graphical abstract: Optical microscope image (reflection mode) of Li{sub x}WO{sub 3} crystals of nominal composition x=0.35. The separation into PTB{sub cubic} (dark areas) and PTB{sub tetragonal} (bright areas) were used to determine the miscibility gap and optical properties.

  3. Catalytic pyrolysis-gc/ms of spirulina: evaluation of a highly proteinaceous biomass source for production of fuels and chemicals

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Pyrolysis of microalgae offers a pathway towards the production of compounds derived from the thermal decomposition of triglycerides, proteins as well as lignocelluloses and their combinations thereof. When catalytically induced, this could lead to the production of fuels and chemicals including aro...

  4. Catalytically active polymers obtained by molecular imprinting and their application in chemical reaction engineering.

    PubMed

    Brüggemann, O

    2001-08-01

    Molecular imprinting is a way of creating polymers bearing artificial receptors. It allows the fabrication of highly selective plastics by polymerizing monomers in the presence of a template. This technique primarily had been developed for the generation of biomimetic materials to be used in chromatographic separation, in extraction approaches and in sensors and assays. Beyond these applications, in the past few years molecular imprinting has become a tool for producing new kinds of catalysts. For catalytic applications, the template must be chosen, so that it is structurally comparable with the transition state (a transition state analogue, TSA) of a reaction, or with the product or substrate. The advantage of using these polymeric catalysts is obvious: the backbone withstands more aggressive conditions than a bio material could ever survive. Results are presented showing the applicability of a molecularly imprinted catalyst in different kinds of chemical reactors. It is demonstrated that the catalysts can be utilized not only in batch but also in continuously driven reactors and that their performance can be improved by means of chemical reaction engineering. PMID:11429307

  5. The chemical origin and catalytic activity of coinage metals: from oxidation to dehydrogenation.

    PubMed

    Syu, Cih-Ying; Yang, Hao-Wen; Hsu, Fu-Hsing; Wang, Jeng-Han

    2014-04-28

    The high oxidation activity of coinage metals (Cu, Ag and Au) has been widely applied in various important reactions, such as oxidation of carbon monoxide, alkenes or alcohols. The catalytic behavior of those inert metals has mostly been attributable to their size effect, the physical effect. In the present study, the chemical effects on their high oxidation activity have been investigated. We mechanistically examine the direct and oxidative dehydrogenation (partial oxidation) reactions of ethanol to acetaldehyde on a series of transition metals (groups 9, 10 and 11) with identical physical characteristics and varied chemical origins using density functional theory (DFT) calculations and electronic structure analyses at the GGA-PW91 level. The energetic results show that coinage metals have much lower activation energies and higher exothermicities for the oxidative dehydrogenation steps although they have higher energy for the direct dehydrogenation reaction. In the electronic structure analyses, coinage metals with saturated d bands can efficiently donate electrons to O* and OH*, or other electronegative adspecies, and better promote their p bands to higher energy levels. The negatively charged O* and OH* with high-lying p bands are responsible for lowering the energies in oxidative steps. The mechanistic understanding well explains the better oxidation activity of coinage metals and provides valuable information on their utilization in other useful applications, for example, the dehydrogenation process. PMID:24626959

  6. The chemical origin and catalytic activity of coinage metals: from oxidation to dehydrogenation.

    PubMed

    Syu, Cih-Ying; Yang, Hao-Wen; Hsu, Fu-Hsing; Wang, Jeng-Han

    2014-04-28

    The high oxidation activity of coinage metals (Cu, Ag and Au) has been widely applied in various important reactions, such as oxidation of carbon monoxide, alkenes or alcohols. The catalytic behavior of those inert metals has mostly been attributable to their size effect, the physical effect. In the present study, the chemical effects on their high oxidation activity have been investigated. We mechanistically examine the direct and oxidative dehydrogenation (partial oxidation) reactions of ethanol to acetaldehyde on a series of transition metals (groups 9, 10 and 11) with identical physical characteristics and varied chemical origins using density functional theory (DFT) calculations and electronic structure analyses at the GGA-PW91 level. The energetic results show that coinage metals have much lower activation energies and higher exothermicities for the oxidative dehydrogenation steps although they have higher energy for the direct dehydrogenation reaction. In the electronic structure analyses, coinage metals with saturated d bands can efficiently donate electrons to O* and OH*, or other electronegative adspecies, and better promote their p bands to higher energy levels. The negatively charged O* and OH* with high-lying p bands are responsible for lowering the energies in oxidative steps. The mechanistic understanding well explains the better oxidation activity of coinage metals and provides valuable information on their utilization in other useful applications, for example, the dehydrogenation process.

  7. Catalytic lignin valorization process for the production of aromatic chemicals and hydrogen.

    PubMed

    Zakzeski, Joseph; Jongerius, Anna L; Bruijnincx, Pieter C A; Weckhuysen, Bert M

    2012-08-01

    With dwindling reserves of fossil feedstock as a resource for chemicals production, the fraction of chemicals and energy supplied by alternative, renewable resources, such as lignin, can be expected to increase in the foreseeable future. Here, we demonstrate a catalytic process to valorize lignin (exemplified with kraft, organosolv, and sugarcane bagasse lignin) using a mixture of cheap, bio-renewable ethanol and water as solvent. Ethanol/water mixtures readily solubilize lignin under moderate temperatures and pressures with little residual solids. The molecular weight of the dissolved lignins was shown to be reduced by gel permeation chromatography and quantitative HSQC NMR methods. The use of liquid-phase reforming of the solubilized lignin over a Pt/Al(2)O(3) catalyst at 498 K and 58 bar is introduced to yield up to 17 % combined yield of monomeric aromatic oxygenates such as guaiacol and substituted guaiacols generating hydrogen as a useful by-product. Reduction of the lignin dissolved in ethanol/water using a supported transition metal catalyst at 473 K and 30 bar hydrogen yields up to 6 % of cyclic hydrocarbons and aromatics. PMID:22740175

  8. Catalytic reactions with bulk-mediated excursions: Mixing fails to restore chemical equilibrium

    NASA Astrophysics Data System (ADS)

    Coppey, M.; Bénichou, O.; Klafter, J.; Moreau, M.; Oshanin, G.

    2004-03-01

    In this paper we analyze the effect of the bulk-mediated excursions (BME) of reactive species on the long-time behavior of the catalytic Langmuir-Hinshelwood-like A+B→0 reactions in systems in which a catalytic plane (CP) is in contact with a liquid phase, containing concentrations of reactive particles. Such BME result from repeated particles desorption from the CP, subsequent diffusion in the liquid phase, and eventual readsorption on the CP away from the initial detachment point. This process leads to an effective superdiffusive transport along the CP. We consider both “batch” reactions, in which all particles of reactive species were initially adsorbed onto the CP, and reactions followed by a steady inflow of particles onto the CP. We show that for batch reactions the BME provide an effective mixing channel and here the mean-field-type behavior emerges. On the contrary, for reaction followed by a steady inflow of particles, we observe essential departures from the mean-field behavior and find that the mixing effect of the BME is insufficient to restore chemical equilibrium. We show that a steady state is established as t→∞, in which the limiting value of the mean coverage of the CP depends on the particles’ diffusion coefficient in the bulk liquid phase, and that the spatial distributions of adsorbed particles are strongly correlated. Moreover, we show that the relaxation to such a steady state is a power-law function of time, in contrast to the exponential time dependence describing the approach to equilibrium in perfectly stirred systems.

  9. A liquid crystalline chirality balance for vapours

    NASA Astrophysics Data System (ADS)

    Ohzono, Takuya; Yamamoto, Takahiro; Fukuda, Jun-Ichi

    2014-04-01

    Chiral discrimination of vapours plays an important role in olfactory perception of biological systems and its realization by artificial sensors has been an intriguing challenge. Here, we report a simple method that tangibly visualizes the chirality of a diverse variety of molecules dissolved from vapours with high sensitivity, by making use of a structural change in a periodic microstructure of a nematic liquid crystal confined in open microchannels. This microstructure is accompanied by a topological line defect of a zigzag form with equal lengths of ‘zig’ and ‘zag.’ We find that a tiny amount of vapour of chiral molecules injected onto the liquid crystal induces the imbalance of ‘zig’ and ‘zag’ depending on its enantiomeric excess within a few seconds. Our liquid-crystal-based ‘chirality balance’ offers a simple, quick and versatile chirality-sensing/-screening method for gas-phase analysis (for example, for odours, environmental chemicals or drugs).

  10. Surface engineering on CeO2 nanorods by chemical redox etching and their enhanced catalytic activity for CO oxidation

    NASA Astrophysics Data System (ADS)

    Gao, Wei; Zhang, Zhiyun; Li, Jing; Ma, Yuanyuan; Qu, Yongquan

    2015-07-01

    Controllable surface properties of nanocerias are desired for various catalytic processes. There is a lack of efficient approaches to adjust the surface properties of ceria to date. Herein, a redox chemical etching method was developed to controllably engineer the surface properties of ceria nanorods. Ascorbic acid and hydrogen peroxide were used to perform the redox chemical etching process, resulting in a rough surface and/or pores on the surface of ceria nanorods. Increasing the etching cycles induced a steady increase of the specific surface area, oxygen vacancies and surface Ce3+ fractions. As a result, the etched nanorods delivered enhanced catalytic activity for CO oxidation, compared to the non-etched ceria nanorods. Our method provides a novel and facile approach to continuously adjust the surface properties of ceria for practical applications.Controllable surface properties of nanocerias are desired for various catalytic processes. There is a lack of efficient approaches to adjust the surface properties of ceria to date. Herein, a redox chemical etching method was developed to controllably engineer the surface properties of ceria nanorods. Ascorbic acid and hydrogen peroxide were used to perform the redox chemical etching process, resulting in a rough surface and/or pores on the surface of ceria nanorods. Increasing the etching cycles induced a steady increase of the specific surface area, oxygen vacancies and surface Ce3+ fractions. As a result, the etched nanorods delivered enhanced catalytic activity for CO oxidation, compared to the non-etched ceria nanorods. Our method provides a novel and facile approach to continuously adjust the surface properties of ceria for practical applications. Electronic supplementary information (ESI) available: Diameter distributions of as-prepared and etched samples, optical images, specific catalytic data of CO oxidation and comparison of CO oxidation. See DOI: 10.1039/c5nr01846c

  11. Catalytic conversion of biomass pyrolysis-derived compounds with chemical liquid deposition (CLD) modified ZSM-5.

    PubMed

    Zhang, Huiyan; Luo, Mengmeng; Xiao, Rui; Shao, Shanshan; Jin, Baosheng; Xiao, Guomin; Zhao, Ming; Liang, Junyu

    2014-03-01

    Chemical liquid deposition (CLD) with KH550, TEOS and methyl silicone oil as the modifiers was used to modify ZSM-5 and deposit its external acid sites. The characteristics of modified catalysts were tested by catalytic conversion of biomass pyrolysis-derived compounds. The effects of different modifying conditions (deposited amount, temperature, and time) on the product yields and selectivities were investigated. The results show KH550 modified ZSM-5 (deposited amount of 4%, temperature of 20°C and time of 6h) produced the maximum yields of aromatics (24.5%) and olefins (16.5%), which are much higher than that obtained with original ZSM-5 catalyst (18.8% aromatics and 9.8% olefins). The coke yield decreased from 44.1% with original ZSM-5 to 26.7% with KH550 modified ZSM-5. The selectivities of low-molecule-weight hydrocarbons (ethylene and benzene) decreased, while that of higher molecule-weight hydrocarbons (propylene, butylene, toluene, and naphthalene) increased comparing with original ZSM-5. PMID:24413482

  12. Electrochemical sensing chemical oxygen demand based on the catalytic activity of cobalt oxide film.

    PubMed

    Wang, Jinqi; Wu, Can; Wu, Kangbing; Cheng, Qin; Zhou, Yikai

    2012-07-29

    Cobalt oxide sensing film was in situ prepared on glassy carbon electrode surface via constant potential oxidation. Controlling at 0.8 V in NaOH solution, the high-valence cobalt catalytically oxidized the reduced compounds, decreasing its surface amount and current signal. The current decline was used as the response signal of chemical oxygen demand (COD) because COD represents the summation of reduced compounds in water. The surface morphology and electrocatalytic activity of cobalt oxide were readily tuned by variation of deposition potential, time, medium and Co(2+) concentration. As confirmed from the atomic force microscopy measurements, the cobalt oxide film, that prepared at 1.3 V for 40 s in pH 4.6 acetate buffer containing 10 mM Co(NO(3))(2), possesses large surface roughness and numerous three-dimensional structures. Electrochemical tests indicated that the prepared cobalt oxide exhibited high electrocatalytic activity to the reduced compounds, accompanied with strong COD signal enhancement. As a result, a novel electrochemical sensor with high sensitivity, rapid response and operational simplicity was developed for COD. The detection limit was as low as 1.1 mg L(-1). The analytical application was studied using a large number of lake water samples, and the accuracy was tested by standard method.

  13. Catalytic reactor for promoting a chemical reaction on a fluid passing therethrough

    NASA Technical Reports Server (NTRS)

    Roychoudhury, Subir (Inventor); Pfefferle, William C. (Inventor)

    2001-01-01

    A catalytic reactor with an auxiliary heating structure for raising the temperature of a fluid passing therethrough whereby the catalytic reaction is promoted. The invention is a apparatus employing multiple electrical heating elements electrically isolated from one another by insulators that are an integral part of the flow path. The invention provides step heating of a fluid as the fluid passes through the reactor.

  14. Surface engineering on CeO₂ nanorods by chemical redox etching and their enhanced catalytic activity for CO oxidation.

    PubMed

    Gao, Wei; Zhang, Zhiyun; Li, Jing; Ma, Yuanyuan; Qu, Yongquan

    2015-07-21

    Controllable surface properties of nanocerias are desired for various catalytic processes. There is a lack of efficient approaches to adjust the surface properties of ceria to date. Herein, a redox chemical etching method was developed to controllably engineer the surface properties of ceria nanorods. Ascorbic acid and hydrogen peroxide were used to perform the redox chemical etching process, resulting in a rough surface and/or pores on the surface of ceria nanorods. Increasing the etching cycles induced a steady increase of the specific surface area, oxygen vacancies and surface Ce(3+) fractions. As a result, the etched nanorods delivered enhanced catalytic activity for CO oxidation, compared to the non-etched ceria nanorods. Our method provides a novel and facile approach to continuously adjust the surface properties of ceria for practical applications.

  15. On-line chemical vapour generation of cadmium in the presence of hexacyanochromate(III) for determination by inductively coupled plasma mass spectrometry (ICP-MS)

    PubMed Central

    Yilmaz, Vedat; Rose, LaKeysha; Little, Maria D.

    2012-01-01

    A vapour generation (VG) procedure has been described for determination of Cd by ICP-MS. Volatile species of Cd were generated on-line by interacting acidic sample solution containing potassium hexacyanochromate(III), K3Cr(CN)6, with sodium borohydride (NaBH4). The hexacyanochromate(III) complex was generated on-line by reacting 0.04 mol L−1 chromium(III) nitrate and 0.16 mol L−1 potassium cyanide (KCN) solutions in water. The resulting suspension of chromium(III) hydroxide, Cr(OH)3, was fed continuously to acidic stream of sample solution in the presence of excess KCN. The experimental conditions were optimized for effective generation of volatile species of Cd. Optimum signals were obtained from reaction of sample solutions in 4% v/v HCl with 2% m/v NaBH4 solution. Presence of K3Cr(CN)6 improved the efficiency of Cd vapour generation substantially affording 15-fold higher sensitivity. This phenomenon was thought to occur through formation of reactive intermediates evolved from interaction of [Cr(CN)6]3− with NaBH4 that react with Cd(II) to increase the yield volatile Cd species. Under the optimum conditions, no significant interferences were observed from the transition metals, including Cu and Ni, up to 1.0 μg mL−1 levels. Among the hydride forming elements, Bi, Pb, Sb and Sn depressed the signals above 0.1 μg mL−1. The detection limits (3s) were 6.2 and 5.2 ng L−1 for 110Cd and 111Cd isotopes, respectively. The method was successfully applied to determination of Cd by ICP-MS in several certified reference materials, including Nearshore seawater (CASS-4), Bone ash (SRM 1400), Dogfish liver (DOLT-4) and Mussel tissue (SRM 2976). PMID:23997384

  16. Energy Efficient Catalytic Activation of Hydrogen peroxide for Green Chemical Processes: Final Report

    SciTech Connect

    Collins, Terrence J.; Horwitz, Colin

    2004-11-12

    A new, highly energy efficient approach for using catalytic oxidation chemistry in multiple fields of technology has been pursued. The new catalysts, called TAML® activators, catalyze the reactions of hydrogen peroxide and other oxidants for the exceptionally rapid decontamination of noninfectious simulants (B. atrophaeus) of anthrax spores, for the energy efficient decontamination of thiophosphate pesticides, for the facile, low temperature removal of color and organochlorines from pulp and paper mill effluent, for the bleaching of dyes from textile mill effluents, and for the removal of recalcitrant dibenzothiophene compounds from diesel and gasoline fuels. Highlights include the following: 1) A 7-log kill of Bacillus atrophaeus spores has been achieved unambiguously in water under ambient conditions within 15 minutes. 2) The rapid total degradation under ambient conditions of four thiophosphate pesticides and phosphonate degradation intermediates has been achieved on treatment with TAML/peroxide, opening up potential applications of the decontamination system for phosphonate structured chemical warfare agents, for inexpensive, easy to perform degradation of stored and aged pesticide stocks (especially in Africa and Asia), for remediation of polluted sites and water bodies, and for the destruction of chemical warfare agent stockpiles. 3) A mill trial conducted in a Pennsylvanian bleached kraft pulp mill has established that TAML catalyst injected into an alkaline peroxide bleach tower can significantly lower color from the effluent stream promising a new, more cost effective, energy-saving approach for color remediation adding further evidence of the value and diverse engineering capacity of the approach to other field trials conducted on effluent streams as they exit the bleach plant. 4) Dibenzothiophenes (DBTs), including 4,6-dimethyldibenzothiophene, the most recalcitrant sulfur compounds in diesel and gasoline, can be completely removed from model gasoline

  17. Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions.

    PubMed

    Parlett, Christopher M A; Isaacs, Mark A; Beaumont, Simon K; Bingham, Laura M; Hondow, Nicole S; Wilson, Karen; Lee, Adam F

    2016-02-01

    The chemical functionality within porous architectures dictates their performance as heterogeneous catalysts; however, synthetic routes to control the spatial distribution of individual functions within porous solids are limited. Here we report the fabrication of spatially orthogonal bifunctional porous catalysts, through the stepwise template removal and chemical functionalization of an interconnected silica framework. Selective removal of polystyrene nanosphere templates from a lyotropic liquid crystal-templated silica sol-gel matrix, followed by extraction of the liquid crystal template, affords a hierarchical macroporous-mesoporous architecture. Decoupling of the individual template extractions allows independent functionalization of macropore and mesopore networks on the basis of chemical and/or size specificity. Spatial compartmentalization of, and directed molecular transport between, chemical functionalities affords control over the reaction sequence in catalytic cascades; herein illustrated by the Pd/Pt-catalysed oxidation of cinnamyl alcohol to cinnamic acid. We anticipate that our methodology will prompt further design of multifunctional materials comprising spatially compartmentalized functions.

  18. Excitation mechanism and thermal emission quenching of Tb ions in silicon rich silicon oxide thin films grown by plasma-enhanced chemical vapour deposition—Do we need silicon nanoclusters?

    SciTech Connect

    Podhorodecki, A. Golacki, L. W.; Zatryb, G.; Misiewicz, J.; Wang, J.; Jadwisienczak, W.; Fedus, K.

    2014-04-14

    In this work, we will discuss the excitation and emission properties of Tb ions in a Silicon Rich Silicon Oxide (SRSO) matrix obtained at different technological conditions. By means of electron cyclotron resonance plasma-enhanced chemical vapour deposition, undoped and doped SRSO films have been obtained with different Si content (33, 35, 39, 50 at. %) and were annealed at different temperatures (600, 900, 1100 °C). The samples were characterized optically and structurally using photoluminescence (PL), PL excitation, time resolved PL, absorption, cathodoluminescence, temperature dependent PL, Rutherford backscattering spectrometry, Fourier transform infrared spectroscopy and positron annihilation lifetime spectroscopy. Based on the obtained results, we discuss how the matrix modifications influence excitation and emission properties of Tb ions.

  19. Development Of Hot Surface Polysilicon-Based Chemical Sensor And Actuator With Integrated Catalytic Micropatterns For Gas Sensing Applications

    NASA Astrophysics Data System (ADS)

    Vereshchagina, E.; Gardeniers, J. G. E.

    2009-05-01

    Over the last twenty years, we have followed a rapid expansion in the development of chemical sensors and microreactors for detection and analysis of volatile organic compounds. However, for many of the developed gas sensors poor sensitivity and selectivity, and high-power consumption remain among one of the main drawbacks. One promising approach to increase selectivity at lower power consumption is calorimetric sensing, performed in a pulsed regime and using specific catalytic materials. In this work, we study kinetics of various catalytic oxidation reactions using micromachined hot surface polysilicon-based sensor containing sensitive and selective catalysts. The sensor acts as both thermal actuator of chemical and biochemical reactions on hot-surfaces and detector of heats (enthalpies) associated with these reactions. Using novel deposition techniques we integrated selective catalysts in an array of hot plates such that they can be thermally actuated and sensed individually. This allows selective detection and analysis of dangerous gas compounds in a mixture, specifically hydrocarbons at concentrations down to low ppm level. In this contribution we compare various techniques for the local immobilization of catalytic material on hot spots of the sensor in terms of process compatibility, mechanical stress, stability and cost.

  20. Non-catalytic direct synthesis of graphene on Si (111) wafers by using inductively-coupled plasma chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Hwang, Sung Won; Shin, Hyunho; Lee, Bongsoo; Choi, Suk-Ho

    2016-08-01

    We employ inductively-coupled plasma chemical vapor deposition for non-catalytic growth of graphene on a Si (111) wafer or glass substrate, which is useful for practical device applications of graphene without transfer processes. At a RF power (P) of 500 W under C2H2 flow, defect-free 3 ˜ 5-layer graphene is grown on Si (111) wafers, but on glass substrate, the layer is thicker and defective, as characterized by Raman spectroscopy and electron microscopy. The graphene is produced on Si (111) for P down to 190 W whereas it is almost not formed on glass for P < 250 W, possibly resulting from the weak catalytic-reaction-like effect on glass. These results are discussed based on possible growth mechanisms.

  1. Chemical Engineering of Enzymes: Altered Catalytic Activity, Predictable Selectivity and Exceptional Stability of the Semisynthetic Peroxidase Seleno-Subtilisin

    NASA Astrophysics Data System (ADS)

    Häring, Dietmar; Schreier, Peter

    The increasing demand for enzymes as highly selective, mild, and environmentally benign catalysts is often limited by the lack of an enzyme with the desired catalytic activity or substrate selectivity and by their instability in biotechnological processes. The previous answers to these problems comprised genetically engineered enzymes and several classes of enzyme mimics. Here we describe the potential of chemical enzyme engineering: native enzymes can be modified by merely chemical means and basic equipment yielding so-called semisynthetic enzymes. Thus, the high substrate selectivity of the enzymatic peptide framework is combined with the catalytic versatility of a synthetic active site. We illustrate the potential of chemically engineered enzymes with the conception of the semisynthetic peroxidase seleno-subtilisin. First, the serine endoprotease subtilisin was crystallized and cross-linked with glutaraldehyde to give cross-linked enzyme crystals which were found to be insoluble in water or organic solvents and highly stable. Second, serine 221 in the active site (Enz-OH) was chemically converted into an oxidized derivative of selenocystein (Enz-SeO2H). As a consequence, the former proteolytic enzyme gained peroxidase activity and catalyzed the selective reduction of hydroperoxides. Due to the identical binding sites of the semisynthetic peroxidase and the protease, the substrate selectivity of seleno-subtilisin was predictable in view of the well-known selectivity of subtilisin.

  2. Functional carbons and carbon nanohybrids for the catalytic conversion of biomass to renewable chemicals in the condensed phase

    SciTech Connect

    Matthiesen, John; Hoff, Thomas; Liu, Chi; Pueschel, Charles; Rao, Radhika; Tessonnier, Jean-Philippe

    2014-06-01

    The production of chemicals from lignocellulosic biomass provides opportunities to synthesize chemicals with new functionalities and grow a more sustainable chemical industry. However, new challenges emerge as research transitions from petrochemistry to biorenewable chemistry. Compared to petrochemisty, the selective conversion of biomass-derived carbohydrates requires most catalytic reactions to take place at low temperatures (< 300°C) and in the condensed phase to prevent reactants and products from degrading. The stability of heterogeneous catalysts in liquid water above the normal boiling point represents one of the major challenges to overcome. Herein, we review some of the latest advances in the field with an emphasis on the role of carbon materials and carbon nanohybrids in addressing this challenge.

  3. Catalytic and non-catalytic pyrolysis of biomass in non-inert environments for production of deoxygenated bio-oil and chemicals

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fast pyrolysis processes are among the most effective methods for liquefaction of lignocellulosic biomass. Catalytic fast pyrolysis (CFP) over HZSM-5 or other zeolites and/or utilization of reactive atmospheres such as in the non-catalytic Tail Gas Reactive Pyrolysis (TRGP) process, a recent patent...

  4. A non-chemically selective top-down approach towards the preparation of hierarchical TS-1 zeolites with improved oxidative desulfurization catalytic performance.

    PubMed

    Du, Shuting; Chen, Xiaoxin; Sun, Qiming; Wang, Ning; Jia, Mingjun; Valtchev, Valentin; Yu, Jihong

    2016-02-28

    Hierarchical TS-1 zeolites with secondary macropores have been successfully prepared by using two different fluoride-containing chemical etching post-treated routes. Hierarchical TS-1 zeolites exhibited a chemical composition similar to that of the parent material and showed remarkably enhanced catalytic activity in oxidative desulfurization reaction. PMID:26846586

  5. Kinetic-quantum chemical model for catalytic cycles: the Haber-Bosch process and the effect of reagent concentration.

    PubMed

    Kozuch, Sebastian; Shaik, Sason

    2008-07-01

    A combined kinetic-quantum chemical model is developed with the goal of estimating in a straightforward way the turnover frequency (TOF) of catalytic cycles, based on the state energies obtained by quantum chemical calculations. We describe how the apparent activation energy of the whole cycle, so-called energetic span (delta E), is influenced by the energy levels of two species: the TOF determining transition state (TDTS) and the TOF determining intermediate (TDI). Because these key species need not be adjoining states, we conclude that for catalysis there are no rate-determining steps, only rate determining states. In addition, we add here the influence of reactants concentrations. And, finally, the model is applied to the Haber-Bosch process of ammonia synthesis, for which we show how to calculate which catalyst will be the most effective under specific reagents conditions.

  6. Mesoporous MgO: Synthesis, physico-chemical, and catalytic properties

    NASA Astrophysics Data System (ADS)

    Maerle, A. A.; Kasyanov, I. A.; Moskovskaya, I. F.; Romanovsky, B. V.

    2016-06-01

    Mesoporous MgO was obtained via the hydrothermal synthesis using both ionogenic and non-ionogenic surfactants as structure-directing templates. The materials prepared were characterized by SEM, BET-N2, XRD, and TG-DTA techniques. MgO particles are spherical 20-μm aggregates of primary oxide particles well shaped as rectangular parallelepipeds. Magnesium oxide samples have the specific surface area of 290-400 m2/g and pore sizes of 3.3-4.1 nm. Their mesoporous structure remained unchanged after calcination up to 350°C. Catalytic activity of mesoporous MgO was studied in acetone condensation reaction.

  7. Convective stability in the presence of a catalytic chemical reaction. I.

    NASA Technical Reports Server (NTRS)

    Wankat, P. C.; Schowalter, W. R.

    1971-01-01

    A linear analysis of hydrodynamic stability has been applied to a problem in which a fluid mixture is contained between two horizontal planes. One species diffuses to the lower plane where it is destroyed by a rapid exothermic or endothermic catalytic reaction. Results show that important coupling takes place between thermal and concentration fields. This coupling gives rise to unusual stabilizing or destabilizing effects, depending upon the value of Lewis number. Several examples are discussed. It is also shown how the results can be applied to other problems involving heat and mass transfer.

  8. A liquid crystalline chirality balance for vapours

    PubMed Central

    Ohzono, Takuya; Yamamoto, Takahiro; Fukuda, Jun-ichi

    2014-01-01

    Chiral discrimination of vapours plays an important role in olfactory perception of biological systems and its realization by artificial sensors has been an intriguing challenge. Here, we report a simple method that tangibly visualizes the chirality of a diverse variety of molecules dissolved from vapours with high sensitivity, by making use of a structural change in a periodic microstructure of a nematic liquid crystal confined in open microchannels. This microstructure is accompanied by a topological line defect of a zigzag form with equal lengths of ‘zig’ and ‘zag.’ We find that a tiny amount of vapour of chiral molecules injected onto the liquid crystal induces the imbalance of ‘zig’ and ‘zag’ depending on its enantiomeric excess within a few seconds. Our liquid-crystal-based ‘chirality balance’ offers a simple, quick and versatile chirality-sensing/-screening method for gas-phase analysis (for example, for odours, environmental chemicals or drugs). PMID:24781531

  9. The Influence of Process Conditions on the Chemical Composition of Pine Wood Catalytic Pyrolysis Oils

    DOE PAGES

    Pereira, J.; Agblevor, F. A.; Beis, S. H.

    2012-01-01

    Pine wood samples were used as model feedstock to study the properties of catalytic fast pyrolysis oils. The influence of two commercial zeolite catalysts (BASF and SudChem) and pretreatment of the pine wood with sodium hydroxide on pyrolysis products were investigated. The pyrolysis oils were first fractionated using column chromatography and characterized using GC-MS. Long chain aliphatic hydrocarbons, levoglucosan, aldehydes and ketones, guaiacols/syringols, and benzenediols were the major compounds identified in the pyrolysis oils. The catalytic pyrolysis increased the polycyclic hydrocarbons fraction. Significant decreases in phthalate derivatives using SudChem and long chain aliphatics using BASF catalyst were observed. Significant amountsmore » of aromatic heterocyclic hydrocarbons and benzene derivatives were formed, respectively, using BASF and SudChem catalysts. Guaiacyl/syringyl and benzenediols derivatives were partly suppressed by the zeolite catalysts, while the sodium hydroxide treatment enriched phenolic derivatives. Zeolite catalyst and sodium hydroxide were employed together; they showed different results for each catalyst.« less

  10. Resveratrol induces catalytic bioscavenger paraoxonase 1 expression and protects against chemical warfare nerve agent toxicity in human cell lines.

    PubMed

    Curtin, Bryan F; Seetharam, Karthik I; Dhoieam, Pilin; Gordon, Richard K; Doctor, Bhupendra P; Nambiar, Madhusoodana P

    2008-04-01

    Current advances in enzyme bioscavenger prophylactic therapy against chemical warfare nerve agent (CWNA) exposure are moving towards the identification of catalytic bioscavengers that can degrade large doses of organophosphate (OP) nerve agents without self destruction. This is a preferred method compared to therapy with the purified stoichiometric bioscavenger, butyrylcholinesterase, which binds OPs 1:1 and would thus require larger doses for treatment. Paraoxonase-1 (PON-1) is one such catalytic bioscavenger that has been shown to hydrolyze OP insecticides and contribute to detoxification in animals and humans. Here we investigated the effects of a common red wine ingredient, Resveratrol (RSV), to induce the expression of PON-1 in the human hepatic cell line HC04 and evaluated the protection against CWNA simulants. Dose-response curves showed that a concentration of 20 microM RSV was optimal in inducing PON-1 expression in HC04 cells. RSV at 20 microM increased the extracellular PON-1 activity approximately 150% without significantly affecting the cells. Higher doses of RSV were cytotoxic to the cells. Resveratrol also induced PON-1 in the human lung cell line A549. RSV pre-treatment significantly (P = 0.05) protected the hepatic cells against exposure to 2x LD(50) of soman and sarin simulants. However, lung cells were protected against soman simulant exposure but not against sarin simulant exposure following RSV treatment. In conclusion, these studies indicate that dietary inducers, such as RSV, can up-regulate PON-1, a catalytic bioscavenger, which can then hydrolyze and protect against CWNA-induced toxicity, providing a prospective new method to protect against CWNA exposure.

  11. Synthesis of multi-walled carbon nanotubes using CoMnMgO catalysts through catalytic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Yang, Wen; Feng, Yan-Yan; Jiang, Cheng-Fa; Chu, Wei

    2014-12-01

    The CoMgO and CoMnMgO catalysts are prepared by a co-precipitation method and used as the catalysts for the synthesis of carbon nanotubes (CNTs) through the catalytic chemical vapor deposition (CCVD). The effects of Mn addition on the carbon yield and structure are investigated. The catalysts are characterized by temperature programmed reduction (TPR) and X-ray diffraction (XRD) techniques, and the synthesized carbon materials are characterized by transmission electron microscopy (TEM) and thermo gravimetric analysis (TG). TEM measurement indicates that the catalyst CoMgO enclosed completely in the produced graphite layer results in the deactivation of the catalyst. TG results suggest that the CoMnMgO catalyst has a higher selectivity for CNTs than CoMgO. Meanwhile, different diameters of CNTs are synthesized by CoMnMgO catalysts with various amounts of Co content, and the results show that the addition of Mn avoids forming the enclosed catalyst, prevents the formation of amorphous carbon, subsequently promotes the growth of CNTs, and the catalyst with decreased Co content is favorable for the synthesis of CNTs with a narrow diameter distribution. The CoMnMgO catalyst with 40% Co content has superior catalytic activity for the growth of carbon nanotubes.

  12. Synthesis of high yield single helical carbon microsprings by catalytic chemical vapor deposition and an experimental investigation of their growth mechanism

    SciTech Connect

    Xie Jining; Varadan, V. K.

    2007-06-01

    A type of single helical carbon microsprings (SHCMSs) was synthesized by catalytic chemical vapor deposition. The as-prepared SHCMSs were characterized by a number of techniques such as scanning and transmission electron microscopy, x-ray powder diffraction, and x-ray photoelectron spectroscopy. Experimental results indicate that during the synthesis both morphology change and crystalline phase transformation occur for cobalt catalytic particles and certain chemical bonding form between cobalt and sulfur atoms. Based on the data from this study, a possible growth mechanism of SHCMSs was discussed.

  13. Model of the catalytic mechanism of human aldose reductase based on quantum chemical calculations.

    SciTech Connect

    Cachau, R. C.; Howard, E. H.; Barth, P. B.; Mitschler, A. M.; Chevrier, B. C.; Lamour, V.; Joachimiak, A.; Sanishvili, R.; Van Zandt, M.; Sibley, E.; Moras, D.; Podjarny, A.; UPR de Biologie Structurale; National Cancer Inst.; Univ. Louis Pasteur; Inst. for Diabetes Discovery, Inc.

    2000-01-01

    Aldose Reductase is an enzyme involved in diabetic complications, thoroughly studied for the purpose of inhibitor development. The structure of an enzyme-inhibitor complex solved at sub-atomic resolution has been used to develop a model for the catalytic mechanism. This model has been refined using a combination of Molecular Dynamics and Quantum calculations. It shows that the proton donation, the subject of previous controversies, is the combined effect of three residues: Lys 77, Tyr 48 and His 110. Lys 77 polarises the Tyr 48 OH group, which donates the proton to His 110, which becomes doubly protonated. His 110 then moves and donates the proton to the substrate. The key information from the sub-atomic resolution structure is the orientation of the ring and the single protonafion of the His 110 in the enzyme-inhibitor complex. This model is in full agreement with all available experimental data.

  14. Catalytic Conversion of Biomass to Fuels and Chemicals Using Ionic Liquids

    SciTech Connect

    Liu, Wei; Zheng, Richard; Brown, Heather; Li, Joanne; Holladay, John; Cooper, Alan; Rao, Tony

    2012-04-13

    This project provides critical innovations and fundamental understandings that enable development of an economically-viable process for catalytic conversion of biomass (sugar) to 5-hydroxymethylfurfural (HMF). A low-cost ionic liquid (Cyphos 106) is discovered for fast conversion of fructose into HMF under moderate reaction conditions without any catalyst. HMF yield from fructose is almost 100% on the carbon molar basis. Adsorbent materials and adsorption process are invented and demonstrated for separation of 99% pure HMF product and recovery of the ionic liquid from the reaction mixtures. The adsorbent material appears very stable in repeated adsorption/regeneration cycles. Novel membrane-coated adsorbent particles are made and demonstrated to achieve excellent adsorption separation performances at low pressure drops. This is very important for a practical adsorption process because ionic liquids are known of high viscosity. Nearly 100% conversion (or dissolution) of cellulose in the catalytic ionic liquid into small molecules was observed. It is promising to produce HMF, sugars and other fermentable species directly from cellulose feedstock. However, several gaps were identified and could not be resolved in this project. Reaction and separation tests at larger scales are needed to minimize impacts of incidental errors on the mass balance and to show 99.9% ionic liquid recovery. The cellulose reaction tests were troubled with poor reproducibility. Further studies on cellulose conversion in ionic liquids under better controlled conditions are necessary to delineate reaction products, dissolution kinetics, effects of mass and heat transfer in the reactor on conversion, and separation of final reaction mixtures.

  15. Catalytic hydrothermal conversion of carboxymethyl cellulose to value-added chemicals over metal-organic framework MIL-53(Al).

    PubMed

    Zi, Guoli; Yan, Zhiying; Wang, Yangxia; Chen, Yongjuan; Guo, Yunlong; Yuan, Fagui; Gao, Wenyu; Wang, Yanmei; Wang, Jiaqiang

    2015-01-22

    Catalytic hydrolysis of biomass over solid catalysts can be one of the most efficient pathways for a future sustainable society dependent on cellulose biomass. In this work metal-organic framework MIL-53(Al) without any functionalization was directly employed as an efficient heterogeneous catalyst for the hydrolysis of carboxymethyl cellulose (CMC) to 5-hydroxymethyl-furaldehyde (5-HMF) in aqueous phase. A 5-HMF molar yield of 40.3% and total reducing sugar (TRS) molar yield of 54.2% were obtained with water as single solvent at 473 K for 4 h. The catalyst could be reused three times without losing activity to a greater extent. With the remarkable advantages such as the use of water as single solvent and MIL-53(Al) as a novel heterogeneous green catalyst, the work provides a new platform for the production of value added chemicals and liquid fuels from biomass. PMID:25439879

  16. Preliminary chemical analysis and biological testing of materials from the HRI catalytic two-stage liquefaction (CTSL) process. [Aliphatic hydrocarbons

    SciTech Connect

    Later, D.W.; Wilson, B.W.

    1985-01-01

    Coal-derived materials from experimental runs of Hydrocarbon Research Incorporated's (HRI) catalytic two-stage liquefaction (CTSL) process were chemically characterized and screened for microbial mutagenicity. This process differs from two-stage coal liquefaction processes in that catalyst is used in both stages. Samples from both the first and second stages were class-fractionated by alumina adsorption chromatography. The fractions were analyzed by capillary column gas chromatography; gas chromatography/mass spectrometry; direct probe, low voltage mass spectrometry; and proton nuclear magnetic resonance spectrometry. Mutagenicity assays were performed with the crude and class fractions in Salmonella typhimurium, TA98. Preliminary results of chemical analyses indicate that >80% CTSL materials from both process stages were aliphatic hydrocarbon and polynuclear aromatic hydrocarbon (PAH) compounds. Furthermore, the gross and specific chemical composition of process materials from the first stage were very similar to those of the second stage. In general, the unfractionated materials were only slightly active in the TA98 mutagenicity assay. Like other coal liquefaction materials investigated in this laboratory, the nitrogen-containing polycyclic aromatic compound (N-PAC) class fractions were responsible for the bulk of the mutagenic activity of the crudes. Finally, it was shown that this activity correlated with the presence of amino-PAH. 20 figures, 9 tables.

  17. Generation of continuous wave terahertz frequency radiation from metal-organic chemical vapour deposition grown Fe-doped InGaAs and InGaAsP

    NASA Astrophysics Data System (ADS)

    Mohandas, Reshma A.; Freeman, Joshua R.; Rosamond, Mark C.; Hatem, Osama; Chowdhury, Siddhant; Ponnampalam, Lalitha; Fice, Martyn; Seeds, Alwyn J.; Cannard, Paul J.; Robertson, Michael J.; Moodie, David G.; Cunningham, John E.; Davies, A. Giles; Linfield, Edmund H.; Dean, Paul

    2016-04-01

    We demonstrate the generation of continuous wave terahertz (THz) frequency radiation from photomixers fabricated on both Fe-doped InGaAs and Fe-doped InGaAsP, grown by metal-organic chemical vapor deposition. The photomixers were excited using a pair of distributed Bragg reflector lasers with emission around 1550 nm, and THz radiation was emitted over a bandwidth of greater than 2.4 THz. Two InGaAs and four InGaAsP wafers with different Fe doping concentrations were investigated, with the InGaAs material found to outperform the InGaAsP in terms of emitted THz power. The dependencies of the emitted power on the photomixer applied bias, incident laser power, and material doping level were also studied.

  18. Chemical modification of Aspergillus niger β-glucosidase and its catalytic properties.

    PubMed

    Ahmed, Samia A; El-Shayeb, Nefisa M A; Hashem, Abdel-Gawad M; Saleh, Shireen A A; Abdel-Fattah, Ahmed F

    2015-03-01

    Aspergillus niger β-glucosidase was modified by covalent coupling to periodate activated polysaccharides (glycosylation). The conjugated enzyme to activated starch showed the highest specific activity (128.5 U/mg protein). Compared to the native enzyme, the conjugated form exhibited: a higher optimal reaction temperature, a lower Ea (activation energy), a higher K m (Michaelis constant) and Vmax (maximal reaction rate), and improved thermal stability. The calculated t 1/2 (half-life) values of heat in-activation at 60 °C and 70 °C were 245.7 and 54.5 min respectively, whereas at these temperatures the native enzyme was less stable (t 1/2 of 200.0 and 49.5 min respectively). The conjugated enzyme retained 32.3 and 29.7%, respectively from its initial activity in presence of 5 mM Sodium Dodecyl Sulphate (SDS) and p -Chloro Mercuri Benzoate ( p -CMB), while the native enzyme showed a remarkable loss of activity (retained activity 1.61 and 13.7%, respectively). The present work has established the potential of glycosylation to enhance the catalytic properties of β-glucosidase enzyme, making this enzyme potentially feasible for biotechnological applications.

  19. Chemical modification of Aspergillus niger β-glucosidase and its catalytic properties

    PubMed Central

    Ahmed, Samia A.; El-Shayeb, Nefisa M.A.; Hashem, Abdel-Gawad M.; Saleh, Shireen A.A.; Abdel-Fattah, Ahmed F.

    2015-01-01

    Aspergillus niger β-glucosidase was modified by covalent coupling to periodate activated polysaccharides (glycosylation). The conjugated enzyme to activated starch showed the highest specific activity (128.5 U/mg protein). Compared to the native enzyme, the conjugated form exhibited: a higher optimal reaction temperature, a lower Ea (activation energy), a higher K m (Michaelis constant) and Vmax (maximal reaction rate), and improved thermal stability. The calculated t 1/2 (half-life) values of heat in-activation at 60 °C and 70 °C were 245.7 and 54.5 min respectively, whereas at these temperatures the native enzyme was less stable (t 1/2 of 200.0 and 49.5 min respectively). The conjugated enzyme retained 32.3 and 29.7%, respectively from its initial activity in presence of 5 mM Sodium Dodecyl Sulphate (SDS) and p -Chloro Mercuri Benzoate ( p -CMB), while the native enzyme showed a remarkable loss of activity (retained activity 1.61 and 13.7%, respectively). The present work has established the potential of glycosylation to enhance the catalytic properties of β-glucosidase enzyme, making this enzyme potentially feasible for biotechnological applications. PMID:26221085

  20. Growth of n-type polycrystalline pyrite (FeS 2) films by metalorganic chemical vapour deposition and their electrical characterization

    NASA Astrophysics Data System (ADS)

    Oertel, J.; Ellmer, K.; Bohne, W.; Röhrich, J.; Tributsch, H.

    1999-03-01

    The compound semiconductor pyrite (FeS 2) has attracted attention as a possible absorber material for thin film solar cells. In this article it is shown for the first time that polycrystalline pyrite films which normally show p-type conductivity, can in situ be doped n-type by using cobalt as a dopant above a concentration of 0.3 at%. The chemical cobalt concentration - determined by high energy heavy ion Rutherford backscattering analysis - is proportional to the cobalt-to-iron ratio in the gas phase. The carrier concentrations are very high (>10 20 cm -3) and the Seebeck coefficients are low (<70 μV/K), pointing at degenerated semiconductor properties. The carrier transport in the films can be described by the grain barrier limited transport model described by Seto (1975). From the temperature dependence of the Hall mobility, barrier heights of 7-37 meV have been determined. The trap density in the grain barriers is about 2×10 13 cm -2, a value which is much higher than in polycrystalline silicon or CdS-films.

  1. Resonant and nonresonant vibrational excitation of ammonia molecules in the growth of gallium nitride using laser-assisted metal organic chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Golgir, Hossein Rabiee; Zhou, Yun Shen; Li, Dawei; Keramatnejad, Kamran; Xiong, Wei; Wang, Mengmeng; Jiang, Li Jia; Huang, Xi; Jiang, Lan; Silvain, Jean Francois; Lu, Yong Feng

    2016-09-01

    The influence of exciting ammonia (NH3) molecular vibration in the growth of gallium nitride (GaN) was investigated by using an infrared laser-assisted metal organic chemical vapor deposition method. A wavelength tunable CO2 laser was used to selectively excite the individual vibrational modes. Resonantly exciting the NH-wagging mode (v2) of NH3 molecules at 9.219 μm led to a GaN growth rate of 84 μm/h, which is much higher than the reported results. The difference between the resonantly excited and conventional thermally populated vibrational states was studied via resonant and nonresonant vibrational excitations of NH3 molecules. Resonant excitation of various vibrational modes was achieved at 9.219, 10.35, and 10.719 μm, respectively. Nonresonant excitation was conducted at 9.201 and 10.591 μm, similar to conventional thermal heating. Compared to nonresonant excitation, resonant excitation noticeably promotes the GaN growth rate and crystalline quality. The full width at half maximum value of the XRD rocking curves of the GaN (0002) and GaN (10-12) diffraction peaks decreased at resonant depositions and reached its minimum value of 45 and 53 arcmin, respectively, at the laser wavelength of 9.219 μm. According to the optical emission spectroscopic studies, resonantly exciting the NH3 v2 mode leads to NH3 decomposition at room temperature, reduces the formation of the TMGa:NH3 adduct, promotes the supply of active species in GaN formation, and, therefore, results in the increased GaN growth rate.

  2. Transmission of photo-catalytic function in a self-replicating chemical system: in situ amphiphile production over two protocell generations.

    PubMed

    Albertsen, A N; Maurer, S E; Nielsen, K A; Monnard, P-A

    2014-08-18

    Glass microsphere supported protocells were built to investigate the transmission of catalytic function during replication. The chemical system's replication was driven through in situ amphiphile production that resulted in the formation of free bilayers, the system's second "generation". It was demonstrated that both generations, once separated, still exhibited the ability to convert amphiphile precursors. This result shows that transmission of function in chemical systems is possible during self-replication. PMID:24983026

  3. Chemically Accelerated Carbon Mineralization: Chemical and Biological Catalytic Enhancement of Weathering of Silicate Minerals as Novel Carbon Capture and Storage

    SciTech Connect

    2010-07-01

    IMPACCT Project: Columbia University is developing a process to pull CO2 out of the exhaust gas of coal-fired power plants and turn it into a solid that can be easily and safely transported, stored above ground, or integrated into value-added products (e.g. paper filler, plastic filler, construction materials, etc.). In nature, the reaction of CO2 with various minerals over long periods of time will yield a solid carbonate—this process is known as carbon mineralization. The use of carbon mineralization as a CO2 capture and storage method is limited by the speeds at which these minerals can be dissolved and CO2 can be hydrated. To facilitate this, Columbia University is using a unique process and a combination of chemical catalysts which increase the mineral dissolution rate, and the enzymatic catalyst carbonic anhydrase which speeds up the hydration of CO2.

  4. On-line speciation of inorganic and methyl mercury in waters and fish tissues using polyaniline micro-column and flow injection-chemical vapour generation-inductively coupled plasma mass spectrometry (FI-CVG-ICPMS).

    PubMed

    Krishna, M V Balarama; Chandrasekaran, K; Karunasagar, D

    2010-04-15

    A simple and efficient method for the determination of ultra-trace amounts of inorganic mercury (iHg) and methylmercury (MeHg) in waters and fish tissues was developed using a micro-column filled with polyaniline (PANI) coupled online to flow injection-chemical vapour generation-inductively coupled plasma mass spectrometry (FI-CVG-ICPMS) system. Preliminary studies indicated that inorganic and methyl mercury species could be separated on PANI column in two different speciation approaches. At pH <3, only iHg could be sorbed and almost no adsorption of MeHg was found (speciation procedure 1). If the sample solution pH is approximately 7, both MeHg and iHg species could be sorbed on the PANI column. Subsequently both the Hg species were selectively eluted with 2% HCl and a mixture of 2% HCl and 0.02% thiourea respectively (speciation procedure 2). The adsorption percentage of iHg on the PANI column was unchanged even with acidity of the sample solution increased to 6 mol L(-1). Therefore, an acidic solution (5 mol L(-1) HCl), used for ultra-sound assisted extraction of the mercury species from biological samples, was used directly to separate MeHg from iHg in the fish tissues (tuna fish ERM-CE 463, ERM-CE 464 and IAEA-350) by PANI column using speciation procedure 1. The determined values were in good agreement with certified values. Under optimal conditions, the limits of detection (LODs) were 2.52 pg and 3.24 pg for iHg and MeHg (as Hg) respectively. The developed method was applied successfully to the direct determination of iHg and MeHg in various waters (tap water, lake water, ground water and sea-water) and the recoveries for the spiked samples were in the range of 96-102% for both the Hg species. PMID:20188947

  5. Experimental and theoretical rationalization of the growth mechanism of silicon quantum dots in non-stoichiometric SiN x : role of chlorine in plasma enhanced chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Mon-Pérez, E.; Salazar, J.; Ramos, E.; Santoyo Salazar, J.; López Suárez, A.; Dutt, A.; Santana, G.; Marel Monroy, B.

    2016-11-01

    Silicon quantum dots (Si-QDs) embedded in an insulator matrix are important from a technological and application point of view. Thus, being able to synthesize them in situ during the matrix growth process is technologically advantageous. The use of SiH2Cl2 as the silicon precursor in the plasma enhanced chemical vapour deposition (PECVD) process allows us to obtain Si-QDs without post-thermal annealing. Foremost in this work, is a theoretical rationalization of the mechanism responsible for Si-QD generation in a film including an analysis of the energy released by the extraction of HCl and the insertion of silylene species into the terminal surface bonds. From the results obtained using density functional theory (DFT), we propose an explanation of the mechanism responsible for the formation of Si-QDs in non-stoichiometric SiN x starting from chlorinated precursors in a PECVD system. Micrograph images obtained through transmission electron microscopy confirmed the presence of Si-QDs, even in nitrogen-rich (N-rich) samples. The film stoichiometry was controlled by varying the growth parameters, in particular the NH3/SiH2Cl2 ratio and hydrogen dilution. Experimental and theoretical results together show that using a PECVD system, along with chlorinated precursors it is possible to obtain Si-QDs at a low substrate temperature without annealing treatment. The optical property studies carried out in the present work highlight the prospects of these thin films for down shifting and as an antireflection coating in silicon solar cells.

  6. On-line speciation of inorganic and methyl mercury in waters and fish tissues using polyaniline micro-column and flow injection-chemical vapour generation-inductively coupled plasma mass spectrometry (FI-CVG-ICPMS).

    PubMed

    Krishna, M V Balarama; Chandrasekaran, K; Karunasagar, D

    2010-04-15

    A simple and efficient method for the determination of ultra-trace amounts of inorganic mercury (iHg) and methylmercury (MeHg) in waters and fish tissues was developed using a micro-column filled with polyaniline (PANI) coupled online to flow injection-chemical vapour generation-inductively coupled plasma mass spectrometry (FI-CVG-ICPMS) system. Preliminary studies indicated that inorganic and methyl mercury species could be separated on PANI column in two different speciation approaches. At pH <3, only iHg could be sorbed and almost no adsorption of MeHg was found (speciation procedure 1). If the sample solution pH is approximately 7, both MeHg and iHg species could be sorbed on the PANI column. Subsequently both the Hg species were selectively eluted with 2% HCl and a mixture of 2% HCl and 0.02% thiourea respectively (speciation procedure 2). The adsorption percentage of iHg on the PANI column was unchanged even with acidity of the sample solution increased to 6 mol L(-1). Therefore, an acidic solution (5 mol L(-1) HCl), used for ultra-sound assisted extraction of the mercury species from biological samples, was used directly to separate MeHg from iHg in the fish tissues (tuna fish ERM-CE 463, ERM-CE 464 and IAEA-350) by PANI column using speciation procedure 1. The determined values were in good agreement with certified values. Under optimal conditions, the limits of detection (LODs) were 2.52 pg and 3.24 pg for iHg and MeHg (as Hg) respectively. The developed method was applied successfully to the direct determination of iHg and MeHg in various waters (tap water, lake water, ground water and sea-water) and the recoveries for the spiked samples were in the range of 96-102% for both the Hg species.

  7. Niobium(V) saponite clay for the catalytic oxidative abatement of chemical warfare agents.

    PubMed

    Carniato, Fabio; Bisio, Chiara; Psaro, Rinaldo; Marchese, Leonardo; Guidotti, Matteo

    2014-09-15

    A Nb(V)-containing saponite clay was designed to selectively transform toxic organosulfur chemical warfare agents (CWAs) under extremely mild conditions into nontoxic products with reduced environmental impact. Thanks to the insertion of Nb(V) sites within the saponite framework, a bifunctional catalyst with strong oxidizing and acid properties was obtained. Remarkable activity and high selectivity were observed for the oxidative abatement of (2-chloroethyl)ethyl sulfide (CEES), a simulant of sulfur mustard, at room temperature with aqueous hydrogen peroxide. This performance was significantly better compared to a conventional commercial decontamination powder.

  8. Hydrodeoxygenation processes: advances on catalytic transformations of biomass-derived platform chemicals into hydrocarbon fuels.

    PubMed

    De, Sudipta; Saha, Basudeb; Luque, Rafael

    2015-02-01

    Lignocellulosic biomass provides an attractive source of renewable carbon that can be sustainably converted into chemicals and fuels. Hydrodeoxygenation (HDO) processes have recently received considerable attention to upgrade biomass-derived feedstocks into liquid transportation fuels. The selection and design of HDO catalysts plays an important role to determine the success of the process. This review has been aimed to emphasize recent developments on HDO catalysts in effective transformations of biomass-derived platform molecules into hydrocarbon fuels with reduced oxygen content and improved H/C ratios. Liquid hydrocarbon fuels can be obtained by combining oxygen removal processes (e.g. dehydration, hydrogenation, hydrogenolysis, decarbonylation etc.) as well as by increasing the molecular weight via C-C coupling reactions (e.g. aldol condensation, ketonization, oligomerization, hydroxyalkylation etc.). Fundamentals and mechanistic aspects of the use of HDO catalysts in deoxygenation reactions will also be discussed. PMID:25443804

  9. Studies of coupled chemical and catalytic coal conversion methods. Ninth quarterly report, October, November, December 1989

    SciTech Connect

    Stock, L.M.

    1989-12-31

    A new base catalyzed C-alkylation reaction that employs a mixture of n-butyllithium and potassium t-butoxide in refluxing heptane to produce coal anions that are subsequently treated with n-alkyl halides at 0{degree}C has been developed. Almost quantitative pyridine solubilization was achieved by C-octylation of a Lower Kittanning coal, PSOC 1197. C-Octylation was less successful for the solubilization of bituminous Illinois No. 6 coal, APCSP 3, and subbituminous Wyodak coal, APCSP 2, which gave 35 and 33% soluble material, respectively. Their O-methyl derivatives yielded 43 and 20% soluble material in the same reaction. The observations are in accord with the concept of Ouchi and his associates that higher rank coals, although more aromatic in character, have a lower degree of polymerization than low rank coals. Relatively mild chemical reactions, such as Calkylation, that lead to modest changes in molecular dimensions, can disrupt intermolecular forces and accomplish solubilization.

  10. An Analytical Framework for Studying Small-Number Effects in Catalytic Reaction Networks: A Probability Generating Function Approach to Chemical Master Equations

    PubMed Central

    Nakagawa, Masaki; Togashi, Yuichi

    2016-01-01

    Cell activities primarily depend on chemical reactions, especially those mediated by enzymes, and this has led to these activities being modeled as catalytic reaction networks. Although deterministic ordinary differential equations of concentrations (rate equations) have been widely used for modeling purposes in the field of systems biology, it has been pointed out that these catalytic reaction networks may behave in a way that is qualitatively different from such deterministic representation when the number of molecules for certain chemical species in the system is small. Apart from this, representing these phenomena by simple binary (on/off) systems that omit the quantities would also not be feasible. As recent experiments have revealed the existence of rare chemical species in cells, the importance of being able to model potential small-number phenomena is being recognized. However, most preceding studies were based on numerical simulations, and theoretical frameworks to analyze these phenomena have not been sufficiently developed. Motivated by the small-number issue, this work aimed to develop an analytical framework for the chemical master equation describing the distributional behavior of catalytic reaction networks. For simplicity, we considered networks consisting of two-body catalytic reactions. We used the probability generating function method to obtain the steady-state solutions of the chemical master equation without specifying the parameters. We obtained the time evolution equations of the first- and second-order moments of concentrations, and the steady-state analytical solution of the chemical master equation under certain conditions. These results led to the rank conservation law, the connecting state to the winner-takes-all state, and analysis of 2-molecules M-species systems. A possible interpretation of the theoretical conclusion for actual biochemical pathways is also discussed. PMID:27047384

  11. An Analytical Framework for Studying Small-Number Effects in Catalytic Reaction Networks: A Probability Generating Function Approach to Chemical Master Equations.

    PubMed

    Nakagawa, Masaki; Togashi, Yuichi

    2016-01-01

    Cell activities primarily depend on chemical reactions, especially those mediated by enzymes, and this has led to these activities being modeled as catalytic reaction networks. Although deterministic ordinary differential equations of concentrations (rate equations) have been widely used for modeling purposes in the field of systems biology, it has been pointed out that these catalytic reaction networks may behave in a way that is qualitatively different from such deterministic representation when the number of molecules for certain chemical species in the system is small. Apart from this, representing these phenomena by simple binary (on/off) systems that omit the quantities would also not be feasible. As recent experiments have revealed the existence of rare chemical species in cells, the importance of being able to model potential small-number phenomena is being recognized. However, most preceding studies were based on numerical simulations, and theoretical frameworks to analyze these phenomena have not been sufficiently developed. Motivated by the small-number issue, this work aimed to develop an analytical framework for the chemical master equation describing the distributional behavior of catalytic reaction networks. For simplicity, we considered networks consisting of two-body catalytic reactions. We used the probability generating function method to obtain the steady-state solutions of the chemical master equation without specifying the parameters. We obtained the time evolution equations of the first- and second-order moments of concentrations, and the steady-state analytical solution of the chemical master equation under certain conditions. These results led to the rank conservation law, the connecting state to the winner-takes-all state, and analysis of 2-molecules M-species systems. A possible interpretation of the theoretical conclusion for actual biochemical pathways is also discussed.

  12. Vapour Intrusion into Buildings - A Literature Review

    EPA Science Inventory

    This chapter provides a review of recent research on vapour intrusion of volatile organic compounds (VOCs) into buildings. The chapter builds on a report from Tillman and Weaver (2005) which reviewed the literature on vapour intrusion through 2005. Firstly, the term ‘vapour intru...

  13. Catalytic oxidation of biorefinery lignin to value-added chemicals to support sustainable biofuel production.

    PubMed

    Ma, Ruoshui; Xu, Yan; Zhang, Xiao

    2015-01-01

    Transforming plant biomass to biofuel is one of the few solutions that can truly sustain mankind's long-term needs for liquid transportation fuel with minimized environmental impact. However, despite decades of effort, commercial development of biomass-to-biofuel conversion processes is still not an economically viable proposition. Identifying value-added co-products along with the production of biofuel provides a key solution to overcoming this economic barrier. Lignin is the second most abundant component next to cellulose in almost all plant biomass; the emerging biomass refinery industry will inevitably generate an enormous amount of lignin. Development of selective biorefinery lignin-to-bioproducts conversion processes will play a pivotal role in significantly improving the economic feasibility and sustainability of biofuel production from renewable biomass. The urgency and importance of this endeavor has been increasingly recognized in the last few years. This paper reviews state-of-the-art oxidative lignin depolymerization chemistries employed in the papermaking process and oxidative catalysts that can be applied to biorefinery lignin to produce platform chemicals including phenolic compounds, dicarboxylic acids, and quinones in high selectivity and yield. The potential synergies of integrating new catalysts with commercial delignification chemistries are discussed. We hope the information will build on the existing body of knowledge to provide new insights towards developing practical and commercially viable lignin conversion technologies, enabling sustainable biofuel production from lignocellulosic biomass to be competitive with fossil fuel.

  14. Catalytic oxidation of biorefinery lignin to value-added chemicals to support sustainable biofuel production.

    PubMed

    Ma, Ruoshui; Xu, Yan; Zhang, Xiao

    2015-01-01

    Transforming plant biomass to biofuel is one of the few solutions that can truly sustain mankind's long-term needs for liquid transportation fuel with minimized environmental impact. However, despite decades of effort, commercial development of biomass-to-biofuel conversion processes is still not an economically viable proposition. Identifying value-added co-products along with the production of biofuel provides a key solution to overcoming this economic barrier. Lignin is the second most abundant component next to cellulose in almost all plant biomass; the emerging biomass refinery industry will inevitably generate an enormous amount of lignin. Development of selective biorefinery lignin-to-bioproducts conversion processes will play a pivotal role in significantly improving the economic feasibility and sustainability of biofuel production from renewable biomass. The urgency and importance of this endeavor has been increasingly recognized in the last few years. This paper reviews state-of-the-art oxidative lignin depolymerization chemistries employed in the papermaking process and oxidative catalysts that can be applied to biorefinery lignin to produce platform chemicals including phenolic compounds, dicarboxylic acids, and quinones in high selectivity and yield. The potential synergies of integrating new catalysts with commercial delignification chemistries are discussed. We hope the information will build on the existing body of knowledge to provide new insights towards developing practical and commercially viable lignin conversion technologies, enabling sustainable biofuel production from lignocellulosic biomass to be competitive with fossil fuel. PMID:25272962

  15. Hydrophobic properties of polytetrafluoroethylene thin films fabricated at various catalyzer temperatures through catalytic chemical vapor deposition using a tungsten catalyzer.

    PubMed

    Cha, Jeong Ok; Yeo, Seung Jun; Pode, Ramchandra; Ahn, Jeung Sun

    2011-07-01

    Using the catalytic chemical vapor deposition (Cat-CVD) method, polytetrafluoroethylene (PTFE) thin films were fabricated on Si(100) substrates at various catalyzer temperatures, using a tungsten catalyzer, and Fourier transform infrared (FTIR) spectroscopy and X-ray photoemission spectroscopy (XPS) were used to confirm the fabrication of the films. An atomic-force microscope (AFM) and a scanning electron microscope (SEM) were employed to study the correlation between the wettability and surface morphology of the samples. It was found that the wettability of the PTFE thin films fabricated via Cat-CVD is strongly correlated with the sizes of the film surfaces' nanoprotrusions, and that superhydrophobic PTFE thin-film surfaces can be easily achieved by controlling the sizes of the nanoprotrusions through the catalyzer temperature. The comparison of the wettability values and surface morphologies of the films confirmed that nanoscale surface roughness enhances the hydrophobic properties of PTFE thin films. Further, the detailed analysis of the films' surface morphologies from their AFM images with the use of the Wenzel and Cassie models confirmed that the nanoscale surface roughness enhanced the hydrophobic property of the PTFE films. Further, the variations of the wettability of the PTFE thin films prepared via Cat-CVD are well explained by the Cassie model. It seems that the increase in the trapping air and the reduction of the liquid-solid contact area are responsible for the superhydrophobicity of the PTFE thin films prepared via Cat-CVD. PMID:22121615

  16. Low Temperature Growth of In2O3and InN Nanocrystals on Si(111) via Chemical Vapour Deposition Based on the Sublimation of NH4Cl in In

    PubMed Central

    2009-01-01

    Indium oxide (In2O3) nanocrystals (NCs) have been obtained via atmospheric pressure, chemical vapour deposition (APCVD) on Si(111) via the direct oxidation of In with Ar:10% O2at 1000 °C but also at temperatures as low as 500 °C by the sublimation of ammonium chloride (NH4Cl) which is incorporated into the In under a gas flow of nitrogen (N2). Similarly InN NCs have also been obtained using sublimation of NH4Cl in a gas flow of NH3. During oxidation of In under a flow of O2the transfer of In into the gas stream is inhibited by the formation of In2O3around the In powder which breaks up only at high temperatures, i.e.T > 900 °C, thereby releasing In into the gas stream which can then react with O2leading to a high yield formation of isolated 500 nm In2O3octahedrons but also chains of these nanostructures. No such NCs were obtained by direct oxidation forTG < 900 °C. The incorporation of NH4Cl in the In leads to the sublimation of NH4Cl into NH3and HCl at around 338 °C which in turn produces an efficient dispersion and transfer of the whole In into the gas stream of N2where it reacts with HCl forming primarily InCl. The latter adsorbs onto the Si(111) where it reacts with H2O and O2leading to the formation of In2O3nanopyramids on Si(111). The rest of the InCl is carried downstream, where it solidifies at lower temperatures, and rapidly breaks down into metallic In upon exposure to H2O in the air. Upon carrying out the reaction of In with NH4Cl at 600 °C under NH3as opposed to N2, we obtain InN nanoparticles on Si(111) with an average diameter of 300 nm. PMID:20596336

  17. Label-Free Chemical Imaging of Catalytic Solids by Coherent Anti-Stokes Raman Scattering and Synchrotron-Based Infrared Microscopy

    SciTech Connect

    Kox, M.; Domke, K; Day, J; Rago, G; Stavitski, E; Bonn, M; Weckhuysen, B

    2009-01-01

    Take a look inside: The combination of coherent anti-Stokes Raman scattering and synchrotron-based IR microscopy during the catalytic conversion of thiophene derivatives on zeolite crystals yields space- and time-resolved chemically specific information without the need for labeling (see picture). The thiophene reactant is mostly present in the center of the crystal, and the product is aligned within the straight pores of the zeolites.

  18. Light propagation through atomic vapours

    NASA Astrophysics Data System (ADS)

    Siddons, Paul

    2014-05-01

    This tutorial presents the theory necessary to model the propagation of light through an atomic vapour. The history of atom-light interaction theories is reviewed, and examples of resulting applications are provided. A numerical model is developed and results presented. Analytic solutions to the theory are found, based on approximations to the numerical work. These solutions are found to be in excellent agreement with experimental measurements.

  19. The application of Cu/SiO2 catalytic system in chemical mechanical planarization based on the stability of SiO2 sol

    NASA Astrophysics Data System (ADS)

    Yan, Li; Yuling, Liu; Aochen, Wang; Zhixin, Yang; Mingbin, Sun; Chuan, Cheng; Yufeng, Zhang; Nannan, Zhang

    2014-06-01

    There is a lot of hydroxyl on the surface of nano SiO2 sol used as an abrasive in the chemical mechanical planarization (CMP) process, and the chemical reaction activity of the hydroxyl is very strong due to the nano effect. In addition to providing a mechanical polishing effect, SiO2 sol is also directly involved in the chemical reaction. The stability of SiO2 sol was characterized through particle size distribution, zeta potential, viscosity, surface charge and other parameters in order to ensure that the chemical reaction rate in the CMP process, and the surface state of the copper film after CMP was not affected by the SiO2 sol. Polarization curves and corrosion potential of different concentrations of SiO2 sol showed that trace SiO2 sol can effectively weaken the passivation film thickness. In other words, SiO2 sol accelerated the decomposition rate of passive film. It was confirmed that the SiO2 sol as reactant had been involved in the CMP process of copper film as reactant by the effect of trace SiO2 sol on the removal rate of copper film in the CMP process under different conditions. In the CMP process, a small amount of SiO2 sol can drastically alter the chemical reaction rate of the copper film, therefore, the possibility that Cu/SiO2 as a catalytic system catalytically accelerated the chemical reaction in the CMP process was proposed. According to the van't Hoff isotherm formula and the characteristics of a catalyst which only changes the chemical reaction rate with out changing the total reaction standard Gibbs free energy, factors affecting the Cu/SiO2 catalytic reaction were derived from the decomposition rate of Cu (OH)2 and the pH value of the system, and then it was concluded that the CuSiO3 as intermediates of Cu/SiO2 catalytic reaction accelerated the chemical reaction rate in the CMP process. It was confirmed that the Cu/SiO2 catalytic system generated the intermediate of the catalytic reaction (CuSiO3) in the CMP process through the removal

  20. Condensation of water vapour on moss-dominated biological soil crust, NW China

    NASA Astrophysics Data System (ADS)

    Wang, Xin-Ping; Pan, Yan-Xia; Hu, Rui; Zhang, Ya-Feng; Zhang, Hao

    2014-03-01

    Characteristics of water vapour condensation, including the onset, duration, and amount of water vapour condensation on moss-dominated biological soil crust (BSC) and dune sand were studied under simulated conditions with varying air temperature and relative humidity. The simulations were performed in a plant growth chamber using an electronic balance recording the weight of condensation. There was a positive linear correlation between the water vapour condensation and relative humidity while the mean temperature was negatively linearly related to amounts of water vapour condensation for both soil surfaces. The amount of water vapour condensation on BSC and dune sand can be described by the difference between air temperature and dew point with an exponential function, indicating that when the difference of air temperature and dew point exceeds a value of 35.3◦C, there will be zero water vapour condensed on BSC. In contrast, when the difference of air temperature and dew point exceeds a value of 20.4◦C, the water vapour condensation will be zero for dune sand. In general, when the air is fully saturated with water and the dew point is equal to the current air temperature, the water vapour condensed on BSC attained its maximum value of 0.398 mm, whereas it was 0.058 mm for dune sand. In comparison, water vapour condensed on BSC was at a relatively high temperature and low relative humidity, while we did not detect water vapour condensation on the dune sand under the similar conditions. Physical and chemical analyses of the samples pointed to a greater porosity, high content of fine particles, and high salinity for BSC compared to the dune sand. These results highlight that soil physicochemical properties are the likely factors influencing the mechanism of water vapour condensation under specific meteorological conditions, as onset was earlier and the duration was longer for water vapour condensation on BSC in comparison with that of dune sand. This contributed to

  1. Isothermal vapour flow in extremely dry soils

    NASA Astrophysics Data System (ADS)

    Todman, L. C.; Ireson, A. M.; Butler, A. P.; Templeton, M. R.

    2012-04-01

    In dry soils hydraulic connectivity within the liquid water phase decreases and vapour flow becomes a significant transport mechanism for water. The temperature or solute concentration of the liquid phase affects the vapour pressure of the surrounding air, thus temperature or solute gradients can drive vapour flows. However, in extremely dry soils where water is retained by adsorptive forces rather than capillarity, vapour flows can also occur. In such soils tiny changes in water content significantly affect the equilibrium vapour pressure in the soil, and hence small differences in water content can initiate vapour pressure gradients. In many field conditions this effect may be negligible compared to vapour flows driven by other factors. However, flows of this type are particularly significant in a new type of subsurface irrigation system which uses pervaporation, via a polymer tubing, as the mechanism for water supply. In this system, water enters the soil in vapour phase. Experiments were performed in laboratory conditions using marine sand that had previously been oven dried and cooled. This dry sand was used to represent the desert conditions in which this irrigation system is intended for use. Experimental results show that isothermal vapour flows can significantly affect the performance of such irrigation systems due to the rapid transport of water through the soil via the vapour phase. When the irrigation pipe was buried at a depth of 10cm a vapour flow from the soil surface was observed in less than 2 hours. These flows therefore affect the loss of mass into the atmosphere and thus must be considered when evaluating the availability of water for the irrigated crop. The experiments also provide a rare opportunity to observe isothermal vapour flows initiating from a subsurface source. Such experiments allow the significance of these flows to be quantified and potentially applied to other areas of arid zone hydrology.

  2. A group contribution method for estimating the vapour pressures of α-pinene oxidation products

    NASA Astrophysics Data System (ADS)

    Capouet, M.; Müller, J.-F.

    2006-05-01

    A prediction method based on group contribution principles is proposed for estimating the vapour pressure of α-pinene oxidation products. Temperature dependent contributions are provided for the following chemical groups: carbonyl, nitrate, hydroxy, hydroperoxy, acyl peroxy nitrate and carboxy. On the basis of observed vapour pressure differences between isomers of diols and dinitrates, a simple refinement is introduced in the method to account for the influence of substitutions on the vapour pressure for alcohols and nitrates. The vapour pressures predicted with this new method have been compared with the predictions from UNIFAC (Asher et al., 2002). Given the large uncertainties of the vapour pressure data for the least volatile compounds, further experimental studies of subcooled vapour pressures of multifunctional compounds at ambient temperatures are required for better parameterizations. Among the α-pinene products identified to date, pinic acid and hydroxy pinonic acid are predicted to be the least volatile compounds, with estimated vapour pressures of 3×10-6 torr and 6×10-7 torr, respectively. The vapour pressure of the other primary products range from 10-5 to 10-3 torr, with hydroxy hydroperoxides presenting the lowest values. Noting that multifunctional carboxylic acids, in particular pinic acid, are believed to be mostly present as dimers in laboratory conditions, we suggest that the partial vapour pressure of the pinic acid dimer should be close to the experimental subcooled vapour pressure for pinic acid (estimated at ~10-6 torr) due to its large contribution to the total concentration (dimer+monomer) in experimental conditions.

  3. Towards outperforming conventional sensor arrays with fabricated individual photonic vapour sensors inspired by Morpho butterflies

    PubMed Central

    Potyrailo, Radislav A.; Bonam, Ravi K.; Hartley, John G.; Starkey, Timothy A.; Vukusic, Peter; Vasudev, Milana; Bunning, Timothy; Naik, Rajesh R.; Tang, Zhexiong; Palacios, Manuel A.; Larsen, Michael; Le Tarte, Laurie A.; Grande, James C.; Zhong, Sheng; Deng, Tao

    2015-01-01

    Combining vapour sensors into arrays is an accepted compromise to mitigate poor selectivity of conventional sensors. Here we show individual nanofabricated sensors that not only selectively detect separate vapours in pristine conditions but also quantify these vapours in mixtures, and when blended with a variable moisture background. Our sensor design is inspired by the iridescent nanostructure and gradient surface chemistry of Morpho butterflies and involves physical and chemical design criteria. The physical design involves optical interference and diffraction on the fabricated periodic nanostructures and uses optical loss in the nanostructure to enhance the spectral diversity of reflectance. The chemical design uses spatially controlled nanostructure functionalization. Thus, while quantitation of analytes in the presence of variable backgrounds is challenging for most sensor arrays, we achieve this goal using individual multivariable sensors. These colorimetric sensors can be tuned for numerous vapour sensing scenarios in confined areas or as individual nodes for distributed monitoring. PMID:26324320

  4. Azadirachta indica plant-assisted green synthesis of Mn3O4 nanoparticles: Excellent thermal catalytic performance and chemical sensing behavior.

    PubMed

    Sharma, Jitendra Kumar; Srivastava, Pratibha; Ameen, Sadia; Akhtar, M Shaheer; Singh, Gurdip; Yadava, Sudha

    2016-06-15

    The leaf extract of Azadirachta indica (Neem) plant was utilized as reducing agent for the green synthesis of Mn3O4 nanoparticles (NPs). The crystalline analysis demonstrated the typical tetragonal hausmannite crystal structure of Mn3O4, which confirmed the formation of Mn3O4 NPs without the existence of other oxides. Green synthesized Mn3O4 NPs were applied for the catalytic thermal decomposition of ammonium perchlorate (AP) and as working electrode for fabricating the chemical sensor. The excellent catalytic effect for the thermal decomposition of AP was observed by decreasing the decomposition temperature by 175 °C with single decomposing step. The fabricated chemical sensor based on green synthesized Mn3O4 NPs displayed high, reliable and reproducible sensitivity of ∼569.2 μA mM(-1) cm(-2) with reasonable limit of detection (LOD) of ∼22.1 μM and the response time of ∼10 s toward the detection of 2-butanone chemical. A relatively good linearity in the ranging from ∼20 to 160 μM was detected for Mn3O4 NPs electrode based 2-butanone chemical sensor.

  5. Catalytic reactor

    SciTech Connect

    Aaron, Timothy Mark; Shah, Minish Mahendra; Jibb, Richard John

    2009-03-10

    A catalytic reactor is provided with one or more reaction zones each formed of set(s) of reaction tubes containing a catalyst to promote chemical reaction within a feed stream. The reaction tubes are of helical configuration and are arranged in a substantially coaxial relationship to form a coil-like structure. Heat exchangers and steam generators can be formed by similar tube arrangements. In such manner, the reaction zone(s) and hence, the reactor is compact and the pressure drop through components is minimized. The resultant compact form has improved heat transfer characteristics and is far easier to thermally insulate than prior art compact reactor designs. Various chemical reactions are contemplated within such coil-like structures such that as steam methane reforming followed by water-gas shift. The coil-like structures can be housed within annular chambers of a cylindrical housing that also provide flow paths for various heat exchange fluids to heat and cool components.

  6. Novel Dextranase Catalyzing Cycloisomaltooligosaccharide Formation and Identification of Catalytic Amino Acids and Their Functions Using Chemical Rescue Approach*

    PubMed Central

    Kim, Young-Min; Kiso, Yoshiaki; Muraki, Tomoe; Kang, Min-Sun; Nakai, Hiroyuki; Saburi, Wataru; Lang, Weeranuch; Kang, Hee-Kwon; Okuyama, Masayuki; Mori, Haruhide; Suzuki, Ryuichiro; Funane, Kazumi; Suzuki, Nobuhiro; Momma, Mitsuru; Fujimoto, Zui; Oguma, Tetsuya; Kobayashi, Mikihiko; Kim, Doman; Kimura, Atsuo

    2012-01-01

    A novel endodextranase from Paenibacillus sp. (Paenibacillus sp. dextranase; PsDex) was found to mainly produce isomaltotetraose and small amounts of cycloisomaltooligosaccharides (CIs) with a degree of polymerization of 7–14 from dextran. The 1,696-amino acid sequence belonging to the glycosyl hydrolase family 66 (GH-66) has a long insertion (632 residues; Thr451–Val1082), a portion of which shares identity (35% at Ala39–Ser1304 of PsDex) with Pro32–Ala755 of CI glucanotransferase (CITase), a GH-66 enzyme that catalyzes the formation of CIs from dextran. This homologous sequence (Val837–Met932 for PsDex and Tyr404–Tyr492 for CITase), similar to carbohydrate-binding module 35, was not found in other endodextranases (Dexs) devoid of CITase activity. These results support the classification of GH-66 enzymes into three types: (i) Dex showing only dextranolytic activity, (ii) Dex catalyzing hydrolysis with low cyclization activity, and (iii) CITase showing CI-forming activity with low dextranolytic activity. The fact that a C-terminal truncated enzyme (having Ala39–Ser1304) has 50% wild-type PsDex activity indicates that the C-terminal 392 residues are not involved in hydrolysis. GH-66 enzymes possess four conserved acidic residues (Asp189, Asp340, Glu412, and Asp1254 of PsDex) of catalytic candidates. Their amide mutants decreased activity (11,500 to 140,000 times), and D1254N had 36% activity. A chemical rescue approach was applied to D189A, D340G, and E412Q using α-isomaltotetraosyl fluoride with NaN3. D340G or E412Q formed a β- or α-isomaltotetraosyl azide, respectively, strongly indicating Asp340 and Glu412 as a nucleophile and acid/base catalyst, respectively. Interestingly, D189A synthesized small sized dextran from α-isomaltotetraosyl fluoride in the presence of NaN3. PMID:22461618

  7. Venus Water Vapour Profiles Obtained by SOIR/VEx

    NASA Astrophysics Data System (ADS)

    Chamberlain, Sarah; Wilquet, Valerie; Mahieux, Arnaud; Robert, Severine; Thomas, Ian; Carine Vandaele, Ann; Bertaux, Jean-Loup

    2015-04-01

    We present up-to-date observations of the water vapour profile at the Venus terminator, between altitudes of 70 - 110km. The data were obtained by the Solar Occultation in the InfraRed (SOIR) instrument on board Venus Express (VEx). The SOIR instrument allows observations of trace gas profiles at altitudes within the Venus lower thermosphere and mesosphere. Due to the observational technique, all observations are taken at the Venus terminator, on either or both of the evening and morning side of the planet and covering almost all latitudes. These are key locations for study as the mesosphere/thermosphere altitudes correspond to the transition in dynamical regime from a retrograde zonal flow to sub-solar to antisolar flow (approximately 90 km) and at these altitudes we expect a steeper than normal temperature gradient across the terminator which would drive chemical reactions and dynamical flows. Water vapour in the mesosphere is involved in the cloud formation process and contributes to several chemical cycles. Isotopologue ratio studies also contribute towards understanding the evolution of the Venus climate and atmosphere. Determining the abundance, distribution and variability of water vapour is therefore a key element to understanding the development, maintenance and links between dynamical features, important chemical cycles and the evolution of the Venus atmosphere. Both water vapour isotopologues are targeted simultaneously in the majority of dedicated SOIR water vapour observations. H2O is detected between 70 - 110km and HDO is detected between 70 - 95km altitude. Early SOIR water vapour observations were published in 2007 and 2008. Previous results show a depletion in the volume mixing ratio (VMR) at 85km in both HDO and H2O and an increase in HDO/H2O ratio above the clouds. No noticeable temporal variability was detected. Numerous subsequent H2O and HDO SOIR observations have been obtained between 2007 - 2014 and with recent improvements in instrument

  8. CATALYTIC OXIDATION OF DIMETHYL SULFIDE WITH OZONE: EFFECTS OF PROMOTER AND PHYSICO-CHEMICAL PROPERTIES OF METAL OXIDE CATALYSTS

    EPA Science Inventory

    This study reports improved catalytic activities and stabilities for the oxidation of dimethyl sulfide (DMS), a major pollutant of pulp and paper mills. Ozone was used as an oxidant and activities of Cu, Mo, Cr and Mn oxides, and mixed metal oxides supported on -alumina, were tes...

  9. CATALYTIC OXIDATION OF DIMETHYL SULFIDE WITH OZONE: EFFECT OF PROMOTER AND PHYSICO-CHEMICAL PROPERTIES OF METAL OXIDE CATALYSTS

    EPA Science Inventory

    This study reports improved catalytic activities and stabilities for the oxidation of dimethyl sulfide (DMS), a major pollutant of pulp and paper mills. Ozone was used as an oxidant and Cu, Mo, V, Cr and Mn metal oxides, and mixed metal oxides support on y-alumina as catalysts ov...

  10. Drastic reduction in the surface recombination velocity of crystalline silicon passivated with catalytic chemical vapor deposited SiN{sub x} films by introducing phosphorous catalytic-doped layer

    SciTech Connect

    Thi, Trinh Cham Koyama, Koichi; Ohdaira, Keisuke; Matsumura, Hideki

    2014-07-28

    We improve the passivation property of n-type crystalline silicon (c-Si) surface passivated with a catalytic chemical vapor deposited (Cat-CVD) Si nitride (SiN{sub x}) film by inserting a phosphorous (P)-doped layer formed by exposing c-Si surface to P radicals generated by the catalytic cracking of PH{sub 3} molecules (Cat-doping). An extremely low surface recombination velocity (SRV) of 2 cm/s can be achieved for 2.5 Ω cm n-type (100) floating-zone Si wafers passivated with SiN{sub x}/P Cat-doped layers, both prepared in Cat-CVD systems. Compared with the case of only SiN{sub x} passivated layers, SRV decreases from 5 cm/s to 2 cm/s. The decrease in SRV is the result of field effect created by activated P atoms (donors) in a shallow P Cat-doped layer. Annealing process plays an important role in improving the passivation quality of SiN{sub x} films. The outstanding results obtained imply that SiN{sub x}/P Cat-doped layers can be used as promising passivation layers in high-efficiency n-type c-Si solar cells.

  11. Mercury vapour suppression by various liquid media.

    PubMed

    Sutow, E J; Foong, W C; Rizkalla, A S; Jones, D W; Power, N L

    1994-09-01

    Fresh and used photographic fixer, Merconvap and water were evaluated for their ability to suppress the vapourization of mercury. Mercury vapour concentration above the four test storage liquids was measured at various times between 10 min and 335 days, using a mercury vapour measuring instrument. The data were analysed using a Student-Newman-Keuls multiple comparison test (P = 0.05). The results showed that fresh and used fixer and Merconvap suppressed the vapourization of mercury to below the detection limit of the measuring instrument (0.01 mg/m3). Water was much less effective compared with the other liquids and showed an increase in mercury vapour concentration with log t. PMID:7996339

  12. A nucleation and growth model of vertically-oriented carbon nanofibers or nanotubes by plasma-enhanced catalytic chemical vapor deposition.

    PubMed

    Cojocaru, C S; Senger, A; Le Normand, F

    2006-05-01

    Carbon nanofibers are grown by direct current and hot filaments-activated catalytic chemical vapor deposition while varying the power of the hot filaments. Observations of these carbon nanofibers vertically oriented on a SiO2 (8 nm thick)/Si(100) substrate covered with Co nanoparticles (10-15 nm particle size) by Scanning Electron and Transmission Electron Microscopies show the presence of a graphitic "nest" either on the surface of the substrate or at the end of the specific nanofiber that does not encapsulate the catalytic particle. Strictly in our conditions, the activation by hot filaments is required to grow nanofibers with a C2H2 - H2 gas mixture, as large amounts of amorphous carbon cover the surface of the substrate without using hot filaments. From these observations as well as data of the literature, it is proposed that the nucleation of carbon nanofibers occurs through a complex process involving several steps: carbon concentration gradient starting from the catalytic carbon decomposition and diffusion from the surface of the catalytic nanoparticles exposed to the activated gas and promoted by energetic ionic species of the gas phase; subsequent graphitic condensation of a "nest" at the interface of the Co particle and substrate. The large concentration of highly reactive hydrogen radicals mainly provided by activation with hot filaments precludes further spreading out of this interfacial carbon nest over the entire surface of the substrate and thus selectively orientates the growth towards the condensation of graphene over facets that are perpendicular to the surface. Carbon nanofibers can then be grown within the well-known Vapor-Liquid-Solid process. Thus the effect of energetic ions and highly reactive neutrals like atomic hydrogen in the preferential etching of carbon on the edge of graphene shells and on the broadening of the carbon nanofiber is underlined.

  13. Sensing response of copper phthalocyanine salt dispersed glass with organic vapours

    NASA Astrophysics Data System (ADS)

    Ridhi, R.; Sachdeva, Sheenam; Saini, G. S. S.; Tripathi, S. K.

    2016-05-01

    Copper Phthalocyanine and other Metal Phthalocyanines are very flexible and tuned easily to modify their structural, spectroscopic, optical and electrical properties by either functionalizing them with various substituent groups or by replacing or adding a ligand to the central metal atom in the phthalocyanine ring and accordingly can be made sensitive and selective to various organic species or gaseous vapours. In the present work, we have dispersed Copper Phthalocyanine Salt (CuPcS) in sol-gel glass form using chemical route sol-gel method and studied its sensing mechanism with organic vapours like methanol and benzene and found that current increases onto their exposure with vapours. A variation in the activation energies was also observed with exposure of vapours.

  14. Vapour phase dehydration of glycerol to acrolein over tungstated zirconia catalysts

    NASA Astrophysics Data System (ADS)

    Rao Ginjupalli, Srinivasa; Mugawar, Sowmya; Rajan N., Pethan; Kumar Balla, Putra; Chary Komandur, V. R.

    2014-08-01

    Tetragonal (TZ) and monoclinic (MZ) polymorphs of zirconia supports were synthesised by sol-gel method followed by variation of the calcination temperature. Tungstated (10 wt% WO3) supported on the zirconia polymorphs were prepared by impregnation method by using ammonium metatungstate precursor. The physico-chemical properties of the calcined catalysts were characterised by X-ray diffraction, UV-vis diffused reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), surface area and pore size distribution measurements to gain insight into the effect of morphology of the catalyst textural properties, and structure. The surface acidic properties have been determined by NH3 TPD method and also with FT-IR spectra of pyridine adsorption. Vapour phase dehydration of glycerol to acrolein was employed to investigate the catalytic functionalities. Glycerol conversion and acrolein selectivity was mainly dependent on the fraction of moderate acid sites with majority of them are due to Brønsted acidic sites. Monoclinic zirconia based catalysts have shown the highest activity and acrolein selectivity compared to the corresponding tetragonal zirconia catalysts.

  15. Water vapour in the UT/LS

    NASA Astrophysics Data System (ADS)

    Schiller, C.

    2003-04-01

    The water vapour abundance increased at all levels in the stratosphere during the last decades. Though the observed increase cannot be explained quantitatively, the water vapour distribution and underlying processes seem to be sufficiently understood in the overworld. In the lowermost stratosphere and in the tropical tropopause layer, however, the complex transport and temperature patterns on different scales result in a high variability and strong gradients of the water vapour distribution. The long-term increase of water vapour seems to be apparent also in the lowermost stratosphere, but its significance is decreasing towards the tropopause. In this presentation, measurements of water vapour in the extratropical UT/LS from several airborne campaigns are discussed and compared to distribution patterns obtained from satellite data sets. A mixing layer with H2O mixing ratios up to 100 ppmv is found above the tropopause, frequently resulting in saturation of these air masses. A seasonal cycle of the water content with a late spring and summer maximum is apparent in the LS. The role of jet streams moistening the lowermost stratosphere will be discussed. In a second part, water vapour distributions in the tropics as the stratospheric source region are presented. As an example, measurements over the Indian ocean are discussed where temperatures and water vapour mixing ratios as low as in the classical 'fountain' region over Micronesia occurred. Frequently, ongoing dehydration was observed in the TTL up to the tropopause, independent on deep convection cells.

  16. The ESA DUE GlobVapour Project

    NASA Astrophysics Data System (ADS)

    Schröder, M.; ESA Due Globvapour Project Team

    2010-12-01

    The European Space Agency (ESA) Data User Element (DUE) project series aims at bridging the gap between research projects and the sustainable provision of Earth Observation (EO) climate data products at an information level that fully responds to the operational needs of user communities. The ultimate objective of GlobVapour is to provide long-term coherent water vapour data sets exploiting the synergistic capabilities of different EO missions aiming at improved accuracies and enhanced temporal and spatial sampling better than those provided by the single sources. The project seeks to utilize the increasing potential of the synergistic capabilities of past, existing and upcoming satellite missions (ERS-1 and -2, ENVISAT, METOP, MSG as well as relevant non-European missions and in-situ data) in order to meet the increasing needs for coherent long-term water vapour datasets required by the scientific community. GlobVapour develops, validates and applies novel water vapour climate data sets derived from various sensors. More specifically, the primary objectives of the GlobVapour project are: 1)The development of multi-annual global water vapour data sets inclusive of error estimates based on carefully calibrated and inter-calibrated radiances. 2)The validation of the water vapour products against ground based, airborne and other satellite based measurements. 3) The provision of an assessment of the quality of different IASI water vapour profile algorithms developed by the project partners and other groups. 4) The provision of a complete processing system that can further strengthen operational production of the developed products. 5) A demonstration of the use of the products in the field of climate modelling, including applying alternative ways of climate model validation using forward radiation operators. 6) The promotion of the strategy of data set construction and the data sets themselves to the global research and operational community. The ultimate goal of the

  17. The chemical versatility of the beta-alpha-beta fold: catalytic promiscuity and divergent evolution in the tautomerase superfamily.

    PubMed

    Poelarends, G J; Veetil, V Puthan; Whitman, C P

    2008-11-01

    Tautomerase superfamily members have an amino-terminal proline and a beta-alpha-beta fold, and include 4-oxalocrotonate tautomerase (4-OT), 5-(carboxymethyl)-2-hydroxymuconate isomerase (CHMI), trans- and cis-3-chloroacrylic acid dehalogenase (CaaD and cis-CaaD, respectively), malonate semialdehyde decarboxylase (MSAD), and macrophage migration inhibitory factor (MIF), which exhibits a phenylpyruvate tautomerase (PPT) activity. Pro-1 is a base (4-OT, CHMI, the PPT activity of MIF) or an acid (CaaD, cis-CaaD, MSAD). Components of the catalytic machinery have been identified and mechanistic hypotheses formulated. Characterization of new homologues shows that these mechanisms are incomplete. 4-OT, CaaD, cis-CaaD, and MSAD also have promiscuous activities with a hydratase activity in CaaD, cis-CaaD, and MSAD, PPT activity in CaaD and cis-CaaD, and CaaD and cis-CaaD activities in 4-OT. The shared promiscuous activities provide evidence for divergent evolution from a common ancestor, give hints about mechanistic relationships, and implicate catalytic promiscuity in the emergence of new enzymes.

  18. Liquid vapour spinodal of pure helium 4

    NASA Astrophysics Data System (ADS)

    Imre, Attila R.; Kraska, Thomas

    2008-10-01

    Unlike gases, liquids can be overheated or stretched only up to a limit. The determination of the mean-field thermodynamic stability limit-the so-called spinodal-is a very difficult theoretical and a more-or-less impossible experimental task. Based on a recent semi-empirical method, the spinodal pressure of helium-4 at given temperature is determined, using liquid-vapour surface tension, interface thickness and vapour pressure data.

  19. An assessment of vapour pressure estimation methods.

    PubMed

    O'Meara, Simon; Booth, Alastair Murray; Barley, Mark Howard; Topping, David; McFiggans, Gordon

    2014-09-28

    Laboratory measurements of vapour pressures for atmospherically relevant compounds were collated and used to assess the accuracy of vapour pressure estimates generated by seven estimation methods and impacts on predicted secondary organic aerosol. Of the vapour pressure estimation methods that were applicable to all the test set compounds, the Lee-Kesler [Reid et al., The Properties of Gases and Liquids, 1987] method showed the lowest mean absolute error and the Nannoolal et al. [Nannoonal et al., Fluid Phase Equilib., 2008, 269, 117-133] method showed the lowest mean bias error (when both used normal boiling points estimated using the Nannoolal et al. [Nannoolal et al., Fluid Phase Equilib., 2004, 226, 45-63] method). The effect of varying vapour pressure estimation methods on secondary organic aerosol (SOA) mass loading and composition was investigated using an absorptive partitioning equilibrium model. The Myrdal and Yalkowsky [Myrdal and Yalkowsky, Ind. Eng. Chem. Res., 1997, 36, 2494-2499] vapour pressure estimation method using the Nannoolal et al. [Nannoolal et al., Fluid Phase Equilib., 2004, 226, 45-63] normal boiling point gave the most accurate estimation of SOA loading despite not being the most accurate for vapour pressures alone. PMID:25105180

  20. Diameter-dependent thermal-oxidative stability of single-walled carbon nanotubes synthesized by a floating catalytic chemical vapor deposition method

    NASA Astrophysics Data System (ADS)

    Ma, Jie; Yu, Fei; Yuan, Zhiwen; Chen, Junhong

    2011-10-01

    In this paper, purified single-walled carbon naotubes (SWCNTs) with three different diameters were synthesized using a floating catalytic chemical vapor deposition method with ethanol as carbon feedstock, ferrocene as catalyst, and thiophene as growth promoter. The thermal-oxidative stability of different-diameter SWCNTs was studied by using thermal analysis (TG, DTA), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) analysis. The results indicate that small diameter SWCNTs (˜1 nm) are less stable and burn at lower temperature (610 °C), however, the larger diameter SWCNTs (˜5 nm) survive after burning at higher temperature (685 °C), the oxidation rate varies inversely with the tube diameter of SWCNTs, which may be concluded that the higher oxidation-resistant temperature of larger diameter SWCNTs can be attributed to the lower curvature-induced strain by rolling the planar graphene sheet for the larger diameter, so small tubes will become thermodynamically unstable.

  1. High efficiency chemical energy conversion system based on a methane catalytic decomposition reaction and two fuel cells. Part II. Exergy analysis

    NASA Astrophysics Data System (ADS)

    Liu, Qinghua; Tian, Ye; Li, Hongjiao; Jia, Lijun; Xia, Chun; Thompson, Levi T.; Li, Yongdan

    A methane catalytic decomposition reactor-direct carbon fuel cell-internal reforming solid oxide fuel cell (MCDR-DCFC-IRSOFC) energy system is highly efficient for converting the chemical energy of methane into electrical energy. A gas turbine cycle is also used to output more power from the thermal energy generated in the IRSOFC. In part I of this work, models of the fuel cells and the system are proposed and validated. In this part, exergy conservation analysis is carried out based on the developed electrochemical and thermodynamic models. The ratio of the exergy destruction of each unit is examined. The results show that the electrical exergy efficiency of 68.24% is achieved with the system. The possibility of further recovery of the waste heat is discussed and the combined power-heat exergy efficiency is over 80%.

  2. Defect termination on crystalline silicon surfaces by hydrogen for improvement in the passivation quality of catalytic chemical vapor-deposited SiNx and SiNx/P catalytic-doped layers

    NASA Astrophysics Data System (ADS)

    Cham Thi, Trinh; Koyama, Koichi; Ohdaira, Keisuke; Matsumura, Hideki

    2016-02-01

    We investigate the role of hydrogen (H) in the improvement in the passivation quality of silicon nitride (SiNx) prepared by catalytic chemical vapor deposition (Cat-CVD) and Cat-CVD SiNx/phosphorus (P) Cat-doped layers on crystalline silicon (c-Si) by annealing. Both structures show promising passivation capabilities for c-Si with extremely low surface recombination velocity (SRV) on n-type c-Si. Defect termination by H is evaluated on the basis of defect density (Nd) determined by electron spin resonance (ESR) spectroscopy and interface state density (Dit) calculated by the Terman method. The two parameters are found to be drastically decreased by annealing after SiNx deposition. The calculated average Dit at midgap (Dit-average) is 2.2 × 1011 eV-1 cm-2 for the SiNx/P Cat-doped c-Si sample with a SRV of 2 cm/s, which is equivalent to 3.1 × 1011 eV-1 cm-2 for the SiNx/c-Si sample with a SRV of 5 cm/s after annealing. The results indicate that H atoms play a critical role in the reduction in Dit for SiNx/c-Si and SiNx/P Cat-doped c-Si, resulting in a drastic reduction in SRV by annealing.

  3. Catalytic distillation process

    DOEpatents

    Smith, Jr., Lawrence A.

    1982-01-01

    A method for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C.sub.4 feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  4. Catalytic distillation process

    DOEpatents

    Smith, L.A. Jr.

    1982-06-22

    A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  5. Catalytic hydrothermal upgrading of crude bio-oils produced from different thermo-chemical conversion routes of microalgae.

    PubMed

    Duan, Peigao; Wang, Bing; Xu, Yuping

    2015-06-01

    This study presents experimental results that compare the use of hydrothermal liquefaction (HTL), alcoholysis (Al), pyrolysis (Py) and hydropyrolysis (HPy) for the production of bio-oil from a microalga (Chlorella pyrenoidosa) and the catalytic hydrothermal upgrading of crude bio-oils produced by these four conversion routes. The yields and compositions of bio-oil, solid residue, and gases were evaluated and compared. HTL resulted in a bio-oil that has a higher energy density and superior fuel properties, such as thermal and storage stabilities, compared with the other three conversion routes. The N in crude bio-oils produced from Py and HPy is more easily removed than that in the bio-oils produced from HTL and Al. The upgraded bio-oils contain reduced amounts of certain O-containing and N-containing compounds and significantly increased saturated hydrocarbon contents. All of the upgraded bio-oils have a larger fraction boiling below 350°C than their corresponding crude bio-oils. PMID:25802049

  6. Physico-Chemical Condition Optimization during Biosynthesis lead to development of Improved and Catalytically Efficient Gold Nano Particles

    PubMed Central

    Kumari, Madhuree; Mishra, Aradhana; Pandey, Shipra; Singh, Satyendra Pratap; Chaudhry, Vasvi; Mudiam, Mohana Krishna Reddy; Shukla, Shatrunajay; Kakkar, Poonam; Nautiyal, Chandra Shekhar

    2016-01-01

    Biosynthesis of nanoparticles has gained great attention in making the process cost-effective and eco-friendly, but there are limited reports which describe the interdependency of physical parameters for tailoring the dimension and geometry of nanoparticles during biological synthesis. In the present study, gold nanoparticles (GNPs) of various shapes and sizes were obtained by modulating different physical parameters using Trichoderma viride filtrate. The particles were characterized on the basis of visual observation, dynamic light scattering, UV-visible spectroscopy, transmission electron microscopy, fourier transform infrared spectroscopy, and X ray diffraction. While the size varied from 2–500 nm, the shapes obtained were nanospheres, nanotriangles, nanopentagons, nanohexagons, and nanosheets. Changing the parameters such as pH, temperature, time, substrate, and culture filtrate concentration influenced the size and geometry of nanoparticles. Catalytic activity of the biosynthesized GNP was evaluated by UV-visible spectroscopy and confirmed by gas chromatography-mass spectrometric analysis for the conversion of 4-nitrophenol into 4-aminophenol which was strongly influenced by their structure and dimension. Common practices for biodegradation are traditional, expensive, require large amount of raw material, and time taking. Controlling shapes and sizes of nanoparticles could revolutionize the process of biodegradation that can remove all the hurdles in current scenario. PMID:27273371

  7. Catalytic hydrothermal upgrading of crude bio-oils produced from different thermo-chemical conversion routes of microalgae.

    PubMed

    Duan, Peigao; Wang, Bing; Xu, Yuping

    2015-06-01

    This study presents experimental results that compare the use of hydrothermal liquefaction (HTL), alcoholysis (Al), pyrolysis (Py) and hydropyrolysis (HPy) for the production of bio-oil from a microalga (Chlorella pyrenoidosa) and the catalytic hydrothermal upgrading of crude bio-oils produced by these four conversion routes. The yields and compositions of bio-oil, solid residue, and gases were evaluated and compared. HTL resulted in a bio-oil that has a higher energy density and superior fuel properties, such as thermal and storage stabilities, compared with the other three conversion routes. The N in crude bio-oils produced from Py and HPy is more easily removed than that in the bio-oils produced from HTL and Al. The upgraded bio-oils contain reduced amounts of certain O-containing and N-containing compounds and significantly increased saturated hydrocarbon contents. All of the upgraded bio-oils have a larger fraction boiling below 350°C than their corresponding crude bio-oils.

  8. Physico-Chemical Condition Optimization during Biosynthesis lead to development of Improved and Catalytically Efficient Gold Nano Particles.

    PubMed

    Kumari, Madhuree; Mishra, Aradhana; Pandey, Shipra; Singh, Satyendra Pratap; Chaudhry, Vasvi; Mudiam, Mohana Krishna Reddy; Shukla, Shatrunajay; Kakkar, Poonam; Nautiyal, Chandra Shekhar

    2016-01-01

    Biosynthesis of nanoparticles has gained great attention in making the process cost-effective and eco-friendly, but there are limited reports which describe the interdependency of physical parameters for tailoring the dimension and geometry of nanoparticles during biological synthesis. In the present study, gold nanoparticles (GNPs) of various shapes and sizes were obtained by modulating different physical parameters using Trichoderma viride filtrate. The particles were characterized on the basis of visual observation, dynamic light scattering, UV-visible spectroscopy, transmission electron microscopy, fourier transform infrared spectroscopy, and X ray diffraction. While the size varied from 2-500 nm, the shapes obtained were nanospheres, nanotriangles, nanopentagons, nanohexagons, and nanosheets. Changing the parameters such as pH, temperature, time, substrate, and culture filtrate concentration influenced the size and geometry of nanoparticles. Catalytic activity of the biosynthesized GNP was evaluated by UV-visible spectroscopy and confirmed by gas chromatography-mass spectrometric analysis for the conversion of 4-nitrophenol into 4-aminophenol which was strongly influenced by their structure and dimension. Common practices for biodegradation are traditional, expensive, require large amount of raw material, and time taking. Controlling shapes and sizes of nanoparticles could revolutionize the process of biodegradation that can remove all the hurdles in current scenario. PMID:27273371

  9. Comparative analysis on the effects of diesel particulate filter and selective catalytic reduction systems on a wide spectrum of chemical species emissions.

    PubMed

    Liu, Z Gerald; Berg, Devin R; Swor, Thaddeus A; Schauer, James J

    2008-08-15

    Two methods, diesel particulate filter (DPF) and selective catalytic reduction (SCR) systems,for controlling diesel emissions have become widely used, either independently or together, for meeting increasingly stringent emissions regulations worldwide. Each of these systems is designed for the reduction of primary pollutant emissions including particulate matter (PM) for DPF and nitrogen oxides (NOx) for SCR. However, there have been growing concerns regarding the secondary reactions that these aftertreatment systems may promote, involving unregulated species emissions. This study was performed to gain an understanding of the effects that these aftertreatment systems may have on the emission levels of a wide spectrum of chemical species found in diesel engine exhaust. Samples were extracted using a source dilution sampling system designed to collect exhaust samples representative of real-world emissions. Testing was conducted on a heavy-duty diesel engine with no aftertreatment devices to establish a baseline measurement and also on the same engine equipped first with a DPF system and then a SCR system. Each of the samples was analyzed for a wide variety of chemical species, including elemental and organic carbon, metals, ions, n-alkanes, aldehydes, and polycyclic aromatic hydrocarbons, in addition to the primary pollutants, due to the potential risks they pose to the environment and public health. The results show that the DPF and SCR systems were capable of substantially reducing PM and NOx emissions, respectively. Further, each of the systems significantly reduced the emission levels of the unregulated chemical species, while the notable formation of new chemical species was not observed. It is expected that a combination of the two systems in some future engine applications would reduce both primary and secondary emissions significantly.

  10. Microwave-assisted catalytic fast pyrolysis of biomass for bio-oil production using chemical vapor deposition modified HZSM-5 catalyst.

    PubMed

    Zhang, Bo; Zhong, Zhaoping; Chen, Paul; Ruan, Roger

    2015-12-01

    Chemical vapor deposition with tetra-ethyl-orthosilicate as the modifier was applied to deposit the external acid sites of HZSM-5, and the modified HZSM-5 samples were used for the microwave-assisted catalytic fast pyrolysis (MACFP) of biomass for bio-oil production. The experimental results showed that the external acid sites of HZSM-5 decreased significantly when SiO2 deposited amount increased from 0% to 5.9%. For product distribution, the coke yield decreased, the oil fraction yield decreased at first and then increased, and the yields of water and gas first increased and then decreased over the range of SiO2 deposited amount studied. For chemical compositions in oil fraction, the relative contents of aliphatic hydrocarbons, aromatic hydrocarbons and oxygen-containing aromatic compounds first increased to maximum values and then decreased, while the relative content of oxygen-containing aliphatic compounds first decreased and then increased with increasing SiO2 deposited amount. PMID:26318925

  11. An Investigation of Tertiary Students' Understanding of Evaporation, Condensation and Vapour Pressure

    ERIC Educational Resources Information Center

    Gopal, Hemant; Kleinsmidt, Jacques; Case, Jennifer; Musonge, Paul

    2004-01-01

    Based on a purposive sample of 15 second-year chemical engineering students, this study investigates students' conceptions of evaporation, condensation and vapour pressure. During individual interviews the students were questioned on three tasks that had been designed around these topics. Qualitative analysis of student responses showed a range of…

  12. An Investigation of Tertiary Students' Understanding of Evaporation, Condensation and Vapour Pressure. Research Report

    ERIC Educational Resources Information Center

    Gopal, Hemant; Kleinsmidt, Jacques; Case, Jennifer; Musonge, Paul

    2004-01-01

    Based on a purposive sample of 15 second-year chemical engineering students, this study investigates students' conceptions of evaporation, condensation and vapour pressure. During individual interviews the students were questioned on three tasks that had been designed around these topics. Qualitative analysis of student responses showed a range of…

  13. Modelling vapour transport in Surtseyan bombs

    NASA Astrophysics Data System (ADS)

    McGuinness, Mark J.; Greenbank, Emma; Schipper, C. Ian

    2016-05-01

    We address questions that arise if a slurry containing liquid water is enclosed in a ball of hot viscous vesicular magma ejected as a bomb in the context of a Surtseyan eruption. We derive a mathematical model for transient changes in temperature and pressure due to flashing of liquid water to vapour inside the bomb. The magnitude of the transient pressure changes that are typically generated are calculated together with their dependence on material properties. A single criterion to determine whether the bomb will fragment as a result of the pressure changes is derived. Timescales for ejection of water vapour from a bomb that remains intact are also revealed.

  14. Revising organic vapour respirator cartridge change schedule: a case study of a paint plant in Iran.

    PubMed

    Karimi, Ali; Jahangiri, Mehdi; Zare Derisi, Forough; Nourozi, Mohammad Amin

    2013-01-01

    After having revised the change schedule for organic vapour respirator cartridges in a paint plant in Iran, we established that it did not provide adequate protection against organic vapours at some workplaces and needed shortening from (48 to 72) h to 4 h. The revision also showed that relying on odour thresholds as the primary means to determine the time to change a chemical cartridge was not effective and that the National Institute for Occupational Safety and Health (NIOSH) MultiVapor service life software program could be applied to develop cartridge change schedules adjusted to specific workplaces.

  15. Revising organic vapour respirator cartridge change schedule: a case study of a paint plant in Iran.

    PubMed

    Karimi, Ali; Jahangiri, Mehdi; Zare Derisi, Forough; Nourozi, Mohammad Amin

    2013-01-01

    After having revised the change schedule for organic vapour respirator cartridges in a paint plant in Iran, we established that it did not provide adequate protection against organic vapours at some workplaces and needed shortening from (48 to 72) h to 4 h. The revision also showed that relying on odour thresholds as the primary means to determine the time to change a chemical cartridge was not effective and that the National Institute for Occupational Safety and Health (NIOSH) MultiVapor service life software program could be applied to develop cartridge change schedules adjusted to specific workplaces. PMID:23585165

  16. Fabrication of high-electron-mobility ZnO epilayers by chemical vapor deposition using catalytically produced excited water

    NASA Astrophysics Data System (ADS)

    Nishiyama, Hiroshi; Miura, Hitoshi; Yasui, Kanji; Inoue, Yasunobu

    2010-02-01

    Hot H 2O jet evolved by the exothermic reaction of H 2 with O 2 on a Pt-dispersed ZrO 2 catalyst was employed for gas-phase hydrolysis of dimethyl zinc to fabricate thin ZnO films. The X-ray diffraction pattern and photoluminescence spectra showed that the ZnO epilayers directly grown on a-sapphire substrate at 873 K had a defect free crystal structure close to a single crystal. The as-grown ZnO epilayers exhibited average transparency higher than 90% in the visible and infrared regions (400-2000 nm). The epilayers had high electron mobilities of 140-170 cm 2 V -1 s -1 and low residual electron concentrations of 1.7-6×10 17 cm -3 that are significantly better than those for ZnO films so far reported by conventional chemical vapor deposition and any other energy-consuming physical method such as pulse laser deposition and molecular beam epitaxy. The present method uses the chemical energy from only H 2 and O 2, which is energy-saving and ecologically friendly, while it is superior in high-quality ZnO fabrication. It is also pointed out that the method raises unlimited possibilities for a wide range of the fabrication of high-quality metal oxide epilayers, because of the availability for various volatile alkyl metals.

  17. Saturated Vapour Pressure and Refrigeration - Part I

    ERIC Educational Resources Information Center

    Bunker, C. A.

    1973-01-01

    The first part of a two-part article describes an experimental approach that can be used in teaching the concept of saturated vapour pressure. This leads to a discussion of refrigeration cycles in the second part of the article. (JR)

  18. Ultrasound promoted catalytic liquid-phase dehydrogenation of isopropanol for Isopropanol-Acetone-Hydrogen chemical heat pump.

    PubMed

    Xu, Min; Xin, Fang; Li, Xunfeng; Huai, Xiulan; Liu, Hui

    2015-03-01

    The apparent kinetic of the ultrasound assisted liquid-phase dehydrogenation of isopropanol over Raney nickel catalyst was determined in the temperature range of 346-353 K. Comparison of the effects of ultrasound and mechanical agitation on the isopropanol dehydrogenation was investigated. The ultrasound assisted dehydrogenation rate was significantly improved when relatively high power density was used. Moreover, the Isopropanol-Acetone-Hydrogen chemical heat pump (IAH-CHP) with ultrasound irradiation, in which the endothermic reaction is exposure to ultrasound, was proposed. A mathematical model was established to evaluate its energy performance in term of the coefficient of performance (COP) and the exergy efficiency, into which the apparent kinetic obtained in this work was incorporated. The operating performances between IAH-CHP with ultrasound and mechanical agitation were compared. The results indicated that the superiority of the IAH-CHP system with ultrasound was present even if more than 50% of the power of the ultrasound equipment was lost. PMID:25246094

  19. Ultrasound promoted catalytic liquid-phase dehydrogenation of isopropanol for Isopropanol-Acetone-Hydrogen chemical heat pump.

    PubMed

    Xu, Min; Xin, Fang; Li, Xunfeng; Huai, Xiulan; Liu, Hui

    2015-03-01

    The apparent kinetic of the ultrasound assisted liquid-phase dehydrogenation of isopropanol over Raney nickel catalyst was determined in the temperature range of 346-353 K. Comparison of the effects of ultrasound and mechanical agitation on the isopropanol dehydrogenation was investigated. The ultrasound assisted dehydrogenation rate was significantly improved when relatively high power density was used. Moreover, the Isopropanol-Acetone-Hydrogen chemical heat pump (IAH-CHP) with ultrasound irradiation, in which the endothermic reaction is exposure to ultrasound, was proposed. A mathematical model was established to evaluate its energy performance in term of the coefficient of performance (COP) and the exergy efficiency, into which the apparent kinetic obtained in this work was incorporated. The operating performances between IAH-CHP with ultrasound and mechanical agitation were compared. The results indicated that the superiority of the IAH-CHP system with ultrasound was present even if more than 50% of the power of the ultrasound equipment was lost.

  20. Novel process and catalytic materials for converting CO2 and H2 containing mixtures to liquid fuels and chemicals.

    PubMed

    Meiri, Nora; Dinburg, Yakov; Amoyal, Meital; Koukouliev, Viatcheslav; Nehemya, Roxana Vidruk; Landau, Miron V; Herskowitz, Moti

    2015-01-01

    Carbon dioxide and water are renewable and the most abundant feedstocks for the production of chemicals and fungible fuels. However, the current technologies for production of hydrogen from water are not competitive. Therefore, reacting carbon dioxide with hydrogen is not economically viable in the near future. Other alternatives include natural gas, biogas or biomass for the production of carbon dioxide, hydrogen and carbon monoxide mixtures that react to yield chemicals and fungible fuels. The latter process requires a high performance catalyst that enhances the reverse water-gas-shift (RWGS) reaction and Fischer-Tropsch synthesis (FTS) to higher hydrocarbons combined with an optimal reactor system. Important aspects of a novel catalyst, based on a Fe spinel and three-reactor system developed for this purpose published in our recent paper and patent, were investigated in this study. Potassium was found to be a key promoter that improves the reaction rates of the RWGS and FTS and increases the selectivity of higher hydrocarbons while producing mostly olefins. It changed the texture of the catalyst, stabilized the Fe-Al-O spinel, thus preventing decomposition into Fe3O4 and Al2O3. Potassium also increased the content of Fe5C2 while shifting Fe in the oxide and carbide phases to a more reduced state. In addition, it increased the relative exposure of carbide iron on the catalysts surface, the CO2 adsorption and the adsorption strength. A detailed kinetic model of the RWGS, FTS and methanation reactions was developed for the Fe spinel catalyst based on extensive experimental data measured over a range of operating conditions. Significant oligomerization activity of the catalyst was found. Testing the pelletized catalyst with CO2, CO and H2 mixtures over a range of operating conditions demonstrated its high productivity to higher hydrocarbons. The composition of the liquid (C5+) was found to be a function of the potassium content and the composition of the feedstock

  1. Novel process and catalytic materials for converting CO2 and H2 containing mixtures to liquid fuels and chemicals.

    PubMed

    Meiri, Nora; Dinburg, Yakov; Amoyal, Meital; Koukouliev, Viatcheslav; Nehemya, Roxana Vidruk; Landau, Miron V; Herskowitz, Moti

    2015-01-01

    Carbon dioxide and water are renewable and the most abundant feedstocks for the production of chemicals and fungible fuels. However, the current technologies for production of hydrogen from water are not competitive. Therefore, reacting carbon dioxide with hydrogen is not economically viable in the near future. Other alternatives include natural gas, biogas or biomass for the production of carbon dioxide, hydrogen and carbon monoxide mixtures that react to yield chemicals and fungible fuels. The latter process requires a high performance catalyst that enhances the reverse water-gas-shift (RWGS) reaction and Fischer-Tropsch synthesis (FTS) to higher hydrocarbons combined with an optimal reactor system. Important aspects of a novel catalyst, based on a Fe spinel and three-reactor system developed for this purpose published in our recent paper and patent, were investigated in this study. Potassium was found to be a key promoter that improves the reaction rates of the RWGS and FTS and increases the selectivity of higher hydrocarbons while producing mostly olefins. It changed the texture of the catalyst, stabilized the Fe-Al-O spinel, thus preventing decomposition into Fe3O4 and Al2O3. Potassium also increased the content of Fe5C2 while shifting Fe in the oxide and carbide phases to a more reduced state. In addition, it increased the relative exposure of carbide iron on the catalysts surface, the CO2 adsorption and the adsorption strength. A detailed kinetic model of the RWGS, FTS and methanation reactions was developed for the Fe spinel catalyst based on extensive experimental data measured over a range of operating conditions. Significant oligomerization activity of the catalyst was found. Testing the pelletized catalyst with CO2, CO and H2 mixtures over a range of operating conditions demonstrated its high productivity to higher hydrocarbons. The composition of the liquid (C5+) was found to be a function of the potassium content and the composition of the feedstock.

  2. Water Vapour Abundance and Distribution in the Lower Venusian Atmosphere

    NASA Astrophysics Data System (ADS)

    Chamberlain, S.; Bailey, J.

    2012-04-01

    We present ground-based observations and modelling studies of water vapour abundance and distribution in the Venusian lower atmosphere through analysis of absorption band depths within the 1.18 μm window. The lower atmosphere of Venus is difficult to study by both in situ and remote instruments. This is due to the planet wide cloud cover that obscures visual wavelengths and surface pressures approaching 100 times that of the Earth. In 1984 ground based observations resulted in the discovery of atmospheric windows on the Venusian nightside (Allen and Crawford, 1984). Here, near infrared radiation originating at the surface and lower atmosphere, pass relatively unimpeded through the Venus clouds. This discovery enabled remote studies of the Venusian subcloud region. Determining the abundance and distribution of water vapour is key to understanding the development, maintenance and links between major radiative and dynamical features of the Venus atmosphere. Water vapour in the lower atmosphere plays an important role in heat transfer and is pertinent to the runaway greenhouse effect and dynamical superrotation observed on Venus. Detailed studies of water vapour abundance and distribution throughout the lower atmosphere of Venus are therefore needed in order to develop accurate chemical, radiative and dynamical models. Ground-based spatially resolved near infrared spectroscopic observations of the Venusian nightside have been obtained from Siding Spring Observatory at each inferior conjunction since 2002. Observations have been made using the IRIS2 instrument on the Anglo-Australian Telescope and CASPIR on the 2.3m ANU telescope. The model VSTAR (Bailey and Kedziora-Chudczer 2012) is used to simulate the observed Venus spectra as seen through the Earth's atmosphere and best fit water vapour abundances are found for approximately 300 locations across the Venus nightside disk. Recent improvements in ground-based near-infrared instruments allow a substantial improvement

  3. Catalytic membranes beckon

    SciTech Connect

    Caruana, C.M.

    1994-11-01

    Chemical engineers here and abroad are finding that the marriage of catalysts and membranes holds promise for faster and more specific reactions, although commercialization of this technology is several years away. Catalytic membrane reactors (CMRs) combine a heterogeneous catalyst and a permselective membrane. Reactions performed by CMRs provide higher yields--sometimes as much as 50% higher--because of better reaction selectivity--as opposed to separation selectivity. CMRs also can work at very high temperatures, using ceramic materials that would not be possible with organic membranes. Although the use of CMRs is not widespread presently, the development of new membranes--particularly porous ceramic and zeolite membranes--will increase the potential to improve yields of many catalytic processes. The paper discusses ongoing studies, metal and advanced materials for membranes, the need for continued research, hydrogen recovery from coal-derived gases, catalytic oxidation of sulfides, CMRs for water purification, and oxidative coupling of methane.

  4. Structural Evolution of Chemically-Driven RuO2 Nanowires and 3-Dimensional Design for Photo-Catalytic Applications

    PubMed Central

    Park, Joonmo; Lee, Jae Won; Ye, Byeong Uk; Chun, Sung He; Joo, Sang Hoon; Park, Hyunwoong; Lee, Heon; Jeong, Hu Young; Kim, Myung Hwa; Baik, Jeong Min

    2015-01-01

    Growth mechanism of chemically-driven RuO2 nanowires is explored and used to fabricate three-dimensional RuO2 branched Au-TiO2 nanowire electrodes for the photostable solar water oxidation. For the real time structural evolution during the nanowire growth, the amorphous RuO2 precursors (Ru(OH)3·H2O) are heated at 180 °C, producing the RuO2 nanoparticles with the tetragonal crystallographic structure and Ru enriched amorphous phases, observed through the in-situ synchrotron x-ray diffraction and the high-resolution transmission electron microscope images. Growth then proceeds by Ru diffusion to the nanoparticles, followed by the diffusion to the growing surface of the nanowire in oxygen ambient, supported by the nucleation theory. The RuO2 branched Au-TiO2 nanowire arrays shows a remarkable enhancement in the photocurrent density by approximately 60% and 200%, in the UV-visible and Visible region, respectively, compared with pristine TiO2 nanowires. Furthermore, there is no significant decrease in the device’s photoconductance with UV-visible illumination during 1 day, making it possible to produce oxygen gas without the loss of the photoactvity. PMID:26149583

  5. Correlating the chemical composition and size of various metal oxide substrates with the catalytic activity and stability of as-deposited Pt nanoparticles for the methanol oxidation reaction

    DOE PAGES

    Megan E. Scofield; Wong, Stanislaus S.; Koenigsmann, Christopher; Bobb-Semple, Dara; Tao, Jing; Tong, Xiao; Wang, Lei; Lewis, Crystal S.; Vuklmirovic, Miomir; Zhu, Yimei; et al

    2015-12-09

    The performance of electrode materials in conventional direct alcohol fuel cells (DAFC) is constrained by (i) the low activity of the catalyst materials relative to their overall cost, (ii) the poisoning of the active sites due to the presence of partially oxidized carbon species (such as but not limited to CO, formate, and acetate) produced during small molecule oxidation, and (iii) the lack of catalytic stability and durability on the underlying commercial carbon support. Therefore, as a viable alternative, we have synthesized various metal oxide and perovskite materials of different sizes and chemical compositions as supports for Pt nanoparticles (NPs).more » Our results including unique mechanistic studies demonstrate that the SrRuO3 substrate with immobilized Pt NPs at its surface evinces the best methanol oxidation performance as compared with all of the other substrate materials tested herein, including commercial carbon itself. In addition, data from electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of electron transfer from bound Pt NPs to surface Ru species within the SrRuO3 substrate itself, thereby suggesting that favorable metal support interactions are responsible for the increased methanol oxidation reaction (MOR) activity of Pt species with respect to the underlying SrRuO3 composite catalyst material.« less

  6. Altering the catalytic activity of thin metal catalyst films for controlled growth of chemical vapor deposited vertically aligned carbon nanotube arrays

    SciTech Connect

    Rouleau, Christopher M; Christen, Hans M; Cui, Hongtao; Eres, Gyula; Puretzky, Alexander A; Geohegan, David B

    2008-01-01

    The growth rate and terminal length of vertically-aligned carbon nanotube arrays (VANTAs) grown by chemical vapor deposition have been dramatically improved through pulsed KrF-excimer laser pretreatments of multilayer metal catalyst films. Silicon wafers coated with Al, Mo, and Fe layers were laser processed in air with single laser shots of varying fluence through circular apertures, then heated to ~750C and exposed to acetylene and ferrocene-containing gas mixtures typically used to grow vertically-aligned nanotube arrays. In situ videography was used to record the growth kinetics of the nanotube arrays in both patterned and unpatterned regions to understand changes in catalytic activity, growth rates, and termination of growth. The height of the patterned regions varied with fluence, with the most successful treatment resulting in 1.4 cm-tall posts of nanotubes embedded in a 0.4 cm-tall nanotube carpet. High-resolution transmission electron microscopy images from the nanotubes in the posts revealed fewer walls, smaller diameters, and a much narrower distribution of diameters compared to nanotubes grown in the carpet. This information, along with data obtained from weighing the material from each region, suggests that pulsed laser processing can also significantly increase the areal density of VANTAs.

  7. Effects of N{sub 2}O gas addition on the properties of ZnO films grown by catalytic reaction-assisted chemical vapor deposition

    SciTech Connect

    Yasui, Kanji Morioka, Makoto; Kanauchi, Shingo; Ohashi, Yuki; Kato, Takahiro; Tamayama, Yasuhiro

    2015-11-15

    The influence of N{sub 2}O gas addition on the properties of zinc oxide (ZnO) films grown on a-plane (11–20) sapphire (a-Al{sub 2}O{sub 3}) substrates was investigated, using a chemical vapor deposition method based on the reaction between dimethylzinc and high-temperature H{sub 2}O produced by a catalytic H{sub 2}-O{sub 2} reaction on platinum (Pt) nanoparticles. The addition of N{sub 2}O was found to increase the size of the crystalline facets and to improve the crystal orientation along the c-axis. The electron mobility at 290 K was also increased to 234 cm{sup 2}/Vs following the addition of N{sub 2}O gas at a pressure of 3.2 × 10{sup −3 }Pa. In addition, the minimum full width at half maximum of the most intense photoluminescence peak derived from neutral donor bound excitons at 10 K decreased to 0.6 meV by the addition of N{sub 2}O gas at a pressure of 3.1 × 10{sup −2 }Pa.

  8. Correlating the chemical composition and size of various metal oxide substrates with the catalytic activity and stability of as-deposited Pt nanoparticles for the methanol oxidation reaction

    SciTech Connect

    Megan E. Scofield; Wong, Stanislaus S.; Koenigsmann, Christopher; Bobb-Semple, Dara; Tao, Jing; Tong, Xiao; Wang, Lei; Lewis, Crystal S.; Vuklmirovic, Miomir; Zhu, Yimei; Adzic, Radoslav R.

    2015-12-09

    The performance of electrode materials in conventional direct alcohol fuel cells (DAFC) is constrained by (i) the low activity of the catalyst materials relative to their overall cost, (ii) the poisoning of the active sites due to the presence of partially oxidized carbon species (such as but not limited to CO, formate, and acetate) produced during small molecule oxidation, and (iii) the lack of catalytic stability and durability on the underlying commercial carbon support. Therefore, as a viable alternative, we have synthesized various metal oxide and perovskite materials of different sizes and chemical compositions as supports for Pt nanoparticles (NPs). Our results including unique mechanistic studies demonstrate that the SrRuO3 substrate with immobilized Pt NPs at its surface evinces the best methanol oxidation performance as compared with all of the other substrate materials tested herein, including commercial carbon itself. In addition, data from electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of electron transfer from bound Pt NPs to surface Ru species within the SrRuO3 substrate itself, thereby suggesting that favorable metal support interactions are responsible for the increased methanol oxidation reaction (MOR) activity of Pt species with respect to the underlying SrRuO3 composite catalyst material.

  9. Effect of temperature for synthesizing single-walled carbon nanotubes by catalytic chemical vapor deposition over Mo-Co-MgO catalyst

    SciTech Connect

    Niu Zhiqiang; Fang Yan

    2008-06-03

    The influence of temperature on synthesizing single-walled carbon nanotubes (SWCNTs) by catalytic chemical vapor deposition of methane over Mo-Co-MgO catalyst was studied by Transmission Electron Microscope (TEM) and Raman scattering. The Mo-Co-MgO bimetallic catalyst was prepared by decomposing the mixture of magnesium nitrate, ammonium molybdate, citric acid, and cobalt nitrate. The results show that Mo-Co-MgO bimetallic catalyst is effective to synthesize SWCNTs. By using Mo-Co-MgO bimetallic catalyst, generation of SWCNTs even at 940 K was demonstrated. The optimum temperature of synthesizing SWCNTs over Mo-Co-MgO bimetallic catalyst may be about 1123 K. At 1123 K, the diameters of SWCNTs are in the range of 0.75-1.65 nm. The content of SWCNTs is increased with the increase of temperature below 1123 K and the carbon yield rate is also increased with the increase of synthesis temperature. Therefore, the amount of SWCNTs increases with the increase of temperature below 1123 K. However, above 1123 K, the content of SWCNTs is decreased with the increase of temperature; therefore, it is not effective to increase the amount of SWCNTs through increasing synthesis temperature above 1123 K.

  10. Recombinant Escherichia coli GMP reductase: kinetic, catalytic and chemical mechanisms, and thermodynamics of enzyme-ligand binary complex formation.

    PubMed

    Martinelli, Leonardo Krás Borges; Ducati, Rodrigo Gay; Rosado, Leonardo Astolfi; Breda, Ardala; Selbach, Bruna Pelegrim; Santos, Diógenes Santiago; Basso, Luiz Augusto

    2011-04-01

    Guanosine monophosphate (GMP) reductase catalyzes the reductive deamination of GMP to inosine monophosphate (IMP). GMP reductase plays an important role in the conversion of nucleoside and nucleotide derivatives of guanine to adenine nucleotides. In addition, as a member of the purine salvage pathway, it also participates in the reutilization of free intracellular bases. Here we present cloning, expression and purification of Escherichia coli guaC-encoded GMP reductase to determine its kinetic mechanism, as well as chemical and thermodynamic features of this reaction. Initial velocity studies and isothermal titration calorimetry demonstrated that GMP reductase follows an ordered bi-bi kinetic mechanism, in which GMP binds first to the enzyme followed by NADPH binding, and NADP(+) dissociates first followed by IMP release. The isothermal titration calorimetry also showed that GMP and IMP binding are thermodynamically favorable processes. The pH-rate profiles showed groups with apparent pK values of 6.6 and 9.6 involved in catalysis, and pK values of 7.1 and 8.6 important to GMP binding, and a pK value of 6.2 important for NADPH binding. Primary deuterium kinetic isotope effects demonstrated that hydride transfer contributes to the rate-limiting step, whereas solvent kinetic isotope effects arise from a single protonic site that plays a modest role in catalysis. Multiple isotope effects suggest that protonation and hydride transfer steps take place in the same transition state, lending support to a concerted mechanism. Pre-steady-state kinetic data suggest that product release does not contribute to the rate-limiting step of the reaction catalyzed by E. coli GMP reductase.

  11. Biological monitoring to assess dermal exposure to ethylene oxide vapours during an incidental release.

    PubMed

    Boogaard, Peter J; van Puijvelde, Mathieu J P; Urbanus, Jan H

    2014-12-15

    During a short incident in an ethylene oxide (EO) producing plant, EO vapour was released under high pressure. Operators wore full respiratory protection during repairs to fix the leak. To check the adequacy of the applied personal protective equipment and to address concerns about potential dermal exposure and subsequent uptake of EO, biological monitoring was applied by determination of the haemoglobin adducts of EO in blood. Based on the results of the biomonitoring, a risk assessment of dermal exposure to EO vapour was made. Calculations to estimate dermal exposure, based on two recently published models and using the relevant physical-chemical properties of EO, indicate that the dermal contribution to total exposure is expected to be negligible under normal operating circumstances. However, the models indicate that under accidental circumstances of product spillage, when high air concentrations can build up quickly and where incident response is conducted under respiratory protection with independently supplied air, the systemic exposure resulting from dermal absorption may reach levels of concern. The model estimates were compared to the actual biomonitoring data in the operators involved in the accidental release of EO vapour. The results suggest that when incidental exposures to high EO vapour concentrations (several thousand ppm) occur during periods in excess of 20-30 min, additional risk management measures, such as wearing chemical impervious suits, should be considered to control dermal uptake of EO.

  12. Textile damage caused by vapour cloud explosions.

    PubMed

    Was-Gubala, J; Krauss, W

    2004-01-01

    The aim of the project was to investigate the damage to garments caused by particular vapour cloud explosions. The authors would like to be able to provide investigators with specific information on how to link clothes to a specific type of crime: a particular case study was the inspiration for the examinations. Experiments were carried out in the fire reconstruction chamber of the laboratory using a selection of 26 clothes and 15 household garments differing in colour, fibre composition and textile construction.

  13. 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

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

    PubMed

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

    2013-10-01

    Nanoflaky MnO(x) on carbon nanotubes (nf-MnO(x)@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 MnO(x) and the obtained catalyst exhibited a large surface area as well. Compared with the MnO(x)/CNT and MnO(x)/TiO₂ catalysts prepared by an impregnation method, the nf-MnO(x)@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 Mn(4+) and more chemisorbed oxygen species existed on the surface of CNTs for nf-MnO(x)@CNTs. The H₂-TPR and NH₃-TPD results demonstrated that the nf-MnO(x)@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-MnO(x)@CNT catalyst has an excellent performance in the low-temperature SCR of NO to N₂ with NH₃. In addition, the nf-MnO(x)@CNT catalyst also presented favourable stability and H₂O resistance.

  15. Metal Vapour Lasers: Physics, Engineering and Applications

    NASA Astrophysics Data System (ADS)

    Little, Christopher E.

    1999-03-01

    Metal Vapour Lasers Christopher E. Little University of St Andrews, St Andrews, Scotland Since the first successful demonstration of a metal vapour laser (MVL) in 1962, this class of laser has become widely used in a broad range of fields including precision materials processing, isotope separation and medicine. The MVLs that are used today have a range of impressive characteristics that are not readily available using other technologies. In particular, the combination of high average output powers, pulse recurrence frequencies and beam quality available from green/yellow Cu vapour lasers (CVLs) and Cu bromide lasers, coupled with the high-quality, multiwatt ultraviolet (265-289 nm) radiation that can be produced using simple nonlinear optical techniques, means that Cu lasers will continue to be important for many years. Metal Vapour Lasers covers all the most commercially important and scientifically interesting pulsed and continuous wave (CW) gas-discharge MVLs, and includes device histories, operating characteristics, engineering, kinetics, commercial exploitation and applications. Short descriptions of gas discharges and excitation techniques make this volume self-consistent. A comprehensive bibliography is also provided. The greater part of this book is devoted to CVLs and their variants, including new sealed-off, high-power 'kinetically enhanced' CVLs and Cu bromide lasers. However, many other self-terminating MVLs are also discussed, including the red AuVL, green/infrared MnVL and infrared BaVL. Pulsed, high-gain, high average power lasers in the UV/violet (373.7, 430.5 nm) spectral regions are represented by Sr¯+ and Ca¯+ discharge-afterglow recombination lasers. The most commercially successful of the MVLs - the CW, UV/blue cataphoretic He-Cd¯+ ion laser - is described. Hollow cathode lasers are represented in two guises: 'white light' (blue/green/red) He-Cd¯+ ion lasers and UV/infrared Ne/He-Cu¯+ ion lasers. This unique volume is an

  16. Formation and Yield of Multi-Walled Carbon Nanotubes Synthesized via Chemical Vapour Deposition Routes Using Different Metal-Based Catalysts of FeCoNiAl, CoNiAl and FeNiAl-LDH

    PubMed Central

    Hussein, Mohd Zobir; Mohamad Jaafar, Adila; Hj. Yahaya, Asmah; Masarudin, Mas Jaffri; Zainal, Zulkarnain

    2014-01-01

    Multi-walled carbon nanotubes (MWCNTs) were prepared via chemical vapor deposition (CVD) using a series of different catalysts, derived from FeCoNiAl, CoNiAl and FeNiAl layered double hydroxides (LDHs). Catalyst-active particles were obtained by calcination of LDHs at 800 °C for 5 h. Nitrogen and hexane were used as the carrier gas and carbon source respectively, for preparation of MWCNTs using CVD methods at 800 °C. MWCNTs were allowed to grow for 30 min on the catalyst spread on an alumina boat in a quartz tube. The materials were subsequently characterized through X-ray diffraction, Fourier transform infrared spectroscopy, surface area analysis, field emission scanning electron microscopy and transmission electron microscopy. It was determined that size and yield of MWCNTs varied depending on the type of LDH catalyst precursor that is used during synthesis. MWCNTs obtained using CoNiAl-LDH as the catalyst precursor showed smaller diameter and higher yield compared to FeCoNiAl and FeNiAl LDHs. PMID:25380526

  17. Formation and yield of multi-walled carbon nanotubes synthesized via chemical vapour deposition routes using different metal-based catalysts of FeCoNiAl, CoNiAl and FeNiAl-LDH.

    PubMed

    Hussein, Mohd Zobir; Jaafar, Adila Mohamad; Yahaya, Asmah Hj; Masarudin, Mas Jaffri; Zainal, Zulkarnain

    2014-01-01

    Multi-walled carbon nanotubes (MWCNTs) were prepared via chemical vapor deposition (CVD) using a series of different catalysts, derived from FeCoNiAl, CoNiAl and FeNiAl layered double hydroxides (LDHs). Catalyst-active particles were obtained by calcination of LDHs at 800 °C for 5 h. Nitrogen and hexane were used as the carrier gas and carbon source respectively, for preparation of MWCNTs using CVD methods at 800 °C. MWCNTs were allowed to grow for 30 min on the catalyst spread on an alumina boat in a quartz tube. The materials were subsequently characterized through X-ray diffraction, Fourier transform infrared spectroscopy, surface area analysis, field emission scanning electron microscopy and transmission electron microscopy. It was determined that size and yield of MWCNTs varied depending on the type of LDH catalyst precursor that is used during synthesis. MWCNTs obtained using CoNiAl-LDH as the catalyst precursor showed smaller diameter and higher yield compared to FeCoNiAl and FeNiAl LDHs. PMID:25380526

  18. Variability of water vapour in the Arctic stratosphere

    NASA Astrophysics Data System (ADS)

    Thölix, L.; Backman, L.; Kivi, R.; Karpechko, A.

    2015-08-01

    This study evaluates the stratospheric water vapour distribution and variability in the Arctic. A FinROSE chemistry climate model simulation covering years 1990-2013 is compared to observations (satellite and frostpoint hygrometer soundings) and the sources of stratospheric water vapour are studied. According to observations and the simulations the water vapour concentration in the Arctic stratosphere started to increase after year 2006, but around 2011 the concentration started to decrease. Model calculations suggest that the increase in water vapour during 2006-2011 (at 56 hPa) is mostly explained by transport related processes, while the photochemically produced water vapour plays a relatively smaller role. The water vapour trend in the stratosphere may have contributed to increased ICE PSC occurrence. The increase of water vapour in the precense of the low winter temperatures in the Arctic stratosphere led to more frequent occurrence of ICE PSCs in the Arctic vortex. The polar vortex was unusually cold in early 2010 and allowed large scale formation of the polar stratospheric clouds. The cold pool in the stratosphere over the Northern polar latitudes was large and stable and a large scale persistent dehydration was observed. Polar stratospheric ice clouds and dehydration were observed at Sodankylä with accurate water vapour soundings in January and February 2010 during the LAPBIAT atmospheric sounding campaign. The observed changes in water vapour were reproduced by the model. Both the observed and simulated decrease of the water vapour in the dehydration layer was up to 1.5 ppm.

  19. [Qualitative Determination of Organic Vapour Using Violet and Visible Spectrum].

    PubMed

    Jiang, Bo; Hu, Wen-zhong; Liu, Chang-jian; Zheng, Wei; Qi, Xiao-hui; Jiang, Ai-li; Wang, Yan-ying

    2015-12-01

    Vapours of organic matters were determined qualitatively employed with ultraviolet-visible absorption spectroscopy. Vapours of organic matters were detected using ultraviolet-visible spectrophotometer employing polyethylene film as medium, the ultraviolet and visible absorption spectra of vegetable oil vapours of soybean oil, sunflower seed oil, peanut oil, rapeseed oil, sesame oil, cotton seed oil, tung tree seed oil, and organic compound vapours of acetone, ethyl acetate, 95% ethanol, glacial acetic acid were obtained. Experimental results showed that spectra of the vegetable oil vapour and the organic compound vapour could be obtained commendably, since ultra violet and visible spectrum of polyethylene film could be deducted by spectrograph zero setting. Different kinds of vegetable oils could been distinguished commendably in the spectra since the λ(max), λ(min), number of absorption peak, position, inflection point in the ultra violet and visible spectra obtained from the vapours of the vegetable oils were all inconsistent, and the vapours of organic compounds were also determined perfectly. The method had a good reproducibility, the ultraviolet and visible absorption spectra of the vapours of sunflower seed oil in 10 times determination were absolutely the same. The experimental result indicated that polyethylene film as a kind of medium could be used for qualitative analysis of ultraviolet and visible absorption spectroscopy. The method for determination of the vapours of the vegetable oils and organic compounds had the peculiarities of fast speed analysis, well reproducibility, accuracy and reliability and low cost, and so on. Ultraviolet and visible absorption spectrum of organic vapour could provide feature information of material vapour and structural information of organic compound, and provide a novel test method for identifying vapour of compound and organic matter.

  20. [Qualitative Determination of Organic Vapour Using Violet and Visible Spectrum].

    PubMed

    Jiang, Bo; Hu, Wen-zhong; Liu, Chang-jian; Zheng, Wei; Qi, Xiao-hui; Jiang, Ai-li; Wang, Yan-ying

    2015-12-01

    Vapours of organic matters were determined qualitatively employed with ultraviolet-visible absorption spectroscopy. Vapours of organic matters were detected using ultraviolet-visible spectrophotometer employing polyethylene film as medium, the ultraviolet and visible absorption spectra of vegetable oil vapours of soybean oil, sunflower seed oil, peanut oil, rapeseed oil, sesame oil, cotton seed oil, tung tree seed oil, and organic compound vapours of acetone, ethyl acetate, 95% ethanol, glacial acetic acid were obtained. Experimental results showed that spectra of the vegetable oil vapour and the organic compound vapour could be obtained commendably, since ultra violet and visible spectrum of polyethylene film could be deducted by spectrograph zero setting. Different kinds of vegetable oils could been distinguished commendably in the spectra since the λ(max), λ(min), number of absorption peak, position, inflection point in the ultra violet and visible spectra obtained from the vapours of the vegetable oils were all inconsistent, and the vapours of organic compounds were also determined perfectly. The method had a good reproducibility, the ultraviolet and visible absorption spectra of the vapours of sunflower seed oil in 10 times determination were absolutely the same. The experimental result indicated that polyethylene film as a kind of medium could be used for qualitative analysis of ultraviolet and visible absorption spectroscopy. The method for determination of the vapours of the vegetable oils and organic compounds had the peculiarities of fast speed analysis, well reproducibility, accuracy and reliability and low cost, and so on. Ultraviolet and visible absorption spectrum of organic vapour could provide feature information of material vapour and structural information of organic compound, and provide a novel test method for identifying vapour of compound and organic matter. PMID:26964229

  1. Understanding vapour plume structure in indoor environments for the detection of explosives

    NASA Astrophysics Data System (ADS)

    Foat, Tim

    2015-11-01

    Dogs remain the most effective method for the detection of explosives in many situations yet the spatially, temporally and chemically varying signature that they sense cannot easily be quantified. Vapour plumes can be highly unsteady and intermittent and the problem is further complicated in indoor spaces where turbulent, transitional and laminar regions may exist and where there may be no dominant flow direction. Intermittent plumes can have peak concentrations that are considerably higher than the time averaged values. As dogs can sample the air at 5 Hz it is possible that these unsteady fluctuations play a key part in their detection process. A low Reynolds number (Re less than 5000 at the inlet) benchmark test case for indoor airflow has been studied using large-eddy simulation computational fluid dynamics. Fixed concentration vapour sources have been included on the floor of the room and the resulting vapour dispersion has been modelled. Sources with different surface areas have been included and their instantaneous and mean concentration profiles compared. The results from this study will provide insight into canine detection of vapour in indoor environments.

  2. Ultrafast vapourization dynamics of laser-activated polymeric microcapsules

    NASA Astrophysics Data System (ADS)

    Lajoinie, Guillaume; Gelderblom, Erik; Chlon, Ceciel; Böhmer, Marcel; Steenbergen, Wiendelt; de Jong, Nico; Manohar, Srirang; Versluis, Michel

    2014-04-01

    Precision control of vapourization, both in space and time, has many potential applications; however, the physical mechanisms underlying controlled boiling are not well understood. The reason is the combined microscopic length scales and ultrashort timescales associated with the initiation and subsequent dynamical behaviour of the vapour bubbles formed. Here we study the nanoseconds vapour bubble dynamics of laser-heated single oil-filled microcapsules using coupled optical and acoustic detection. Pulsed laser excitation leads to vapour formation and collapse, and a simple physical model captures the observed radial dynamics and resulting acoustic pressures. Continuous wave laser excitation leads to a sequence of vapourization/condensation cycles, the result of absorbing microcapsule fragments moving in and out of the laser beam. A model incorporating thermal diffusion from the capsule shell into the oil core and surrounding water reveals the mechanisms behind the onset of vapourization. Excellent agreement is observed between the modelled dynamics and experiment.

  3. Textile damage caused by vapour cloud explosions.

    PubMed

    Was-Gubala, J; Krauss, W

    2004-01-01

    The aim of the project was to investigate the damage to garments caused by particular vapour cloud explosions. The authors would like to be able to provide investigators with specific information on how to link clothes to a specific type of crime: a particular case study was the inspiration for the examinations. Experiments were carried out in the fire reconstruction chamber of the laboratory using a selection of 26 clothes and 15 household garments differing in colour, fibre composition and textile construction. PMID:15527183

  4. Variability of water vapour in the Arctic stratosphere

    NASA Astrophysics Data System (ADS)

    Thölix, Laura; Backman, Leif; Kivi, Rigel; Karpechko, Alexey Yu.

    2016-04-01

    This study evaluates the stratospheric water vapour distribution and variability in the Arctic. A FinROSE chemistry transport model simulation covering the years 1990-2014 is compared to observations (satellite and frost point hygrometer soundings), and the sources of stratospheric water vapour are studied. In the simulations, the Arctic water vapour shows decadal variability with a magnitude of 0.8 ppm. Both observations and the simulations show an increase in the water vapour concentration in the Arctic stratosphere after the year 2006, but around 2012 the concentration started to decrease. Model calculations suggest that this increase in water vapour is mostly explained by transport-related processes, while the photochemically produced water vapour plays a relatively smaller role. The increase in water vapour in the presence of the low winter temperatures in the Arctic stratosphere led to more frequent occurrence of ice polar stratospheric clouds (PSCs) in the Arctic vortex. We perform a case study of ice PSC formation focusing on January 2010 when the polar vortex was unusually cold and allowed large-scale formation of PSCs. At the same time a large-scale persistent dehydration was observed. Ice PSCs and dehydration observed at Sodankylä with accurate water vapour soundings in January and February 2010 during the LAPBIAT (Lapland Atmosphere-Biosphere facility) atmospheric measurement campaign were well reproduced by the model. In particular, both the observed and simulated decrease in water vapour in the dehydration layer was up to 1.5 ppm.

  5. Comparative stability and catalytic and chemical properties of the sulfate-activating enzymes from Penicillium chrysogenum (mesophile) and Penicillium duponti (thermophile).

    PubMed

    Renosto, F; Schultz, T; Re, E; Mazer, J; Chandler, C J; Barron, A; Segel, I H

    1985-11-01

    ATP sulfurylases from Penicillium chrysogenum (a mesophile) and from Penicillium duponti (a thermophile) had a native molecular weight of about 440,000 and a subunit molecular weight of about 69,000. (The P. duponti subunit appeared to be a little smaller than the P. chrysogenum subunit.) The P. duponti enzyme was about 100 times more heat stable than the P. chrysogenum enzyme; k inact (the first-order rate constant for inactivation) at 65 degrees C = 3.3 X 10(-4) s-1 for P. duponti and 3.0 X 10(-2) s-1 for P. chrysogenum. The P. duponti enzyme was also more stable to low pH and urea at 30 degrees C. Rabbit serum antibodies to each enzyme showed heterologous cross-reaction. Amino acid analyses disclosed no major compositional differences between the two enzymes. The analogous Km and Ki values of the forward and reverse reactions were also essentially identical at 30 degrees C. At 30 degrees C, the physiologically important adenosine 5'-phosphosulfate (APS) synthesis activity of the P. duponti enzyme was 4 U mg of protein-1, which is about half that of the P. chrysogenum enzyme. The molybdolysis and ATP synthesis activities of the P. duponti enzyme at 30 degrees C were similar to those of the P. chrysogenum enzyme. At 50 degrees C, the APS synthesis activity of the P. duponti enzyme was 12 to 19 U mg of protein-1, which was higher than that of the P. chrysogenum enzyme at 30 degrees C (8 +/- 1 U mg of protein-1). Treatment of the P. chrysogenum enzyme with 5,5'-dithiobis(2-nitrobenzoate) (DTNB) at 30 degrees C under nondenaturing conditions modified one free sulfhydryl group per subunit. Vmax was not significantly altered, but the catalytic activity at low magnesium-ATP or SO4(2-) (or MoO4(2-)) was markedly reduced. Chemical modification with tetranitromethane had the same results on the kinetics. The native P. duponti enzyme was relatively unreactive toward DTNB or tetranitromethane at 30 degrees C and pH 8.0 or pH 9.0, but at 50 degrees C and pH 8.0, DTNB rapidly

  6. Chemical and Biological Catalytic Enhancement of Weathering of Silicate Minerals and industrial wastes as a Novel Carbon Capture and Storage Technology

    NASA Astrophysics Data System (ADS)

    Park, A. H. A.

    2014-12-01

    Increasing concentration of CO2 in the atmosphere is attributed to rising consumption of fossil fuels around the world. The development of solutions to reduce CO2 emissions to the atmosphere is one of the most urgent needs of today's society. One of the most stable and long-term solutions for storing CO2 is via carbon mineralization, where minerals containing metal oxides of Ca or Mg are reacted with CO2 to produce thermodynamically stable Ca- and Mg-carbonates that are insoluble in water. Carbon mineralization can be carried out in-situ or ex-situ. In the case of in-situ mineralization, the degree of carbonation is thought to be limited by both mineral dissolution and carbonate precipitation reaction kinetics, and must be well understood to predict the ultimate fate of CO2 within geological reservoirs. While the kinetics of in-situ mineral trapping via carbonation is naturally slow, it can be enhanced at high temperature and high partial pressure of CO2. The addition of weak organic acids produced from food waste has also been shown to enhance mineral weathering kinetics. In the case of the ex-situ carbon mineralization, the role of these ligand-bearing organic acids can be further amplified for silicate mineral dissolution. Unfortunately, high mineral dissolution rates often lead to the formation of a silica-rich passivation layer on the surface of silicate minerals. Thus, the use of novel solvent mixture that allows chemically catalyzed removal of this passivation layer during enhanced Mg-leaching surface reaction has been proposed and demonstrated. Furthermore, an engineered biological catalyst, carbonic anhydrase, has been developed and evaluated to accelerate the hydration of CO2, which is another potentially rate-limiting step of the carbonation reaction. The development of these novel catalytic reaction schemes has significantly improved the overall efficiency and sustainability of in-situ and ex-situ mineral carbonation technologies and allowed direct

  7. Deciphering a nanocarbon-based artificial peroxidase: chemical identification of the catalytically active and substrate-binding sites on graphene quantum dots.

    PubMed

    Sun, Hanjun; Zhao, Andong; Gao, Nan; Li, Kai; Ren, Jinsong; Qu, Xiaogang

    2015-06-01

    The design and construction of efficient artificial enzymes is highly desirable. Recent studies have demonstrated that a series of carbon nanomaterials possess intrinsic peroxidase activity. Among them, graphene quantum dots (GQDs) have a high enzymatic activity. However, the catalytic mechanism remains unclear. Therefore, in this report, we chose to decipher their peroxidase activity. By selectively deactivating the ketonic carbonyl, carboxylic, or hydroxy groups and investigating the catalytic activities of these GQD derivatives, we obtained evidence that the -C=O groups were the catalytically active sites, whereas the O=C-O- groups acted as substrate-binding sites, and -C-OH groups can inhibit the activity. These results were corroborated by theoretical studies. This work should not only enhance our understanding of nanocarbon-based artificial enzymes, but also facilitate the design and construction of other types of target-specific artificial enzymes.

  8. High performance vapour-cell frequency standards

    NASA Astrophysics Data System (ADS)

    Gharavipour, M.; Affolderbach, C.; Kang, S.; Bandi, T.; Gruet, F.; Pellaton, M.; Mileti, G.

    2016-06-01

    We report our investigations on a compact high-performance rubidium (Rb) vapour-cell clock based on microwave-optical double-resonance (DR). These studies are done in both DR continuous-wave (CW) and Ramsey schemes using the same Physics Package (PP), with the same Rb vapour cell and a magnetron-type cavity with only 45 cm3 external volume. In the CW-DR scheme, we demonstrate a DR signal with a contrast of 26% and a linewidth of 334 Hz; in Ramsey-DR mode Ramsey signals with higher contrast up to 35% and a linewidth of 160 Hz have been demonstrated. Short-term stabilities of 1.4×10-13 τ-1/2 and 2.4×10-13 τ-1/2 are measured for CW-DR and Ramsey-DR schemes, respectively. In the Ramsey-DR operation, thanks to the separation of light and microwave interactions in time, the light-shift effect has been suppressed which allows improving the long-term clock stability as compared to CW-DR operation. Implementations in miniature atomic clocks are considered.

  9. Properties of meso-Erythritol; phase state, accommodation coefficient and saturation vapour pressure

    NASA Astrophysics Data System (ADS)

    Emanuelsson, Eva; Tschiskale, Morten; Bilde, Merete

    2016-04-01

    Introduction Saturation vapour pressure and the associated temperature dependence (enthalpy ΔH), are key parameters for improving predictive atmospheric models. Generally, the atmospheric aerosol community lack experimentally determined values of these properties for relevant organic aerosol compounds (Bilde et al., 2015). In this work we have studied the organic aerosol component meso-Erythritol. Methods Sub-micron airborne particles of meso-Erythritol were generated by nebulization from aqueous solution, dried, and a mono disperse fraction of the aerosol was selected using a differential mobility analyser. The particles were then allowed to evaporate in the ARAGORN (AaRhus Atmospheric Gas phase OR Nano particle) flow tube. It is a temperature controlled 3.5 m long stainless steel tube with an internal diameter of 0.026 m (Bilde et al., 2003, Zardini et al., 2010). Changes in particle size as function of evaporation time were determined using a scanning mobility particle sizer system. Physical properties like air flow, temperature, humidity and pressure were controlled and monitored on several places in the setup. The saturation vapour pressures were then inferred from the experimental results in the MATLAB® program AU_VaPCaP (Aarhus University_Vapour Pressure Calculation Program). Results Following evaporation, meso-Erythriol under some conditions showed a bimodal particle size distribution indicating the formation of particles of two different phase states. The issue of physical phase state, along with critical assumptions e.g. the accommodation coefficient in the calculations of saturation vapour pressures of atmospheric relevant compounds, will be discussed. Saturation vapour pressures from the organic compound meso-Erythritol will be presented at temperatures between 278 and 308 K, and results will be discussed in the context of atmospheric chemistry. References Bilde, M. et al., (2015), Chemical Reviews, 115 (10), 4115-4156. Bilde, M. et. al., (2003

  10. Is there a solar signal in lower stratospheric water vapour?

    NASA Astrophysics Data System (ADS)

    Schieferdecker, Tobias; Lossow, Stefan; Stiller, Gabriele; von Clarmann, Thomas

    2016-04-01

    A merged time series of stratospheric water vapour built from the Halogen Occultation Instrument (HALOE) and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) data between 60 deg S and 60 deg N and 15 to 30 km, and covering the years 1992 to 2012, was analysed by multivariate linear regression, including an 11-year solar cycle proxy. Lower stratospheric water vapour was found to reveal a phase-shifted anti-correlation with the solar cycle, with lowest water vapour after solar maximum. The phase shift is composed of an inherent constant time lag of about 2 years and a second component following the stratospheric age of air. The amplitudes of the water vapour response are largest close to the tropical tropopause (up to 0.35 ppmv) and decrease with altitude and latitude. Including the solar cycle proxy in the regression results in linear trends of water vapour being negative over the full altitude/latitude range, while without the solar proxy, positive water vapour trends in the lower stratosphere were found. We conclude from these results that a solar signal seems to be generated at the tropical tropopause which is most likely imprinted on the stratospheric water vapour abundances and transported to higher altitudes and latitudes via the Brewer-Dobson circulation. Hence it is concluded that the tropical tropopause temperature at the final dehydration point of air may also be governed to some degree by the solar cycle. The negative water vapour trends obtained when considering the solar cycle impact on water vapour abundances can possibly solve the "water vapour conundrum" of increasing stratospheric water vapour abundances despite constant or even decreasing tropopause temperatures.

  11. Is there a solar signal in lower stratospheric water vapour?

    NASA Astrophysics Data System (ADS)

    Schieferdecker, T.; Lossow, S.; Stiller, G. P.; von Clarmann, T.

    2015-09-01

    A merged time series of stratospheric water vapour built from the Halogen Occultation Instrument (HALOE) and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) data between 60° S and 60° N and 15 to 30 km and covering the years 1992 to 2012 was analysed by multivariate linear regression, including an 11-year solar cycle proxy. Lower stratospheric water vapour was found to reveal a phase-shifted anti-correlation with the solar cycle, with lowest water vapour after solar maximum. The phase shift is composed of an inherent constant time lag of about 2 years and a second component following the stratospheric age of air. The amplitudes of the water vapour response are largest close to the tropical tropopause (up to 0.35 ppmv) and decrease with altitude and latitude. Including the solar cycle proxy in the regression results in linear trends of water vapour being negative over the full altitude/latitude range, while without the solar proxy, positive water vapour trends in the lower stratosphere were found. We conclude from these results that a solar signal seems to be generated at the tropical tropopause which is most likely imprinted on the stratospheric water vapour abundances and transported to higher altitudes and latitudes via the Brewer-Dobson circulation. Hence it is concluded that the tropical tropopause temperature at the final dehydration point of air may also be governed to some degree by the solar cycle. The negative water vapour trends obtained when considering the solar cycle impact on water vapour abundances can possibly solve the "water vapour conundrum" of increasing stratospheric water vapour abundances despite constant or even decreasing tropopause temperatures.

  12. Prevalence of Bimolecular Routes in the Activation of Diatomic Molecules with Strong Chemical Bonds (O2, NO, CO, N2) on Catalytic Surfaces.

    PubMed

    Hibbitts, David; Iglesia, Enrique

    2015-05-19

    Dissociation of the strong bonds in O2, NO, CO, and N2 often involves large activation barriers on low-index planes of metal particles used as catalysts. These kinetic hurdles reflect the noble nature of some metals (O2 activation on Au), the high coverages of co-reactants (O2 activation during CO oxidation on Pt), or the strength of the chemical bonds (NO on Pt, CO and N2 on Ru). High barriers for direct dissociations from density functional theory (DFT) have led to a consensus that "defects", consisting of low-coordination exposed atoms, are required to cleave such bonds, as calculated by theory and experiments for model surfaces at low coverages. Such sites, however, bind intermediates strongly, rendering them unreactive at the high coverages prevalent during catalysis. Such site requirements are also at odds with turnover rates that often depend weakly on cluster size or are actually higher on larger clusters, even though defects, such as corners and edges, are most abundant on small clusters. This Account illustrates how these apparent inconsistencies are resolved through activations of strong bonds assisted by co-adsorbates on crowded low-index surfaces. Catalytic oxidations occur on Au clusters at low temperatures in spite of large activation barriers for O2 dissociation on Au(111) surfaces, leading to proposals that O2 activation requires low-coordination Au atoms or Au-support interfaces. When H2O is present, however, O2 dissociation proceeds with low barriers on Au(111) because chemisorbed peroxides (*OOH* and *HOOH*) form and weaken O-O bonds before cleavage, thus allowing activation on low-index planes. DFT-derived O2 dissociation barriers are much lower on bare Pt surfaces, but such surfaces are nearly saturated with CO* during CO oxidation. A dearth of vacant sites causes O2* to react with CO* to form *OOCO* intermediates that undergo O-O cleavage. NO-H2 reactions occur on Pt clusters saturated with NO* and H*; direct NO* dissociation requires vacant

  13. Atmospheric pressure chemical vapour deposition of vanadium oxides

    NASA Astrophysics Data System (ADS)

    Manning, Troy Darrell

    The APCVD of vanadium(IV) oxide thin films from halide precursors was investigated. It was found that the phase of vanadium oxide obtained could be controlled by the reactor temperature and precursor ratio. For vanadium(IV) chloride and water, reactor temperatures > 550 °C and an excess of water over VCI4 was required to produce VO2 thin films. For vanadium(V) oxytrichloride and water, reactor temperatures > 550 °C and an excess of water over VOCI3 also produced VO2 but required low total gas flow rates (< 1 L min 1) for complete coverage of the substrate. Vanadium(IV) oxide thin films doped with metal ions (W, Cr, Nb, Ti, Mo or Sn) were also prepared by the APCVD process in order to reduce the thermochromic transition temperature (TC) from 68 °C for the undoped material to < 30 °C. The most successful dopant was tungsten, introduced into the VOCl3, and water system as WCI6, which lowered T to 5 °C for a 3 atom% tungsten doped thin film. Tungsten (VI) ethoxide was introduced into the VCI4 and water system and reduced TC, of VO2, to 42 °C for a 1 atom% tungsten doped thin film. Chromium, introduced as CrCO2Cl2, formed a chromium vanadium oxide that did not display any thermochromic properties. Niobium, introduced as NbCl5 into the VOCl3 system, reduced TC of VO2, but the amount of niobium introduced could not be easily controlled. Molybdenum, introduced as MoCI5, also reduced TC of VO2, but the form of the molybdenum appeared to be different from that required for complete control of TC, Titanium, introduced as TiCl4, produced phase segregated films of VO2 and TiO2, with interesting multifunctional properties and a reduced TC. Tin, introduced as SnCl4, also formed a phase segregated material of VO2, and SnO2, with a slightly reduced TC.

  14. The interaction of an atmospheric pressure plasma jet using argon or argon plus hydrogen peroxide vapour addition with bacillus subtilis

    NASA Astrophysics Data System (ADS)

    Deng, San-Xi; Cheng, Cheng; Ni, Guo-Hua; Meng, Yue-Dong; Chen, Hua

    2010-10-01

    This paper reports that an atmospheric pressure dielectric barrier discharge plasma jet, which uses argon or argon + hydrogen peroxide vapour as the working gas, is designed to sterilize the bacillus subtilis. Compared with the pure argon plasma, the bacterial inactivation efficacy has a significant improvement when hydrogen peroxide vapour is added into the plasma jet. In order to determine which factors play the main role in inactivation, several methods are used, such as determination of optical emission spectra, high temperature dry air treatment, protein leakage quantification, and scanning electron microscope. These results indicate that the possible inactivation mechanisms are the synergistic actions of chemically active species and charged species.

  15. Catalytic reaction in confined flow channel

    DOEpatents

    Van Hassel, Bart A.

    2016-03-29

    A chemical reactor comprises a flow channel, a source, and a destination. The flow channel is configured to house at least one catalytic reaction converting at least a portion of a first nanofluid entering the channel into a second nanofluid exiting the channel. The flow channel includes at least one turbulating flow channel element disposed axially along at least a portion of the flow channel. A plurality of catalytic nanoparticles is dispersed in the first nanofluid and configured to catalytically react the at least one first chemical reactant into the at least one second chemical reaction product in the flow channel.

  16. Age and structure of a model vapour-deposited glass

    PubMed Central

    Reid, Daniel R.; Lyubimov, Ivan; Ediger, M. D.; de Pablo, Juan J.

    2016-01-01

    Glass films prepared by a process of physical vapour deposition have been shown to have thermodynamic and kinetic stability comparable to those of ordinary glasses aged for thousands of years. A central question in the study of vapour-deposited glasses, particularly in light of new knowledge regarding anisotropy in these materials, is whether the ultra-stable glassy films formed by vapour deposition are ever equivalent to those obtained by liquid cooling. Here we present a computational study of vapour deposition for a two-dimensional glass forming liquid using a methodology, which closely mimics experiment. We find that for the model considered here, structures that arise in vapour-deposited materials are statistically identical to those observed in ordinary glasses, provided the two are compared at the same inherent structure energy. We also find that newly deposited hot molecules produce cascades of hot particles that propagate far into the film, possibly influencing the relaxation of the material. PMID:27762262

  17. Novel Catalytic Membrane Reactors

    SciTech Connect

    Stuart Nemser, PhD

    2010-10-01

    There are many industrial catalytic organic reversible reactions with amines or alcohols that have water as one of the products. Many of these reactions are homogeneously catalyzed. In all cases removal of water facilitates the reaction and produces more of the desired chemical product. By shifting the reaction to right we produce more chemical product with little or no additional capital investment. Many of these reactions can also relate to bioprocesses. Given the large number of water-organic compound separations achievable and the ability of the Compact Membrane Systems, Inc. (CMS) perfluoro membranes to withstand these harsh operating conditions, this is an ideal demonstration system for the water-of-reaction removal using a membrane reactor. Enhanced reaction synthesis is consistent with the DOE objective to lower the energy intensity of U.S. industry 25% by 2017 in accord with the Energy Policy Act of 2005 and to improve the United States manufacturing competitiveness. The objective of this program is to develop the platform technology for enhancing homogeneous catalytic chemical syntheses.

  18. A solar signal in lower stratospheric water vapour?

    NASA Astrophysics Data System (ADS)

    Schieferdecker, T.; Lossow, S.; Stiller, G. P.; von Clarmann, T.

    2015-04-01

    A merged time series of stratospheric water vapour built from HALOE and MIPAS data between 60° S and 60° N and 15 to 30 km and covering the years 1992 to 2012 was analyzed by multivariate linear regression including an 11 year solar cycle proxy. Lower stratospheric water vapour was found to reveal a phase-shifted anti-correlation with the solar cycle, with lowest water vapour after solar maximum. The phase shift is composed of an inherent constant time lag of about 2 years and a second component following the stratospheric age of air. The amplitudes of the water vapour response are largest close to the tropical tropopause (up to 0.35 ppmv) and decrease with altitude and latitude. Including the solar cycle proxy in the regression results in linear trends of water vapour being negative over the full altitude/latitude range, while without the solar proxy positive water wapour trends in the lowermost stratosphere were found. We conclude from these results that a solar signal generated at the tropical tropopause is imprinted on the stratospheric water vapour abundances and transported to higher altitudes and latitudes via the Brewer-Dobson circulation. Hence it is concluded that the tropical tropopause temperature at the final dehydration point of air is also governed to some degree by the solar cycle. The negative water vapour trends obtained when considering the solar cycle impact on water vapour abundances can solve the water vapour conundrum of increasing stratospheric water vapour abundances at constant or even decreasing tropopause temperatures.

  19. Localisation of an Unknown Number of Land Mines Using a Network of Vapour Detectors

    PubMed Central

    Chhadé, Hiba Haj; Abdallah, Fahed; Mougharbel, Imad; Gning, Amadou; Julier, Simon; Mihaylova, Lyudmila

    2014-01-01

    We consider the problem of localising an unknown number of land mines using concentration information provided by a wireless sensor network. A number of vapour sensors/detectors, deployed in the region of interest, are able to detect the concentration of the explosive vapours, emanating from buried land mines. The collected data is communicated to a fusion centre. Using a model for the transport of the explosive chemicals in the air, we determine the unknown number of sources using a Principal Component Analysis (PCA)-based technique. We also formulate the inverse problem of determining the positions and emission rates of the land mines using concentration measurements provided by the wireless sensor network. We present a solution for this problem based on a probabilistic Bayesian technique using a Markov chain Monte Carlo sampling scheme, and we compare it to the least squares optimisation approach. Experiments conducted on simulated data show the effectiveness of the proposed approach. PMID:25384008

  20. Localisation of an unknown number of land mines using a network of vapour detectors.

    PubMed

    Chhadé, Hiba Haj; Abdallah, Fahed; Mougharbel, Imad; Gning, Amadou; Julier, Simon; Mihaylova, Lyudmila

    2014-11-06

    We consider the problem of localising an unknown number of land mines using concentration information provided by a wireless sensor network. A number of vapour sensors/detectors, deployed in the region of interest, are able to detect the concentration of the explosive vapours, emanating from buried land mines. The collected data is communicated to a fusion centre. Using a model for the transport of the explosive chemicals in the air, we determine the unknown number of sources using a Principal Component Analysis (PCA)-based technique. We also formulate the inverse problem of determining the positions and emission rates of the land mines using concentration measurements provided by the wireless sensor network. We present a solution for this problem based on a probabilistic Bayesian technique using a Markov chain Monte Carlo sampling scheme, and we compare it to the least squares optimisation approach. Experiments conducted on simulated data show the effectiveness of the proposed approach.

  1. Developments in vapour cloud explosion blast modeling.

    PubMed

    Mercx, W P; van den Berg, A C; Hayhurst, C J; Robertson, N J; Moran, K C

    2000-01-01

    TNT Equivalency methods are widely used for vapour cloud explosion blast modeling. Presently, however, other types of models are available which do not have the fundamental objections TNT Equivalency models have. TNO Multi-Energy method is increasingly accepted as a more reasonable alternative to be used as a simple and practical method. Computer codes based on computational fluid dynamics (CFD) like AutoReaGas, developed by TNO and Century Dynamics, could be used also in case a more rigorous analysis is required. Application of the Multi-Energy method requires knowledge of two parameters describing the explosion: a charge size and a charge strength. During the last years, research has led to an improved determination of the charge strength (i.e., the class number or source overpressure) to be chosen to apply the blast charts. A correlation has been derived relating the charge strength to a set of parameters describing the boundary conditions of the flammable cloud and the fuel in the cloud. A simple approach may not be satisfactory in all situations. The overpressure distribution inside a vapour cloud explosion is generally not homogeneous and the presence of obstructions causes directional blast propagation in the near field. A CFD approach, in which the actual situation is modeled, supplies case-specific results. An overview of the key aspects relevant to the application of the Multi-Energy method and CFD modeling is provided. Then the application of the two methods is demonstrated for an example problem involving the calculation of the explosion blast load on a structure at some distance from the explosion in an offshore platform complex.

  2. The ignitability of petrol vapours and potential for vapour phase explosion by use of TASER® law enforcement electronic control device.

    PubMed

    Clarke, C; Andrews, S P

    2014-12-01

    An experimental study was made of the potential of the TASER-X26™ law enforcement electronic control device to ignite petrol vapours if used by an officer to incapacitate a person soaked in petrol, or within a flammable atmosphere containing petrol vapour. Bench scale tests have shown that a wooden mannequin with pig skin covering the chest was a suitable representation of a human target. Full scale tests using the mannequin have shown that the arc from a TASER-X26™ is capable of igniting petrol/air vapours on a petrol-soaked person. Further tests in a 1/5 scale and a full scale compartment have shown that if a TASER is used within a compartment, a petrol vapour explosion (deflagration) may be achieved. It is evident from this research that if used in a flammable vapour rich environment, the device could prove fatal not only to the target but the TASER® operator as well.

  3. Catalytic oxidizers and Title V requirements

    SciTech Connect

    Uberoi, M.; Rach, S.E.

    1999-07-01

    Catalytic oxidizers have been used to reduce VOC emissions from various industries including printing, chemical, paint, coatings, etc. A catalytic oxidizer uses a catalyst to reduce the operating temperature for combustion to approximately 600 F, which is substantially lower than thermal oxidation unit. Title V requirements have renewed the debate on the best methods to assure compliance of catalytic oxidizers, with some suggesting the need for continuous emission monitoring equipment. This paper will discuss the various aspects of catalytic oxidation and consider options such as monitoring inlet/outlet temperatures, delta T across the catalyst, periodic laboratory testing of catalyst samples, and preventive maintenance procedures as means of assuring continuous compliance.

  4. [CO2-gas exchange of mosses following water vapour uptake].

    PubMed

    Lange, O L

    1969-03-01

    The CO2-gas exchange of dry mosses which were exposed to air of high water vapour content has been followed. Some moss species behave as do lichens and aerophilic green algae: they are able to take up enough water vapour to make a rather high photosynthetic activity possible. Other species lack this ability. They need liquid water for reactivation of photosynthesis, as do poikilohydric ferns and phanerogams. In this respect too the mosses are located between the real thallophytes and the cormophytes. From this point of view they are useful objects for studying the relationships between water vapour reactivation, morphological organisation and ecological capability.

  5. [CO2-gas exchange of mosses following water vapour uptake].

    PubMed

    Lange, O L

    1969-03-01

    The CO2-gas exchange of dry mosses which were exposed to air of high water vapour content has been followed. Some moss species behave as do lichens and aerophilic green algae: they are able to take up enough water vapour to make a rather high photosynthetic activity possible. Other species lack this ability. They need liquid water for reactivation of photosynthesis, as do poikilohydric ferns and phanerogams. In this respect too the mosses are located between the real thallophytes and the cormophytes. From this point of view they are useful objects for studying the relationships between water vapour reactivation, morphological organisation and ecological capability. PMID:24504355

  6. Pattern recognition applied to vapour-phase infrared spectra: characteristics of νOH bands

    NASA Astrophysics Data System (ADS)

    Jalsovszky, G.; Holly, S.

    1988-05-01

    With the commercial availability of infrared spectrum libraries in computer accessible form, a new application of these libraries, the investigation of structure-spectrum correlations, has become possible in addition to the conventional application, the identification of unknown substances on the basis of spectral search in the library. This paper deals with the νOH bands of alcohols, also including diols and diol monoether type compounds, investigating correlations between chemical structure and the features of spectra. For monoalcohols, the frequencies measured in dilute solution and vapour phase, respectively, are correlated; the former were taken from literature, the latter from the vapour phase spectrum library of EPA. For the other types of compound, vapour phase νOH frequencies of free and hydrogen bonded hydroxy groups were studied, and the differences correlated with the hydrogen bonded structures. Peak maxima were determined by a peak picking program; in the case of overlapping bands Fourier self-deconvolution was applied prior to peak picking. For more seriously overlapping bands least-squares curve fitting was applied. In studying correlations, a cluster analysis method (KMEANS) was also used.

  7. Alcohol vapour detection at the three phase interface using enzyme-conducting polymer composites.

    PubMed

    Winther-Jensen, Orawan; Kerr, Robert; Winther-Jensen, Bjorn

    2014-02-15

    Immobilisation of enzymes on a breathable electrode can be useful for various applications where the three-phase interface between gas or chemical vapour, electrolyte and electrode is crucial for the reaction. In this paper, we report the further development of the breathable electrode concept by immobilisation of alcohol dehydrogenase into vapour-phase polymerised poly(3,4-ethylene dioxythiophene) that has been coated onto a breathable membrane. Typical alcohol sensing, whereby the coenzyme β-Nicotinamide adenine dinucleotide (NADH) is employed as a redox-mediator, was successfully used as a model reaction for the oxidation of ethanol. This indicates that the ethanol vapour from the backside of the membrane has access to the active enzyme embedded in the electrode. The detecting range of the sensor is suitable for the detection of ethanol in fruit juices and for the baseline breath ethanol concentration of drunken driving. After continuous operation for 4.5h the system only showed a 20% decrease in the current output. The electrodes maintained 62% in current output after being refrigerated for 76 days. This work is continuing the progress of the immobilisation of specific enzymes for certain electrochemical reactions whereby the three-phase interface has to be maintained and/or the simultaneous separation of gas from liquid is required.

  8. The impact of deep overshooting convection on the water vapour and trace gas distribution in the TTL and lower stratosphere

    NASA Astrophysics Data System (ADS)

    Frey, W.; Schofield, R.; Hoor, P. M.; Ravegnani, F.; Ulanovsky, A.; Viciani, S.; D'Amato, F.; Lane, T. P.

    2014-12-01

    Overshooting convection penetrating the tropical tropopause layer (TTL) and the lower stratosphere has a significant impact on the redistribution of water vapour and further trace gases. This is of importance for the stratospheric water vapour budget, which plays a central role in radiative and chemical processes. Modelling studies and in situ measurements show the hydration potential of convective overshooting partly by direct injection of ice particles into the stratosphere and subsequent sublimation. However, processes leading to dehydration of the TTL may also impact the stratospheric humidity by limiting the amount of water vapour carried aloft. While the large scale drives some of the dehydrating processes, others are of convective origin, for example gravity waves and cooling associated with overshooting turrets. Furthermore, downdrafts may transport dry and ozone rich air masses from the stratosphere into the TTL. Improving our understanding of overshooting convection and its influence on TTL water vapour will ultimately place better constraints on the budget of water vapour in the stratosphere.In this study we use three-dimensional cloud resolving (WRF-ARW) simulations of a deep convective thunderstorm (Hector) to study the redistribution of water vapour and trace gases in the upper TTL/lower stratosphere. Passive tracers are initialised to investigate the transport of air masses. The simulations focus on an Hector event that has been probed by aircraft during the SCOUT-O3 field campaign. Observations were performed in and around overshoots that even penetrated the stratosphere. These observations as well as the model simulations show downward transport and mixing of air masses from the stratosphere, though less strong and more localised in the simulation. Furthermore, the simulations shows a layering of hydrated and dehydrated air masses post-convection in the upper TTL and lower stratosphere. Here we use the model to explain the processes causing the

  9. Trends and transport of water vapour in the middle atmosphere

    NASA Astrophysics Data System (ADS)

    Urban, Joachim

    2012-07-01

    J. Urban with data contributions from the SAGE, HALOE, Odin, MIPAS, ACE, MLS, and SABER teams The evolution and spatio-temporal variability of water vapour in the tropical tropopause region, stratosphere, and mesosphere is analyzed using "historical" (SAGE-II, UARS/HALOE) and "recent" (Odin/SMR, TIMED/SABER, ENVISAT/MIPAS, ACE/FTS, Aura/MLS) satellite limb measurements. Water vapour mixing ratios in the tropical lower stratosphere are correlated with changes of the very variable tropical tropopause cold-point temperatures and the water vapour entry signal is further modulated and altered by transport and mixing of air masses. A water vapour signal originating and ascending in the tropical tropopause region can within certain limits be followed through the stratosphere and mesosphere allowing us for example to test consistency with "age-of-air" estimates and present understanding of poleward transport in this atmospheric region.

  10. Plastic optical fibre sensor for detecting vapour phase alcohol

    NASA Astrophysics Data System (ADS)

    Morisawa, Masayuki; Amemiya, Yumiko; Kohzu, Hidenori; Liang, Chuan Xin; Muto, Shinzo

    2001-07-01

    New plastic optical fibre sensors for detecting alcohol vapour have been studied. A certain kind of polymer such as a Novolac resin causes swelling when it is exposed to alcohol vapour. This effect produces a change in the polymer refractive index. Based on this principle, the plastic optical fibre (POF) type sensor head was fabricated by coating Novolac-resin and Novolac/Fe:SO complex film as a cladding layer on the plastic fibre core. When this sensor head was exposed to ethanol and methanol vapour, the light intensity passing through the sensor head changed remarkably depending on the vapour pressure. The sensor response was also found to be fast, stable and reproducible.

  11. Decomposition of O,S-dimethyl methylphosphonothiolate by ammonia on magnesium oxide: a theoretical study of catalytic detoxification of a chemical warfare agent.

    PubMed

    Sahu, Chandan; Ghosh, Deepanwita; Sen, Kaushik; Das, Abhijit K

    2015-08-21

    The adsorption of a model nerve agent, O,S-dimethyl methylphosphonothiolate (DMPT), on the hydroxylated and unhydroxylated nano-crystalline magnesium oxide surface followed by the nucleophilic attack of ammonia (NH3) is investigated at the M06-2X/6-311++G(d,p) level of theory using the representative cluster models. The geometries of DMPT and NH3 are fully optimized, while the geometry of the oxide fragment is kept frozen. The main insight of this study is the incorporation of the Eley-Rideal mechanism for the first time in the detoxification process, where one of the reactant molecules (DMPT) is adsorbed and the other one (NH3) reacts with it directly impinging from the gas phase. There are two possible pathways of nucleophilic detoxification, either concerted or stepwise. The nature of the first transition state of nucleophilic attack in both pathways is the vital step for degradation. Our calculated results predict that the reaction of DMPT with NH3 gives rise to both P-S and P-O bond cleavage completely. Also, the P-S cleavage is found to be the favorable one over P-O bond breaking. The exploration of the overall reaction mechanism has established the catalytic activity of nano-crystalline MgO in nucleophilic DMPT degradation, as in all cases the activation barriers have reduced compared to the previously reported aminolysis of DMPT in the gas phase. Interestingly, the hydroxylated model has better catalytic performance than the unhydroxylated one.

  12. Raney nickel catalytic device

    DOEpatents

    O'Hare, Stephen A.

    1978-01-01

    A catalytic device for use in a conventional coal gasification process which includes a tubular substrate having secured to its inside surface by expansion a catalytic material. The catalytic device is made by inserting a tubular catalytic element, such as a tubular element of a nickel-aluminum alloy, into a tubular substrate and heat-treating the resulting composite to cause the tubular catalytic element to irreversibly expand against the inside surface of the substrate.

  13. Variability of winter-time middle atmospheric water vapour over the Arctic as observed with a ground-based microwave radiometer

    NASA Astrophysics Data System (ADS)

    Tschanz, Brigitte; Kivi, Rigel; Rüfenacht, Rolf; Kämpfer, Niklaus

    2014-05-01

    Middle atmospheric water vapour has a long chemical lifetime and can therefore be used as a tracer for dynamics. The ground-based microwave radiometer MIAWARA-C is designed for the use on campaigns and measures profiles of water vapour in the upper stratosphere and mesosphere and thus provides valuable data for the investigation of atmospheric processes. It has been operational for five years and has successfully participated in measurement campaigns under various climatic conditions in Germany, Switzerland, California, Finland and on la Réunion. The temporal resolution of the obtained water vapour profiles approximately 2 hours depending on tropospheric conditions. During two campaigns from January to June 2010 and from July 2011 to April 2013 in Sodankylä, Finland, MIAWARA-C monitored time series of polar middle atmospheric water vapour for three winters with three Sudden Stratospheric Warmings (SSW) occurring in early 2010, 2012 and 2013. The obtained time series are used to study the effects of the three SSWs on middle-atmospheric water vapour. During an SSW, humid mid- to low-latitude air is transported towards the polar region resulting in a fast increase in water vapour. The descent of water vapour after the SSW allows the estimation of the descent rate over the polar region as the normal wintertime circulation reforms. Results from the three SSWs are compared. The ground-based water vapour data is combined with sonde data of the Finnish Meteorological Institute and ground-based microwave wind measurements for one winter in order to obtain a more complete picture of the dynamics in the polar winter atmosphere.

  14. Examination of surface phenomena of V₂O₅ loaded on new nanostructured TiO₂ prepared by chemical vapor condensation for enhanced NH₃-based selective catalytic reduction (SCR) at low temperatures.

    PubMed

    Cha, Woojoon; Yun, Seong-Taek; Jurng, Jongsoo

    2014-09-01

    In this article, we describe the investigation and surface characterization of a chemical vapor condensation (CVC)-TiO2 support material used in a V2O5/TiO2 catalyst for enhanced selective catalytic reduction (SCR) activity and confirm the mechanism of surface reactions. On the basis of previous studies and comparison with a commercial TiO2 catalyst, we examine four fundamental questions: first, the reason for increased surface V(4+) ion concentrations; second, the origin of the increase in surface acid sites; third, a basis for synergistic influences on improvements in SCR activity; and fourth, a reason for improved catalytic activity at low reaction temperatures. In this study, we have cited the result of SCR with NH3 activity for removing NOx and analyzed data using the reported result and data from previous studies on V2O5/CVC-TiO2 for the SCR catalyst. In order to determine the properties of suitable CVC-TiO2 surfaces for efficient SCR catalysis at low temperatures, CVC-TiO2 specimens were prepared and characterized using techniques such as XRD, BET, HR-TEM, XPS, FT-IR, NH3-TPD, photoluminescence (PL) spectroscopy, H2-TPR, and cyclic voltammetry. The results obtained for the CVC-TiO2 materials were also compared with those of commercial TiO2. PMID:25045767

  15. Examination of surface phenomena of V₂O₅ loaded on new nanostructured TiO₂ prepared by chemical vapor condensation for enhanced NH₃-based selective catalytic reduction (SCR) at low temperatures.

    PubMed

    Cha, Woojoon; Yun, Seong-Taek; Jurng, Jongsoo

    2014-09-01

    In this article, we describe the investigation and surface characterization of a chemical vapor condensation (CVC)-TiO2 support material used in a V2O5/TiO2 catalyst for enhanced selective catalytic reduction (SCR) activity and confirm the mechanism of surface reactions. On the basis of previous studies and comparison with a commercial TiO2 catalyst, we examine four fundamental questions: first, the reason for increased surface V(4+) ion concentrations; second, the origin of the increase in surface acid sites; third, a basis for synergistic influences on improvements in SCR activity; and fourth, a reason for improved catalytic activity at low reaction temperatures. In this study, we have cited the result of SCR with NH3 activity for removing NOx and analyzed data using the reported result and data from previous studies on V2O5/CVC-TiO2 for the SCR catalyst. In order to determine the properties of suitable CVC-TiO2 surfaces for efficient SCR catalysis at low temperatures, CVC-TiO2 specimens were prepared and characterized using techniques such as XRD, BET, HR-TEM, XPS, FT-IR, NH3-TPD, photoluminescence (PL) spectroscopy, H2-TPR, and cyclic voltammetry. The results obtained for the CVC-TiO2 materials were also compared with those of commercial TiO2.

  16. Chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors.

    PubMed

    Lebedeva, Maria A; Chamberlain, Thomas W; Thomas, Alice; Thomas, Bradley E; Stoppiello, Craig T; Volkova, Evgeniya; Suyetin, Mikhail; Khlobystov, Andrei N

    2016-06-01

    A series of explorative cross-coupling reactions have been developed to investigate the local nanoscale environment around catalytically active Pd(ii)complexes encapsulated within hollow graphitised nanofibers (GNF). Two new fullerene-containing and fullerene-free Pd(ii)Salen catalysts have been synthesised, and their activity and selectivity towards different substrates has been explored in nanoreactors. The catalysts not only show a significant increase in activity and stability upon heterogenisation at the graphitic step-edges inside the GNF channel, but also exhibit a change in selectivity affected by the confinement which alters the distribution of isomeric products of the reaction. Furthermore, the observed selectivity changes reveal unprecedented details regarding the location and orientation of the catalyst molecules inside the GNF nanoreactor, inaccessible by any spectroscopic or microscopic techniques, thus shedding light on the precise reaction environment inside the molecular catalyst-GNF nanoreactor.

  17. Chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors

    NASA Astrophysics Data System (ADS)

    Lebedeva, Maria A.; Chamberlain, Thomas W.; Thomas, Alice; Thomas, Bradley E.; Stoppiello, Craig T.; Volkova, Evgeniya; Suyetin, Mikhail; Khlobystov, Andrei N.

    2016-06-01

    A series of explorative cross-coupling reactions have been developed to investigate the local nanoscale environment around catalytically active Pd(ii)complexes encapsulated within hollow graphitised nanofibers (GNF). Two new fullerene-containing and fullerene-free Pd(ii)Salen catalysts have been synthesised, and their activity and selectivity towards different substrates has been explored in nanoreactors. The catalysts not only show a significant increase in activity and stability upon heterogenisation at the graphitic step-edges inside the GNF channel, but also exhibit a change in selectivity affected by the confinement which alters the distribution of isomeric products of the reaction. Furthermore, the observed selectivity changes reveal unprecedented details regarding the location and orientation of the catalyst molecules inside the GNF nanoreactor, inaccessible by any spectroscopic or microscopic techniques, thus shedding light on the precise reaction environment inside the molecular catalyst-GNF nanoreactor.A series of explorative cross-coupling reactions have been developed to investigate the local nanoscale environment around catalytically active Pd(ii)complexes encapsulated within hollow graphitised nanofibers (GNF). Two new fullerene-containing and fullerene-free Pd(ii)Salen catalysts have been synthesised, and their activity and selectivity towards different substrates has been explored in nanoreactors. The catalysts not only show a significant increase in activity and stability upon heterogenisation at the graphitic step-edges inside the GNF channel, but also exhibit a change in selectivity affected by the confinement which alters the distribution of isomeric products of the reaction. Furthermore, the observed selectivity changes reveal unprecedented details regarding the location and orientation of the catalyst molecules inside the GNF nanoreactor, inaccessible by any spectroscopic or microscopic techniques, thus shedding light on the precise reaction

  18. Catalytic performances of HZSM-5, NaY and MCM-41 in two-stage catalytic pyrolysis of pinewood

    NASA Astrophysics Data System (ADS)

    Wang, Y. M.; Wang, J.

    2016-08-01

    Experiments were carried out in an atmospheric two-stage fixed bed reactor to investigate the catalytic cracking of pinewood pyrolysis vapour over three single catalysts, HZSM-5, NaY and MCM-41. The pinewood was pyrolyzed in the first stage reactor at a heating rate of 10 °C min-1 from room temperature to 700 °C, and the resultant vapour was cracked through the second reactor at a temperature of 500, 600 or 700 °C with and without catalyst. Both the gases and liquid compounds were thoroughly determined. It was found that all three catalysts had significant catalytic effects on the vapour cracking especially in the range of 500-600 °C. However, three catalysts showed dissimilarity to each other with respect to the distributions of products. Among three catalysts, HZSM-5 displayed the highest selectivity for the formation of olefins and light aromatics, with the least deposit of coke, though NaY showed the strongest capability of deoxygenation. The HZSM-5 cracking at 600 °C was preferred to balance the yield and quality of bio-products. MCM-41 behaved as a worse catalyst in the deoxygenation, and its resultant liquid product contained more heavy aromatics.

  19. Measurements of Isotopic Composition of Vapour on the Antarctic Plateau

    NASA Astrophysics Data System (ADS)

    Casado, M.; Landais, A.; Masson-Delmotte, V.; Genthon, C.; Prie, F.; Kerstel, E.; Kassi, S.; Arnaud, L.; Steen-Larsen, H. C.; Vignon, E.

    2015-12-01

    The oldest ice core records are obtained on the East Antarctic plateau. The composition in stable isotopes of water (δ18O, δD, δ17O) permits to reconstruct the past climatic conditions over the ice sheet and also at the evaporation source. Paleothermometer accuracy relies on good knowledge of processes affecting the isotopic composition of surface snow in Polar Regions. Both simple models such as Rayleigh distillation and global atmospheric models with isotopes provide good prediction of precipitation isotopic composition in East Antarctica but post deposition processes can alter isotopic composition on site, in particular exchanges with local vapour. To quantitatively interpret the isotopic composition of water archived in ice cores, it is thus essential to study the continuum water vapour - precipitation - surface snow - buried snow. While precipitation and snow sampling are routinely performed in Antarctica, climatic conditions in Concordia, very cold (-55°C in average) and very dry (less than 1000ppmv), impose difficult conditions to measure the water vapour isotopic composition. New developments in infrared spectroscopy enable now the measurement of isotopic composition in water vapour traces (down to 20ppmv). Here we present the results of a campaign of measurement of isotopic composition in Concordia in 2014/2015. Two infrared spectrometers have been deployed or the first time on top of the East Antarctic Plateau allowing a continuous vapour measurement for a month. Comparison of the results from infrared spectroscopy with cryogenic trapping validates the relevance of the method to measure isotopic composition in dry conditions. Identification of different behaviour of isotopic composition in the water vapour associated to turbulent or stratified regime indicates a strong impact of meteorological processes in local vapour/snow interaction.

  20. ``OPTICAL Catalytic Nanomotors''

    NASA Astrophysics Data System (ADS)

    Rosary-Oyong, Se, Glory

    D. Kagan, et.al, 2009:'' a motion-based chemical sensing involving fuel-driven nanomotors is demonstrated. The new protocol relies on the use of an optical microscope for tracking charge in the speed of nanowire motors in the presence of target analyte''. Synthetic nanomotors are propelled by catalytic decomposition of .. they do not require external electric, magnetic or optical fields as energy... Accompanying Fig 2.6(a) of optical micrograph of a partial monolayer of silica microbeads [J.Gibbs, 2011 ] retrieves WF Paxton:''rods were characterized by transmission electron & dark-field optical microscopy..'' & LF Valadares:''dimer due to the limited resolution of optical microscopy, however the result..'. Acknowledged to HE. Mr. Prof. SEDIONO M.P. TJONDRONEGORO.

  1. Nanofluidic transport governed by the liquid/vapour interface

    NASA Astrophysics Data System (ADS)

    Lee, Jongho; Laoui, Tahar; Karnik, Rohit

    2014-04-01

    Liquid/vapour interfaces govern the behaviour of a wide range of systems but remain poorly understood, leaving ample margin for the exploitation of intriguing functionalities for applications. Here, we systematically investigate the role of liquid/vapour interfaces in the transport of water across apposing liquid menisci in osmosis membranes comprising short hydrophobic nanopores that separate two fluid reservoirs. We show experimentally that mass transport is limited by molecular reflection from the liquid/vapour interface below a certain length scale, which depends on the transmission probability of water molecules across the nanopores and on the condensation probability of a water molecule incident on the liquid surface. This fundamental yet elusive condensation property of water is measured under near-equilibrium conditions and found to decrease from 0.36 +/- 0.21 at 30 °C to 0.18 +/- 0.09 at 60 °C. These findings define the regime in which liquid/vapour interfaces govern nanofluidic transport and have implications for understanding mass transport in nanofluidic devices, droplets and bubbles, biological components and porous media involving liquid/vapour interfaces.

  2. Vapour phase hydrogenation of phenol over rhodium on SBA-15 and SBA-16.

    PubMed

    Giraldo, Liliana; Bastidas-Barranco, Marlon; Moreno-Piraján, Juan Carlos

    2014-12-10

    In the present work, mesoporous SBA-15 and SBA-16 were synthesised using classical methods, and their physicochemical properties were investigated by X-ray diffraction (XRD), FTIR, TEM and N2 adsorption-desorption. Rhodium (Rh, 1 wt %) was loaded on the mesoporous SBA-15 and SBA-16 by an impregnation method. The Rh surface coverage, dispersion and crystallite size were determined by room temperature H2 chemisorption on reduced samples. The catalytic activity of Rh supported on mesoporous SBA-15 and SBA-16 was evaluated for the first time in the hydrogenation of phenol in vapour phase in a temperature range between 130 and 270 °C at atmospheric pressure. The reaction over Rh/SBA-15 at 180 °C produced cyclohexanone as the major product (about 60%) along with lower amounts of cyclohexanol (about 35%) and cyclohexane (about 15%). The influences of temperature, H2/phenol ratio, contact time and the nature of the solvent on the catalytic performance were systematically investigated. The Rh/SBA-16 system offered lower phenol conversion compared to Rh/SBA-15, but both have a very high selectivity for cyclohexanone (above 60%).

  3. Evolution of the Structure and Chemical State of Pd Nanoparticles During the in Situ Catalytic Reduction of NO with H2

    SciTech Connect

    K Paredis; L Ono; F Behafarid; Z Zhang; J Yang; A Frenkel; B Roldan Cuenya

    2011-12-31

    An in-depth understanding of the fundamental structure of catalysts during operation is indispensable for tailoring future efficient and selective catalysts. We report the evolution of the structure and oxidation state of ZrO{sub 2}-supported Pd nanocatalysts (5 nm) during the in situ reduction of NO with H{sub 2} using X-ray absorption fine-structure spectroscopy and X-ray photoelectron spectroscopy. Prior to the onset of the reaction ({le}120 C), a NO-induced redispersion of our initial metallic Pd nanoparticles over the ZrO{sub 2} support was observed, and Pd{sup {delta}+} species were detected. This process parallels the high production of N{sub 2}O observed at the onset of the reaction (>120 C), while at higher temperatures ({ge}150 C) the selectivity shifts mainly toward N{sub 2} ({approx}80%). Concomitant with the onset of N{sub 2} production, the Pd atoms aggregate again into large (6.5 nm) metallic Pd nanoparticles, which were found to constitute the active phase for the H{sub 2}-reduction of NO. Throughout the entire reaction cycle, the formation and stabilization of PdO{sub x} was not detected. Our results highlight the importance of in situ reactivity studies to unravel the microscopic processes governing catalytic reactivity.

  4. Main problems in the theory of modeling of catalytic processes

    SciTech Connect

    Pisarenko, V.N.

    1994-09-01

    This paper formulates the main problems in the theory of modeling of catalytic processes yet to be solved and describes the stages of modeling. Fundamental problems of model construction for the physico-chemical phenomena and processes taking place in a catalytic reactor are considered. New methods for determining the mechanism of a catalytic reaction and selecting a kinetic model for it are analyzed. The use of the results of specially controlled experiments for the construction of models of a catalyst grain and a catalytic reactor is discussed. Algorithms are presented for determining the muliplicity of stationary states in the operation of a catalyst grain and a catalytic reactor.

  5. CO2-fluxing collapses metal mobility in magmatic vapour

    DOE PAGES

    van Hinsberg, V. J.; Berlo, K.; Migdisov, A. A.; Williams-Jones, A. E.

    2016-05-18

    Magmatic systems host many types of ore deposits, including world-class deposits of copper and gold. Magmas are commonly an important source of metals and ore-forming fluids in these systems. In many magmatic-hydrothermal systems, low-density aqueous fluids, or vapours, are significant metal carriers. Such vapours are water-dominated shallowly, but fluxing of CO2-rich vapour exsolved from deeper magma is now recognised as ubiquitous during open-system magma degassing. Furthermore, we show that such CO2-fluxing leads to a sharp drop in element solubility, up to a factor of 10,000 for Cu, and thereby provides a highly efficient, but as yet unrecognised mechanism for metalmore » deposition.« less

  6. The ignitability of petrol vapours and potential for vapour phase explosion by use of TASER® law enforcement electronic control device.

    PubMed

    Clarke, C; Andrews, S P

    2014-12-01

    An experimental study was made of the potential of the TASER-X26™ law enforcement electronic control device to ignite petrol vapours if used by an officer to incapacitate a person soaked in petrol, or within a flammable atmosphere containing petrol vapour. Bench scale tests have shown that a wooden mannequin with pig skin covering the chest was a suitable representation of a human target. Full scale tests using the mannequin have shown that the arc from a TASER-X26™ is capable of igniting petrol/air vapours on a petrol-soaked person. Further tests in a 1/5 scale and a full scale compartment have shown that if a TASER is used within a compartment, a petrol vapour explosion (deflagration) may be achieved. It is evident from this research that if used in a flammable vapour rich environment, the device could prove fatal not only to the target but the TASER® operator as well. PMID:25498927

  7. Intercomparison of TCCON and MUSICA Water Vapour Products

    NASA Astrophysics Data System (ADS)

    Weaver, D.; Strong, K.; Deutscher, N. M.; Schneider, M.; Blumenstock, T.; Robinson, J.; Notholt, J.; Sherlock, V.; Griffith, D. W. T.; Barthlott, S.; García, O. E.; Smale, D.; Palm, M.; Jones, N. B.; Hase, F.; Kivi, R.; Ramos, Y. G.; Yoshimura, K.; Sepúlveda, E.; Gómez-Peláez, Á. J.; Gisi, M.; Kohlhepp, R.; Warneke, T.; Dohe, S.; Wiegele, A.; Christner, E.; Lejeune, B.; Demoulin, P.

    2014-12-01

    We present an intercomparison between the water vapour products from the Total Carbon Column Observing Network (TCCON) and the MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water (MUSICA), two datasets from ground-based Fourier Transform InfraRed (FTIR) spectrometers with good global representation. Where possible, comparisons to radiosondes are also included. The near-infrared TCCON measurements are optimized to provide precise monitoring of greenhouse gases for carbon cycle studies; however, TCCON's retrievals also produce water vapour products. The mid-infrared MUSICA products result from retrievals optimized to give precise and accurate information about H2O, HDO, and δD. The MUSICA water vapour products have been validated by extensive intercomparisons with H2O and δD in-situ measurements made from ground, radiosonde, and aircraft (Schneider et al. 2012, 2014), as well as by intercomparisons with satellite-based H2O and δD remote sensing measurements (Wiegele et al., 2014). This dataset provides a valuable reference point for other measurements of water vapour. This study is motivated by the limited intercomparisons performed for TCCON water vapour products and limited characterisation of their uncertainties. We compare MUSICA and TCCON products to assess the potential for TCCON measurements to contribute to studies of the water cycle, water vapour's role in climate and use as a tracer for atmospheric dynamics, and to evaluate the performance of climate models. The TCCON and MUSICA products result from measurements taken using the same FTIR instruments, enabling a comparison with constant instrumentation. The retrieval techniques differ, however, in their method and a priori information. We assess the impact of these differences and characterize the comparability of the TCCON and MUSICA datasets.

  8. High temperature catalytic membrane reactors

    SciTech Connect

    Not Available

    1990-03-01

    Current state-of-the-art inorganic oxide membranes offer the potential of being modified to yield catalytic properties. The resulting modules may be configured to simultaneously induce catalytic reactions with product concentration and separation in a single processing step. Processes utilizing such catalytically active membrane reactors have the potential for dramatically increasing yield reactions which are currently limited by either thermodynamic equilibria, product inhibition, or kinetic selectivity. Examples of commercial interest include hydrogenation, dehydrogenation, partial and selective oxidation, hydrations, hydrocarbon cracking, olefin metathesis, hydroformylation, and olefin polymerization. A large portion of the most significant reactions fall into the category of high temperature, gas phase chemical and petrochemical processes. Microporous oxide membranes are well suited for these applications. A program is proposed to investigate selected model reactions of commercial interest (i.e. dehydrogenation of ethylbenzene to styrene and dehydrogenation of butane to butadiene) using a high temperature catalytic membrane reactor. Membranes will be developed, reaction dynamics characterized, and production processes developed, culminating in laboratory-scale demonstration of technical and economic feasibility. As a result, the anticipated increased yield per reactor pass economic incentives are envisioned. First, a large decrease in the temperature required to obtain high yield should be possible because of the reduced driving force requirement. Significantly higher conversion per pass implies a reduced recycle ratio, as well as reduced reactor size. Both factors result in reduced capital costs, as well as savings in cost of reactants and energy.

  9. Single molecule TPM analysis of the catalytic pentad mutants of Cre and Flp site-specific recombinases: contributions of the pentad residues to the pre-chemical steps of recombination.

    PubMed

    Fan, Hsiu-Fang; Cheng, Yong-Song; Ma, Chien-Hui; Jayaram, Makkuni

    2015-03-31

    Cre and Flp site-specific recombinase variants harboring point mutations at their conserved catalytic pentad positions were characterized using single molecule tethered particle motion (TPM) analysis. The findings reveal contributions of these amino acids to the pre-chemical steps of recombination. They suggest functional differences between positionally conserved residues in how they influence recombinase-target site association and formation of 'non-productive', 'pre-synaptic' and 'synaptic' complexes. The most striking difference between the two systems is noted for the single conserved lysine. The pentad residues in Cre enhance commitment to recombination by kinetically favoring the formation of pre-synaptic complexes. These residues in Flp serve a similar function by promoting Flp binding to target sites, reducing non-productive binding and/or enhancing the rate of assembly of synaptic complexes. Kinetic comparisons between Cre and Flp, and between their derivatives lacking the tyrosine nucleophile, are consistent with a stronger commitment to recombination in the Flp system. The effect of target site orientation (head-to-head or head-to-tail) on the TPM behavior of synapsed DNA molecules supports the selection of anti-parallel target site alignment prior to the chemical steps. The integrity of the synapse, whose establishment/stability is fostered by strand cleavage in the case of Flp but not Cre, appears to be compromised by the pentad mutations.

  10. The Role of Water Vapour in Earth's Energy Flows

    NASA Astrophysics Data System (ADS)

    Allan, Richard P.

    2012-07-01

    Water vapour modulates energy flows in Earth's climate system through transfer of latent heat by evaporation and condensation and by modifying the flows of radiative energy both in the longwave and shortwave portions of the electromagnetic spectrum. This article summarizes the role of water vapour in Earth's energy flows with particular emphasis on (1) the powerful thermodynamic constraint of the Clausius Clapeyron equation, (2) dynamical controls on humidity above the boundary layer (or free-troposphere), (3) uncertainty in continuum absorption in the relatively transparent "window" regions of the radiative spectrum and (4) implications for changes in the atmospheric hydrological cycle.

  11. Spontaneuos and Parametric Processes in Warm Rubidium Vapours

    NASA Astrophysics Data System (ADS)

    Dąbrowski, M.; Parniak, M.; Pęcak, D.; Chrapkiewicz, R.; Wasilewski, W.

    2014-12-01

    Warm rubidium vapours are known to be a versatile medium for a variety of experiments in atomic physics and quantum optics. Here we present experimental results on producing the frequency converted light for quantum applications based on spontaneous and stimulated processes in rubidium vapours. In particular, we study the efficiency of spontaneously initiated stimulated Raman scattering in the Λ-level configuration and conditions of generating the coherent blue light assisted by multi-photon transitions in the diamond-level configuration. Our results will be helpful in search for new types of interfaces between light and atomic quantum memories.

  12. ECUT: Energy Conversion and utilization Technologies program biocatalysis research activity. Generation of chemical intermediates by catalytic oxidative decarboxylation of dilute organic acids

    NASA Technical Reports Server (NTRS)

    Distefano, S.; Gupta, A.; Ingham, J. D.

    1983-01-01

    A rhodium-based catalyst was prepared and preliminary experiments were completed where the catalyst appeared to decarboxylate dilute acids at concentrations of 1 to 10 vol%. Electron spin resonance spectroscoy was used to characterize the catalyst as a first step leading toward modeling and optimization of rhodium catalysts. Also, a hybrid chemical/biological process for the production of hydrocarbons has been assessed. These types of catalysts could greatly increase energy efficiency of this process.

  13. Efficient, chemical-catalytic approach to the production of 3-hydroxypropanoic acid by oxidation of biomass-derived levulinic acid with hydrogen peroxide.

    PubMed

    Wu, Linglin; Dutta, Saikat; Mascal, Mark

    2015-04-13

    3-Hydroxypropanoic acid (HPA), a precursor to acrylic acid, can be produced in high yield by oxidation of the biomass-derived platform chemical levulinic acid. While treatment of levulinic acid with H2 O2 under acidic conditions gives predominantly succinic acid, a remarkable reversal of selectivity is observed under basic conditions, leading either directly to HPA or, under modified conditions, initially to 3-(hydroperoxy)propanoic acid, which can be quantitatively hydrogenated to HPA. PMID:25736835

  14. Switchable catalytic DNA catenanes.

    PubMed

    Hu, Lianzhe; Lu, Chun-Hua; Willner, Itamar

    2015-03-11

    Two-ring interlocked DNA catenanes are synthesized and characterized. The supramolecular catenanes show switchable cyclic catalytic properties. In one system, the catenane structure is switched between a hemin/G-quadruplex catalytic structure and a catalytically inactive state. In the second catenane structure the catenane is switched between a catalytically active Mg(2+)-dependent DNAzyme-containing catenane and an inactive catenane state. In the third system, the interlocked catenane structure is switched between two distinct catalytic structures that include the Mg(2+)- and the Zn(2+)-dependent DNAzymes. PMID:25642796

  15. Thermodynamics of catalytic nanoparticle morphology

    NASA Astrophysics Data System (ADS)

    Zwolak, Michael; Sharma, Renu; Lin, Pin Ann

    Metallic nanoparticles are an important class of industrial catalysts. The variability of their properties and the environment in which they act, from their chemical nature & surface modification to their dispersion and support, allows their performance to be optimized for many chemical processes useful in, e.g., energy applications and other areas. Their large surface area to volume ratio, as well as varying sizes and faceting, in particular, makes them an efficient source for catalytically active sites. These characteristics of nanoparticles - i.e., their morphology - can often display intriguing behavior as a catalytic process progresses. We develop a thermodynamic model of nanoparticle morphology, one that captures the competition of surface energy with other interactions, to predict structural changes during catalytic processes. Comparing the model to environmental transmission electron microscope images of nickel nanoparticles during carbon nanotube (and other product) growth demonstrates that nickel deformation in response to the nanotube growth is due to a favorable interaction with carbon. Moreover, this deformation is halted due to insufficient volume of the particles. We will discuss the factors that influence morphology and also how the model can be used to extract interaction strengths from experimental observations.

  16. Influence of catalytic gold and silver metal nanoparticles on structural, optical, and vibrational properties of silicon nanowires synthesized by metal-assisted chemical etching

    NASA Astrophysics Data System (ADS)

    Dawood, M. K.; Tripathy, S.; Dolmanan, S. B.; Ng, T. H.; Tan, H.; Lam, J.

    2012-10-01

    We report on the structural and vibrational characterization of silicon (Si) nanowire arrays synthesized by metal-assisted chemical etching (MACE) of Si deposited with metal nanoparticles. Gold (Au) and silver (Ag) metal nanoparticles were synthesized by glancing angle deposition, and MACE was performed in a mixture of H2O2 and HF solution. We studied the structural differences between Au and Ag-etched Si nanowires. The morphology of the synthesized nanowires was characterized by scanning electron microscopy and transmission electron microscopy. The optical and vibrational properties of the Si nanostructures were studied by photoluminescence and Raman spectroscopy using three different excitation sources (UV, visible, and near-infrared) and are correlated to their microstructures. The structural differences between Au-etched and Ag-etched nanowires are due to the higher degree of hole injection by the Au nanoparticle and diffusion into the Si nanowires, causing enhanced Si etching by HF on the nanowire surface. Au-etched nanowires were observed to be mesoporous throughout the nanowire while Ag-etched nanowires consisted of a thin porous layer around the crystalline core. In addition, the surface-enhanced resonant Raman scattering observed is attributed to the presence of the sunken metal nanoparticles. Such Si nanostructures may be useful for a wide range of applications such as photovoltaic and biological and chemical sensing.

  17. The influence of low concentrations of irritants on skin barrier function as determined by water vapour loss.

    PubMed

    van der Valk, P G; Nater, J P; Bleumink, E

    1985-01-01

    The effect of some irritants on the barrier function of the skin was assessed by means of water vapour loss measurements. 100 microliter of the test substance in distilled water were applied to the skin for a period of 48 h, using large Finn chambers. The exposures were done in a test panel of 42 subjects. Sodium lauryl sulfate (2%), cocobetaine (2%), crotonaldehyde (0.75%) with sodium lauryl sulfate (0.5%) and dimethyl sulfoxide (50%) markedly influenced water vapour loss. Sodium hydroxide (1%) had less effect on water vapour loss, although the increase was significant (p less than 0.05). Phenol (5%) and benzalkonium chloride (0.2%) did not significantly influence the loss of water through the skin. It is concluded that subclinical effects of chemicals on the barrier function may be of importance in the development of irritant contact dermatitis, but that this capacity is probably not the only factor which determines the potential of a substance to contribute to the development of irritant contact dermatitis. A chemical which has little or no effect on the function of the horny layer may have a toxic effect on the viable cells of deeper layers of the skin. This toxic effect may also be an important subclinical factor in the development of irritant contact dermatitis.

  18. The boiling liquid expanding vapour explosion (BLEVE): mechanism, consequence assessment, management.

    PubMed

    Abbasi, Tasneem; Abbasi, S A

    2007-03-22

    Among the most devastating of accidents likely in chemical process industry is the boiling liquid expanding vapour explosion (BLEVE). It is accompanied by highly destructive blast waves and missiles. In most situations there is also a fireball or a toxic gas cloud. The damaging effect of BLEVEs is reflected in the fact that the 80-odd major BLEVEs that have occurred between 1940 and 2005 have claimed over a 1000 lives and have injured over 10,000 persons besides harming property worth billions of dollars. Release of toxic chemicals like chlorine and phosgene from BLEVEs have damaged large chunks of areas surrounding the BLEVE site. This paper presents an overview of the mechanism, the causes, the consequences, and the preventive strategies associated with BLEVEs. PMID:17113225

  19. No sodium in the vapour plumes of Enceladus.

    PubMed

    Schneider, Nicholas M; Burger, Matthew H; Schaller, Emily L; Brown, Michael E; Johnson, Robert E; Kargel, Jeffrey S; Dougherty, Michele K; Achilleos, Nicholas A

    2009-06-25

    The discovery of water vapour and ice particles erupting from Saturn's moon Enceladus fuelled speculation that an internal ocean was the source. Alternatively, the source might be ice warmed, melted or crushed by tectonic motions. Sodium chloride (that is, salt) is expected to be present in a long-lived ocean in contact with a rocky core. Here we report a ground-based spectroscopic search for atomic sodium near Enceladus that places an upper limit on the mixing ratio in the vapour plumes orders of magnitude below the expected ocean salinity. The low sodium content of escaping vapour, together with the small fraction of salt-bearing particles, argues against a situation in which a near-surface geyser is fuelled by a salty ocean through cracks in the crust. The lack of observable sodium in the vapour is consistent with a wide variety of alternative eruption sources, including a deep ocean, a freshwater reservoir, or ice. The existing data may be insufficient to distinguish between these hypotheses.

  20. Distillation with Vapour Compression. An Undergraduate Experimental Facility.

    ERIC Educational Resources Information Center

    Pritchard, Colin

    1986-01-01

    Discusses the need to design distillation columns that are more energy efficient. Describes a "design and build" project completed by two college students aimed at demonstrating the principles of vapour compression distillation in a more energy efficient way. General design specifications are given, along with suggestions for teaching and…

  1. No sodium in the vapour plumes of Enceladus.

    PubMed

    Schneider, Nicholas M; Burger, Matthew H; Schaller, Emily L; Brown, Michael E; Johnson, Robert E; Kargel, Jeffrey S; Dougherty, Michele K; Achilleos, Nicholas A

    2009-06-25

    The discovery of water vapour and ice particles erupting from Saturn's moon Enceladus fuelled speculation that an internal ocean was the source. Alternatively, the source might be ice warmed, melted or crushed by tectonic motions. Sodium chloride (that is, salt) is expected to be present in a long-lived ocean in contact with a rocky core. Here we report a ground-based spectroscopic search for atomic sodium near Enceladus that places an upper limit on the mixing ratio in the vapour plumes orders of magnitude below the expected ocean salinity. The low sodium content of escaping vapour, together with the small fraction of salt-bearing particles, argues against a situation in which a near-surface geyser is fuelled by a salty ocean through cracks in the crust. The lack of observable sodium in the vapour is consistent with a wide variety of alternative eruption sources, including a deep ocean, a freshwater reservoir, or ice. The existing data may be insufficient to distinguish between these hypotheses. PMID:19553993

  2. Impact of major volcanic eruptions on stratospheric water vapour

    NASA Astrophysics Data System (ADS)

    Löffler, M.; Brinkop, S.; Jöckel, P.

    2015-12-01

    Volcanic eruptions can have significant impact on the earth's weather and climate system. Besides the subsequent tropospheric changes also the stratosphere is influenced by large eruptions. Here changes in stratospheric water vapour after the two major volcanic eruptions of El Chichón in Mexico in 1982 and Mount Pinatubo on the Philippines in 1991 are investigated with chemistry-climate model simulations. This study is based on two simulations with specified dynamics of the EMAC model, performed within the Earth System Chemistry integrated Modelling (ESCiMo) project, of which only one includes the volcanic forcing through prescribed aerosol optical properties. The results show a significant increase in stratospheric water vapour after the eruptions, resulting from increased heating rates and the subsequent changes in stratospheric and tropopause temperatures in the tropics. The tropical vertical advection and the South Asian summer monsoon are identified as important sources for the additional water vapour in the stratosphere. Additionally, volcanic influences on the tropospheric water vapour and ENSO are evident.

  3. Impact of major volcanic eruptions on stratospheric water vapour

    NASA Astrophysics Data System (ADS)

    Löffler, Michael; Brinkop, Sabine; Jöckel, Patrick

    2016-05-01

    Volcanic eruptions can have a significant impact on the Earth's weather and climate system. Besides the subsequent tropospheric changes, the stratosphere is also influenced by large eruptions. Here changes in stratospheric water vapour after the two major volcanic eruptions of El Chichón in Mexico in 1982 and Mount Pinatubo on the Philippines in 1991 are investigated with chemistry-climate model simulations. This study is based on two simulations with specified dynamics of the European Centre for Medium-Range Weather Forecasts Hamburg - Modular Earth Submodel System (ECHAM/MESSy) Atmospheric Chemistry (EMAC) model, performed within the Earth System Chemistry integrated Modelling (ESCiMo) project, of which only one includes the long-wave volcanic forcing through prescribed aerosol optical properties. The results show a significant increase in stratospheric water vapour induced by the eruptions, resulting from increased heating rates and the subsequent changes in stratospheric and tropopause temperatures in the tropics. The tropical vertical advection and the South Asian summer monsoon are identified as sources for the additional water vapour in the stratosphere. Additionally, volcanic influences on tropospheric water vapour and El Niño-Southern Oscillation (ENSO) are evident, if the long-wave forcing is strong enough. Our results are corroborated by additional sensitivity simulations of the Mount Pinatubo period with reduced nudging and reduced volcanic aerosol extinction.

  4. Detection of explosive vapour using surface-enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Fang, X.; Ahmad, S. R.

    2009-11-01

    A commercially available nano-structured gold substrate was used for activating surface-enhanced Raman scattering (SERS). Raman spectra of the vapour of explosive material, triacetonetriperoxide (TATP), at trace concentrations produced from adsorbed molecules on such surfaces have been studied. Prominent Raman lines of the explosive molecular species were recorded at a sample temperature of ˜35°C, which is near to human body temperature. For this study, the concentration of the adsorbed TATP molecules on the nano-structured surface was varied by heating the sample to different temperatures and exposing the substrate to the sample vapour for different lengths of time. The intensities of the Raman lines have been found to increase with the increase in temperature and also with the increase in the duration of exposure for a fixed temperature. However, as expected, the Raman intensities have been found to saturate at higher temperatures and longer exposures. These saturation effects of the strengths of the Raman lines in the SERS of TATP vapour have been investigated in this paper. The results indicate that the optimisation for vapour deposition on the surface could be a crucial factor for any quantitative estimate of the concentration of the molecular species adsorbed on the nano-structured substrates.

  5. THE INTERACTION OF VAPOUR PHASE ORGANIC COMPOUNDS WITH INDOOR SINKS

    EPA Science Inventory

    The interaction of indoor air pollutants with interior surfaces (i.e., sinks) is a well known, but poorly understood, phenomenon. Studies have shown that re-emissions of adsorbed organic vapours can contribute to elevated concentrations of organics in indoor environments. Researc...

  6. Breakdown and dc discharge in low-pressure water vapour

    NASA Astrophysics Data System (ADS)

    Sivoš, J.; Škoro, N.; Marić, D.; Malović, G.; Petrović, Z. Lj

    2015-10-01

    In this paper we report studies of basic properties of breakdown, low-current Townsend discharge and high-current discharge regimes in water vapour. Paschen curves and the corresponding distributions of emission intensities at low current were recorded in the range of pd (pressure x electrode gap) from 0.1 to 10 Torrcm covering the region of Paschen minimum. From the experimental profiles we obtained effective ionization coefficient of water vapour for the E/N range 650 Td-7 kTd and fitted the results by using the extended Townsend analytical formula. Using the obtained ionization coefficient, we calculated the effective yield of secondary electrons from the copper cathode. Results of the measurements of Volt-Ampere characteristics in water vapour were presented together with the images of the axial structure of the discharge in a wide range of discharge currents for two pd values. Recorded profiles showed development of the spatial structure of the discharge in different operating regimes. We were able to identify conditions where processes induced by heavy particles, probably fast hydrogen atoms, are dominant in inducing emission from the discharge. Finally, standard scaling laws were tested for low current and glow discharges in water vapour.

  7. Ellipsometry study of (0001) cadmium crystal faces during vapour growth

    NASA Astrophysics Data System (ADS)

    Gauch, M.; Quentel, G.

    1981-07-01

    Ellipsometry analysis of (0001) cadium faces during vapour growth reveal periodic fluctuations of the dielectric constant which are related to supersaturation. We show that they can be interpreted by the instability of monoatomic step trains produced by spiral growth. Such a model of surface roughness is also treated using the effective medium approximation of Bruggeman, which corroborates the experimental results.

  8. ESA DUE GlobVapour water vapor products: Validation

    SciTech Connect

    Schneider, Nadine; Schroeder, Marc; Stengel, Martin; Lindstrot, Ramus; Preusker, Rene; Collaboration: ESA DUE GlobVapour Consortium

    2013-05-10

    The main objective of the European Space Agency (ESA) Data User Element (DUE) GlobVapour project was the development of multi-annual global water vapor data sets. Since water vapour is a key climate variable it is important to have a good understanding of its behavior in the climate system. The ESA DUE GlobVapour project provides water vapor data, including error estimates, based on carefully calibrated and inter-calibrated satellite radiances in response to user requirements for long time series satellite observations. ESA DUE GlobVapour total columnar water vapor (TCWV) products derived from GOME/SCIA/GOME-2 (1996-2008) and SSM/I+MERIS (2003-2008) have been validated for the mentioned period, using satellite-based (AIRS, ATOVS) and ground-based measurements (radiosondes and microwave radiometer). The validation results are discussed in the following. The technical specifications on bias (1 kg/m{sup 2} for SSMI+MERIS and 2 kg/m{sup 2} for GOME/SCIA/GOME-2) are generally met. For more information, documents and data download follow the link: www.globvapour.info.

  9. Turkish Undergraduates' Misconceptions of Evaporation, Evaporation Rate, and Vapour Pressure

    ERIC Educational Resources Information Center

    Canpolat, Nurtac

    2006-01-01

    This study focused on students' misconceptions related to evaporation, evaporation rate, and vapour pressure. Open-ended diagnostic questions were used with 107 undergraduates in the Primary Science Teacher Training Department in a state university in Turkey. In addition, 14 students from that sample were interviewed to clarify their written…

  10. Catalytic Enantioselective Functionalization of Unactivated Terminal Alkenes.

    PubMed

    Coombs, John R; Morken, James P

    2016-02-18

    Terminal alkenes are readily available functional groups which appear in α-olefins produced by the chemical industry, and they appear in the products of many contemporary synthetic reactions. While the organic transformations that apply to alkenes are amongst the most studied reactions in all of chemical synthesis, the number of reactions that apply to nonactivated terminal alkenes in a catalytic enantioselective fashion is small in number. This Minireview highlights the cases where stereocontrol in catalytic reactions of 1-alkenes is high enough to be useful for asymmetric synthesis. PMID:26764019

  11. Catalytic Enantioselective Functionalization of Unactivated Terminal Alkenes.

    PubMed

    Coombs, John R; Morken, James P

    2016-02-18

    Terminal alkenes are readily available functional groups which appear in α-olefins produced by the chemical industry, and they appear in the products of many contemporary synthetic reactions. While the organic transformations that apply to alkenes are amongst the most studied reactions in all of chemical synthesis, the number of reactions that apply to nonactivated terminal alkenes in a catalytic enantioselective fashion is small in number. This Minireview highlights the cases where stereocontrol in catalytic reactions of 1-alkenes is high enough to be useful for asymmetric synthesis.

  12. Evaluating the vapour shift concept in agriculture: some aspects

    NASA Astrophysics Data System (ADS)

    Schmidt, S.; Metselaar, K.; van Dam, J. C.; Klik, A.

    2009-04-01

    Human population growth leads to an increasing pressure on freshwater resources. By 2050 Falkenmark et al. (2004) estimate a global water deficit for crop production of 5800 km3.y-1. This has important consequences for management of fresh water resources at different scales, and new strategies at different scales are required. One of the strategies suggested is that of managing crops in such a way that the use of rainfall and irrigation is shifted as much as possible from evaporation towards transpiration, a so-called vapour shift. The suggested savings are in the order of 330 km3.y-1, and are based on estimates of the magnitude of three processes: Reducing early season evaporation; increasing canopy cover; and increasing yield levels. The vapour shift concept was evaluated empirically, and in a simulation study. The empirical evaluation using results for wheat, maize, millet, cotton, and barley suggests the estimate of potential savings is 37% lower than the estimate by Falkenmark et al. (2004). The uncertainty is large and due to the limited number of experiments in which a separation of evapotranspiration in evaporation and transpiration has been made over the entire growing season. This suggests that theoretical support for the vapour shift concept should become more important. In the simulation approach two management options, mulching and planting density, are evaluated for a site in India for an irrigated wheat crop using a simulation approach for water limited crop yield. Given the simulation model used, and the management options investigated, the assumption implicit in the vapour shift concept - decreasing evaporation with increasing yield level - does not hold in irrigated areas, or in areas in which water is the most limiting factor. This suggests that vapour shift will be largest in those areas where nutrients and pests- and diseases are still limiting or reducing crop yields, and measures are taken to reduce those limitations.

  13. Vapour-liquid equilibrium relationship between toluene and mixed surfactants.

    PubMed

    Tian, Senlin; Li, Yingjie; Mo, Hong; Ning, Ping

    2012-01-01

    Micellar partitioning of volatile organic compounds (VOCs) in surfactant solutions and its effects on vapour-liquid equilibrium is fundamental to the overall design and implementation ofsurfactant-enhanced remediation. Knowledge of the vapour-liquid equilibrium partitioning coefficients for VOCs, especially in contaminated soils and groundwater in which they exist, is required. Headspace experiments were performed to quantify the effect of three mixed surfactants, cetyltrimethyl ammonium bromide (CTMAB) with tetrabutylammonium bromide (TBAB), sodium dodecyl sulphate (SDS) with Triton X-405 (TX405), and CTMAB with Triton X-100 (TX100), on the apparent Henry's constants (Hc) of toluene at temperatures ranging from 25 degrees C to 40 degrees C. The Hc values were significantly reduced in the presence of all three mixed surfactants at concentrations above their critical micelle concentrations (CMC). Mixed micellar partitioning, showing effects on the vapour-liquid equilibrium of toluene, was primarily responsible for the significant reduction of Hc in their mixed systems. The mixed surfactants CTMAB-TX100 had the greatest effect on Hc above the CMC, followed by SDS-TX405, then CTMAB-TBAB. Mixed systems of CTMAB-TX100 decreased Hc at concentrations significantly lower than the SDS-TX405 and CTMAB-TBAB concentrations, because of to the lower CMC of CTMAB-TX100. Vapour-liquid equilibrium data were also tested against the model (Hc = H/(1 + K(X - CMC)) that described the partitioning of VOCs in vapour-water-micelle phases. The correlation of Hc with mixed surfactant concentrations (X) and CMC can be utilized as an effective tool to predict the Hc by mixed surfactants. PMID:22988616

  14. Vapour-liquid equilibrium relationship between toluene and mixed surfactants.

    PubMed

    Tian, Senlin; Li, Yingjie; Mo, Hong; Ning, Ping

    2012-01-01

    Micellar partitioning of volatile organic compounds (VOCs) in surfactant solutions and its effects on vapour-liquid equilibrium is fundamental to the overall design and implementation ofsurfactant-enhanced remediation. Knowledge of the vapour-liquid equilibrium partitioning coefficients for VOCs, especially in contaminated soils and groundwater in which they exist, is required. Headspace experiments were performed to quantify the effect of three mixed surfactants, cetyltrimethyl ammonium bromide (CTMAB) with tetrabutylammonium bromide (TBAB), sodium dodecyl sulphate (SDS) with Triton X-405 (TX405), and CTMAB with Triton X-100 (TX100), on the apparent Henry's constants (Hc) of toluene at temperatures ranging from 25 degrees C to 40 degrees C. The Hc values were significantly reduced in the presence of all three mixed surfactants at concentrations above their critical micelle concentrations (CMC). Mixed micellar partitioning, showing effects on the vapour-liquid equilibrium of toluene, was primarily responsible for the significant reduction of Hc in their mixed systems. The mixed surfactants CTMAB-TX100 had the greatest effect on Hc above the CMC, followed by SDS-TX405, then CTMAB-TBAB. Mixed systems of CTMAB-TX100 decreased Hc at concentrations significantly lower than the SDS-TX405 and CTMAB-TBAB concentrations, because of to the lower CMC of CTMAB-TX100. Vapour-liquid equilibrium data were also tested against the model (Hc = H/(1 + K(X - CMC)) that described the partitioning of VOCs in vapour-water-micelle phases. The correlation of Hc with mixed surfactant concentrations (X) and CMC can be utilized as an effective tool to predict the Hc by mixed surfactants.

  15. Chemical speciation of PM emissions from heavy-duty diesel vehicles equipped with diesel particulate filter (DPF) and selective catalytic reduction (SCR) retrofits

    NASA Astrophysics Data System (ADS)

    Biswas, Subhasis; Verma, Vishal; Schauer, James J.; Sioutas, Constantinos

    Four heavy-duty diesel vehicles (HDDVs) in six retrofitted configurations (CRT ®, V-SCRT ®, Z-SCRT ®, Horizon, DPX and CCRT ®) and a baseline vehicle operating without after--treatment were tested under cruise (50 mph), transient UDDS and idle driving modes. As a continuation of the work by Biswas et al. [Biswas, S., Hu, S., Verma, V., Herner, J., Robertson, W.J., Ayala, A., Sioutas, C., 2008. Physical properties of particulate matter (PM) from late model heavy-duty diesel vehicles operating with advanced emission control technologies. Atmospheric Environment 42, 5622-5634.] on particle physical parameters, this paper focuses on PM chemical characteristics (Total carbon [TC], Elemental carbon [EC], Organic Carbon [OC], ions and water-soluble organic carbon [WSOC]) for cruise and UDDS cycles only. Size-resolved PM collected by MOUDI-Nano-MOUDI was analyzed for TC, EC and OC and ions (such as sulfate, nitrate, ammonium, potassium, sodium and phosphate), while Teflon coated glass fiber filters from a high volume sampler were extracted to determine WSOC. The introduction of retrofits reduced PM mass emissions over 90% in cruise and 95% in UDDS. Similarly, significant reductions in the emission of major chemical constituents (TC, OC and EC) were achieved. Sulfate dominated PM composition in vehicle configurations (V-SCRT ®-UDDS, Z-SCRT ®-Cruise, CRT ® and DPX) with considerable nucleation mode and TC was predominant for configurations with less (Z-SCRT ®-UDDS) or insignificant (CCRT ®, Horizon) nucleation. The transient operation increases EC emissions, consistent with its higher accumulation PM mode content. In general, solubility of organic carbon is higher (average ˜5 times) for retrofitted vehicles than the baseline vehicle. The retrofitted vehicles with catalyzed filters (DPX, CCRT ®) had decreased OC solubility (WSOC/OC: 8-25%) unlike those with uncatalyzed filters (SCRT ®s, Horizon; WSOC/OC ˜ 60-100%). Ammonium was present predominantly in the

  16. Rich catalytic injection

    DOEpatents

    Veninger, Albert

    2008-12-30

    A gas turbine engine includes a compressor, a rich catalytic injector, a combustor, and a turbine. The rich catalytic injector includes a rich catalytic device, a mixing zone, and an injection assembly. The injection assembly provides an interface between the mixing zone and the combustor. The injection assembly can inject diffusion fuel into the combustor, provides flame aerodynamic stabilization in the combustor, and may include an ignition device.

  17. Chemical Waste Management, Inc. PO*WW*ER (trade name) evaporation-catalytic oxidation technology. Technology evalution report. Volume 2. Final report, June-October 1992

    SciTech Connect

    Not Available

    1993-11-01

    The PRC SITE Team conducted sampling and analysis for the SITE demonstration of the Chemical Waste Management, Inc. (CWM) PO*WW*ER process at the Lake Charles Treatment Center in Carlyss, Louisiana. Samples were collected on September 24, 25, 26, 28, 29, and 30, 1992. During the first three days of sampling, the PO*WW*ER process operated with natural (unspiked) feed waste. For the last three days of sampling, the feed waste was spiked with sulfate salts of cadmium, copper, nickel, iron and mercury, and with phenol, toluene, tetrachloroethene, and methylene chloride. This report presents results and quality assurance/quality control (QA/QC) data for samples analyzed by Engineering-Science, Inc., along with vent gas emission rate and volumetric concentration results calculated from Ross analytical data. Analytical results are presented in Section 2.0. QA/QC results are presented in Section 3.0. Re-extraction and reanalysis results for brine samples are presented and discussed in Section 4.0. Appendix A contains chain of custody forms associated with the samples, and Appendix B contains a key to sample identification.

  18. Two stage catalytic combustor

    NASA Technical Reports Server (NTRS)

    Alvin, Mary Anne (Inventor); Bachovchin, Dennis (Inventor); Smeltzer, Eugene E. (Inventor); Lippert, Thomas E. (Inventor); Bruck, Gerald J. (Inventor)

    2010-01-01

    A catalytic combustor (14) includes a first catalytic stage (30), a second catalytic stage (40), and an oxidation completion stage (49). The first catalytic stage receives an oxidizer (e.g., 20) and a fuel (26) and discharges a partially oxidized fuel/oxidizer mixture (36). The second catalytic stage receives the partially oxidized fuel/oxidizer mixture and further oxidizes the mixture. The second catalytic stage may include a passageway (47) for conducting a bypass portion (46) of the mixture past a catalyst (e.g., 41) disposed therein. The second catalytic stage may have an outlet temperature elevated sufficiently to complete oxidation of the mixture without using a separate ignition source. The oxidation completion stage is disposed downstream of the second catalytic stage and may recombine the bypass portion with a catalyst exposed portion (48) of the mixture and complete oxidation of the mixture. The second catalytic stage may also include a reticulated foam support (50), a honeycomb support, a tube support or a plate support.

  19. Resolution and Characterization of Chemical Steps in Enzyme Catalytic Sequences by Using Low-Temperature and Time-Resolved, Full-Spectrum EPR Spectroscopy in Fluid Cryosolvent and Frozen Solution Systems.

    PubMed

    Wang, Miao; Zhu, Chen; Kohne, Meghan; Warncke, Kurt

    2015-01-01

    Approaches to the resolution and characterization of individual chemical steps in enzyme catalytic sequences, by using temperatures in the cryogenic range of 190-250 K, and kinetics measured by time-resolved, full-spectrum electron paramagnetic resonance spectroscopy in fluid cryosolvent and frozen solution systems, are described. The preparation and performance of the adenosylcobalamin-dependent ethanolamine ammonia-lyase enzyme from Salmonella typhimurium in the two systems exemplifies the biochemical and spectroscopic methods. General advantages of low-temperature studies are (1) slowing of reaction steps, so that measurements can be made by using straightforward T-step kinetic methods and commercial instrumentation, (2) resolution of individual reaction steps, so that first-order kinetic analysis can be applied, and (3) accumulation of intermediates that are not detectable at room temperatures. The broad temperature range from room temperature to 190 K encompasses three regimes: (1) temperature-independent mean free energy surface (corresponding to native behavior); (2) the narrow temperature region of a glass-like transition in the protein, over which the free energy surface changes, revealing dependence of the native reaction on collective protein/solvent motions; and (3) the temperature range below the glass transition region, for which persistent reaction corresponds to nonnative, alternative reaction pathways, in the vicinity of the native configurational envelope. Representative outcomes of low-temperature kinetics studies are portrayed on Eyring and free energy surface (landscape) plots, and guidelines for interpretations are presented.

  20. Chemical-physical properties of spinel CoMn2O4 nano-powders and catalytic activity in the 2-propanol and toluene combustion: Effect of the preparation method.

    PubMed

    Hosseini, Seyed Ali; Salari, Dariush; Niaei, Aligholi; Deganello, Francesca; Pantaleo, Giuseppe; Hojati, Pejman

    2011-01-01

    Spinel-type CoMn(2)O(4)nano-powders are prepared using sol-gel auto combustion (SGC) and co-precipitation (CP) methods and their catalytic activities are evaluated in combustion of 2-propanol and toluene. The chemical-physical properties of the oxides are characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), N(2)-adsorption-desorption, temperature programmed reduction (TPR) and scanning electron microscopy (SEM). After calcination at 700°C, CoMn(2)O(4)-SGC shows higher amounts of the normal-type spinel phase and is more crystalline than CoMn(2)O(4)-CP. Higher calcination temperatures (850°C) do not affect very much the weight percentage of the normal-type spinel phase; although the crystal size slightly increased. The TPR analysis evidences a large number of Mn(3+) cations in CoMn(2)O(4)-SGC compared to CoMn(2)O(4)-CP. This difference, together with the higher surface area, could justify the higher activity of CoMn(2)O(4)-SGC in both the investigated reactions.

  1. Role of chemical composition in the enhanced catalytic activity of Pt-based alloyed ultrathin nanowires for the hydrogen oxidation reaction under alkaline conditions

    DOE PAGES

    Megan E. Scofield; Wong, Stanislaus S.; Zhou, Yuchen; Yue, Shiyu; Wang, Lei; Su, Dong; Tong, Xiao; Vukmirovic, Miomir B.; Adzic, Radoslav R.

    2016-05-19

    With the increased interest in the development of hydrogen fuel cells as a plausible alternative to internal combustion engines, recent work has focused on creating alkaline fuel cells (AFC), which employ an alkaline environment. Working in alkaline as opposed to acidic media yields a number of tangible benefits, including (i) the ability to use cheaper and plentiful precious-metal-free catalysts, due to their increased stability, (ii) a reduction in the amount of degradation and corrosion of Pt-based catalysts, and (iii) a longer operational lifetime for the overall fuel cell configuration. However, in the absence of Pt, no catalyst has achieved activitiesmore » similar to those of Pt. Herein, we have synthesized a number of crystalline ultrathin PtM alloy nanowires (NWs) (M = Fe, Co, Ru, Cu, Au) in order to replace a portion of the costly Pt metal without compromising on activity while simultaneously adding in metals known to exhibit favorable synergistic ligand and strain effects with respect to the host lattice. In fact, our experiments confirm theoretical insights about a clear and correlative dependence between measured activity and chemical composition. We have conclusively demonstrated that our as-synthesized alloy NW catalysts yield improved hydrogen oxidation reaction (HOR) activities as compared with a commercial Pt standard as well as with our as-synthesized Pt NWs. The Pt7Ru3 NW system, in particular, quantitatively achieved an exchange current density of 0.493 mA/cm2, which is higher than the corresponding data for Pt NWs alone. In addition, the HOR activities follow the same expected trend as their calculated hydrogen binding energy (HBE) values, thereby confirming the critical importance and correlation of HBE with the observed activities.« less

  2. Catalytic Membrane Sensors

    SciTech Connect

    Boyle, T.J.; Brinker, C.J.; Gardner, T.J.; Hughes, R.C.; Sault, A.G.

    1998-12-01

    The proposed "catalytic membrane sensor" (CMS) was developed to generate a device which would selectively identify a specific reagent in a complex mixture of gases. This was to be accomplished by modifying an existing Hz sensor with a series of thin films. Through selectively sieving the desired component from a complex mixture and identifying it by decomposing it into Hz (and other by-products), a Hz sensor could then be used to detect the presence of the select component. The proposed "sandwich-type" modifications involved the deposition of a catalyst layered between two size selective sol-gel layers on a Pd/Ni resistive Hz sensor. The role of the catalyst was to convert organic materials to Hz and organic by-products. The role of the membraneo was to impart both chemical specificity by molecukir sieving of the analyte and converted product streams, as well as controlling access to the underlying Pd/Ni sensor. Ultimately, an array of these CMS elements encompassing different catalysts and membranes were to be developed which would enable improved selectivity and specificity from a compiex mixture of organic gases via pattern recognition methodologies. We have successfully generated a CMS device by a series of spin-coat deposited methods; however, it was determined that the high temperature required to activate the catalyst, destroys the sensor.

  3. Analysis of petrol and diesel vapour and vehicle engine exhaust gases using selected ion flow tube mass spectrometry.

    PubMed

    Smith, David; Cheng, Ping; Spanel, Patrik

    2002-01-01

    We have used selected ion flow tube mass spectrometry (SIFT-MS) to analyse the vapours emitted by petrol and diesel fuels and the exhaust gases from petrol (spark ignition) and diesel (compression ignition) engine vehicles fitted with catalytic converters. Only those components of these media that have significant vapour pressures at ambient temperatures were analysed and thus particulates were obviously not detected. These media have been analysed using the full scope of SIFT-MS, i.e., with the three available precursor ions H3O+, NO+ and O2+. The combination of the H3O+ and NO+ analyses is seen to be essential to distinguish between different product ions at the same mass-to-charge ratio (m/z) especially in identifying aldehydes in the exhaust gases. The O2+ precursor ions are used to detect and quantify the large amount of nitric oxide present in the exhaust gases from both engine types. The petrol and diesel vapours consist almost exclusively of aliphatic alkanes, alkenes and alkynes (and dienes) and aromatic hydrocarbons. Some of these compounds appear in the exhaust gases together with several aldehydes, viz. formaldehyde, acetaldehyde, pentanal, pentenal (acrolein), butenal, and also methanol and ethanol. Acetone, nitric oxide and ammonia are also present, acetone and nitric oxide being much more abundant in the diesel exhaust gas than in the petrol exhaust gas. These data were obtained from samples collected into pre-evacuated stainless steel vessels. Trapping of the volatile compounds from the gas samples is not required and analysis was completed a few minutes later. All the above compounds are detected simultaneously, which demonstrates the value of SIFT-MS in this area of research.

  4. Modeling a Transient Catalytic Combustor

    NASA Technical Reports Server (NTRS)

    Tien, J. S.

    1985-01-01

    Transient model of monolith catalytic combustor presented in report done under NASA/DOE contract. Model assumes quasi-steady gas phase and thermally "thin" solid. In gas-phase treatment, several quasi-global chemical reactions assumed capable of describing CO and unburnt hydrocarbon emissions in fuel-lean operations. In steady-state computation presented, influence of selected operating and design parameters on minimum combustor length studied. When fast transient responses required, both steady and unsteady studies made to achieve meaningful compromise in design.

  5. Molecular catalytic coal liquid conversion

    SciTech Connect

    Stock, L.M.; Yang, Shiyong

    1995-12-31

    This research, which is relevant to the development of new catalytic systems for the improvement of the quality of coal liquids by the addition of dihydrogen, is divided into two tasks. Task 1 centers on the activation of dihydrogen by molecular basic reagents such as hydroxide ion to convert it into a reactive adduct (OH{center_dot}H{sub 2}){sup {minus}} that can reduce organic molecules. Such species should be robust withstanding severe conditions and chemical poisons. Task 2 is focused on an entirely different approach that exploits molecular catalysts, derived from organometallic compounds that are capable of reducing monocyclic aromatic compounds under very mild conditions. Accomplishments and conclusions are discussed.

  6. Catalytic membranes for fuel cells

    DOEpatents

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2011-04-19

    A fuel cell of the present invention comprises a cathode and an anode, one or both of the anode and the cathode including a catalyst comprising a bundle of longitudinally aligned graphitic carbon nanotubes including a catalytically active transition metal incorporated longitudinally and atomically distributed throughout the graphitic carbon walls of said nanotubes. The nanotubes also include nitrogen atoms and/or ions chemically bonded to the graphitic carbon and to the transition metal. Preferably, the transition metal comprises at least one metal selected from the group consisting of Fe, Co, Ni, Mn, and Cr.

  7. Catalytic distillation structure

    DOEpatents

    Smith, Jr., Lawrence A.

    1984-01-01

    Catalytic distillation structure for use in reaction distillation columns, a providing reaction sites and distillation structure and consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and being present with the catalyst component in an amount such that the catalytic distillation structure consist of at least 10 volume % open space.

  8. Removal of vapour phase PCDD/Fs in electric arc furnace steelmaking emissions by sorption using plastics.

    PubMed

    Ooi, Tze Chean; Ewan, Bruce C R; Cliffe, Keith R; Anderson, David R; Fisher, Raymond; Thompson, Dennis

    2008-08-01

    Plastics are potentially suitable for the removal of vapour phase PCDD/Fs in emissions from the electric arc furnace (EAF) steelmaking process. Three different commercial plastics, i.e. polypropylene BE170MO (Borealis A/S, Denmark), polypropylene in the form of 5 mm spheres (The Precision Plastic Ball Co. Ltd., UK) and polyethylene LD605BA (ExxonMobil Chemical, Belgium), have been studied using a novel experimental apparatus for the removal of vapour phase PCDD/Fs. Polypropylene BE170MO was identified to be the most suitable product amongst the three plastics in terms of PCDD/F sorption and potential industrial application. The optimum temperature for PCDD/F sorption on polypropylene BE170MO was below 90 degrees C for a removal efficiency of >99% at an average vapour phase PCDD/F concentration of 3.5 ng I-TEQ/Nm(3). At 130 degrees C, 53% of the PCDD/Fs trapped on polypropylene BE170MO were desorbed.

  9. Mapping of tritium emissions using absorption vapour samplers.

    PubMed

    Vodila, Gergely; Molnár, Mihály; Veres, Mihály; Svingor, Eva; Futó, István; Barnabás, István; Kapitány, Sándor

    2009-02-01

    Püspökszilágy Radioactive Waste Treatment and Disposal Facility (RWTDF) is a typical near-surface engineered repository designated to store low- and intermediate-level wastes from various institutes, research facilities and hospitals in Hungary. Two automatic combined (14)C-tritium sampling units installed at the facility sample the air 2 m above surface. The one installed near the vaults detects tritium (T) activities two orders of magnitude higher than the far reference sampling unit. To localize the T emissions, 19 small absorption vapour samplers filled with silica gel were settled onto the ground surface. After the saturation of the silica gel, the water was recovered and its T concentration was measured with a low-background liquid scintillation counter. The absorption vapour samplers are cheap, simple and easy-to-use. We present the samplers and the T distribution map constructed from the data, which helps to localize the T emission. PMID:19027205

  10. Structural insights into the recovery of aldolase activity in N-acetylneuraminic acid lyase by replacement of the catalytically active lysine with γ-thialysine by using a chemical mutagenesis strategy.

    PubMed

    Timms, Nicole; Windle, Claire L; Polyakova, Anna; Ault, James R; Trinh, Chi H; Pearson, Arwen R; Nelson, Adam; Berry, Alan

    2013-03-01

    Chemical modification has been used to introduce the unnatural amino acid γ-thialysine in place of the catalytically important Lys165 in the enzyme N-acetylneuraminic acid lyase (NAL). The Staphylococcus aureus nanA gene, encoding NAL, was cloned and expressed in E. coli. The protein, purified in high yield, has all the properties expected of a class I NAL. The S. aureus NAL which contains no natural cysteine residues was subjected to site-directed mutagenesis to introduce a cysteine in place of Lys165 in the enzyme active site. Subsequently chemical mutagenesis completely converted the cysteine into γ-thialysine through dehydroalanine (Dha) as demonstrated by ESI-MS. Initial kinetic characterisation showed that the protein containing γ-thialysine regained 17 % of the wild-type activity. To understand the reason for this lower activity, we solved X-ray crystal structures of the wild-type S. aureus NAL, both in the absence of, and in complex with, pyruvate. We also report the structures of the K165C variant, and the K165-γ-thialysine enzyme in the presence, or absence, of pyruvate. These structures reveal that γ-thialysine in NAL is an excellent structural mimic of lysine. Measurement of the pH-activity profile of the thialysine modified enzyme revealed that its pH optimum is shifted from 7.4 to 6.8. At its optimum pH, the thialysine-containing enzyme showed almost 30 % of the activity of the wild-type enzyme at its pH optimum. The lowered activity and altered pH profile of the unnatural amino acid-containing enzyme can be rationalised by imbalances of the ionisation states of residues within the active site when the pK(a) of the residue at position 165 is perturbed by replacement with γ-thialysine. The results reveal the utility of chemical mutagenesis for the modification of enzyme active sites and the exquisite sensitivity of catalysis to the local structural and electrostatic environment in NAL.

  11. Leidenfrost point and estimate of the vapour layer thickness

    NASA Astrophysics Data System (ADS)

    Gianino, Concetto

    2008-11-01

    In this article I describe an experiment involving the Leidenfrost phenomenon, which is the long lifetime of a water drop when it is deposited on a metal that is much hotter than the boiling point of water. The experiment was carried out with high-school students. The Leidenfrost point is measured and the heat laws are used to estimate the thickness of the vapour layer, d≈0.06 mm, which prevents the drop from touching the hotplate.

  12. Infrared Laser Optoacoustic Detection Of Gases And Vapours

    NASA Astrophysics Data System (ADS)

    Johnson, S. A.; Cummins, P. G.; Bone, S. A.; Davies, P. B.

    1988-10-01

    Mid-infrared laser optoacoustic spectroscopy has been used to detect a variety of gases and vapours. Performance was calibrated using the signal from a known concentration of ethene, and then the method applied to the perfume alcohol geraniol. Detection limits were found to be 1 ppb for ethene and 70 ppb for geraniol on their strongest absorption lines for a few seconds measurement time.

  13. Land cover change and water vapour flows: learning from Australia.

    PubMed Central

    Gordon, Line; Dunlop, Michael; Foran, Barney

    2003-01-01

    Australia is faced with large-scale dryland salinization problems, largely as a consequence of the clearing of native vegetation for cropland and grassland. We estimate the change in continental water vapour flow (evapotranspiration) of Australia during the past 200 years. During this period there has been a substantial decrease in woody vegetation and a corresponding increase in croplands and grasslands. The shift in land use has caused a ca. 10% decrease in water vapour flows from the continent. This reduction corresponds to an annual freshwater flow of almost 340 km(3). The society-induced alteration of freshwater flows is estimated at more than 15 times the volume of run-off freshwater that is diverted and actively managed in the Australian society. These substantial water vapour flow alterations were previously not addressed in water management but are now causing serious impacts on the Australian society and local economies. Global and continental freshwater assessments and policy often neglects the interplay between freshwater flows and landscape dynamics. Freshwater issues on both regional and global levels must be rethought and the interplay between terrestrial ecosystems and freshwater better incorporated in freshwater and ecosystem management. PMID:14728792

  14. Structure and properties of molecular and ionic clusters in vapour over caesium fluoride

    NASA Astrophysics Data System (ADS)

    Mwanga, Stanley F.; Pogrebnaya, Tatiana P.; Pogrebnoi, Alexander M.

    2015-06-01

    The properties of neutral molecules Cs2F2, Cs3F3, and Cs4F4, and positive and negative cluster ions Cs2F+, CsF2-, Cs3F2+, Cs2F3-, Cs4F3+, and Cs5F4+ were studied by several of quantum chemical methods implementing density function theory and Möller-Plesset perturbation theory of second and fourth orders. For all species, the equilibrium geometrical structure and vibrational spectra were determined. Different isomers have been revealed for the trimer neutral molecule Cs3F3; pentaatomic, both positive and negative, Cs3F2+, Cs2F3-; and heptaatomic Cs4F3+ ions. The most abundant isomers in the saturated vapour were determined. Enthalpies of dissociation reactions and enthalpies of formation of the species were obtained.

  15. Ionizable Side Chains at Catalytic Active Sites of Enzymes

    PubMed Central

    Jimenez-Morales, David; Liang, Jie

    2012-01-01

    Catalytic active sites of enzymes of known structure can be well defined by a modern program of computational geometry. The CASTp program was used to define and measure the volume of the catalytic active sites of 573 enzymes in the Catalytic Site Atlas database. The active sites are identified as catalytic because the amino acids they contain are known to participate in the chemical reaction catalyzed by the enzyme. Acid and base side chains are reliable markers of catalytic active sites. The catalytic active sites have 4 acid and 5 base side chains, in an average volume of 1072 Å3. The number density of acid side chains is 8.3 M (in chemical units); the number density of basic side chains is 10.6 M. The catalytic active site of these enzymes is an unusual electrostatic and steric environment in which side chains and reactants are crowded together in a mixture more like an ionic liquid than an ideal infinitely dilute solution. The electrostatics and crowding of reactants and side chains seems likely to be important for catalytic function. In three types of analogous ion channels, simulation of crowded charges accounts for the main properties of selectivity measured in a wide range of solutions and concentrations. It seems wise to use mathematics designed to study interacting complex fluids when making models of the catalytic active sites of enzymes. PMID:22484856

  16. Catalytic bioscavengers in nerve agent poisoning: A promising approach?

    PubMed

    Worek, Franz; Thiermann, Horst; Wille, Timo

    2016-02-26

    The repeated use of the nerve agent sarin against civilians in Syria in 2013 emphasizes the continuing threat by chemical warfare agents. Multiple studies demonstrated a limited efficacy of standard atropine-oxime treatment in nerve agent poisoning and called for the development of alternative and more effective treatment strategies. A novel approach is the use of stoichiometric or catalytic bioscavengers for detoxification of nerve agents in the systemic circulation prior to distribution into target tissues. Recent progress in the design of enzyme mutants with reversed stereo selectivity resulting in improved catalytic activity and their use in in vivo studies supports the concept of catalytic bioscavengers. Yet, further research is necessary to improve the catalytic activity, substrate spectrum and in vivo biological stability of enzyme mutants. The pros and cons of catalytic bioscavengers will be discussed in detail and future requirements for the development of catalytic bioscavengers will be proposed.

  17. Controlled synthesis of porous platinum nanostructures for catalytic applications.

    PubMed

    Cao, Yanqin; Zhang, Junwei; Yang, Yong; Huang, Zhengren; Long, Nguyen Viet; Nogami, Masayuki

    2014-02-01

    Porous platinum, that has outstanding catalytic and electrical properties and superior resistant characteristics to corrosion, has been widely applied in chemical, petrochemical, pharmaceutical, electronic, and automotive industries. As the catalytic activity and selectivity depend on the size, shape and structure of nanomaterials, the strategies for controlling these factors of platinum nanomaterials to get excellent catalytic properties are discussed. Here, recent advances in the design and preparation of various porous platinum nanostructures are reviewed, including wet-chemical synthesis, electro-deposition, galvanic replacement reaction and de-alloying technology. The applications of various platinum nanostructures are also discussed, especially in fuel cells. PMID:24749422

  18. Influence of water and water vapour on the characteristics of KI treated HgI 2 detectors

    NASA Astrophysics Data System (ADS)

    Ponpon, J. P.; Amann, M.; Sieskind, M.

    After being cleaned using a potassium iodide solution in water followed by a water rinse, the surface of mercuric iodide is covered by a chemical complex identified as being KHgI 3·H 2O. This compound can adsorb large quantities of water and its electrical properties are strongly sensitive to water and water vapour. The consequences on the manufacturing and storing conditions (especially the relative humidity), of mercuric iodide-based devices are therefore of great concern. They are illustrated by the study of the electrical and spectrometric properties of HgI 2 nuclear radiation detectors.

  19. Evolution of catalytic function

    NASA Technical Reports Server (NTRS)

    Joyce, G. F.

    1993-01-01

    An RNA-based evolution system was constructed in the laboratory and used to develop RNA enzymes with novel catalytic function. By controlling the nature of the catalytic task that the molecules must perform in order to survive, it is possible to direct the evolving population toward the expression of some desired catalytic behavior. More recently, this system has been coupled to an in vitro translation procedure, raising the possibility of evolving protein enzymes in the laboratory to produce novel proteins with desired catalytic properties. The aim of this line of research is to reduce darwinian evolution, the fundamental process of biology, to a laboratory procedure that can be made to operate in the service of organic synthesis.

  20. Catalytic distillation structure

    DOEpatents

    Smith, L.A. Jr.

    1984-04-17

    Catalytic distillation structure is described for use in reaction distillation columns, and provides reaction sites and distillation structure consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and is present with the catalyst component in an amount such that the catalytic distillation structure consists of at least 10 volume % open space. 10 figs.

  1. Clean catalytic combustor program

    NASA Technical Reports Server (NTRS)

    Ekstedt, E. E.; Lyon, T. F.; Sabla, P. E.; Dodds, W. J.

    1983-01-01

    A combustor program was conducted to evolve and to identify the technology needed for, and to establish the credibility of, using combustors with catalytic reactors in modern high-pressure-ratio aircraft turbine engines. Two selected catalytic combustor concepts were designed, fabricated, and evaluated. The combustors were sized for use in the NASA/General Electric Energy Efficient Engine (E3). One of the combustor designs was a basic parallel-staged double-annular combustor. The second design was also a parallel-staged combustor but employed reverse flow cannular catalytic reactors. Subcomponent tests of fuel injection systems and of catalytic reactors for use in the combustion system were also conducted. Very low-level pollutant emissions and excellent combustor performance were achieved. However, it was obvious from these tests that extensive development of fuel/air preparation systems and considerable advancement in the steady-state operating temperature capability of catalytic reactor materials will be required prior to the consideration of catalytic combustion systems for use in high-pressure-ratio aircraft turbine engines.

  2. A Study of a QCM Sensor Based on TiO2 Nanostructures for the Detection of NO2 and Explosives Vapours in Air

    PubMed Central

    Procek, Marcin; Stolarczyk, Agnieszka; Pustelny, Tadeusz; Maciak, Erwin

    2015-01-01

    The paper deals with investigations concerning the construction of sensors based on a quartz crystal microbalance (QCM) containing a TiO2 nanostructures sensor layer. A chemical method of synthesizing these nanostructures is presented. The prepared prototype of the QCM sensing system, as well as the results of tests for detecting low NO2 concentrations in an atmosphere of synthetic air have been described. The constructed NO2 sensors operate at room temperature, which is a great advantage, because resistance sensors based on wide gap semiconductors often require much higher operation temperatures, sometimes as high as 500 °C. The sensors constructed by the authors can be used, among other applications, in medical and chemical diagnostics, and also for the purpose of detecting explosive vapours. Reactions of the sensor to nitroglycerine vapours are presented as an example of its application. The influence of humidity on the operation of the sensor was studied. PMID:25912352

  3. Experimental study of multipass copper vapour laser amplifiers

    SciTech Connect

    Karpukhin, Vyacheslav T; Malikov, Mikhail M

    2008-12-31

    Repetitively pulsed multipass copper vapour amplifiers are studied experimentally. A considerable increase in the peak power of laser pulses was achieved by using a special scheme of the amplifier. It is found that the main reasons preventing an increase in the peak power during many passages of the beam are the competitive development of lasing from spontaneous seeds in a parasitic resonator formed by the fold mirrors of a multipass amplifier, a decrease in the amplification during the last passages, and an increase in the pulse width at the amplifier output. (lasers. amplifiers)

  4. A diamond-windowed IR-cell for inorganic vapours

    NASA Astrophysics Data System (ADS)

    Rytter, E.; Hvistendahl, J.; Tomita, T.

    An evacuable cell system which can be used for recording infrared spectra of corrosive vapours has been developed. The cell body is made of gold-plated nickel, and sealing of the diamond windows is performed with gold O-rings. The excellent transmittance of type IIa diamond makes it possible to scan the far infrared region below 1500 cm -1. Furthermore, isothermal conditions can be maintained up to approximately 600°C before the windows turn opaque. Use of minor exchangeable parts gives the opportunity of both transmission and emission spectroscopy.

  5. Plasma formation in water vapour layers in high conductivity liquids

    NASA Astrophysics Data System (ADS)

    Kelsey, C. P.; Schaper, L.; Stalder, K. R.; Graham, W. G.

    2011-10-01

    The vapour layer development stage of relatively low voltage plasmas in conducting solutions has already been well explored. The nature of the discharges formed within the vapour layer however is still largely unexplored. Here we examine the nature of such discharges through a combination of fast imaging and spatially, temporally resolved spectroscopy and electrical characterisation. The experimental setup used is a pin-to-plate discharge configuration with a -350V, 200 μs pulse applied at a repetition rate of 2Hz. A lens, followed by beam splitter allows beams to one Andor ICCD camera to capture images of the plasma emission with a second camera at the exit of a high resolution spectrometer. Through synchronization of the camera images at specified times after plasma ignition (as determined from current-voltage characteristics) they can be correlated with the spectra features. Initial measurements reveal two apparently different plasma formations. Stark broadening of the hydrogen Balmer beta line indicate electron densities of 3 to 5 ×1020 m-3 for plasmas produced early in the voltage pulse and an order of magnitude less for the later plasmas. The vapour layer development stage of relatively low voltage plasmas in conducting solutions has already been well explored. The nature of the discharges formed within the vapour layer however is still largely unexplored. Here we examine the nature of such discharges through a combination of fast imaging and spatially, temporally resolved spectroscopy and electrical characterisation. The experimental setup used is a pin-to-plate discharge configuration with a -350V, 200 μs pulse applied at a repetition rate of 2Hz. A lens, followed by beam splitter allows beams to one Andor ICCD camera to capture images of the plasma emission with a second camera at the exit of a high resolution spectrometer. Through synchronization of the camera images at specified times after plasma ignition (as determined from current

  6. Combined Dial Sounding of Ozone, Water Vapour and Aerosol

    NASA Astrophysics Data System (ADS)

    Trickl, Thomas; Vogelmann, Hannes

    2016-06-01

    Routine high-quality lidar measurements of ozone, water vapour and aerosol at Garmisch-Partenkirchen since 2007 have made possible more comprehensive atmospheric studies and lead to a growing insight concerning the most frequently occurring long-range transport pathways. In this contribution we present as examples results on stratospheric layers travelling in the free troposphere for extended periods of time without eroding. In particular, we present a case of an intrusion layer that subsided over as many as fifteen days and survived the interference by strong Canadian fires. These results impose a challenge on atmospheric modelling that grossly overestimates free-tropospheric mixing.

  7. The Seasonal Cycle of Water Vapour on Mars from Assimilation of Thermal Emission Spectrometer Data

    NASA Technical Reports Server (NTRS)

    Steele, Liam J.; Lewis, Stephen R.; Patel, Manish R.; Montmessin, Franck; Forget, Francois; Smith, Michael D.

    2014-01-01

    We present for the first time an assimilation of Thermal Emission Spectrometer (TES) water vapour column data into a Mars global climate model (MGCM). We discuss the seasonal cycle of water vapour, the processes responsible for the observed water vapour distribution, and the cross-hemispheric water transport. The assimilation scheme is shown to be robust in producing consistent reanalyses, and the global water vapour column error is reduced to around 2-4 pr micron depending on season. Wave activity is shown to play an important role in the water vapour distribution, with topographically steered flows around the Hellas and Argyre basins acting to increase transport in these regions in all seasons. At high northern latitudes, zonal wavenumber 1 and 2 stationary waves during northern summer are responsible for spreading the sublimed water vapour away from the pole. Transport by the zonal wavenumber 2 waves occurs primarily to the west of Tharsis and Arabia Terra and, combined with the effects of western boundary currents, this leads to peak water vapour column abundances here as observed by numerous spacecraft. A net transport of water to the northern hemisphere over the course of one Mars year is calculated, primarily because of the large northwards flux of water vapour which occurs during the local dust storm around L(sub S) = 240-260deg. Finally, outlying frost deposits that surround the north polar cap are shown to be important in creating the peak water vapour column abundances observed during northern summer.

  8. Evidence for a link between global lightning activity and upper tropospheric water vapour

    PubMed

    Price

    2000-07-20

    Tropospheric water vapour is a key element of the Earth's climate, which has direct effects as a greenhouse gas, as well as indirect effects through interaction with clouds, aerosols and tropospheric chemistry. Small changes in upper-tropospheric water vapour have a much larger impact on the greenhouse effect than small changes in water vapour in the lower atmosphere, but whether this impact is a positive or negative feedback remains uncertain. The main challenge in addressing this question is the difficulty in monitoring upper-tropospheric water vapour globally over long timescales. Here I show that upper-tropospheric water-vapour variability and global lightning activity are closely linked, suggesting that upper-tropospheric water-vapour changes can be inferred from records of global lightning activity, readily obtained from observations at a single location on the Earth's surface. This correlation reflects the fact that continental deep-convective thunderstorms transport large amounts of water vapour into the upper troposphere and thereby dominate the variations of global upper-tropospheric water vapour while producing most of the lightning on Earth. As global lightning induces Schumann resonances, an electromagnetic phenomenon in the atmosphere that can be observed easily at low cost, monitoring of these resonances might provide a convenient method for tracking upper-tropospheric water-vapour variability and hence contribute to a better understanding of the processes affecting climate change.

  9. Catalytic combustion over hexaaluminates

    SciTech Connect

    Ramesh, K.S.; Kingsley, J.J.; Hubler, T.L.; McCready, D.E.; Cox, J.L.

    1997-12-31

    Combustion is the oldest and most extensively used process for the production of light, heat, and energy utilization. Mankind has sought to control combustion since prehistoric times to more effectively utilize the combustible material, control the products of combustion, and harness the energy released during combustion. Catalysts provide the means to control the reactions of combustion beyond what can be achieved in the homogeneous gas phase (1). Catalysts also enable operation outside the range of flammability limits and control atmospheric pollutants of combustion, mainly NO{sub x}, carbon monoxide, and particles of incomplete combustion (soot). The major technical difficulty that has hindered widespread application of catalytic combustion devices is their poor performance, particularly durability of their ceramic substrates and catalytically active phases in the high temperature environment. Catalytic combustion of hydrocarbons over metals and metal oxide catalysts has been explored extensively. Recent reviews of materials for high temperature catalytic combustion have been provided by Marcus et al. (2) and Trim (3). Hexaaluminates which show good thermal stability above 1200{degrees}C are one class of metal oxides receiving consideration for application in high temperature combustion devices. Matsuda et al. (4) have developed thermally stable La-hexaaluminates with the same layer structure as Ba-hexaaluminate and have investigated their catalytic application. Machida et al. (5-7) have investigated the catalytic properties of a number of hexaaluminates of BaMAl{sub 11}O{sub 19-{alpha}}(M=Cr, Mn,Fe,Co,Ni). Here we report the synthesis, properties and catalytic combustion of some new hexaaluminates.

  10. Parameters of immunity acute phase reaction in men in relation to exposure duration to mercury vapours.

    PubMed

    Moszczynski, P; Moszczynski, P; Słowinski, S; Bem, S; Bartus, R

    1991-01-01

    The study was carried out in 89 men aged 21 to 57 years with a history of exposure to mercury vapour from 2 to 26 years during occupational work involving chlorine production by the method of mercury electrolysis. The workers were divided into three groups depending on the duration of occupational exposure: 1) 32 workers with a short history of exposure 2-10 years, 2) 37 workers with medium-long exposure - 11-20 years, and 3) 20 workers with a history of long exposure - 21-26 years. The urinary concentrations of mercury in these individuals was 73 +/- 60 microliters x 1(-1), and in blood this concentration was not exceeding 50 microliters x 1(-1). The control group comprised 40 men aged 17 to 52 years. They had not had any occupational exposure to chemicals, or harmful physical factors. On the basis of clinical, haematological and biochemical studies 89 workers with occupational exposure to mercury vapour were regarded as clinically healthy. None of them had any symptoms and signs of the complete neurasthenic syndrome or organic brain injury. Increased nervous excitability was the complaint of 24 workers, 9 had headaches, sleep disturbances were reported by 5, and a feeling of tiredness and apathy was mentioned by 5 men. EEG recording demonstrated 81 normal tracings, and moderately pathological records in 8 men. The parameters of immunity and proteins acute phase reaction were determined, measuring the concentration of immunoglobulins, lysozyme, C3c, C4, alpha 1-acid glycoprotein, haptoglobin and ceruloplasmin in serum. A lower level of IgA, IgG and lysozyme was only noted in individuals with occupational exposure exceeding 20 years.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:1725175

  11. Parameters of immunity acute phase reaction in men in relation to exposure duration to mercury vapours.

    PubMed

    Moszczynski, P; Moszczynski, P; Słowinski, S; Bem, S; Bartus, R

    1991-01-01

    The study was carried out in 89 men aged 21 to 57 years with a history of exposure to mercury vapour from 2 to 26 years during occupational work involving chlorine production by the method of mercury electrolysis. The workers were divided into three groups depending on the duration of occupational exposure: 1) 32 workers with a short history of exposure 2-10 years, 2) 37 workers with medium-long exposure - 11-20 years, and 3) 20 workers with a history of long exposure - 21-26 years. The urinary concentrations of mercury in these individuals was 73 +/- 60 microliters x 1(-1), and in blood this concentration was not exceeding 50 microliters x 1(-1). The control group comprised 40 men aged 17 to 52 years. They had not had any occupational exposure to chemicals, or harmful physical factors. On the basis of clinical, haematological and biochemical studies 89 workers with occupational exposure to mercury vapour were regarded as clinically healthy. None of them had any symptoms and signs of the complete neurasthenic syndrome or organic brain injury. Increased nervous excitability was the complaint of 24 workers, 9 had headaches, sleep disturbances were reported by 5, and a feeling of tiredness and apathy was mentioned by 5 men. EEG recording demonstrated 81 normal tracings, and moderately pathological records in 8 men. The parameters of immunity and proteins acute phase reaction were determined, measuring the concentration of immunoglobulins, lysozyme, C3c, C4, alpha 1-acid glycoprotein, haptoglobin and ceruloplasmin in serum. A lower level of IgA, IgG and lysozyme was only noted in individuals with occupational exposure exceeding 20 years.(ABSTRACT TRUNCATED AT 250 WORDS)

  12. Performance characterization of a hydrogen catalytic heater.

    SciTech Connect

    Johnson, Terry Alan; Kanouff, Michael P.

    2010-04-01

    This report describes the performance of a high efficiency, compact heater that uses the catalytic oxidation of hydrogen to provide heat to the GM Hydrogen Storage Demonstration System. The heater was designed to transfer up to 30 kW of heat from the catalytic reaction to a circulating heat transfer fluid. The fluid then transfers the heat to one or more of the four hydrogen storage modules that make up the Demonstration System to drive off the chemically bound hydrogen. The heater consists of three main parts: (1) the reactor, (2) the gas heat recuperator, and (3) oil and gas flow distribution manifolds. The reactor and recuperator are integrated, compact, finned-plate heat exchangers to maximize heat transfer efficiency and minimize mass and volume. Detailed, three-dimensional, multi-physics computational models were used to design and optimize the system. At full power the heater was able to catalytically combust a 10% hydrogen/air mixture flowing at over 80 cubic feet per minute and transfer 30 kW of heat to a 30 gallon per minute flow of oil over a temperature range from 100 C to 220 C. The total efficiency of the catalytic heater, defined as the heat transferred to the oil divided by the inlet hydrogen chemical energy, was characterized and methods for improvement were investigated.

  13. Transient catalytic combustor model

    NASA Technical Reports Server (NTRS)

    Tien, J. S.

    1981-01-01

    A quasi-steady gas phase and thermally thin substrate model is used to analyze the transient behavior of catalytic monolith combustors in fuel lean operation. The combustor response delay is due to the substrate thermal inertia. Fast response is favored by thin substrate, short catalytic bed length, high combustor inlet and final temperatures, and small gas channel diameters. The calculated gas and substrate temperature time history at different axial positions provides an understanding of how the catalytic combustor responds to an upstream condition change. The computed results also suggest that the gas residence times in the catalytic bed in the after bed space are correlatable with the nondimensional combustor response time. The model also performs steady state combustion calculations; and the computed steady state emission characteristics show agreement with available experimental data in the range of parameters covered. A catalytic combustor design for automotive gas turbine engine which has reasonably fast response ( 1 second) and can satisfy the emission goals in an acceptable total combustor length is possible.

  14. Catalytic nanoporous membranes

    DOEpatents

    Pellin, Michael J; Hryn, John N; Elam, Jeffrey W

    2013-08-27

    A nanoporous catalytic membrane which displays several unique features Including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity. Also provided is a method for producing a catalytic membrane having flow-through pores and discreet catalytic clusters adhering to the inside surfaces of the pores.

  15. Catalytic coherence transformations

    NASA Astrophysics Data System (ADS)

    Bu, Kaifeng; Singh, Uttam; Wu, Junde

    2016-04-01

    Catalytic coherence transformations allow the otherwise impossible state transformations using only incoherent operations with the aid of an auxiliary system with finite coherence that is not being consumed in any way. Here we find the necessary and sufficient conditions for the deterministic and stochastic catalytic coherence transformations between a pair of pure quantum states. In particular, we show that the simultaneous decrease of a family of Rényi entropies of the diagonal parts of the states under consideration is a necessary and sufficient condition for the deterministic catalytic coherence transformations. Similarly, for stochastic catalytic coherence transformations we find the necessary and sufficient conditions for achieving a higher optimal probability of conversion. We thus completely characterize the coherence transformations among pure quantum states under incoherent operations. We give numerous examples to elaborate our results. We also explore the possibility of the same system acting as a catalyst for itself and find that indeed self-catalysis is possible. Further, for the cases where no catalytic coherence transformation is possible we provide entanglement-assisted coherence transformations and find the necessary and sufficient conditions for such transformations.

  16. Residual neurobehavioural effects associated with chronic exposure to mercury vapour.

    PubMed Central

    Kishi, R; Doi, R; Fukuchi, Y; Satoh, H; Satoh, T; Ono, A; Moriwaka, F; Tashiro, K; Takahata, N; Sasatani, H

    1994-01-01

    To find the residual effects of long term exposure to mercury vapour, neurobehavioural tests were given to ex-mercury miners about 18 years after the end of mercury exposure. Seventy six male ex-mercury miners who had been exposed to high concentrations of mercury vapour (over 1.0 mg/m3) and with a history of mercury intoxication were compared with controls matched for age (within 3 years), sex, and education. Although the extent of the workers' symptoms caused by mercury poisoning, termed erethismus merculialis, decreased considerably after the end of exposure, matched paired comparison showed that performances of motor coordination, simple reaction time, and short term memory had deteriorated significantly in the exposed group. Multiple linear regression analysis of exposure variables with neurological examination measures showed positive correlations between poorer neurological performance and variables related to mercury exposure. Thus the duration of exposure correlated with poorer performance of hand-eye coordination, tapping, and a colour card reading test. Job categories classified by exposure to mercury also had a significant negative correlation with these performances. The period of years after the end of exposure had a significant correlation with better performance of reaction time and digit span. On the other hand, the history of intoxication itself had no significant correlation with any of the current neurobehavioural performances. These results suggest that there are slight but persistent effects on neurobehavioural function, especially on motor coordination, among mercury miners even more than 10 years after the end of exposure. PMID:8124461

  17. Improved grand canonical sampling of vapour-liquid transitions

    NASA Astrophysics Data System (ADS)

    Wilding, Nigel B.

    2016-10-01

    Simulation within the grand canonical ensemble is the method of choice for accurate studies of first order vapour-liquid phase transitions in model fluids. Such simulations typically employ sampling that is biased with respect to the overall number density in order to overcome the free energy barrier associated with mixed phase states. However, at low temperature and for large system size, this approach suffers a drastic slowing down in sampling efficiency. The culprits are geometrically induced transitions (stemming from the periodic boundary conditions) which involve changes in droplet shape from sphere to cylinder and cylinder to slab. Since the overall number density does not discriminate sufficiently between these shapes, it fails as an order parameter for biasing through the transitions. Here we report two approaches to ameliorating these difficulties. The first introduces a droplet shape based order parameter that generates a transition path from vapour to slab states for which spherical and cylindrical droplets are suppressed. The second simply biases with respect to the number density in a tetragonal subvolume of the system. Compared to the standard approach, both methods offer improved sampling, allowing estimates of coexistence parameters and vapor-liquid surface tension for larger system sizes and lower temperatures.

  18. Detecting vapour bubbles in simulations of metastable water.

    PubMed

    González, Miguel A; Menzl, Georg; Aragones, Juan L; Geiger, Philipp; Caupin, Frederic; Abascal, Jose L F; Dellago, Christoph; Valeriani, Chantal

    2014-11-14

    The investigation of cavitation in metastable liquids with molecular simulations requires an appropriate definition of the volume of the vapour bubble forming within the metastable liquid phase. Commonly used approaches for bubble detection exhibit two significant flaws: first, when applied to water they often identify the voids within the hydrogen bond network as bubbles thus masking the signature of emerging bubbles and, second, they lack thermodynamic consistency. Here, we present two grid-based methods, the M-method and the V-method, to detect bubbles in metastable water specifically designed to address these shortcomings. The M-method incorporates information about neighbouring grid cells to distinguish between liquid- and vapour-like cells, which allows for a very sensitive detection of small bubbles and high spatial resolution of the detected bubbles. The V-method is calibrated such that its estimates for the bubble volume correspond to the average change in system volume and are thus thermodynamically consistent. Both methods are computationally inexpensive such that they can be used in molecular dynamics and Monte Carlo simulations of cavitation. We illustrate them by computing the free energy barrier and the size of the critical bubble for cavitation in water at negative pressure. PMID:25399176

  19. Detecting vapour bubbles in simulations of metastable water

    SciTech Connect

    González, Miguel A.; Abascal, Jose L. F.; Valeriani, Chantal E-mail: cvaleriani@quim.ucm.es; Menzl, Georg; Geiger, Philipp; Dellago, Christoph E-mail: cvaleriani@quim.ucm.es; Aragones, Juan L.; Caupin, Frederic

    2014-11-14

    The investigation of cavitation in metastable liquids with molecular simulations requires an appropriate definition of the volume of the vapour bubble forming within the metastable liquid phase. Commonly used approaches for bubble detection exhibit two significant flaws: first, when applied to water they often identify the voids within the hydrogen bond network as bubbles thus masking the signature of emerging bubbles and, second, they lack thermodynamic consistency. Here, we present two grid-based methods, the M-method and the V-method, to detect bubbles in metastable water specifically designed to address these shortcomings. The M-method incorporates information about neighbouring grid cells to distinguish between liquid- and vapour-like cells, which allows for a very sensitive detection of small bubbles and high spatial resolution of the detected bubbles. The V-method is calibrated such that its estimates for the bubble volume correspond to the average change in system volume and are thus thermodynamically consistent. Both methods are computationally inexpensive such that they can be used in molecular dynamics and Monte Carlo simulations of cavitation. We illustrate them by computing the free energy barrier and the size of the critical bubble for cavitation in water at negative pressure.

  20. Detecting vapour bubbles in simulations of metastable water.

    PubMed

    González, Miguel A; Menzl, Georg; Aragones, Juan L; Geiger, Philipp; Caupin, Frederic; Abascal, Jose L F; Dellago, Christoph; Valeriani, Chantal

    2014-11-14

    The investigation of cavitation in metastable liquids with molecular simulations requires an appropriate definition of the volume of the vapour bubble forming within the metastable liquid phase. Commonly used approaches for bubble detection exhibit two significant flaws: first, when applied to water they often identify the voids within the hydrogen bond network as bubbles thus masking the signature of emerging bubbles and, second, they lack thermodynamic consistency. Here, we present two grid-based methods, the M-method and the V-method, to detect bubbles in metastable water specifically designed to address these shortcomings. The M-method incorporates information about neighbouring grid cells to distinguish between liquid- and vapour-like cells, which allows for a very sensitive detection of small bubbles and high spatial resolution of the detected bubbles. The V-method is calibrated such that its estimates for the bubble volume correspond to the average change in system volume and are thus thermodynamically consistent. Both methods are computationally inexpensive such that they can be used in molecular dynamics and Monte Carlo simulations of cavitation. We illustrate them by computing the free energy barrier and the size of the critical bubble for cavitation in water at negative pressure.

  1. Detecting vapour bubbles in simulations of metastable water

    NASA Astrophysics Data System (ADS)

    González, Miguel A.; Menzl, Georg; Aragones, Juan L.; Geiger, Philipp; Caupin, Frederic; Abascal, Jose L. F.; Dellago, Christoph; Valeriani, Chantal

    2014-11-01

    The investigation of cavitation in metastable liquids with molecular simulations requires an appropriate definition of the volume of the vapour bubble forming within the metastable liquid phase. Commonly used approaches for bubble detection exhibit two significant flaws: first, when applied to water they often identify the voids within the hydrogen bond network as bubbles thus masking the signature of emerging bubbles and, second, they lack thermodynamic consistency. Here, we present two grid-based methods, the M-method and the V-method, to detect bubbles in metastable water specifically designed to address these shortcomings. The M-method incorporates information about neighbouring grid cells to distinguish between liquid- and vapour-like cells, which allows for a very sensitive detection of small bubbles and high spatial resolution of the detected bubbles. The V-method is calibrated such that its estimates for the bubble volume correspond to the average change in system volume and are thus thermodynamically consistent. Both methods are computationally inexpensive such that they can be used in molecular dynamics and Monte Carlo simulations of cavitation. We illustrate them by computing the free energy barrier and the size of the critical bubble for cavitation in water at negative pressure.

  2. Biological and chemical studies on overheated brewed coffee.

    PubMed

    Sasaki, Y; Shibamoto, T; Wei, C I; Fernando, S

    1987-03-01

    Vapour formed from overheated decaffeinated coffee was condensed and tested for mutagenicity using the Ames assay in Salmonella typhimurium strains TA98 and TA100. Vapour produced at 73 and 100 degrees C exhibited no mutagenicity. The basic fraction of vapour produced at 350 degrees C showed weak mutagenicity towards strains TA98 with metabolic activation. The chemical analysis of this fraction identified pyridines and pyrazines as the major constituents. None of the compounds identified in this fraction has been reported as mutagenic when tested in the Ames assay. PMID:3570110

  3. Catalytic hydrotreating process

    DOEpatents

    Karr, Jr., Clarence; McCaskill, Kenneth B.

    1978-01-01

    Carbonaceous liquids boiling above about 300.degree. C such as tars, petroleum residuals, shale oils and coal-derived liquids are catalytically hydrotreated by introducing the carbonaceous liquid into a reaction zone at a temperature in the range of 300.degree. to 450.degree. C and a pressure in the range of 300 to 4000 psig for effecting contact between the carbonaceous liquid and a catalytic transition metal sulfide in the reaction zone as a layer on a hydrogen permeable transition metal substrate and then introducing hydrogen into the reaction zone by diffusing the hydrogen through the substrate to effect the hydrogenation of the carbonaceous liquid in the presence of the catalytic sulfide layer.

  4. Catalytic molecular beacons.

    PubMed

    Stojanovic, M N; de Prada, P; Landry, D W

    2001-06-01

    We have constructed catalytic molecular beacons from a hammerhead-type deoxyribozyme by a modular design. The deoxyribozyme was engineered to contain a molecular beacon stem-loop module that, when closed, inhibits the deoxyribozyme module and is complementary to a target oligonucleotide. Binding of target oligonucleotides opens the beacon stem-loop and allosterically activates the deoxyribozyme module, which amplifies the recognition event through cleavage of a doubly labeled fluorescent substrate. The customized modular design of catalytic molecular beacons allows for any two single-stranded oligonucleotide sequences to be distinguished in homogenous solution in a single step. Our constructs demonstrate that antisense conformational triggers based on molecular beacons can be used to initiate catalytic events. The selectivity of the system is sufficient for analytical applications and has potential for the construction of deoxyribozyme-based drug delivery tools specifically activated in cells containing somatic mutations.

  5. Fluid catalytic cracking

    SciTech Connect

    Bartley, B.H.; Petty, R.H.

    1982-08-17

    Gaseous sulfur compounds are removed from a sulfur-containing gas mixture by reacting sulfur oxides in the gas mixture with alumina in association with bismuth. The process is particularly useful in fluid catalytic cracking of sulfur-containing petroleum charge stocks wherein sulfur is contained in coke deposited on the fluidized cracking catalyst. By the process of this invention, sulfur oxides may be removed from regenerator off-gases from a fluidized catalytic cracking unit by incorporating particulate alumina impregnated with bismuth in particulate cracking catalyst whereby sulfur oxides generated in the regeneration of the catalyst are reacted with bismuth-impregnated alumina. Sulfur oxides produced during regeneration of the catalyst by burning the coke with air are captured and converted to hydrogen sulfide in the cracking reactor. The hydrogen sulfide so produced is readily separated from petroleum products of the catalytic cracking reaction process.

  6. Steam reformer with catalytic combustor

    DOEpatents

    Voecks, Gerald E.

    1990-03-20

    A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.

  7. Steam reformer with catalytic combustor

    NASA Technical Reports Server (NTRS)

    Voecks, Gerald E. (Inventor)

    1990-01-01

    A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.

  8. Fluid catalytic cracking

    SciTech Connect

    Petty, R.H.; Bartley, B.H.

    1984-05-01

    A fluid catalytic cracking process is disclosed for sulfur-containing petroleum charge stocks. Sulfur contained in coke deposited on the fluidized cracking catalyst in the reactor is converted to sulfur oxides in the regenerator and removed from regenerator off-gases by incorporating a composite of alumina and bismuth oxides in a particulate cracking catalyst. Sulfur oxides produced during regeneration of the catalyst by burning the coke with air in the regenerator are captured by the alumina-bismuth oxides composite and converted to hydrogen sulfide in the cracking reactor. The hydrogen sulfide so produced is readily separated from petroleum products of the catalytic cracking reaction process.

  9. Reaction pathway in vapour phase hydrogenation of maleic anhydride and its esters to {gamma}-butyrolactone

    SciTech Connect

    Messori, M.; Vaccari, A.

    1994-11-01

    The catalytic reactivity of maleic anhydride (MA), succinic anhydride (SA) and their dimethyl esters (dimethyl maleate and dimethyl succinate) in the vapour phase hydrogenation to {gamma}-butyrolacetone (GBL) was investigated. In order to obtain general data, both a multicomponent catalyst (CAT 1: Cu/Zn/Mg/Cr = 40:5:5:50, atomic ratio %), obtained by reduction of a nonstoichiometric spinel-type precursor, and a commercial catalyst (CAT 2: Cu/Mn/Ba/Cr = 44:8:1:47, atomic ratio %) were used. The MA/GBL solution exhibited the highest GBL production, while the SA/GBL solution was converted only partially due to a competitive adsorption of GBL on the active sites, as evidenced by the similar reactivities observed with pure anhydrides. The best carbon balances were observed with the esters, probably the result of lowest light hydrocarbon synthesis and tar formation. With all the feedstocks, the activity of CAT 2 is higher than that of CAT 1, which, however, gives the best yield in GBL due its lower activity in the overhydrogenation and hydrogenolysis reaction. It was found that n-butanol (BuOH) and butyric acid (BuA) derived mainly from GBL. On this basis, the reactivities of the main products observed were investigated separately, confirming the stability of tetrahydrofuran (THF), which reacted only at high temperature with low conversions to ethanol. On the other hand, GBL gave rise to overhydrogenation and/or hydrogenolysis, with high conversion (mainly with CAT 2), confirming its key role in both reactions. Furthermore, the formation in the catalytic tests with BuA and BuOH of n-butanal, notwithstanding the high H{sub 2}/organic ratio, implies that it is the main intermediate in the hydrogenolysis reactions. A new reaction scheme is proposed, pointing out the key role of GBL as the {open_quotes}intersection{close_quotes} of two possible reaction pathways, giving rise to THF or overhydrogenation and hydrogenolysis products, respectively. 44 refs., 4 figs., 6 tabs.

  10. Physico-Chemical Property and Catalytic Activity of a CeO2-Doped MnO(x)-TiO2 Catalyst with SO2 Resistance for Low-Temperature NH3-SCR of NO(x).

    PubMed

    Shin, Byeongkil; Chun, Ho Hwan; Cha, Jin-Sun; Shin, Min-Chul; Lee, Heesoo

    2016-05-01

    The effects of CeO2 addition on the catalytic activity and the SO2 resistance of CeO2-doped MnO(x)-TiO2 catalysts were investigated for the low-temperature selective catalytic reduction (SCR) with NH3 of NO(x) emissions in marine applications. The most active catalyst was obtained from 30 wt% CeO2-MnO(x)-TiO2 catalyst in the whole temperature range of 100-300 degrees C at a low gas hourly space velocity (GHSV) of 10,000 h(-)1, and its de-NO(x) efficiency was higher than 90% over 250 degrees C. The enhanced catalytic activity may contribute to the dispersion state and catalytic acidity on the catalyst surface, and the highly dispersed Mn and Ce on the nano-scaled TiO2 catalyst affects the increase of Lewis and Brønsted acid sites. A CeO2-rich additive on MnO(x)-TiO2 could provide stronger catalytic acid sites, associated with NH3 adsorption and the SCR performance. As the results of sulfur resistance in flue gas that contains SO2, the de-NO(x) efficiency of MnO(x)-TiO2 decreased by 15% over 200 degrees C, whereas that of 30 wt% ceria-doped catalyst increased by 14-21% over 150 degrees C. The high SO2 resistance of CeO2-MnO(x)-TiO2 catalysts that resulted from the addition of ceria suppressed the formation of Mn sulfate species, which led to deactivation on the surface of nano-catalyst. PMID:27483759

  11. Physico-Chemical Property and Catalytic Activity of a CeO2-Doped MnO(x)-TiO2 Catalyst with SO2 Resistance for Low-Temperature NH3-SCR of NO(x).

    PubMed

    Shin, Byeongkil; Chun, Ho Hwan; Cha, Jin-Sun; Shin, Min-Chul; Lee, Heesoo

    2016-05-01

    The effects of CeO2 addition on the catalytic activity and the SO2 resistance of CeO2-doped MnO(x)-TiO2 catalysts were investigated for the low-temperature selective catalytic reduction (SCR) with NH3 of NO(x) emissions in marine applications. The most active catalyst was obtained from 30 wt% CeO2-MnO(x)-TiO2 catalyst in the whole temperature range of 100-300 degrees C at a low gas hourly space velocity (GHSV) of 10,000 h(-)1, and its de-NO(x) efficiency was higher than 90% over 250 degrees C. The enhanced catalytic activity may contribute to the dispersion state and catalytic acidity on the catalyst surface, and the highly dispersed Mn and Ce on the nano-scaled TiO2 catalyst affects the increase of Lewis and Brønsted acid sites. A CeO2-rich additive on MnO(x)-TiO2 could provide stronger catalytic acid sites, associated with NH3 adsorption and the SCR performance. As the results of sulfur resistance in flue gas that contains SO2, the de-NO(x) efficiency of MnO(x)-TiO2 decreased by 15% over 200 degrees C, whereas that of 30 wt% ceria-doped catalyst increased by 14-21% over 150 degrees C. The high SO2 resistance of CeO2-MnO(x)-TiO2 catalysts that resulted from the addition of ceria suppressed the formation of Mn sulfate species, which led to deactivation on the surface of nano-catalyst.

  12. Catalytic coal liquefaction process

    DOEpatents

    Garg, D.; Sunder, S.

    1986-12-02

    An improved process for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a solvent comprises using as catalyst a mixture of a 1,2- or 1,4-quinone and an alkaline compound, selected from ammonium, alkali metal, and alkaline earth metal oxides, hydroxides or salts of weak acids. 1 fig.

  13. Catalytic coal liquefaction process

    DOEpatents

    Garg, Diwakar; Sunder, Swaminathan

    1986-01-01

    An improved process for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a solvent comprises using as catalyst a mixture of a 1,2- or 1,4-quinone and an alkaline compound, selected from ammonium, alkali metal, and alkaline earth metal oxides, hydroxides or salts of weak acids.

  14. Catalytic efficiency of designed catalytic proteins

    PubMed Central

    Korendovych, Ivan V; DeGrado, William F

    2014-01-01

    The de novo design of catalysts that mimic the affinity and specificity of natural enzymes remains one of the Holy Grails of chemistry. Despite decades of concerted effort we are still unable to design catalysts as efficient as enzymes. Here we critically evaluate approaches to (re)design of novel catalytic function in proteins using two test cases: Kemp elimination and ester hydrolysis. We show that the degree of success thus far has been modest when the rate enhancements seen for the designed proteins are compared with the rate enhancements by small molecule catalysts in solvents with properties similar to the active site. Nevertheless, there are reasons for optimism: the design methods are ever improving and the resulting catalyst can be efficiently improved using directed evolution. PMID:25048695

  15. Catalytic efficiency of designed catalytic proteins.

    PubMed

    Korendovych, Ivan V; DeGrado, William F

    2014-08-01

    The de novo design of catalysts that mimic the affinity and specificity of natural enzymes remains one of the Holy Grails of chemistry. Despite decades of concerted effort we are still unable to design catalysts as efficient as enzymes. Here we critically evaluate approaches to (re)design of novel catalytic function in proteins using two test cases: Kemp elimination and ester hydrolysis. We show that the degree of success thus far has been modest when the rate enhancements seen for the designed proteins are compared with the rate enhancements by small molecule catalysts in solvents with properties similar to the active site. Nevertheless, there are reasons for optimism: the design methods are ever improving and the resulting catalyst can be efficiently improved using directed evolution.

  16. Hierarchically arranged helical fibre actuators driven by solvents and vapours.

    PubMed

    Chen, Peining; Xu, Yifan; He, Sisi; Sun, Xuemei; Pan, Shaowu; Deng, Jue; Chen, Daoyong; Peng, Huisheng

    2015-12-01

    Mechanical responsiveness in many plants is produced by helical organizations of cellulose microfibrils. However, simple mimicry of these naturally occurring helical structures does not produce artificial materials with the desired tunable actuations. Here, we show that actuating fibres that respond to solvent and vapour stimuli can be created through the hierarchical and helical assembly of aligned carbon nanotubes. Primary fibres consisting of helical assemblies of multiwalled carbon nanotubes are twisted together to form the helical actuating fibres. The nanoscale gaps between the nanotubes and micrometre-scale gaps among the primary fibres contribute to the rapid response and large actuation stroke of the actuating fibres. The compact coils allow the actuating fibre to rotate reversibly. We show that these fibres, which are lightweight, flexible and strong, are suitable for a variety of applications such as energy-harvesting generators, deformable sensing springs and smart textiles. PMID:26367106

  17. Hierarchically arranged helical fibre actuators driven by solvents and vapours

    NASA Astrophysics Data System (ADS)

    Chen, Peining; Xu, Yifan; He, Sisi; Sun, Xuemei; Pan, Shaowu; Deng, Jue; Chen, Daoyong; Peng, Huisheng

    2015-12-01

    Mechanical responsiveness in many plants is produced by helical organizations of cellulose microfibrils. However, simple mimicry of these naturally occurring helical structures does not produce artificial materials with the desired tunable actuations. Here, we show that actuating fibres that respond to solvent and vapour stimuli can be created through the hierarchical and helical assembly of aligned carbon nanotubes. Primary fibres consisting of helical assemblies of multiwalled carbon nanotubes are twisted together to form the helical actuating fibres. The nanoscale gaps between the nanotubes and micrometre-scale gaps among the primary fibres contribute to the rapid response and large actuation stroke of the actuating fibres. The compact coils allow the actuating fibre to rotate reversibly. We show that these fibres, which are lightweight, flexible and strong, are suitable for a variety of applications such as energy-harvesting generators, deformable sensing springs and smart textiles.

  18. Atmospheric pressure vapour phase decomposition: a proof of principle.

    PubMed

    Cinosi, Amedeo; Andriollo, Nunzio; Tibaldi, Francesca; Monticelli, Damiano

    2012-11-15

    In the present work we demonstrated that the digestion of difficult matrices (high boiling petrochemical fractions and distillation bottoms) can be achieved by oxidation with nitric acid vapours at atmospheric pressure employing simple laboratory glassware. The application of this procedure as a digestion method prior to Total Reflection X-Ray Fluorescence (TXRF) is presented, although the employment of other detection techniques may be foreseen. The method ensured a fast, less than half an hour, treatment time and detection limits in the range 20-100 μg/kg for As, Bi, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, Zn, whereas higher values were obtained for Ba, Ca, K, P, Rh, Ti and V (0.3-3 mg/kg). The potentialities and limitations of this procedure were discussed: the application to a broad range of matrices may be foreseen. PMID:23158304

  19. Atmospheric pressure vapour phase decomposition: a proof of principle.

    PubMed

    Cinosi, Amedeo; Andriollo, Nunzio; Tibaldi, Francesca; Monticelli, Damiano

    2012-11-15

    In the present work we demonstrated that the digestion of difficult matrices (high boiling petrochemical fractions and distillation bottoms) can be achieved by oxidation with nitric acid vapours at atmospheric pressure employing simple laboratory glassware. The application of this procedure as a digestion method prior to Total Reflection X-Ray Fluorescence (TXRF) is presented, although the employment of other detection techniques may be foreseen. The method ensured a fast, less than half an hour, treatment time and detection limits in the range 20-100 μg/kg for As, Bi, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, Zn, whereas higher values were obtained for Ba, Ca, K, P, Rh, Ti and V (0.3-3 mg/kg). The potentialities and limitations of this procedure were discussed: the application to a broad range of matrices may be foreseen.

  20. Impedimetric detection of alcohol vapours using nanostructured zinc ferrite.

    PubMed

    Kannan, Padmanathan Karthick; Saraswathi, Ramiah

    2014-11-01

    A comparative study on the sensing characteristics of nanostructured zinc ferrite to three primary alcohols viz. methanol, ethanol and propanol has been carried out. The zinc ferrite has been prepared by a combustion method and characterized by XRD, FTIR, AFM and SEM. Impedance studies in the alcohol concentration range varying from 100 to 1000 ppm show definite variations in response to both the nature of the alcohol and its concentration. The nanostructured zinc ferrite shows the highest sensor response to methanol and least to propanol. Equivalent circuit modelling and calibration have been made for all the three alcohol sensors. The material shows a better selectivity to the alcohols compared to formaldehyde, ammonia and acetone vapours.

  1. Hierarchically arranged helical fibre actuators driven by solvents and vapours.

    PubMed

    Chen, Peining; Xu, Yifan; He, Sisi; Sun, Xuemei; Pan, Shaowu; Deng, Jue; Chen, Daoyong; Peng, Huisheng

    2015-12-01

    Mechanical responsiveness in many plants is produced by helical organizations of cellulose microfibrils. However, simple mimicry of these naturally occurring helical structures does not produce artificial materials with the desired tunable actuations. Here, we show that actuating fibres that respond to solvent and vapour stimuli can be created through the hierarchical and helical assembly of aligned carbon nanotubes. Primary fibres consisting of helical assemblies of multiwalled carbon nanotubes are twisted together to form the helical actuating fibres. The nanoscale gaps between the nanotubes and micrometre-scale gaps among the primary fibres contribute to the rapid response and large actuation stroke of the actuating fibres. The compact coils allow the actuating fibre to rotate reversibly. We show that these fibres, which are lightweight, flexible and strong, are suitable for a variety of applications such as energy-harvesting generators, deformable sensing springs and smart textiles.

  2. Novel Metal Nanomaterials and Their Catalytic Applications.

    PubMed

    Wang, Jiaqing; Gu, Hongwei

    2015-01-01

    In the rapidly developing areas of nanotechnology, nano-scale materials as heterogeneous catalysts in the synthesis of organic molecules have gotten more and more attention. In this review, we will summarize the synthesis of several new types of noble metal nanostructures (FePt@Cu nanowires, Pt@Fe₂O₃ nanowires and bimetallic Pt@Ir nanocomplexes; Pt-Au heterostructures, Au-Pt bimetallic nanocomplexes and Pt/Pd bimetallic nanodendrites; Au nanowires, CuO@Ag nanowires and a series of Pd nanocatalysts) and their new catalytic applications in our group, to establish heterogeneous catalytic system in "green" environments. Further study shows that these materials have a higher catalytic activity and selectivity than previously reported nanocrystal catalysts in organic reactions, or show a superior electro-catalytic activity for the oxidation of methanol. The whole process might have a great impact to resolve the energy crisis and the environmental crisis that were caused by traditional chemical engineering. Furthermore, we hope that this article will provide a reference point for the noble metal nanomaterials' development that leads to new opportunities in nanocatalysis. PMID:26393550

  3. A graphene-based smart catalytic system with superior catalytic performances and temperature responsive catalytic behaviors.

    PubMed

    Qi, Junjie; Lv, Weipeng; Zhang, Guanghui; Li, Yang; Zhang, Guoliang; Zhang, Fengbao; Fan, Xiaobin

    2013-07-21

    We have successfully developed a unique graphene-based smart catalytic system which consists of the graphene supported Au-Pt bimetallic nanocatalyst with a well-defined core-shell structure and a dextran-based temperature-responsive polymer. The unique catalytic system possesses excellent catalytic performances and the catalytic activities could be readily switched on or off at different temperature windows. PMID:23740038

  4. Fundamentals of Chemical Processes.

    ERIC Educational Resources Information Center

    Moser, William R.

    1985-01-01

    Describes a course that provides students with a fundamental understanding of the chemical, catalytic, and engineering sciences related to the chemical reactions taking place in a variety of reactors of different configurations. Also describes the eight major lecture topics, course examinations, and term papers. The course schedule is included.…

  5. Halogen Chemistry on Catalytic Surfaces.

    PubMed

    Moser, Maximilian; Pérez-Ramírez, Javier

    2016-01-01

    Halogens are key building blocks for the manufacture of high-value products such as chemicals, plastics, and pharmaceuticals. The catalytic oxidation of HCl and HBr is an attractive route to recover chlorine and bromine in order to ensure the sustainability of the production processes. Very few materials withstand the high corrosiveness and the strong exothermicity of the reactions and among them RuO2 and CeO2-based catalysts have been successfully applied in HCl oxidation. The search for efficient systems for HBr oxidation was initiated by extrapolating the results of HCl oxidation based on the chemical similarity of these reactions. Interestingly, despite its inactivity in HCl oxidation, TiO2 was found to be an outstanding HBr oxidation catalyst, which highlighted that the latter reaction is more complex than previously assumed. Herein, we discuss the results of recent comparative studies of HCl and HBr oxidation on both rutile-type (RuO2, IrO2, and TiO2) and ceria-based catalysts using a combination of advanced experimental and theoretical methods to provide deeper molecular-level understanding of the reactions. This knowledge aids the design of the next-generation catalysts for halogen recycling. PMID:27131113

  6. Modelling of metal vapour in pulsed TIG including influence of self-absorption

    NASA Astrophysics Data System (ADS)

    Iwao, Toru; Mori, Yusuke; Okubo, Masato; Sakai, Tadashi; Tashiro, Shinichi; Tanaka, Manabu; Yumoto, Motoshige

    2010-11-01

    Pulsed TIG (tungsten inert gas) welding is used to improve the stability and speed of arc welding, and to allow greater control over the heat input to the weld. The temperature and the radiation power density of the pulsed arc vary as a function of time, as does the distribution of metal vapour, and its effects on the arc. A self-consistent two-dimensional model of the arc and electrodes is used to calculate the properties of the arc as a function of time. Self-absorption of radiation is treated by two methods, one taking into account absorption of radiation only within the control volume of emission, and the other taking into account absorption throughout the plasma. The relation between metal vapour and radiation power density is analysed by calculating the iron vapour distribution. The results show that the transport of iron vapour is strongly affected by the fast convective flow during the peak current period. During the base current period, the region containing a low concentration of metal vapour expands because of the low convective flow. The iron vapour distribution does not closely follow the current pulses. The temperature, iron vapour and radiation power density distributions depend on the self-absorption model used. The temperature distribution becomes broader when self-absorption of radiation from all directions is considered.

  7. Catalytic thermal barrier coatings

    DOEpatents

    Kulkarni, Anand A.; Campbell, Christian X.; Subramanian, Ramesh

    2009-06-02

    A catalyst element (30) for high temperature applications such as a gas turbine engine. The catalyst element includes a metal substrate such as a tube (32) having a layer of ceramic thermal barrier coating material (34) disposed on the substrate for thermally insulating the metal substrate from a high temperature fuel/air mixture. The ceramic thermal barrier coating material is formed of a crystal structure populated with base elements but with selected sites of the crystal structure being populated by substitute ions selected to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a higher rate than would the base compound without the ionic substitutions. Precious metal crystallites may be disposed within the crystal structure to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a lower light-off temperature than would the ceramic thermal barrier coating material without the precious metal crystallites.

  8. Catalytic, hollow, refractory spheres

    NASA Technical Reports Server (NTRS)

    Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

    1987-01-01

    Improved, heterogeneous, refractory catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitable formed of a shell (12) of refractory such as alumina having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be itself catalytic or a catalytically active material coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

  9. Water Vapour Profiles from SCIAMACHY Solar Occultation Measurements derived with Onion Peeling DOAS

    NASA Astrophysics Data System (ADS)

    Noël, S.; Bramstedt, K.; Rozanov, A.; Bovensmann, H.; Burrows, J. P.

    2009-04-01

    Water vapour is the most important greenhouse gas and plays a key role in atmospheric chemistry and transport. Most of the water vapour is located in the troposphere where it significantly contributes to weather and climate. Because the tropopause acts as a cold trap, the water vapour density in the stratosphere is significantly lower and decreases rapidly with increasing altitude. However, the amount of stratospheric water vapour plays an important role in the generation of Polar Stratospheric Clouds (PSCs), which in turn influence strongly the amount of ozone in polar regions. Trends in stratospheric water vapour are determined by methane oxidation, transport through the tropopause and by the Brewer-Dobson circulation. To seperate the various effects there is a clear need for global long term measurements of lower stratospheric water vapour, which can be provided by satellite measurements. A new retrieval method (called "Onion Peeling DOAS") has been developed to derive water vapour number density profiles from solar occultation measurements of the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY). This method is intentionally kept simple and based on a combination of an onion peeling approach with a modified DOAS (Differential Optical Absorption Spectroscopy) fit in the wavelength region around 940 nm. The resulting water vapour profiles currently cover the altitude range 15-50 km. Here, first retrieval results and comparisons of the SCIAMACHY profiles with water vapour data provided by the Atmospheric Chemistry Explorer Fourier Transform Spectrometer (ACE-FTS) and model data of the European Centre for Medium Range Weather Forecasts (ECMWF) are shown.

  10. Catalytic nanoporous membranes

    DOEpatents

    Pellin, Michael J.; Hryn, John N.; Elam, Jeffrey W.

    2009-12-01

    A nanoporous catalytic membrane which displays several unique features including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity.

  11. Evaluation of Trichloroethylene vapour fluxes using measurements at the soil-air interface and in the atmosphere close to the soil surface

    NASA Astrophysics Data System (ADS)

    Cotel, Solenn; Nagel, Vincent; Schäfer, Gerhard; Marzougui, Salsabil; Razakarisoa, Olivier; Millet, Maurice

    2013-04-01

    Industrialization during the 19th and 20th century led to the use of chemical products such as chlorinated solvents, e.g., trichloroethylene (TCE). At locations where volatile organic compounds were accidentally spilled on the soil during transport or leaked from their storage places, they could have migrated vertically through the unsaturated zone towards the underlying groundwater. As a result of their high volatility a large vapour plume is consequently formed. Understanding when, at which concentrations and how long, these pollutants will be present in soil, groundwater, atmosphere or indoor air, still remains a challenge up to date. This study was conducted as part of a broader experiment of TCE multiphase mass transfer in a large (25m×12m×3m) well-instrumented artificial basin. TCE was injected as liquid phase in the vadose zone and experiments were conducted during several months. Firstly, TCE vapour fluxes were experimentally determined in two different ways: (a) direct measurements at the soil-air interface using a flux chamber and (b) evaluations based on measurements of TCE concentrations in the air above the soil surface using a modular experimental flume (5m×1m×1m) with a fixed air flow. Secondly, numerical simulations were conducted to analyse the differences between these two types of fluxes. Several positions of the flume on the soil surface were tested. Based on the TCE concentrations measured in the air, vapour fluxes were determined with the aerodynamic method using the modified Thornthwaite-Holzmann equation. It assumes that the concentrations and velocities are temporally and spatially constant in horizontal planes and requires data on the gradients of concentration, horizontal wind velocity and temperature. TCE vapour fluxes measured at the soil-air interface decrease with distance from the source zone. However, this decrease was either high, at the first stage of experiment (120μg/(m2s) near the source zone compared to 1,1μg/(m2s) 2m

  12. Preconversion catalytic deoxygenation of phenolic functional groups

    SciTech Connect

    Kubiak, C.P.

    1991-01-01

    The deoxygenation of phenols is a conceptually simple, but unusually difficult chemical transformation to achieve. Aryl carbon-oxygen bond cleavage is a chemical transformation of importance in coal liquefaction and the upgrading of coal liquids as well as in the synthesis of natural products. This proposed research offers the possibility of effecting the selective catalytic deoxygenation of phenolic functional groups using CO. A program of research for the catalytic deoxygenation of phenols, via a low energy mechanistic pathway that is based on the use of the CO/CO{sub 2} couple to remove phenolic oxygen atoms, is underway. We are focusing on systems which have significant promise as catalysts: Ir(triphos)OPh, (Pt(triphos)OPh){sup +} and Rh(triphos)OPh. Our studies of phenol deoxygenation focus on monitoring the reactions for the elementary processes upon which catalytic activity will depend: CO insertion into M-OPh bonds, CO{sub 2} elimination from aryloxy carbonyls {l brace}M-C(O)-O-Ph{r brace}, followed by formation of a coordinated benzyne intermediate.

  13. A revolution in micropower : the catalytic nanodiode.

    SciTech Connect

    Cross, Karen Charlene; Heller, Edwin J.; Figiel, Jeffrey James; Coker, Eric Nicholas; Creighton, James Randall; Koleske, Daniel David; Bogart, Katherine Huderle Andersen; Coltrin, Michael Elliott; Pawlowski, Roger Patrick; Baucom, Kevin C.

    2010-11-01

    Our ability to field useful, nano-enabled microsystems that capitalize on recent advances in sensor technology is severely limited by the energy density of available power sources. The catalytic nanodiode (reported by Somorjai's group at Berkeley in 2005) was potentially an alternative revolutionary source of micropower. Their first reports claimed that a sizable fraction of the chemical energy may be harvested via hot electrons (a 'chemicurrent') that are created by the catalytic chemical reaction. We fabricated and tested Pt/GaN nanodiodes, which eventually produced currents up to several microamps. Our best reaction yields (electrons/CO{sub 2}) were on the order of 10{sup -3}; well below the 75% values first reported by Somorjai (we note they have also been unable to reproduce their early results). Over the course of this Project we have determined that the whole concept of 'chemicurrent', in fact, may be an illusion. Our results conclusively demonstrate that the current measured from our nanodiodes is derived from a thermoelectric voltage; we have found no credible evidence for true chemicurrent. Unfortunately this means that the catalytic nanodiode has no future as a micropower source.

  14. Vapor-Driven Propulsion of Catalytic Micromotors.

    PubMed

    Dong, Renfeng; Li, Jinxing; Rozen, Isaac; Ezhilan, Barath; Xu, Tailin; Christianson, Caleb; Gao, Wei; Saintillan, David; Ren, Biye; Wang, Joseph

    2015-08-18

    Chemically-powered micromotors offer exciting opportunities in diverse fields, including therapeutic delivery, environmental remediation, and nanoscale manufacturing. However, these nanovehicles require direct addition of high concentration of chemical fuel to the motor solution for their propulsion. We report the efficient vapor-powered propulsion of catalytic micromotors without direct addition of fuel to the micromotor solution. Diffusion of hydrazine vapor from the surrounding atmosphere into the sample solution is instead used to trigger rapid movement of iridium-gold Janus microsphere motors. Such operation creates a new type of remotely-triggered and powered catalytic micro/nanomotors that are responsive to their surrounding environment. This new propulsion mechanism is accompanied by unique phenomena, such as the distinct off-on response to the presence of fuel in the surrounding atmosphere, and spatio-temporal dependence of the motor speed borne out of the concentration gradient evolution within the motor solution. The relationship between the motor speed and the variables affecting the fuel concentration distribution is examined using a theoretical model for hydrazine transport, which is in turn used to explain the observed phenomena. The vapor-powered catalytic micro/nanomotors offer new opportunities in gas sensing, threat detection, and environmental monitoring, and open the door for a new class of environmentally-triggered micromotors.

  15. Vapor-Driven Propulsion of Catalytic Micromotors

    PubMed Central

    Dong, Renfeng; Li, Jinxing; Rozen, Isaac; Ezhilan, Barath; Xu, Tailin; Christianson, Caleb; Gao, Wei; Saintillan, David; Ren, Biye; Wang, Joseph

    2015-01-01

    Chemically-powered micromotors offer exciting opportunities in diverse fields, including therapeutic delivery, environmental remediation, and nanoscale manufacturing. However, these nanovehicles require direct addition of high concentration of chemical fuel to the motor solution for their propulsion. We report the efficient vapor-powered propulsion of catalytic micromotors without direct addition of fuel to the micromotor solution. Diffusion of hydrazine vapor from the surrounding atmosphere into the sample solution is instead used to trigger rapid movement of iridium-gold Janus microsphere motors. Such operation creates a new type of remotely-triggered and powered catalytic micro/nanomotors that are responsive to their surrounding environment. This new propulsion mechanism is accompanied by unique phenomena, such as the distinct off-on response to the presence of fuel in the surrounding atmosphere, and spatio-temporal dependence of the motor speed borne out of the concentration gradient evolution within the motor solution. The relationship between the motor speed and the variables affecting the fuel concentration distribution is examined using a theoretical model for hydrazine transport, which is in turn used to explain the observed phenomena. The vapor-powered catalytic micro/nanomotors offer new opportunities in gas sensing, threat detection, and environmental monitoring, and open the door for a new class of environmentally-triggered micromotors. PMID:26285032

  16. Kinetic studies of BTEX vapour adsorption onto surfaces of calix-4-resorcinarene films

    NASA Astrophysics Data System (ADS)

    Hassan, A. K.; Ray, A. K.; Nabok, A. V.; Wilkop, T.

    2001-10-01

    The exposure of spun films of an amphiphilic calix-4-resorcinarene (C-4-RA) derivative to vapours of benzene, toluene, ethylbenzene, and m-xylene (BTEX) has produced a graded response, promising for the development of multisensor arrays. Fast and reversible adsorption of ethylbenzene was associated with changing the refractive index of the sensing layer and is believed to be due to the host-guest interaction between the cavitand C-4-RA molecules and the vapour molecules. Prolonged irradiation of the films with a focused laser beam has resulted in an initial increase of film sensitivity to the different organic vapours.

  17. Deuterium excess in the atmospheric water vapour of a Mediterranean coastal wetland: regional vs. local signatures

    NASA Astrophysics Data System (ADS)

    Delattre, H.; Vallet-Coulomb, C.; Sonzogni, C.

    2015-09-01

    Stable isotopes of water vapour represent a powerful tool for tracing atmospheric vapour origin and mixing processes. Laser spectrometry recently allowed high time-resolution measurements, but despite an increasing number of experimental studies, there is still a need for a better understanding of the isotopic signal variability at different time scales. We present results of in situ measurements of δ18O and δD during 36 consecutive days in summer 2011 in atmospheric vapour of a Mediterranean coastal wetland exposed to high evaporation (Camargue, Rhône River delta, France). The mean composition of atmospheric vapour (δv) is δ18O = -14.66 ‰ and δD = - 95.4 ‰, with data plotting clearly above the local meteoric water line on a δ18O-δD plot, and an average deuterium excess (d) of 21.9 ‰. Important diurnal d variations are observed, and an hourly time scale analysis is necessary to interpret the main processes involved in its variability. After having classified the data according to air mass back trajectories, we analyse the average daily cycles relating to the two main meteorological situations, i.e. air masses originating from North Atlantic Ocean and Mediterranean Sea. In both situations, we show that diurnal fluctuations are driven by (1) the influence of local evaporation, culminating during daytime, and leading to an increase in absolute water vapour concentration associated to a δv enrichment and d increase; (2) vertical air mass redistribution when the Planetary Boundary Layer collapses in the evening, leading to a d decrease, and (3) dew formation during the night, producing a δv depletion with d remaining stable. Using a two-component mixing model, we calculate the average composition of the locally evaporated vapour (δE). We find higher d(E) under North Atlantic air mass conditions, which is consistent with lower humidity conditions. We also suggest that δv measured when the PBL collapses is the most representative of a regional signal

  18. Investigations of vapour-phase deposited transition metal dichalcogenide films for future electronic applications

    NASA Astrophysics Data System (ADS)

    Gatensby, Riley; Hallam, Toby; Lee, Kangho; McEvoy, Niall; Duesberg, Georg S.

    2016-11-01

    Two-dimensional (2D) transitional metal dichalcogenides (TMDs) are of major interest to the research and electrical engineering community. A number of TMDs are semiconducting and have a wide range of bandgaps, they can exhibit n- or p-type behaviour, and the electronic structure changes with the number of layers. These exceptional properties hold much promise for a host of electrical applications including low- or high power field-effect transistors, sensors and diodes. Moreover, the unique optical properties of TMDs make them attractive for optoelectronic applications such as light-emitting diodes, photodiodes, and photovoltaic cells. A prerequisite for all of these applications is a synthesis route which is well controlled, scalable, reproducible and compatible with semiconductor industry process flows. Thermally assisted conversion (TAC), a variant of chemical vapour deposition, shows much promise for meeting these requirements. Herein we review the current progress and challenges of research on 2D semiconducting materials for electronics with a special focus on TAC produced TMD thin films.

  19. Evolution of catalytic RNA in the laboratory

    NASA Technical Reports Server (NTRS)

    Joyce, Gerald F.

    1992-01-01

    We are interested in the biochemistry of existing RNA enzymes and in the development of RNA enzymes with novel catalytic function. The focal point of our research program has been the design and operation of a laboratory system for the controlled evolution of catalytic RNA. This system serves as working model of RNA-based life and can be used to explore the catalytic potential of RNA. Evolution requires the integration of three chemical processes: amplification, mutation, and selection. Amplification results in additional copies of the genetic material. Mutation operates at the level of genotype to introduce variability, this variability in turn being expressed as a range of phenotypes. Selection operates at the level of phenotype to reduce variability by excluding those individuals that do not conform to the prevailing fitness criteria. These three processes must be linked so that only the selected individuals are amplified, subject to mutational error, to produce a progeny distribution of mutant individuals. We devised techniques for the amplification, mutation, and selection of catalytic RNA, all of which can be performed rapidly in vitro within a single reaction vessel. We integrated these techniques in such a way that they can be performed iteratively and routinely. This allowed us to conduct evolution experiments in response to artificially-imposed selection constraints. Our objective was to develop novel RNA enzymes by altering the selection constraints in a controlled manner. In this way we were able to expand the catalytic repertoire of RNA. Our long-range objective is to develop an RNA enzyme with RNA replicase activity. If such an enzyme had the ability to produce additional copies of itself, then RNA evolution would operate autonomously and the origin of life will have been realized in the laboratory.

  20. Catalytic pyrolysis of palm kernel shell waste in a fluidized bed.

    PubMed

    Kim, Sung Won; Koo, Bon Seok; Lee, Dong Hyun

    2014-09-01

    The catalytic pyrolysis of palm kernel shell was investigated in a fluidized bed with zsm-5 and equilibrium FCC (Ecat) catalysts. Catalytic pyrolysis oil yields were remarkably reduced and gas yields were increased due to the higher catalytic reaction of primary volatiles compared to non-catalytic pyrolysis. Char yields were affected by temperature and the pore structure of the catalysts. The pyrolysis oil was characterized by lower H/C and O/C molar ratios due to aromatization and deoxygenation of volatiles by the catalysts. The catalytic pyrolysis oils contained more oxygen and nitrogen and less sulfur than petroleum oils. The oils had a high concentration of nitriles, with a carbon number distribution similar to fatty acids. The catalytic pyrolysis oils featured high nitriles yield with Ecat and high aromatics yield in the light fraction with zsm-5, due to characteristics of the catalyst. The catalytic pyrolysis oils showed potentials as feedstocks for bio-diesel and chemicals.

  1. Assessment of chronic neuropsychological effects of mercury vapour poisoning in chloral-alkali plant workers.

    PubMed

    Pranjić, Nurka; Sinanović, Osman; Karamehić, Jasenko; Jakubović, Rusid

    2002-12-01

    A prospective case study was conducted in the Department of Occupational Medicine, Tuzla. The purpose of this study was to indicate negative effects from occupational exposure to mercury on behavioural and mental health, memory and psychomotor function that was tested in 46 chloral-alkali plant workers (mean age was 38. 8+/- 5. 7 years; mean age of occupational history 16. 5+/- 6. 0 years). Data on toxicological monitoring on atomic absorption spectrometer, and data on mental health were collected, psychiatric and other subjective symptoms, and behavioural, psychomotor and memory function tested. The data were compared to control group, 32 healthy non exposed workers. The study was designed to assess blood and urine mercury levels and length of occupational exposure and investigate its relationships to effects on the mental health. The mean air mercury levels were 0.23 mg/m3, the mean blood mercury concentrations was 3. 6 mg/ dl and the mean urine mercury concentrations were 151.7 +/- 180.4 mg/l. In 25 (53%) workers exposed to mercury vapour was identified Depression-Hypochondrias Syndrome (p trend < 0. 001) with higher scores for scales: Hysteria (p trend <0. 001), Schizoid and Psychoastenia (MMPI). All psychological parameters were in highly significantly correlations with mercury levels and length of occupational exposure. Pathological parameters were possible general identified if the concentration of blood mercury levels are >2. 9 mg/ dl, or urine mercury levels > 87 mg/l workers exposed to mercury vapour knew that toxic effects in body resulted in loosing some of intellectual abilities, and that people who handle chemicals had an increased health risk (ESW questionnaire). The occupational mercury exposed workers had introvert behaviour (EPQ). Aggressiveness was found in 71.7% workers. The cognitive disturbances: short-term memory loss, difficult to concentrate on tasks which require attention and thinking, were significantly differed compared to those of

  2. Water Vapour Mixing Ratio Measurements in Potenza in the Frame of the International Network for the Detection of Atmospheric Composition Change - NDACC

    NASA Astrophysics Data System (ADS)

    De Rosa, Benedetto; Di Girolamo, Paolo; Summa, Donato; Stelitano, Dario; Mancini, Ignazio

    2016-06-01

    In November 2012 the University of BASILicata Raman Lidar system (BASIL) was approved to enter the International Network for the Detection of Atmospheric Composition Change (NDACC). This network includes more than 70 high-quality, remote-sensing research stations for observing and understanding the physical and chemical state of the upper troposphere and stratosphere and for assessing the impact of stratosphere changes on the underlying troposphere and on global climate. As part of this network, more than thirty groundbased Lidars deployed worldwide are routinely operated to monitor atmospheric ozone, temperature, aerosols, water vapour, and polar stratospheric clouds. In the frame of NDACC, BASIL performs measurements on a routine basis each Thursday, typically from local noon to midnight, covering a large portion of the daily cycle. Measurements from BASIL are included in the NDACC database both in terms of water vapour mixing ratio and temperature. This paper illustrates some measurement examples from BASIL, with a specific focus on water vapour measurements, with the goal to try and characterize the system performances.

  3. Water vapour correction of the daily 1 km AVHRR global land dataset: Part I validation and use of the Water Vapour input field

    USGS Publications Warehouse

    DeFelice, Thomas P.; Lloyd, D.; Meyer, D.J.; Baltzer, T. T.; Piraina, P.

    2003-01-01

    An atmospheric correction algorithm developed for the 1 km Advanced Very High Resolution Radiometer (AVHRR) global land dataset was modified to include a near real-time total column water vapour data input field to account for the natural variability of atmospheric water vapour. The real-time data input field used for this study is the Television and Infrared Observational Satellite (TIROS) Operational Vertical Sounder (TOVS) Pathfinder A global total column water vapour dataset. It was validated prior to its use in the AVHRR atmospheric correction process using two North American AVHRR scenes, namely 13 June and 28 November 1996. The validation results are consistent with those reported by others and entail a comparison between TOVS, radiosonde, experimental sounding, microwave radiometer, and data from a hand-held sunphotometer. The use of this data layer as input to the AVHRR atmospheric correction process is discussed.

  4. Superior CO catalytic oxidation on novel Pt/clay nanocomposites.

    PubMed

    Varade, Dharmesh; Abe, Hideki; Yamauchi, Yusuke; Haraguchi, Kazutoshi

    2013-11-27

    Nanostructured novel Pt/Clay nanocomposites consisting of well-defined Pt nanoparticles prepared by clay-mediated in situ reduction displays very high thermal stability, large BET surface area and superior catalytic activity for CO oxidation as compared to a model reference Pt/SiO2 catalysts. CO oxidation has attracted renewed attention because of its technological importance in the area of pollution control. The Pt/Clay system consisting of Pt nanoparticles strongly immobilized between the atomic layers of clay inhibits nanoparticle sintering and loss of catalytic activity even after prolonged heating at high temperatures. At elevated temperatures (300 °C), the Pt/Clay system demonstrates significant enhancement of catalytic activity, with almost 100% CO conversion in less than 5 min. Emphasis is given to the role played by the clay supporting material which is chemically and thermally stable under the catalytic conditions of exhaust purification.

  5. Accidental inhalation of mercury vapour: respiratory and toxicologic consequences.

    PubMed Central

    Lien, D. C.; Todoruk, D. N.; Rajani, H. R.; Cook, D. A.; Herbert, F. A.

    1983-01-01

    Four adults, including a pregnant woman, and three children were admitted to hospital following accidental exposure to mercury vapour produced by heating mercury-gold amalgam. Initial symptoms and signs included a paroxysmal cough, dyspnea, chest pain, tachypnea, nausea, vomiting, fever and leukocytosis. Pulmonary function testing performed on the second day after exposure revealed air-flow obstruction and minor restrictive defects in three patients. The diffusing capacity of the lung for carbon monoxide was reduced in two of these patients. The mean initial blood mercury level (+/- one standard deviation) for the seven patients was 30.8 +/- 1.5 micrograms/dl. A computer analysis showed mercury to behave as a two-compartment system, the compartments having half-lives of 2 and 8 days. The four adults received chelation therapy with D-penicillamine, which did not affect the urinary excretion of mercury. The pregnant woman's infant, born 26 days after exposure, had no detectable clinical abnormalities. The levels of mercury in the blood of the mother and infant at birth and 6 days later were comparable, indicating free transfer of the metal across the placenta. Images FIG. 1 FIG. 2 PMID:6883261

  6. On the vapour trail of an atmospheric imprint in insects.

    PubMed

    Ellwood, M D Farnon; Northfield, Roger G W; Mejia-Chang, Monica; Griffiths, Howard

    2011-08-23

    Terrestrial arthropods, at constant risk from desiccation, are highly sensitive to atmospheric temperature and humidity. A physiological marker of these abiotic conditions could highlight phenotypic adaptations, indicate niche partitioning, and predict responses to climate change for a group representing three-quarters of the Earth's animal species. We show that the (18)O composition of insect haemolymph is such a measure, providing a dynamic and quantitatively predictable signal for respiratory gas exchange and inputs from atmospheric humidity. Using American cockroaches (Periplaneta americana) under defined experimental conditions, we show that insects respiring at low humidity demonstrate the expected enrichment in the (18)O composition of haemolymph because of evaporation. At high humidity, however, diffusional influx of atmospheric water vapour into the animal forces haemolymph to become depleted in (18)O. Additionally, using cockroaches sampled from natural habitats, we show that the haemolymph (18)O signature is transferred to the organic material of the insect's exoskeleton. Insect cuticle, therefore, exhibits the mean atmospheric conditions surrounding the animals prior to moulting. This discovery will help to define the climatic tolerances of species and their habitat preferences, and offers a means of quantifying the balance between niche partitioning and 'neutral' processes in shaping complex tropical forest communities.

  7. Water vapour in the atmosphere of a transiting extrasolar planet.

    PubMed

    Tinetti, Giovanna; Vidal-Madjar, Alfred; Liang, Mao-Chang; Beaulieu, Jean-Philippe; Yung, Yuk; Carey, Sean; Barber, Robert J; Tennyson, Jonathan; Ribas, Ignasi; Allard, Nicole; Ballester, Gilda E; Sing, David K; Selsis, Franck

    2007-07-12

    Water is predicted to be among the most abundant (if not the most abundant) molecular species after hydrogen in the atmospheres of close-in extrasolar giant planets ('hot Jupiters'). Several attempts have been made to detect water on such planets, but have either failed to find compelling evidence for it or led to claims that should be taken with caution. Here we report an analysis of recent observations of the hot Jupiter HD 189733b (ref. 6) taken during the transit, when the planet passed in front of its parent star. We find that absorption by water vapour is the most likely cause of the wavelength-dependent variations in the effective radius of the planet at the infrared wavelengths 3.6 mum, 5.8 mum (both ref. 7) and 8 mum (ref. 8). The larger effective radius observed at visible wavelengths may arise from either stellar variability or the presence of clouds/hazes. We explain the report of a non-detection of water on HD 189733b (ref. 4) as being a consequence of the nearly isothermal vertical profile of the planet's atmosphere.

  8. Copper vapour laser ID labelling on metal dentures and restorations.

    PubMed

    Ling, B C; Nambiar, P; Low, K S; Lee, C K

    2003-06-01

    Denture marking is accepted as a means of identifying dentures and persons in geriatric institutions, or post-mortem during war, crimes, civil unrest, natural and mass disasters. Labelling on the acrylic resin component of the denture can easily be damaged or destroyed by fire but on cobalt-chromium components it would be more resistant. A copper vapour laser (CVL) can be used to label the cobalt-chromium components of dentures and metal restorations easily, and legibly, and miniaturised for the incorporation of more personal particulars necessary for the identification of the deceased person. The CVL beam is focussed by its optics and delivered to the material surface by the two-axis scanner mounted with mirrors. A personal computer controls the movement of the scanner and the firing of the CVL. The high peak power of the pulsed CVL is focussed to very high energy density producing plasma ablation of the alloy surface. Very fine markings of a few microns width can be produced enabling the storage of detailed information of the deceased person on a metal surface for the purpose of rapid identification.

  9. Pressure effects on water vapour lines: beyond the Voigt profile.

    PubMed

    Ngo, N H; Tran, H; Gamache, R R; Hartmann, J M

    2012-06-13

    A short overview of recent results on the effects of pressure (collisions) regarding the shape of isolated infrared lines of water vapour is presented. The first part of this study considers the basic collisional quantities, which are the pressure-broadening and -shifting coefficients, central parameters of the Lorentzian (and Voigt) profile and thus of any sophisticated line-shape model. Through comparisons of measured values with semi-classical calculations, the influences of the molecular states (both rotational and vibrational) involved and of the temperature are analysed. This shows the relatively unusual behaviour of H(2)O broadening, with evidence of a significant vibrational dependence and the fact that the broadening coefficient (in cm(-1) atm(-1)) of some lines increases with temperature. In the second part of this study, line shapes beyond the Voigt model are considered, thus now taking 'velocity effects' into account. These include both the influence of collisionally induced velocity changes that lead to the so-called Dicke narrowing and the influence of the dependence of collisional parameters on the speed of the radiating molecule. Experimental evidence of deviations from the Voigt shape is presented and analysed. The interest of classical molecular dynamics simulations, to model velocity changes, together with semi-classical calculations of the speed-dependent collisional parameters for line-shape predictions from 'first principles', are discussed. PMID:22547229

  10. Calibration of the Purple Crow Lidar vibrational Raman water-vapour mixing ratio and temperature measurements

    NASA Astrophysics Data System (ADS)

    Argall, P. S.; Sica, R. J.; Bryant, C. R.; Algara-Siller, M.; Schijns, H.

    2007-02-01

    Purple Crow Lidar (PCL) measurements of the vibrational Raman-shifted backscatter from water vapour and nitrogen molecules allows height profiles of the water-vapour mixing ratio to be measured from 500 m up into the lower stratosphere. In addition, the Raman nitrogen measurements allow the determination of temperature profiles from about 10 to 40 km altitude. However, external calibration of these measurements is necessary to compensate for instrumental effects, uncertainties in our knowledge of the relevant molecular cross sections, and atmospheric transmission. A comparison of the PCL-derived water-vapour concentration and temperature profiles with routine radiosonde measurements from Detroit and Buffalo on 37 and 141 nights, respectively, was undertaken to provide this calibration. The calibration is then applied to the measurements and monthly mean-temperature and water-vapour profiles are determined.

  11. Vapour sensitivity of an ALD hierarchical photonic structure inspired by Morpho.

    PubMed

    Poncelet, Olivier; Tallier, Guillaume; Mouchet, Sébastien R; Crahay, André; Rasson, Jonathan; Kotipalli, Ratan; Deparis, Olivier; Francis, Laurent A

    2016-06-01

    The unique architecture of iridescent Morpho butterfly scales is known to exhibit different optical responses to various vapours. However, the mechanism behind this phenomenon is not fully quantitatively understood. This work reports on process developments in the micro-fabrication of a Morpho-inspired photonic structure in atomic layer deposited (ALD) materials in order to investigate the vapour optical sensitivity of such artificial nanostructures. By developing recipes for dry and wet etching of ALD oxides, we micro-fabricated two structures: one combining Al2O3 and TiO2, and the other combining Al2O3 and HfO2. For the first time, we report the optical response of such ALD Morpho-like structures measured under a controlled flow of either ethanol or isopropyl alcohol (IPA) vapour. In spite of the small magnitude of the effect, the results show a selective vapour response (depending on the materials used). PMID:27159922

  12. Design Of A Geosynchronous SAR System For Water-Vapour Maps And Deformation Estimation

    NASA Astrophysics Data System (ADS)

    Guarnieri, Andrea Monti; Perletta, Luca; Rocca, Fabio; Scapin, Diego; Tebaldini, Stefano; Broquetas, Antoni; Ruiz, Josep

    2012-01-01

    In this paper, we propose a geosynchronous SAR concept that makes use of dual frequencies to achieve WIDE and SPOT coverage, aiming at continuous monitoring of deformation and generation of water vapour maps at high space-temporal resolution.

  13. Vapour sensitivity of an ALD hierarchical photonic structure inspired by Morpho.

    PubMed

    Poncelet, Olivier; Tallier, Guillaume; Mouchet, Sébastien R; Crahay, André; Rasson, Jonathan; Kotipalli, Ratan; Deparis, Olivier; Francis, Laurent A

    2016-05-09

    The unique architecture of iridescent Morpho butterfly scales is known to exhibit different optical responses to various vapours. However, the mechanism behind this phenomenon is not fully quantitatively understood. This work reports on process developments in the micro-fabrication of a Morpho-inspired photonic structure in atomic layer deposited (ALD) materials in order to investigate the vapour optical sensitivity of such artificial nanostructures. By developing recipes for dry and wet etching of ALD oxides, we micro-fabricated two structures: one combining Al2O3 and TiO2, and the other combining Al2O3 and HfO2. For the first time, we report the optical response of such ALD Morpho-like structures measured under a controlled flow of either ethanol or isopropyl alcohol (IPA) vapour. In spite of the small magnitude of the effect, the results show a selective vapour response (depending on the materials used).

  14. Catalytic reforming methods

    DOEpatents

    Tadd, Andrew R; Schwank, Johannes

    2013-05-14

    A catalytic reforming method is disclosed herein. The method includes sequentially supplying a plurality of feedstocks of variable compositions to a reformer. The method further includes adding a respective predetermined co-reactant to each of the plurality of feedstocks to obtain a substantially constant output from the reformer for the plurality of feedstocks. The respective predetermined co-reactant is based on a C/H/O atomic composition for a respective one of the plurality of feedstocks and a predetermined C/H/O atomic composition for the substantially constant output.

  15. Vapour transport of rare earth elements (REE) in volcanic gas: Evidence from encrustations at Oldoinyo Lengai

    NASA Astrophysics Data System (ADS)

    Gilbert, C. D.; Williams-Jones, A. E.

    2008-10-01

    Fumarolic encrustations and natrocarbonatite lava from the active crater of Oldoinyo Lengai volcano, Tanzania, were sampled and analysed. Two types of encrustation were distinguished on the basis of their REE content, enriched (~ 2800-5600 × [REE chondrite]) and depleted (~ 100-200 × [REE chondrite]) relative to natrocarbonatite (1700-1900 × [REE chondrite]. REE-enriched encrustations line the walls of actively degassing fumaroles, whereas REE-depleted encrustations occur mainly along cracks in and as crusts on cooling natrocarbonatite lava flows; one of the low REE encrustation samples was a stalactite from the wall of a possible fumarole. The encrustations are interpreted to have different origins, the former precipitating from volcanic gas and the latter from meteoric/ground water converted to steam by the heat of the overlying lava flow(s). REE-profiles of encrustations and natrocarbonatite are parallel, suggesting that there was no preferential mobilization of specific REE by either volcanic vapour or meteoric water vapour. The elevated REE-content of the first group of encrustations suggests that direct REE-transport from natrocarbonatite to volcanic vapour is possible. The REE trends observed in samples precipitating directly from the volcanic vapour cannot be explained by dry volatility based on the available data as there is no evidence in the encrustation compositions of the greatly enhanced volatility predicted for Yb and Eu. The observed extreme REE-fractionation with steep La/Sm slopes parallel to those of the natrocarbonatite reflects solvation and complexation reactions in the vapour phase that did not discriminate amongst the different REE or similar transport of REE in both the natrocarbonatite magma and its exsolving vapour. The low concentrations of REE in the encrustations produced by meteoric vapour suggest that the temperature was too low or that this vapour did not contain the ligands necessary to permit significant mobilization of the REE.

  16. Mesoscale modelling of water vapour in the tropical UTLS: two case studies from the HIBISCUS campaign

    NASA Astrophysics Data System (ADS)

    Marécal, V.; Durry, G.; Longo, K.; Freitas, S.; Rivière, E. D.; Pirre, M.

    2006-08-01

    In this study, we evaluate the ability of the BRAMS mesoscale model compared to ECMWF global analysis to simulate the observed vertical variations of water vapour in the tropical upper troposphere and lower stratosphere (UTLS). The observations are balloon-borne measurements of water vapour mixing ratio and temperature from micro-SDLA (Tunable Diode Laser Spectrometer) instrument. Data from two balloon flights performed during the 2004 HIBISCUS field campaign are used to compare with the mesoscale simulations and to ECMWF analysis. The mesoscale model performs significantly better than ECMWF analysis for water vapour in the upper troposphere and similarly or slightly worse for temperature. The improvement provided by the mesoscale model for water vapour comes mainly from (i) the enhanced vertical resolution in the UTLS (250 m for BRAMS and ~1 km for ECMWF model) and (ii) the more detailed microphysical parameterization providing ice supersaturations as in the observations. The ECMWF vertical resolution (~1 km) is too coarse to capture the observed fine scale vertical variations of water vapour in the UTLS. In near saturated or supersaturated layers, the mesoscale model relative humidity with respect to ice saturation is close to observations provided that the temperature profile is realistic. For temperature, ECMWF analysis gives good results partly thanks to data assimilation. The analysis of the mesoscale model results showed that in undersaturated layers, the water vapour profile depends mainly on the dynamics. In saturated/supersaturated layers, microphysical processes play an important role and have to be taken into account on top of the dynamical processes to understand the water vapour profiles. In the lower stratosphere, the ECMWF model and the BRAMS model give very similar water vapour profiles that are significantly dryer than micro-SDLA measurements. This similarity comes from the fact that BRAMS is initialised using ECMWF analysis and that no mesoscale

  17. Temporal evolution of temperature and OH density produced by nanosecond repetitively pulsed discharges in water vapour at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Sainct, F. P.; Lacoste, D. A.; Kirkpatrick, M. J.; Odic, E.; Laux, C. O.

    2014-02-01

    We report on an experimental study of the temporal evolution of OH density and gas temperature in spark discharges created by nanosecond repetitively pulsed discharges in pure water vapour at 475 K and atmospheric pressure. The plasma was generated by 20 kV, 20 ns pulses, at a repetition frequency of 10 kHz. The temperature was measured during the discharge by optical emission spectroscopy of the second positive system of N2, and between two discharges by two-colour OH-planar laser induced fluorescence (OH-PLIF) using two pairs of rotational transitions. Between two successive discharges, the relative density of OH was measured by OH-PLIF and was found to decay very slowly, with a 1/e decay time of about 50 µs. With the use of a chemical kinetics model, the OH density was placed on an absolute scale.

  18. Influence of metal vapour on arc temperatures in gas-metal arc welding: convection versus radiation

    NASA Astrophysics Data System (ADS)

    Murphy, Anthony B.

    2013-06-01

    The presence of metal vapour in gas-metal arc welding has been shown to have two strong effects on the arc plasma: a decrease in temperature throughout the arc, and the formation of a local temperature minimum near the arc axis. These effects have been attributed, on the basis of different computational models, to either the increased radiative emission associated with the presence of metal vapour in the arc plasma, or the influence of the metal vapour influx on convective flow in the arc. This question is investigated using a three-dimensional computational model in which the production and the transport of metal vapour are taken into account self-consistently. Parameters relevant to welding of thin sheets of aluminum are examined. For these conditions, it is found that the first effect (the decrease in temperature throughout the arc) is due to both the increased radiative emission and the influence of the metal vapour influx on flow. The second effect (the local temperature minimum, which in this case occurs just below the wire electrode) is a consequence of the influence of aluminum vapour produced from the wire electrode on flow in the arc. By examining published results and the energy balance in the plasma, it is shown that for welding of steel with higher arc currents, the increased radiative emission can lead to a local temperature minimum at a greater distance from the wire electrode.

  19. Observations and recent evolution of stratospheric water vapour isotopologues derived from satellite measurements

    NASA Astrophysics Data System (ADS)

    Urban, Joachim; Jones, Ashley; Lossow, Stefan; Murtagh, Donal

    Water vapour, a strong greenhouse gas and source gas of the HOx family, plays an essential role for dynamics and chemistry of the middle atmosphere. Global measurements of isotopologues of water vapour have been made by the Odin Sub-Millimetre Radiometer (SMR) during nearly nine years since 2001. The long-term evolution of stratospheric water vapour has been studied by extending the historical satellite time-series from SAGE and HALOE, available until 2005, to present day by using data from Odin and other more recently launched satellites (Envisat, ACE). The recent evolution and variability of the water vapour isotopologues H2O-17, H2O-18, and HDO, as well as related trace gases and temperature has also been analysed and results of this study will be presented. Comparison and combination of various stratospheric water vapour time-series moreover provides a critical test of the quality of the different new satellite water vapour data sets. Odin is a Swedish-led satellite project funded jointly by Sweden (SNSB), Canada (CSA), Fin-land (TEKES), and France (CNES), with support by the 3rd party mission programme of the European Space Agency (ESA).

  20. Selective Catalytic Synthesis Using the Combination of Carbon Dioxide and Hydrogen: Catalytic Chess at the Interface of Energy and Chemistry.

    PubMed

    Klankermayer, Jürgen; Wesselbaum, Sebastian; Beydoun, Kassem; Leitner, Walter

    2016-06-20

    The present Review highlights the challenges and opportunities when using the combination CO2 /H2 as a C1 synthon in catalytic reactions and processes. The transformations are classified according to the reduction level and the bond-forming processes, covering the value chain from high volume basic chemicals to complex molecules, including biologically active substances. Whereas some of these concepts can facilitate the transition of the energy system by harvesting renewable energy into chemical products, others provide options to reduce the environmental impact of chemical production already in today's petrochemical-based industry. Interdisciplinary fundamental research from chemists and chemical engineers can make important contributions to sustainable development at the interface of the energetic and chemical value chain. The present Review invites the reader to enjoy this exciting area of "catalytic chess" and maybe even to start playing some games in her or his laboratory. PMID:27237963

  1. Selective Catalytic Synthesis Using the Combination of Carbon Dioxide and Hydrogen: Catalytic Chess at the Interface of Energy and Chemistry.

    PubMed

    Klankermayer, Jürgen; Wesselbaum, Sebastian; Beydoun, Kassem; Leitner, Walter

    2016-06-20

    The present Review highlights the challenges and opportunities when using the combination CO2 /H2 as a C1 synthon in catalytic reactions and processes. The transformations are classified according to the reduction level and the bond-forming processes, covering the value chain from high volume basic chemicals to complex molecules, including biologically active substances. Whereas some of these concepts can facilitate the transition of the energy system by harvesting renewable energy into chemical products, others provide options to reduce the environmental impact of chemical production already in today's petrochemical-based industry. Interdisciplinary fundamental research from chemists and chemical engineers can make important contributions to sustainable development at the interface of the energetic and chemical value chain. The present Review invites the reader to enjoy this exciting area of "catalytic chess" and maybe even to start playing some games in her or his laboratory.

  2. Catalytic Products from a Bench-Scale, Simulated Fluidized-Bed Pyrolyzer

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Biomass (e.g. lignocellulosics and lipids) were catalytically converted under thermochemical conditions to bio-based, fungible industrial chemicals and products. The focus was on high temperature catalytic conversions of feedstocks in a bench-scale reactor designed to replicate a packed- or fluidiz...

  3. Catalytic properties of composite amorphous carbon-platinum layers in fuel cells

    SciTech Connect

    Nechitailov, A. A. Zvonareva, T. K.; Remenyuk, A. D.; Tolmachev, V. A.; Goryachev, D. N.; El'tsina, O. S.; Belyakov, L. V.; Sreseli, O. M.

    2008-10-15

    Catalytic properties of composite amorphous carbon-platinum layers produced by magnetron cosputtering have been studied. The layers were characterized by electron microscopy, IR spectroscopy, ellipsometry, gravimetry, and spectrophotometric chemical analysis. The catalytic activity of the layers was studied in an air-hydrogen fuel cell by measuring its load and power characteristics.

  4. Chemical evidence for the pH-dependent control of ion-pair geometry in cathepsin B. Benzofuroxan as a reactivity probe sensitive to differences in the mutual disposition of the thiolate and imidazolium components of cysteine proteinase catalytic sites.

    PubMed

    Willenbrock, F; Brocklehurst, K

    1986-08-15

    Benzofuroxan reacts with the catalytic-site thiol group of cathepsin B (EC 3.4.22.1) to produce stoichiometric amount of the chromophoric reduction product, o-benzoquinone dioxime. In a study of the pH-dependence of the kinetics of this reaction, most data were collected for the bovine spleen enzyme, but the more limited data collected for the rat liver enzyme were closely similar both in the magnitude of the values of the second-order rate constants (k) and in the shape of the pH-k profile. In acidic and weakly alkaline media, the reaction is faster than the reactions of benzofuroxan with some other cysteine proteinases. For example, in the pH region around 5-6, the reaction of cathepsin B is about 10 times faster than that of papain, 15 times faster than that of stem bromelain and 6 times faster than that of ficin. The pH-dependence of k for the reaction of cathepsin B with benzofuroxan was determined in the pH range 2.7-8.3. In marked contrast with the analogous reactions of papain, ficin and stem bromelain [reported by Shipton & Brocklehurst (1977) Biochem. J. 167, 799-810], the pH-k profile for the cathepsin B reaction contains a sigmoidal component with pKa 5.2 in which k increases with decrease in pH. This modulation of the reactivity of the catalytic-site -S-/-ImH+ ion-pair state of cathepsin B (produced by protonic dissociation from -SH/-ImH+ with pKa approx. 3) towards a small, rigid, electrophilic reagent, in a reaction that appears to involve both components of the ion-pair for efficient reaction, suggests that the state of ionization of a group associated with a molecular pKa of approx. 5 may control ion-pair geometry. This might account for the remarkable finding [reported by Willenbrock & Brocklehurst (1984) Biochem. J. 222, 805-814] that, although the ion-pair appears to be generated in cathepsin B as the pH is increased across pKa 3.4, catalytic competence is not generated until the pH is increased across pKa 5-6.

  5. Catalytic ammonia decomposition over industrial-waste-supported Ru catalysts

    SciTech Connect

    Pei Fang Ng; Li Li; Shaobin Wang; Zhonghua Zhu; Gaoqing Lu; Zifeng Yan

    2007-05-15

    Industrial solid wastes (fly ash and red mud, a by-product of the aluminium industry) have been employed as supports for preparation of Ru-based catalysts. Physical and chemical treatments on red mud were conducted and these modified supports were also used for preparation of Ru-based catalysts. Those Ru catalysts were characterized by various techniques such as N2 adsorption, H{sub 2} adsorption, XRD, XPS, and temperature-programmed reduction (TPR), and were then tested for catalytic ammonia decomposition to hydrogen. It was found that red-mud-supported Ru catalyst exhibits higher ammonia conversion and hydrogen production than fly-ash-supported catalyst. Heat and chemical treatments of the red mud greatly improve the catalytic activity. Moreover, a combination of acid and heat treatments produces the highest catalytic conversion of ammonia. 35 refs., 4 figs., 4 tabs.

  6. The millennium water vapour drop in chemistry-climate model simulations

    NASA Astrophysics Data System (ADS)

    Brinkop, Sabine; Dameris, Martin; Jöckel, Patrick; Garny, Hella; Lossow, Stefan; Stiller, Gabriele

    2016-07-01

    This study investigates the abrupt and severe water vapour decline in the stratosphere beginning in the year 2000 (the "millennium water vapour drop") and other similarly strong stratospheric water vapour reductions by means of various simulations with the state-of-the-art Chemistry-Climate Model (CCM) EMAC (ECHAM/MESSy Atmospheric Chemistry Model). The model simulations differ with respect to the prescribed sea surface temperatures (SSTs) and whether nudging is applied or not. The CCM EMAC is able to most closely reproduce the signature and pattern of the water vapour drop in agreement with those derived from satellite observations if the model is nudged. Model results confirm that this extraordinary water vapour decline is particularly obvious in the tropical lower stratosphere and is related to a large decrease in cold point temperature. The drop signal propagates under dilution to the higher stratosphere and to the poles via the Brewer-Dobson circulation (BDC). We found that the driving forces for this significant decline in water vapour mixing ratios are tropical sea surface temperature (SST) changes due to a coincidence with a preceding strong El Niño-Southern Oscillation event (1997/1998) followed by a strong La Niña event (1999/2000) and supported by the change of the westerly to the easterly phase of the equatorial stratospheric quasi-biennial oscillation (QBO) in 2000. Correct (observed) SSTs are important for triggering the strong decline in water vapour. There are indications that, at least partly, SSTs contribute to the long period of low water vapour values from 2001 to 2006. For this period, the specific dynamical state of the atmosphere (overall atmospheric large-scale wind and temperature distribution) is important as well, as it causes the observed persistent low cold point temperatures. These are induced by a period of increased upwelling, which, however, has no corresponding pronounced signature in SSTs anomalies in the tropics. Our free

  7. GPS tomographic experiment on water vapour dynamics in the troposphere over Lisbon

    NASA Astrophysics Data System (ADS)

    Benevides, Pedro; Catalao, Joao; Miranda, Pedro

    2015-04-01

    Quantification of the water vapour variability on the atmosphere remains a difficult task, affecting the weather prediction. Coarse water vapour resolution measurements in space and time affect the numerical weather prediction solution models causing artifacts in the prediction of severe weather phenomena. The GNSS atmospheric processing has been developed in the past years providing integrated water vapour estimates comparable with the meteorological sensor measurements, with studies registering 1 to 2 kg/m2 bias, but lack a vertical determination of the atmospheric processes. The GNSS tomography in the troposphere is one of the most promising techniques for sensing the three-dimensional water vapour state of the atmosphere. The determination of the integrated water vapour profile by means of the widely accepted GNSS meteorology techniques, allows the reconstruction of several slant path delay rays in the satellite line of view, providing an opportunity to sense the troposphere at tree-dimensions plus time. The tomographic system can estimate an image solution of the water vapour but impositions have to be introduced to the system of equations inversion because of the non-optimal GNSS observation geometry. Application of this technique on atmospheric processes like large convective precipitation or mesoscale water vapour circulation have been able to describe its local dynamic vertical variation. A 3D tomographic experiment was developed over an area of 60x60 km2 around Lisbon (Portugal). The GNSS network available composed by 9 receivers was used for an experiment of densification of the permanent network using 8 temporarily installed GPS receivers (totalling 17 stations). This study was performed during several weeks in July 2013, where a radiosonde campaign was also held in order to validate the tomographic inversion solution. 2D integrated water vapour maps directly obtained from the GNSS processing were also evaluated and local coastal breeze circulation

  8. Catalytic Enantioselective Synthesis of Quaternary Carbon Stereocenters

    PubMed Central

    Quasdorf, Kyle W.; Overman, Larry E.

    2015-01-01

    Preface Quaternary carbon stereocenters–carbon atoms to which four distinct carbon substituents are attached–are common features of molecules found in nature. However, prior to recent advances in chemical catalysis, there were few methods available for constructing single stereoisomers of this important structural motif. Here we discuss the many catalytic enantioselective reactions developed during the past decade for synthesizing organic molecules containing such carbon atoms. This progress now makes it possible to selectively incorporate quaternary stereocenters in many high-value organic molecules for use in medicine, agriculture, and other areas. PMID:25503231

  9. Bifunctional catalytic electrode

    NASA Technical Reports Server (NTRS)

    Cisar, Alan (Inventor); Murphy, Oliver J. (Inventor); Clarke, Eric (Inventor)

    2005-01-01

    The present invention relates to an oxygen electrode for a unitized regenerative hydrogen-oxygen fuel cell and the unitized regenerative fuel cell having the oxygen electrode. The oxygen electrode contains components electrocatalytically active for the evolution of oxygen from water and the reduction of oxygen to water, and has a structure that supports the flow of both water and gases between the catalytically active surface and a flow field or electrode chamber for bulk flow of the fluids. The electrode has an electrocatalyst layer and a diffusion backing layer interspersed with hydrophilic and hydrophobic regions. The diffusion backing layer consists of a metal core having gas diffusion structures bonded to the metal core.

  10. Catalytic hollow spheres

    NASA Technical Reports Server (NTRS)

    Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

    1989-01-01

    The improved, heterogeneous catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitably formed of a shell (12) of metal such as aluminum having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be, itself, catalytic or the catalyst can be coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

  11. Modelling ignition characteristics of rich H2/O2 mixture in a monolithic catalytic reactor

    NASA Technical Reports Server (NTRS)

    Tien, Ta-Ching; T'Ien, James S.

    1988-01-01

    Ignition of rich hydrogen-oxygen mixture in a monolithic catalytic reactor is studied using a transient combustion model. The model assumes a quasi-steady gas phase and a thermally-thin substrate. The ignition time lag is due to the thermal inertia of the substrate. One-step global chemical reaction is assumed both on the surface and in the gas phase. An effectiveness factor is introduced to account for the transition from a kinetically-limited catalytic surface reaction to a diffusion-limit one during ignition. Results presented include a catalytic ignition boundary, ignition delay time and the transient response in the catalytic bed.

  12. Continuous measurements of isotopic composition of water vapour on the East Antarctic Plateau

    NASA Astrophysics Data System (ADS)

    Casado, Mathieu; Landais, Amaelle; Masson-Delmotte, Valérie; Genthon, Christophe; Kerstel, Erik; Kassi, Samir; Arnaud, Laurent; Picard, Ghislain; Prie, Frederic; Cattani, Olivier; Steen-Larsen, Hans-Christian; Vignon, Etienne; Cermak, Peter

    2016-07-01

    Water stable isotopes in central Antarctic ice cores are critical to quantify past temperature changes. Accurate temperature reconstructions require one to understand the processes controlling surface snow isotopic composition. Isotopic fractionation processes occurring in the atmosphere and controlling snowfall isotopic composition are well understood theoretically and implemented in atmospheric models. However, post-deposition processes are poorly documented and understood. To quantitatively interpret the isotopic composition of water archived in ice cores, it is thus essential to study the continuum between surface water vapour, precipitation, surface snow and buried snow. Here, we target the isotopic composition of water vapour at Concordia Station, where the oldest EPICA Dome C ice cores have been retrieved. While snowfall and surface snow sampling is routinely performed, accurate measurements of surface water vapour are challenging in such cold and dry conditions. New developments in infrared spectroscopy enable now the measurement of isotopic composition in water vapour traces. Two infrared spectrometers have been deployed at Concordia, allowing continuous, in situ measurements for 1 month in December 2014-January 2015. Comparison of the results from infrared spectroscopy with laboratory measurements of discrete samples trapped using cryogenic sampling validates the relevance of the method to measure isotopic composition in dry conditions. We observe very large diurnal cycles in isotopic composition well correlated with temperature diurnal cycles. Identification of different behaviours of isotopic composition in the water vapour associated with turbulent or stratified regime indicates a strong impact of meteorological processes in local vapour/snow interaction. Even if the vapour isotopic composition seems to be, at least part of the time, at equilibrium with the local snow, the slope of δD against δ18O prevents us from identifying a unique origin leading

  13. Metal-organic chemical vapour deposition of polycrystalline tetragonal indium sulphide (InS) thin films

    NASA Technical Reports Server (NTRS)

    Macinnes, Andrew N.; Cleaver, William M.; Barron, Andrew R.; Power, Michael B.; Hepp, Aloysius F.

    1992-01-01

    The dimeric indium thiolate /(t Bu)2In(mu-S sup t Bu)/2 has been used as a single-source precursor for the MOCVD of InS thin films. The dimeric In2S2 core is proposed to account for the formation of the nonequilibrium high-pressure tetragonal phase in the deposited films. Analysis of the deposited films has been obtained by TEM, with associated energy-dispersive X-ray analysis and X-ray photoelectron spectroscopy.

  14. Piezoelectric effect in chemical vapour deposition-grown atomic-monolayer triangular molybdenum disulfide piezotronics.

    PubMed

    Qi, Junjie; Lan, Yann-Wen; Stieg, Adam Z; Chen, Jyun-Hong; Zhong, Yuan-Liang; Li, Lain-Jong; Chen, Chii-Dong; Zhang, Yue; Wang, Kang L

    2015-01-01

    High-performance piezoelectricity in monolayer semiconducting transition metal dichalcogenides is highly desirable for the development of nanosensors, piezotronics and photo-piezotransistors. Here we report the experimental study of the theoretically predicted piezoelectric effect in triangle monolayer MoS2 devices under isotropic mechanical deformation. The experimental observation indicates that the conductivity of MoS2 devices can be actively modulated by the piezoelectric charge polarization-induced built-in electric field under strain variation. These polarization charges alter the Schottky barrier height on both contacts, resulting in a barrier height increase with increasing compressive strain and decrease with increasing tensile strain. The underlying mechanism of strain-induced in-plane charge polarization is proposed and discussed using energy band diagrams. In addition, a new type of MoS2 strain/force sensor built using a monolayer MoS2 triangle is also demonstrated. Our results provide evidence for strain-gating monolayer MoS2 piezotronics, a promising avenue for achieving augmented functionalities in next-generation electronic and mechanical-electronic nanodevices. PMID:26109177

  15. Binding of Vapour-Phase Mercury (Hg0) on Chemically Treated Bauxite Residues (Red Mud)

    EPA Science Inventory

    In this study, Hg capture using red mud, seawater-neutralized red mud, and acid-treated red mud is evaluated and compared to other, more conventional sorbent materials. Red mud (also known as bauxite residue) is a by-product of extracting alumina from ground bauxite ore by treati...

  16. Chemical vapour deposition of nitrogen-doped titanium dioxide thin films.

    PubMed

    Alexandrov, S E; Baryshnikova, M V; Filatov, L A; Shahmin, A L; Andreeva, V D

    2011-09-01

    Nitrogen-doped titanium dioxide is often considered as a promising nanomaterial for photocatalytic applications. Here we report the first results of a study of APCVD of N-doped TiO2 thin films prepared with the use of ammonia as a source of nitrogen and titanium tetraisopropoxide (TTIP) as a source of Ti and O atoms. The obtained films were analyzed with X-ray diffraction, infrared spectroscopy, atomic force microscopy, X-ray photoelectron spectroscopy, UV-Vis spectroscopy, and ellipsometry. It was found that the film growth rate in the TTIP-NH3-Ar reaction system varied insignificantly with substrate temperature in the range of 450,..., 750 degrees C and did not exceed 4.4 nm/min. Yellow and orange layers with nitrogen content of about 7.6% were formed at the deposition temperature higher than 600 degrees C. The results of the structure analysis of the deposited films showed that addition of ammonia led to stabilization of the amorphous phase in the films. The effect of ammonia on optical and photocatalytic properties was also considered. PMID:22097568

  17. Piezoelectric effect in chemical vapour deposition-grown atomic-monolayer triangular molybdenum disulfide piezotronics

    PubMed Central

    Qi, Junjie; Lan, Yann-Wen; Stieg, Adam Z.; Chen, Jyun-Hong; Zhong, Yuan-Liang; Li, Lain-Jong; Chen, Chii-Dong; Zhang, Yue; Wang, Kang L.

    2015-01-01

    High-performance piezoelectricity in monolayer semiconducting transition metal dichalcogenides is highly desirable for the development of nanosensors, piezotronics and photo-piezotransistors. Here we report the experimental study of the theoretically predicted piezoelectric effect in triangle monolayer MoS2 devices under isotropic mechanical deformation. The experimental observation indicates that the conductivity of MoS2 devices can be actively modulated by the piezoelectric charge polarization-induced built-in electric field under strain variation. These polarization charges alter the Schottky barrier height on both contacts, resulting in a barrier height increase with increasing compressive strain and decrease with increasing tensile strain. The underlying mechanism of strain-induced in-plane charge polarization is proposed and discussed using energy band diagrams. In addition, a new type of MoS2 strain/force sensor built using a monolayer MoS2 triangle is also demonstrated. Our results provide evidence for strain-gating monolayer MoS2 piezotronics, a promising avenue for achieving augmented functionalities in next-generation electronic and mechanical–electronic nanodevices. PMID:26109177

  18. Piezoelectric effect in chemical vapour deposition-grown atomic-monolayer triangular molybdenum disulfide piezotronics.

    PubMed

    Qi, Junjie; Lan, Yann-Wen; Stieg, Adam Z; Chen, Jyun-Hong; Zhong, Yuan-Liang; Li, Lain-Jong; Chen, Chii-Dong; Zhang, Yue; Wang, Kang L

    2015-06-25

    High-performance piezoelectricity in monolayer semiconducting transition metal dichalcogenides is highly desirable for the development of nanosensors, piezotronics and photo-piezotransistors. Here we report the experimental study of the theoretically predicted piezoelectric effect in triangle monolayer MoS2 devices under isotropic mechanical deformation. The experimental observation indicates that the conductivity of MoS2 devices can be actively modulated by the piezoelectric charge polarization-induced built-in electric field under strain variation. These polarization charges alter the Schottky barrier height on both contacts, resulting in a barrier height increase with increasing compressive strain and decrease with increasing tensile strain. The underlying mechanism of strain-induced in-plane charge polarization is proposed and discussed using energy band diagrams. In addition, a new type of MoS2 strain/force sensor built using a monolayer MoS2 triangle is also demonstrated. Our results provide evidence for strain-gating monolayer MoS2 piezotronics, a promising avenue for achieving augmented functionalities in next-generation electronic and mechanical-electronic nanodevices.

  19. Catalytic activities of zeolite compounds for decomposing aqueous ozone.

    PubMed

    Kusuda, Ai; Kitayama, Mikito; Ohta, Yoshio

    2013-12-01

    The advanced oxidation process (AOP), chemical oxidation using aqueous ozone in the presence of appropriate catalysts to generate highly reactive oxygen species, offers an attractive option for removing poorly biodegradable pollutants. Using the commercial zeolite powders with various Si/Al ratios and crystal structures, their catalytic activities for decomposing aqueous ozone were evaluated by continuously flowing ozone to water containing the zeolite powders. The hydrophilic zeolites (low Si/Al ratio) with alkali cations in the crystal structures were found to possess high catalytic activity for decomposing aqueous ozone. The hydrophobic zeolite compounds (high Si/Al ratio) were found to absorb ozone very well, but to have no catalytic activity for decomposing aqueous ozone. Their catalytic activities were also evaluated by using the fixed bed column method. When alkali cations were removed by acid rinsing or substituted by alkali-earth cations, the catalytic activities was significantly deteriorated. These results suggest that the metal cations on the crystal surface of the hydrophilic zeolite would play a key role for catalytic activity for decomposing aqueous ozone.

  20. Catalytic activities of zeolite compounds for decomposing aqueous ozone.

    PubMed

    Kusuda, Ai; Kitayama, Mikito; Ohta, Yoshio

    2013-12-01

    The advanced oxidation process (AOP), chemical oxidation using aqueous ozone in the presence of appropriate catalysts to generate highly reactive oxygen species, offers an attractive option for removing poorly biodegradable pollutants. Using the commercial zeolite powders with various Si/Al ratios and crystal structures, their catalytic activities for decomposing aqueous ozone were evaluated by continuously flowing ozone to water containing the zeolite powders. The hydrophilic zeolites (low Si/Al ratio) with alkali cations in the crystal structures were found to possess high catalytic activity for decomposing aqueous ozone. The hydrophobic zeolite compounds (high Si/Al ratio) were found to absorb ozone very well, but to have no catalytic activity for decomposing aqueous ozone. Their catalytic activities were also evaluated by using the fixed bed column method. When alkali cations were removed by acid rinsing or substituted by alkali-earth cations, the catalytic activities was significantly deteriorated. These results suggest that the metal cations on the crystal surface of the hydrophilic zeolite would play a key role for catalytic activity for decomposing aqueous ozone. PMID:25078817

  1. Catalytic and reactive polypeptides and methods for their preparation and use

    DOEpatents

    Schultz, Peter

    1993-01-01

    Catalytic and reactive polypeptides include a binding site specific for a reactant or reactive intermediate involved in a chemical reaction of interest. The polypeptides further include at least one active functionality proximate the bi.

  2. Characterization of a catalytically efficient acidic RNA-cleaving deoxyribozyme.

    PubMed

    Kandadai, Srinivas A; Li, Yingfu

    2005-01-01

    We previously demonstrated--through the isolation of RNA-cleaving deoxyribozymes by in vitro selection that are catalytically active in highly acidic solutions--that DNA, despite its chemical simplicity, could perform catalysis under challenging chemical conditions [Liu,Z., Mei,S.H., Brennan,J.D. and Li,Y. (2003) J. Am. Chem. Soc. 125, 7539-7545]. One remarkable DNA molecule therefrom is pH4DZ1, a self-cleaving deoxyribozyme that exhibits a k(obs) of approximately 1 min(-1) at pH 3.8. In this study, we carried out a series of experiments to examine the sequence and catalytic properties of this acidic deoxyribozyme. Extensive nucleotide truncation experiments indicated that pH4DZ1 was a considerably large deoxyribozyme, requiring approximately 80 out of the original 123 nt for the optimal catalytic activity. A reselection experiment identified ten absolutely conserved nucleotides that are distributed in three catalytically crucial sequence elements. In addition, a trans deoxyribozyme was successfully designed. Comparison of the observed rate constant of pH4DZ1 with experimentally determined rate constant for the uncatalyzed reaction revealed that pH4DZ1 achieved a rate enhancement of approximately 10(6)-fold. This study provides valuable information about this low-pH-functional deoxyribozyme and paves way for further structural and mechanistic characterization of this unique catalytic DNA. PMID:16391005

  3. Unsteady catalytic processes and sorption-catalytic technologies

    NASA Astrophysics Data System (ADS)

    Zagoruiko, A. N.

    2007-07-01

    Catalytic processes that occur under conditions of the targeted unsteady state of the catalyst are considered. The highest efficiency of catalytic processes was found to be ensured by a controlled combination of thermal non-stationarity and unsteady composition of the catalyst surface. The processes based on this principle are analysed, in particular, catalytic selective reduction of nitrogen oxides, deep oxidation of volatile organic impurities, production of sulfur by the Claus process and by hydrogen sulfide decomposition, oxidation of sulfur dioxide, methane steam reforming and anaerobic combustion, selective oxidation of hydrocarbons, etc.

  4. Novel Catalytic Membrane Reactors

    SciTech Connect

    2009-02-01

    This factsheet describes a research project that will focus on the development and application of nonporous high gas flux perfluoro membranes with high temperature rating and excellent chemical resistance.

  5. Sensitivity of polar stratospheric cloud formation to changes in water vapour and temperature

    NASA Astrophysics Data System (ADS)

    Khosrawi, F.; Urban, J.; Lossow, S.; Stiller, G.; Weigel, K.; Braesicke, P.; Pitts, M. C.; Rozanov, A.; Burrows, J. P.; Murtagh, D.

    2016-01-01

    More than a decade ago it was suggested that a cooling of stratospheric temperatures by 1 K or an increase of 1 ppmv of stratospheric water vapour could promote denitrification, the permanent removal of nitrogen species from the stratosphere by solid polar stratospheric cloud (PSC) particles. In fact, during the two Arctic winters 2009/10 and 2010/11 the strongest denitrification in the recent decade was observed. Sensitivity studies along air parcel trajectories are performed to test how a future stratospheric water vapour (H2O) increase of 1 ppmv or a temperature decrease of 1 K would affect PSC formation. We perform our study based on measurements made during the Arctic winter 2010/11. Air parcel trajectories were calculated 6 days backward in time based on PSCs detected by CALIPSO (Cloud Aerosol Lidar and Infrared Pathfinder satellite observations). The sensitivity study was performed on single trajectories as well as on a trajectory ensemble. The sensitivity study shows a clear prolongation of the potential for PSC formation and PSC existence when the temperature in the stratosphere is decreased by 1 K and water vapour is increased by 1 ppmv. Based on 15 years of satellite measurements (2000-2014) from UARS/HALOE, Envisat/MIPAS, Odin/SMR, Aura/MLS, Envisat/SCIAMACHY and SCISAT/ACE-FTS it is further investigated if there is a decrease in temperature and/or increase of water vapour (H2O) observed in the polar regions similar to that observed at midlatitudes and in the tropics. Performing linear regression analyses we derive from the Envisat/MIPAS (2002-2012) and Aura/MLS (2004-2014) observations predominantly positive changes in the potential temperature range 350 to 1000 K. The linear changes in water vapour derived from Envisat/MIPAS observations are largely insignificant, while those from Aura/MLS are mostly significant. For the temperature neither of the two instruments indicate any significant changes. Given the strong inter-annual variation observed in

  6. Tomographic retrieval of water vapour and temperature around polar mesospheric clouds using Odin-SMR

    NASA Astrophysics Data System (ADS)

    Christensen, O. M.; Eriksson, P.; Urban, J.; Murtagh, D.; Hultgren, K.; Gumbel, J.

    2014-11-01

    A special observation mode of the Odin satellite provides the first simultaneous measurements of water vapour, temperature and polar mesospheric cloud (PMC) brightness over a large geographical area while still resolving both horizontal and vertical structures in the clouds and background atmosphere. The observation mode has been activated during June, July and August of 2010, 2011 and 2014, and for latitudes between 50 and 82° N. This paper focuses on the water vapour and temperature measurements carried out with Odin's sub-millimetre radiometer (SMR). The tomographic retrieval approach used provides water vapour and temperature between 75-90 km with a vertical resolution of about 2.5 km and a horizontal resolution of about 200 km. The precision of the measurements is estimated to 0.5 ppm for water vapour and 3 K for temperature. Due to limited information about the pressure at the measured altitudes, the results have large uncertainties (> 3 ppm) in the retrieved water vapour. These errors, however, influence mainly the mean atmosphere retrieved for each orbit, and variations around this mean are still reliably captured by the measurements. SMR measurements are performed using two different mixer chains, denoted as frequency mode 19 and 13. Systematic differences between the two frontends have been noted. A first comparison with the Solar Occultation For Ice Experiment instrument (SOFIE) on-board the Aeronomy of Ice in the Mesosphere (AIM) satellite and the Fourier Transform Spectrometer of the Atmospheric Chemistry Experiment (ACE-FTS) on-board SCISAT indicates that the measurements using the frequency mode 19 have a significant low bias in both temperature (> 20 K) and water vapour (> 1 ppm), while the measurements using frequency mode 13 agree with the other instruments considering estimated errors. PMC brightness data are provided by the OSIRIS, Odin's other sensor. Combined SMR and OSIRIS data for some example orbits are considered. For these orbits

  7. Tomographic retrieval of water vapour and temperature around polar mesospheric clouds using Odin-SMR

    NASA Astrophysics Data System (ADS)

    Christensen, O. M.; Eriksson, P.; Urban, J.; Murtagh, D.; Hultgren, K.; Gumbel, J.

    2015-05-01

    A special observation mode of the Odin satellite provides the first simultaneous measurements of water vapour, temperature and polar mesospheric cloud (PMC) brightness over a large geographical area while still resolving both horizontal and vertical structures in the clouds and background atmosphere. The observation mode was activated during June, July and August of 2010 and 2011, and for latitudes between 50 and 82° N. This paper focuses on the water vapour and temperature measurements carried out with Odin's sub-millimetre radiometer (SMR). The tomographic retrieval approach used provides water vapour and temperature between 75 and 90 km with a vertical resolution of about 2.5 km and a horizontal resolution of about 200 km. The precision of the measurements is estimated to 0.2 ppmv for water vapour and 2 K for temperature. Due to limited information about the pressure at the measured altitudes, the results have large uncertainties (> 3 ppmv) in the retrieved water vapour. These errors, however, influence mainly the mean atmosphere retrieved for each orbit, and variations around this mean are still reliably captured by the measurements. SMR measurements are performed using two different mixer chains, denoted as frequency mode 19 and 13. Systematic differences between the two frontends have been noted. A first comparison with the Solar Occultation For Ice Experiment instrument (SOFIE) on-board the Aeronomy of Ice in the Mesosphere (AIM) satellite and the Fourier Transform Spectrometer of the Atmospheric Chemistry Experiment (ACE-FTS) on-board SCISAT indicates that the measurements using the frequency mode 19 have a significant low bias in both temperature (> 15 K) and water vapour (> 0.5 ppmv), while the measurements using frequency mode 13 agree with the other instruments considering estimated errors. PMC brightness data is provided by OSIRIS, Odin's other sensor. Combined SMR and OSIRIS data for some example orbits is considered. For these orbits, effects of

  8. Water vapour variability in the high-latitude upper troposphere - Part 2: Impact of volcanic eruptions

    NASA Astrophysics Data System (ADS)

    Sioris, Christopher E.; Zou, Jason; McElroy, C. Thomas; Boone, Chris D.; Sheese, Patrick E.; Bernath, Peter F.

    2016-02-01

    The impact of volcanic eruptions on water vapour in the high-latitude upper troposphere is studied using deseasonalized time series based on observations by the Atmospheric Chemistry Experiment (ACE) water vapour sensors, namely MAESTRO (Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) and the Fourier Transform Spectrometer (ACE-FTS). The two eruptions with the greatest impact on the high-latitude upper troposphere during the time frame of this satellite-based remote sensing mission are chosen. The Puyehue-Cordón Caulle volcanic eruption in June 2011 was the most explosive in the past 24 years and is shown to be able to account for the observed (50 ± 12) % increase in water vapour in the southern high-latitude upper troposphere in July 2011 after a minor adjustment for the simultaneous influence of the Antarctic oscillation. Eyjafjallajökull erupted in the spring of 2010, increasing water vapour in the upper troposphere at northern high latitudes significantly for a period of ˜ 1 month. These findings imply that extratropical volcanic eruptions in windy environments can lead to significant perturbations to high-latitude upper tropospheric humidity mostly due to entrainment of lower tropospheric moisture by wind-blown plumes. The Puyehue-Cordón Caulle eruption must be taken into account to properly determine the magnitude of the trend in southern high-latitude upper tropospheric water vapour over the last decade.

  9. Water vapour profiles from SCIAMACHY solar occultation measurements derived with an onion peeling approach

    NASA Astrophysics Data System (ADS)

    Noël, S.; Bramstedt, K.; Rozanov, A.; Bovensmann, H.; Burrows, J. P.

    2010-01-01

    A new retrieval method has been developed to derive water vapour number density profiles from solar occultation measurements of the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY). This method is intentionally kept simple and based on a combination of an onion peeling approach with a modified DOAS (Differential Optical Absorption Spectroscopy) fit in the wavelength region around 940 nm. Reasonable resulting water vapour profiles are currently obtained in the altitude range 15-45 km. Comparisons of the SCIAMACHY profiles with water vapour data provided by the Atmospheric Chemistry Explorer Fourier Transform Spectrometer (ACE-FTS) show an average agreement within about 5% between 20 and 45 km. SCIAMACHY water vapour data tend to be systematically higher than ACE-FTS. These results are in principal confirmed by comparisons with water vapour profiles derived from model data of the European Centre for Medium Range Weather Forecasts (ECMWF), although ECMWF concentrations are systematicly lower than both corresponding SCIAMACHY and ACE-FTS data at all altitudes.

  10. Water vapour profiles from SCIAMACHY solar occultation measurements derived with an onion peeling approach

    NASA Astrophysics Data System (ADS)

    Noël, S.; Bramstedt, K.; Rozanov, A.; Bovensmann, H.; Burrows, J. P.

    2010-04-01

    A new retrieval method has been developed to derive water vapour number density profiles from solar occultation measurements of the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY). This method is intentionally kept simple and based on a combination of an onion peeling approach with a modified DOAS (Differential Optical Absorption Spectroscopy) fit in the wavelength region around 940 nm. Reasonable resulting water vapour profiles are currently obtained in the altitude range 15-45 km. Comparisons of the SCIAMACHY profiles with water vapour data provided by the Atmospheric Chemistry Explorer Fourier Transform Spectrometer (ACE-FTS) show an average agreement within about 5% between 20 and 45 km. SCIAMACHY water vapour data tend to be systematically higher than ACE-FTS. These results are in principal confirmed by comparisons with water vapour profiles derived from model data of the European Centre for Medium Range Weather Forecasts (ECMWF), although ECMWF concentrations are systematicly lower than both corresponding SCIAMACHY and ACE-FTS data at all altitudes.

  11. Analysis of characteristics of a diode-pumped rubidium vapour laser using a kinetic algorithm

    NASA Astrophysics Data System (ADS)

    Cai, He; Wang, You; Zhang, Wei; Xue, Liangping; Wang, Hongyuan; Han, Juhong; An, Guofei; Jiang, Zhigang; Gao, Ming; Zhou, Jie; Liao, Zhiye

    2016-08-01

    We consider diode-pumped alkali vapour lasers (DPALs), which make it possible to achieve a high output power. Characteristics of such DPALs strongly depend on the physical properties of buffer gases and on structural parameters of a vapour cell. Special attention is paid to a diode-pumped rubidium vapour laser (DPRVL): We have investigated the effect of different conditions on its characteristics. The results show that the linewidth of the D2 line of a DPRVL and the fine-structure mixing rate between two excited energy levels, which are two crucial factors in implementing a high-power DPRVL, increase with the pressure of buffer gases and the temperature of the vapour cell. It is demonstrated that the population ratio of two excited energy levels is close to that corresponding to a thermal equilibrium as the pressure of buffer gases and the temperature of the vapour cell become higher. We have found that the optimal values of the methane pressure, the cell temperature and the cell length can be determined through a kinetic analysis. The conclusions can be valuable for designing configurations of an end-pumped DPAL.

  12. Catalytic Microtube Rocket Igniter

    NASA Technical Reports Server (NTRS)

    Schneider, Steven J.; Deans, Matthew C.

    2011-01-01

    Devices that generate both high energy and high temperature are required to ignite reliably the propellant mixtures in combustion chambers like those present in rockets and other combustion systems. This catalytic microtube rocket igniter generates these conditions with a small, catalysis-based torch. While traditional spark plug systems can require anywhere from 50 W to multiple kW of power in different applications, this system has demonstrated ignition at less than 25 W. Reactants are fed to the igniter from the same tanks that feed the reactants to the rest of the rocket or combustion system. While this specific igniter was originally designed for liquid methane and liquid oxygen rockets, it can be easily operated with gaseous propellants or modified for hydrogen use in commercial combustion devices. For the present cryogenic propellant rocket case, the main propellant tanks liquid oxygen and liquid methane, respectively are regulated and split into different systems for the individual stages of the rocket and igniter. As the catalyst requires a gas phase for reaction, either the stored boil-off of the tanks can be used directly or one stream each of fuel and oxidizer can go through a heat exchanger/vaporizer that turns the liquid propellants into a gaseous form. For commercial applications, where the reactants are stored as gases, the system is simplified. The resulting gas-phase streams of fuel and oxidizer are then further divided for the individual components of the igniter. One stream each of the fuel and oxidizer is introduced to a mixing bottle/apparatus where they are mixed to a fuel-rich composition with an O/F mass-based mixture ratio of under 1.0. This premixed flow then feeds into the catalytic microtube device. The total flow is on the order of 0.01 g/s. The microtube device is composed of a pair of sub-millimeter diameter platinum tubes connected only at the outlet so that the two outlet flows are parallel to each other. The tubes are each

  13. Learning the Fundamentals of Kinetics and Reaction Engineering with the Catalytic Oxidation of Methane

    ERIC Educational Resources Information Center

    Cybulskis, Viktor J.; Smeltz, Andrew D.; Zvinevich, Yury; Gounder, Rajamani; Delgass, W. Nicholas; Ribeiro, Fabio H.

    2016-01-01

    Understanding catalytic chemistry, collecting and interpreting kinetic data, and operating chemical reactors are critical skills for chemical engineers. This laboratory experiment provides students with a hands-on supplement to a course in chemical kinetics and reaction engineering. The oxidation of methane with a palladium catalyst supported on…

  14. Concentration of Specific Amino Acids at the Catalytic/Active Centers of Highly-Conserved ``Housekeeping'' Enzymes of Central Metabolism in Archaea, Bacteria and Eukaryota: Is There a Widely Conserved Chemical Signal of Prebiotic Assembly?

    NASA Astrophysics Data System (ADS)

    Pollack, J. Dennis; Pan, Xueliang; Pearl, Dennis K.

    2010-06-01

    In alignments of 1969 protein sequences the amino acid glycine and others were found concentrated at most-conserved sites within ˜15 Å of catalytic/active centers (C/AC) of highly conserved kinases, dehydrogenases or lyases of Archaea, Bacteria and Eukaryota. Lysine and glutamic acid were concentrated at least-conserved sites furthest from their C/ACs. Logistic-regression analyses corroborated the “movement” of glycine towards and lysine away from their C/ACs: the odds of a glycine occupying a site were decreased by 19%, while the odds for a lysine were increased by 53%, for every 10 Å moving away from the C/AC. Average conservation of MSA consensus sites was highest surrounding the C/AC and directly decreased in transition toward model’s peripheries. Findings held with statistical confidence using sequences restricted to individual Domains or enzyme classes or to both. Our data describe variability in the rate of mutation and likelihoods for phylogenetic trees based on protein sequence data and endorse the extension of substitution models by incorporating data on conservation and distance to C/ACs rather than only using cumulative levels. The data support the view that in the most-conserved environment immediately surrounding the C/AC of taxonomically distant and highly conserved essential enzymes of central metabolism there are amino acids whose identity and degree of occupancy is similar to a proposed amino acid set and frequency associated with prebiotic evolution.

  15. Concentration of specific amino acids at the catalytic/active centers of highly-conserved "housekeeping" enzymes of central metabolism in archaea, bacteria and Eukaryota: is there a widely conserved chemical signal of prebiotic assembly?

    PubMed

    Pollack, J Dennis; Pan, Xueliang; Pearl, Dennis K

    2010-06-01

    In alignments of 1969 protein sequences the amino acid glycine and others were found concentrated at most-conserved sites within approximately 15 A of catalytic/active centers (C/AC) of highly conserved kinases, dehydrogenases or lyases of Archaea, Bacteria and Eukaryota. Lysine and glutamic acid were concentrated at least-conserved sites furthest from their C/ACs. Logistic-regression analyses corroborated the "movement" of glycine towards and lysine away from their C/ACs: the odds of a glycine occupying a site were decreased by 19%, while the odds for a lysine were increased by 53%, for every 10 A moving away from the C/AC. Average conservation of MSA consensus sites was highest surrounding the C/AC and directly decreased in transition toward model's peripheries. Findings held with statistical confidence using sequences restricted to individual Domains or enzyme classes or to both. Our data describe variability in the rate of mutation and likelihoods for phylogenetic trees based on protein sequence data and endorse the extension of substitution models by incorporating data on conservation and distance to C/ACs rather than only using cumulative levels. The data support the view that in the most-conserved environment immediately surrounding the C/AC of taxonomically distant and highly conserved essential enzymes of central metabolism there are amino acids whose identity and degree of occupancy is similar to a proposed amino acid set and frequency associated with prebiotic evolution.

  16. Catalytic hydrogenation of carbon monoxide

    SciTech Connect

    Wayland, B.B.

    1992-12-01

    This project is focused on developing strategies to accomplish the reduction and hydrogenation of carbon monoxide to produce organic oxygenates at mild conditions. Our approaches to this issue are based on the recognition that rhodium macrocycles have unusually favorable thermodynamic values for producing a series of intermediate implicated in the catalytic hydrogenation of CO. Observations of metalloformyl complexes produced by reactions of H{sub 2} and CO, and reductive coupling of CO to form metallo {alpha}-diketone species have suggested a multiplicity of routes to organic oxygenates that utilize these species as intermediates. Thermodynamic and kinetic-mechanistic studies are used in constructing energy profiles for a variety of potential pathways, and these schemes are used in guiding the design of new metallospecies to improve the thermodynamic and kinetic factors for individual steps in the overall process. Variation of the electronic and steric effects associated with the ligand arrays along with the influences of the reaction medium provide the chemical tools for tuning these factors. Emerging knowledge of the factors that contribute to M-H, M-C and M-O bond enthalpies is directing the search for ligand arrays that will expand the range of metal species that have favorable thermodynamic parameters to produce the primary intermediates for CO hydrogenation. Studies of rhodium complexes are being extended to non-macrocyclic ligand complexes that emulate the favorable thermodynamic features associated with rhodium macrocycles, but that also manifest improved reaction kinetics. Multifunctional catalyst systems designed to couple the ability of rhodium complexes to produce formyl and diketone intermediates with a second catalyst that hydrogenates these imtermediates are promising approaches to accomplish CO hydrogenation at mild conditions.

  17. Catalytic gasification of biomass

    NASA Astrophysics Data System (ADS)

    Robertus, R. J.; Mudge, L. K.; Sealock, L. J., Jr.; Mitchell, D. H.; Weber, S. L.

    1981-12-01

    Methane and methanol synthesis gas can be produced by steam gasification of biomass in the presence of appropriate catalysts. This concept is to use catalysts in a fluidized bed reactor which is heated indirectly. The objective is to determine the technical and economic feasibility of the concept. Technically the concept has been demonstrated on a 50 lb per hr scale. Potential advantages over conventional processes include: no oxygen plant is needed, little tar is produced so gas and water treatment are simplified, and yields and efficiencies are greater than obtained by conventional gasification. Economic studies for a plant processing 2000 T/per day dry wood show that the cost of methanol from wood by catalytic gasification is competitive with the current price of methanol. Similar studies show the cost of methane from wood is competitive with projected future costs of synthetic natural gas. When the plant capacity is decreased to 200 T per day dry wood, neither product is very attractive in today's market.

  18. Distribution of tritium in water vapour and precipitation around Wolsung nuclear power plant.

    PubMed

    Chae, Jung-Seok; Lee, Sang-Kuk; Kim, Yongjae; Lee, Jung-Min; Cho, Heung-Joon; Cho, Yong-Woo; Yun, Ju-Yong

    2011-07-01

    The distribution of tritium in water vapour and precipitation with discharge of tritiated water vapour and meteorological factors was studied around the Wolsung nuclear power plant (NPP) site during the period 2004-2008. The tritium concentrations in atmospheric water vapour and precipitation had a temporal variation with relatively high values in the early summer. Spatial distribution of tritium concentrations was affected by various factors such as distance from the NPP site, wind direction, tritium discharge into the atmosphere and atmospheric dispersion factor. The annual mean concentrations of atmospheric HTO and precipitation were correlated with the amount of gaseous tritium released from the Wolsung NPP. The tritium concentrations in precipitation decrease exponentially with an increase of the distance from the Wolsung NPP site.

  19. Shock wave and material vapour plume propagation during excimer laser ablation of aluminium samples

    NASA Astrophysics Data System (ADS)

    Jeong, S. H.; Greif, R.; Russo, R. E.

    1999-10-01

    A probe beam deflection technique was utilized to measure the propagation of a shock wave and material vapour plume generated during excimer laser ablation of aluminium samples. The measured transit time of the laser-induced shock wave was compared with the prediction based on an ideal blast-wave model, using the Sedov-Taylor solution. The prediction of the incident laser energy converted into the laser-induced gasdynamic flow utilizing this blast-wave model overestimated the efficiency, even under conditions when the measured shock-wave velocity follows the correct model relation. The propagation of material vapour was measured from the deflection of the probe beam at later times. The propagation velocity of material vapour ranged from 20-40 m s-1 with a greater velocity near the target surface.

  20. Kinetic model of water vapour adsorption by gluten-free starch

    NASA Astrophysics Data System (ADS)

    Ocieczek, Aneta; Kostek, Robert; Ruszkowska, Millena

    2015-01-01

    This study evaluated the kinetics of water vapour adsorption on the surface of starch molecules derived from wheat. The aim of the study was to determine an equation that would allow estimation of water content in tested material in any timepoint of the adsorption process aimed at settling a balance with the environment. An adsorption isotherm of water vapour on starch granules was drawn. The parameters of the Guggenheim, Anderson, and De Boer equation were determined by characterizing the tested product and adsorption process. The equation of kinetics of water vapour adsorption on the surface of starch was determined based on the Guggenheim, Anderson, and De Boer model describing the state of equilibrium and on the model of a first-order linear inert element describing the changes in water content over time.

  1. The measurement of water vapour transfer rate through clothing system with air gap between layers

    NASA Astrophysics Data System (ADS)

    Oh, Ae-Gyeong

    2008-02-01

    The experiments described in this paper are designed to test the water vapour transfer rates through outdoor clothing system with air gap between layers under conditions more closely actual wear. It was adopted distance of 5 mm to ensure no disturbance of the air gap thickness between layers throughout the measurement period with all fabrics. The results have indicated that the water vapour transfer rates of clothing system decrease very slightly with time, it is shown that they approached nearly equilibrium state throughout the experiment. It is revealed that the water vapour transfer rates of the clothing system were ordered into groups determined by the type of waterproof breathable fabric as a shell layer being ordered.

  2. Prediction of clothing thermal insulation and moisture vapour resistance of the clothed body walking in wind.

    PubMed

    Qian, Xiaoming; Fan, Jintu

    2006-11-01

    Clothing thermal insulation and moisture vapour resistance are the two most important parameters in thermal environmental engineering, functional clothing design and end use of clothing ensembles. In this study, clothing thermal insulation and moisture vapour resistance of various types of clothing ensembles were measured using the walking-able sweating manikin, Walter, under various environmental conditions and walking speeds. Based on an extensive experimental investigation and an improved understanding of the effects of body activities and environmental conditions, a simple but effective direct regression model has been established, for predicting the clothing thermal insulation and moisture vapour resistance under wind and walking motion, from those when the manikin was standing in still air. The model has been validated by using experimental data reported in the previous literature. It has shown that the new models have advantages and provide very accurate prediction.

  3. Vapour phase polymerisation of conducting and non-conducting polymers: a review.

    PubMed

    Lawal, Abdulazeez T; Wallace, Gordon G

    2014-02-01

    Vapour phase polymerisation (VPP) is a well established technique in which the monomer is introduced to an oxidant-coated substrate in vapour form. Polymerisation then takes place at the oxidant vapour interface. VPP is a technique that could be used to immobilise materials to the modified electrode surface. This review article concentrates on the VPP of conducting polymers such as Polypyrrole (PPy) polythiophen (PT) and polyaniline (PANi). VPP of conducting polymers and other non-conducting polymers have extensively been investigated. This review article is divided into three main parts as given in Table of contents related to the VPP process of some important conducting polymers such as PPy, PT, PANi and Poly(3,4-ethylenedioxythiophene). A total of 181 references are cited in this review article and it attempts to look into VPP from inception of the method till present day. PMID:24401395

  4. Vapours of US and EU Market Leader Electronic Cigarette Brands and Liquids Are Cytotoxic for Human Vascular Endothelial Cells

    PubMed Central

    Putzhammer, Raphaela; Doppler, Christian; Jakschitz, Thomas; Heinz, Katharina; Förste, Juliane; Danzl, Katarina; Messner, Barbara; Bernhard, David

    2016-01-01

    The present study was conducted to provide toxicological data on e-cigarette vapours of different e-cigarette brands and liquids from systems viewed as leaders in the e-cigarette market and to compare e-cigarette vapour toxicity to the toxicity of conventional strong high-nicotine cigarette smoke. Using an adapted version of a previously constructed cigarette smoke constituent sampling device, we collected the hydrophilic fraction of e-cigarette vapour and exposed human umbilical vein endothelial cells (HUVECs) to the mixture of compounds present in the vapour of 4 different single-use e-cigarettes, 6 different liquid vapours produced by the same refillable e-cigarette, and one e-cigarette with an exchangeable liquid cartridge. After incubation of cells with various concentrations and for various periods of time we analysed cell death induction, proliferation rates, the occurrence of intra-cellular reactive oxygen species, cell morphology, and we also measured e-cigarette heating coil temperatures. Overall, conventional cigarette smoke extract showed the most severe impact on endothelial cells. However, some e-cigarette vapour extracts showed high cytotoxicity, inhibition of cell proliferation, and alterations in cell morphology, which were comparable to conventional high-nicotine cigarettes. The vapours generated from different liquids using the same e-cigarette show substantial differences, pointing to the liquids as an important source for toxicity. E-cigarette vapour-mediated induction of oxidative stress was significant in one out of the 11 analysed vapours. There is a high variability in the acute cytotoxicity of e-cigarette vapours depending on the liquid and on the e-cigarettes used. Some products showed toxic effects close to a conventional high-nicotine cigarette. Liquid nicotine, menthol content, and the formation of acute intracellular reactive oxygen species do not seem to be the central elements in e-cigarette vapour toxicity. PMID:27351725

  5. Vapour and Liquid-Phase Artemisia annua Essential Oil Activities against Several Clinical Strains of Candida.

    PubMed

    Santomauro, Francesca; Donato, Rosa; Sacco, Cristiana; Pini, Gabriella; Flamini, Guido; Bilia, Anna Rita

    2016-07-01

    Candida spp. are often the cause of infection in immune-compromised individuals. They are characterized by a strong resistance to antimicrobial drugs and disinfectants. The activity of Artemisia annua essential oil against Candida spp. was determined by vapour contact and microdilution assay. The oil was characterized by the presence of oxygenated monoterpenes (more than 75 % of the constituents), mainly represented by the irregular monoterpene artemisia ketone (ca. 22 %), and the widespread monoterpenes 1,8 cineole (ca. 19 %) and camphor (ca. 17 %). Other representative constituents were artemisia alcohol (5.9 %), α-pinene (5.7 %), and pinocarvone (3.0 %). Thujone, a typical toxic constituent of the Artemisia species, was not detected. The results are reported as minimum inhibitory concentration, minimum fungicidal concentration, and diameter of inhibition zone obtained by the vapour diffusion assay. We tested 10 clinical Candida strains, coming from both clinical samples and international collections. The results show that the antifungal activity of A. annua is influenced by the type of method adopted. The inhibitory action of the essential oil was, in fact, higher in the vapour than in the liquid phase. Our results show an average minimum inhibitory concentration in the liquid phase of 11.88 µL/mL, while in the vapour phase, the growth of all Candida strains tested at a concentration of 2.13 µL/cm(3) was inhibited. A strain of Candida glabrata was found to be less susceptible to the liquid medium than the vapour assay (50 µL/mL vs. 0.64 µL/cm(3), respectively). Candida albicans and Candida dubliniensis were the most susceptible to the vapour test, while Candida parapsilosis was the most resistant. PMID:27286334

  6. Upper tropospheric water vapour variability at high latitudes - Part 1: Influence of the annular modes

    NASA Astrophysics Data System (ADS)

    Sioris, Christopher E.; Zou, Jason; Plummer, David A.; Boone, Chris D.; McElroy, C. Thomas; Sheese, Patrick E.; Moeini, Omid; Bernath, Peter F.

    2016-03-01

    Seasonal and monthly zonal medians of water vapour in the upper troposphere and lower stratosphere (UTLS) are calculated for both Atmospheric Chemistry Experiment (ACE) instruments for the northern and southern high-latitude regions (60-90° N and 60-90° S). Chosen for the purpose of observing high-latitude processes, the ACE orbit provides sampling of both regions in 8 of 12 months of the year, with coverage in all seasons. The ACE water vapour sensors, namely MAESTRO (Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) and the Fourier Transform Spectrometer (ACE-FTS) are currently the only satellite instruments that can probe from the lower stratosphere down to the mid-troposphere to study the vertical profile of the response of UTLS water vapour to the annular modes. The Arctic oscillation (AO), also known as the northern annular mode (NAM), explains 64 % (r = -0.80) of the monthly variability in water vapour at northern high latitudes observed by ACE-MAESTRO between 5 and 7 km using only winter months (January to March, 2004-2013). Using a seasonal time step and all seasons, 45 % of the variability is explained by the AO at 6.5 ± 0.5 km, similar to the 46 % value obtained for southern high latitudes at 7.5 ± 0.5 km explained by the Antarctic oscillation or southern annular mode (SAM). A large negative AO event in March 2013 produced the largest relative water vapour anomaly at 5.5 km (+70 %) over the ACE record. A similarly large event in the 2010 boreal winter, which was the largest negative AO event in the record (1950-2015), led to > 50 % increases in water vapour observed by MAESTRO and ACE-FTS at 7.5 km.

  7. Different physiological and behavioural effects of e-cigarette vapour and cigarette smoke in mice.

    PubMed

    Ponzoni, L; Moretti, M; Sala, M; Fasoli, F; Mucchietto, V; Lucini, V; Cannazza, G; Gallesi, G; Castellana, C N; Clementi, F; Zoli, M; Gotti, C; Braida, D

    2015-10-01

    Nicotine is the primary addictive substance in tobacco smoke and electronic cigarette (e-cig) vapour. Methodological limitations have made it difficult to compare the role of the nicotine and non-nicotine constituents of tobacco smoke. The aim of this study was to compare the effects of traditional cigarette smoke and e-cig vapour containing the same amount of nicotine in male BALB/c mice exposed to the smoke of 21 cigarettes or e-cig vapour containing 16.8 mg of nicotine delivered by means of a mechanical ventilator for three 30-min sessions/day for seven weeks. One hour after the last session, half of the animals were sacrificed for neurochemical analysis, and the others underwent mecamylamine-precipitated or spontaneous withdrawal for the purposes of behavioural analysis. Chronic intermittent non-contingent, second-hand exposure to cigarette smoke or e-cig vapour led to similar brain cotinine and nicotine levels, similar urine cotinine levels and the similar up-regulation of α4β2 nicotinic acetylcholine receptors in different brain areas, but had different effects on body weight, food intake, and the signs of mecamylamine-precipitated and spontaneous withdrawal episodic memory and emotional responses. The findings of this study demonstrate for the first time that e-cig vapour induces addiction-related neurochemical, physiological and behavioural alterations. The fact that inhaled cigarette smoke and e-cig vapour have partially different dependence-related effects indicates that compounds other than nicotine contribute to tobacco dependence. PMID:26141510

  8. Tailoring the Catalytic Properties of Metal Nanoparticles via Support Interactions.

    PubMed

    Ahmadi, M; Mistry, H; Roldan Cuenya, B

    2016-09-01

    The development of new catalysts for energy technology and environmental remediation requires a thorough knowledge of how the physical and chemical properties of a catalyst affect its reactivity. For supported metal nanoparticles (NPs), such properties can include the particle size, shape, composition, and chemical state, but a critical parameter which must not be overlooked is the role of the NP support. Here, we highlight the key mechanisms behind support-induced enhancement in the catalytic properties of metal NPs. These include support-induced changes in the NP morphology, stability, electronic structure, and chemical state, as well as changes in the support due to the NPs. Utilizing the support-dependent phenomena described in this Perspective may allow significant breakthroughs in the design and tailoring of the catalytic activity and selectivity of metal nanoparticles. PMID:27530730

  9. Fuel-Rich Catalytic Combustion

    NASA Technical Reports Server (NTRS)

    Brabbs, Theodore A.; Olson, Sandra L.

    1987-01-01

    Two-stage combustion system reduces particulate emissions. Program on catalytic oxidation of iso-octane demonstrates feasibility of two-stage combustion system for reducing particulate emissions. With fuel-rich (fuel/air equivalence ratios of 4.8 to 7.8) catalytic-combustion preburner as first stage, combustion process free of soot at reactor-outlet temperatures of 1,200 K or less.

  10. A novel experimental setup to study the nucleation of atmospheric vapours on small nanoparticles

    NASA Astrophysics Data System (ADS)

    Nachbar, M.; Duft, D.; Leisner, T.

    2015-10-01

    We present a novel supersaturation chamber which allows us to expose nanoscale particles to supersaturated vapors in the wide range of temperatures occurring in planetary atmospheres. This chamber, the molecular flow ice cell (MICE), is integrated in the vacuum setup TRAPS and enables us to study adsorption, nucleation and growth processes of condensable vapours as for instance water vapour and carbon dioxide. We will present the experimental setup with focus on MICE. The general function principal of MICE and its limitations will be highlighted and we will elaborate that this new device is able to study adsorption, ice nucleation and growth processes exemplified with CO2 nucleation experiments in the mesosphere of Mars.

  11. Application of copper vapour lasers for controlling activity of uranium isotopes

    SciTech Connect

    Barmina, E V; Sukhov, I A; Lepekhin, N M; Priseko, Yu S; Filippov, V G; Simakin, Aleksandr V; Shafeev, Georgii A

    2013-06-30

    Beryllium nanoparticles are generated upon ablation of a beryllium target in water by a copper vapour laser. The average size of single crystalline nanoparticles is 12 nm. Ablation of a beryllium target in aqueous solutions of uranyl chloride leads to a significant (up to 50 %) decrease in the gamma activity of radionuclides of the uranium-238 and uranium-235 series. Data on the recovery of the gamma activity of these nuclides to new steady-state values after laser irradiation are obtained. The possibility of application of copper vapour lasers for radioactive waste deactivation is discussed. (laser applications and other topics in quantum electronics)

  12. Development and field testing of a miniaturized sampling system for simultaneous sampling of vapours and droplets.

    PubMed

    Breuer, Dietmar; Dragan, George C; Friedrich, Claudia; Möhlmann, Carsten; Zimmermann, Ralf

    2015-02-01

    The sampling of semi volatiles (SV) in workplaces may lead to different results as measurements may be affected by sampling bias. The new European Standard EN 13936 defines "semi-volatiles" as substances with vapour pressures in the range between 0.001 and 100 Pa at room temperature. EN 13936 regulates the basic requirements for SV compounds that can occur as vapour and particle at the same time. Vapour and particles shall not be sampled separately and particles have to be sampled as inhalable fraction. Following EN 13936, the Institute for Occupational Safety and Health (Institut für Arbeitsschutz - IFA) has developed a miniaturized droplet-vapour sampler (GGP-Mini) which is designed to sample the inhalable aerosol fraction at low flow rates. The GGP-Mini uses 13 mm filters for particle sampling combined with adsorption tubes for vapour sampling. Laboratory tests were performed on 11 polar and non-polar compounds in a boiling point range from 188 °C to 318 °C. The substances were spiked directly on the filter followed by aspiration of 40 litres of air. Substances with boiling points below 230 °C were almost completely evaporated. Substances with boiling points above 230 °C up to 300 °C were found on both filter and charcoal tube. Lower-volatile compounds remained almost completely on the filter. For polar substances, the atmospheric humidity had a considerable influence upon the distribution of the liquid and vaporous components. A strong influence of the sampling temperature was found in the range from 0 °C to 50 °C. Droplet-vapour mixtures of n-hexadecane and diethylene glycol with droplet sizes between 1 μm and 4 μm were generated in a flow tube to verify the laboratory results. The aerosol concentrations were analysed on-line with a particle sizer and a flame ionisation detector, while parallel off-line samples were taken with the GGP-Mini. Evaporation losses from filters could be studied by comparing the on-line with off-line measurements. All

  13. Fabrication of liquid crystal based sensor for detection of hydrazine vapours

    NASA Astrophysics Data System (ADS)

    Nandi, Rajib; Singh, Sachin Kumar; Singh, Hemant Kumar; Singh, Bachcha; Singh, Ranjan K.

    2014-10-01

    A novel liquid crystal (LC) based sensor to detect trace level amount of hydrazine vapour has been developed. The LC 4‧-pentyl-4-biphenylcarbonitrile (5CB) doped with 0.5 wt% 4-decyloxy benzaldehyde (DBA) shows dark to bright optical texture upon exposure of hydrazine vapours as revealed by polarizing optical microscopy under crossed polarizers. The hydrazine interacts with the doped DBA and form diimine compound which disrupt the orientation of aligned 5CB. The interaction between DBA and hydrazine has been also studied by Raman spectroscopy.

  14. Zinc oxide nanowires and nanorods fabricated by vapour-phase transport at low temperature

    NASA Astrophysics Data System (ADS)

    Xu, C. X.; Sun, X. W.; Dong, Z. L.; Yu, M. B.; My, T. D.; Zhang, X. H.; Chua, S. J.; White, T. J.

    2004-07-01

    Using zinc chloride as source material, zinc oxide nanowires and nanorods were fabricated by a vapour-phase transport method at low temperature. The nanowires grown on gold-coated silicon showed a uniform diameter of about 40 nm, and the nanorods on copper-coated silicon grew upwards to form flower-like arrays. The x-ray diffraction and transmission electron microscopy analyses demonstrated that the nanostructural zinc oxide grew along the [0001] direction. The growth process was attributed to a vapour-liquid-solid mechanism. Distinct photoluminescent behaviours were observed for zinc oxide nanostructures grown on gold-coated and copper-coated silicon wafers.

  15. Catalytic and reactive polypeptides and methods for their preparation and use

    DOEpatents

    Schultz, Peter

    1994-01-01

    Catalytic and reactive polypeptides include a binding site specific for a reactant or reactive intermediate involved in a chemical reaction of interest. The polypeptides further include at least one active functionality proximate the binding site, where the active functionality is capable of catalyzing or chemically participating in the chemical reaction in such a way that the reaction rate is enhanced. Methods for preparing the catalytic peptides include chemical synthesis, site-directed mutagenesis of antibody and enzyme genes, covalent attachment of the functionalities through particular amino acid side chains, and the like.

  16. Advantages of catalytically de-waxed lubricant base oils

    SciTech Connect

    Schoonmaker, J.P.; Stiponavic, A.J.

    1996-10-01

    The production of base oils used in the formulation of lubricants involves the vacuum distillation of crude oil followed by a series of processing steps that improve physical and chemical properties including viscosity index and oxidative stability. An important stage in this process is the removal of linear parafins (wax) from the base oil which can crystalize causing poor flow properties at low temperatures. {open_quotes}De-waxing{close_quotes} may be accomplished using a solvent precipitation batch process (solvent de-waxing: SDW) or through a more modern continuous catalytic process (catalytic de-waxing: CDW) which offers many advantages. In general, catalytically de-waxed base oils exhibit improved low temperature fluidity which provides enhanced performance for transmission fluids and other lubricants required to operate efficiently at temperature reaching -40{degrees}C. A discussion of the molecular mechanisms involved in CDW and results of viscometric testing at low temperatures will be presented.

  17. Catalytic antibodies: balancing between Dr. Jekyll and Mr. Hyde.

    PubMed

    Belogurov, Alexey; Kozyr, Arina; Ponomarenko, Natalia; Gabibov, Alexander

    2009-11-01

    The immunoglobulin molecule is a perfect template for the de novo generation of biocatalytic functions. Catalytic antibodies, or abzymes, obtained by the structural mimicking of enzyme active sites have been shown to catalyze numerous chemical reactions. Natural enzyme analogs for some of these reactions have not yet been found or possibly do not exist at all. Nowadays, the dramatic breakthrough in antibody engineering and expression technologies has promoted a considerable expansion of immunoglobulin's medical applications and is offering abzymes a unique chance to become a promising source of high-precision "catalytic vaccines." At the same time, the discovery of natural abzymes on the background of autoimmune disease revealed their beneficial and pathogenic roles in the disease progression. Thus, the conflicting Dr. Jekyll and Mr. Hyde protective and destructive essences of catalytic antibodies should be carefully considered in the development of therapeutic abzyme applications. PMID:19795406

  18. Catalytically Increased Prebiotic Peptide Formation: Ditryptophan, Dilysine, and Diserine

    NASA Astrophysics Data System (ADS)

    Plankensteiner, Kristof; Reiner, Hannes; Rode, Bernd M.

    2005-10-01

    “Mutual” amino acid catalysis of glycine on the formation of ditryptophan, dilysine, and diserine in the prebiotically relevant Salt-Induced Peptide Formation (SIPF) Reaction was investigated varying the starting concentration and chirality of the educt amino acid, and analyzing the increase of yield resulting from this catalytic effect. Our results show the possibility of an amplified diverse pool of peptides being available for chemical evolution of larger peptides and proteins using also these more complicated amino acids for the evolution of more complex functions in future biochemical cycles and thus for the emergence of life. Catalytic effects are especially high in the case of serine, the most basic amino acid of the three, but are also significant for the other two examples investigated in the present work. Besides that, especially for serine, but also in the case of tryptophan, differences in catalytic yield increase according to the chiral form of the amino acid used could be observed.

  19. Measurement of atmospheric NO3 1. Improved removal of water vapour absorption features in the analysis for NO3

    NASA Astrophysics Data System (ADS)

    Aliwell, S. R.; Jones, R. L.

    Atmospheric measurements of the nitrate radical generally detect its absorption of visible radiation in the band near 662 nm. This band is negatively correlated with strong absorptions due to tropospheric water vapour which must therefore be fitted in the spectral analysis to reduce the spectral residual to the level at which sufficient sensitivity to NO3 can be obtained. Previously this had been fitted using a cross-section typically derived from spectra obtained just before sunset or just after sunrise which took no account of the diurnal variation in temperature and water vapour column amounts. An improved method of accounting for water vapour absorptions is presented here. When fitted together with their temperature dependence, water vapour cross-sections calculated using a line-by-line approach gave a more accurate fitting of water vapour absorptions, thus improving the analysis for NO3.

  20. Leidenfrost vapour layer moderation of the drag crisis and trajectories of superhydrophobic and hydrophilic spheres falling in water.

    PubMed

    Vakarelski, Ivan U; Chan, Derek Y C; Thoroddsen, Sigurdur T

    2014-08-21

    We investigate the dynamic effects of a Leidenfrost vapour layer sustained on the surface of heated steel spheres during free fall in water. We find that a stable vapour layer sustained on the textured superhydrophobic surface of spheres falling through 95 °C water can reduce the hydrodynamic drag by up to 75% and stabilize the sphere trajectory for the Reynolds number between 10(4) and 10(6), spanning the drag crisis in the absence of the vapour layer. For hydrophilic spheres under the same conditions, the transition to drag reduction and trajectory stability occurs abruptly at a temperature different from the static Leidenfrost point. The observed drag reduction effects are attributed to the disruption of the viscous boundary layer by the vapour layer whose thickness depends on the water temperature. Both the drag reduction and the trajectory stabilization effects are expected to have significant implications for development of sustainable vapour layer based technologies.