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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. PMID:20887996

  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. Ethylene vinylacetate copolymer and nanographite composite as chemical vapour sensor

    NASA Astrophysics Data System (ADS)

    Stepina, Santa; Sakale, Gita; Knite, Maris

    2013-12-01

    Polymer-nanostructured carbon composite as chemical vapour sensor is described, made by the dissolution method of a non-conductive polymer, ethylene vinylacetate copolymer, mixed with conductive nanographite particles (carbon black). Sensor exhibits relative electrical resistance change in chemical vapours, like ethanol and toluene. Since the sensor is relatively cheap, easy to fabricate, it can be used in air quality monitoring and at industries to control hazardous substance concentration in the air, for example, to protect workers from exposure to chemical spills.

  5. Infrared hyperspectral imaging for chemical vapour detection

    NASA Astrophysics Data System (ADS)

    Ruxton, K.; Robertson, G.; Miller, W.; Malcolm, G. P. A.; Maker, G. T.; Howle, C. R.

    2012-10-01

    Active hyperspectral imaging is a valuable tool in a wide range of applications. One such area is the detection and identification of chemicals, especially toxic chemical warfare agents, through analysis of the resulting absorption spectrum. This work presents a selection of results from a prototype midwave infrared (MWIR) hyperspectral imaging instrument that has successfully been used for compound detection at a range of standoff distances. Active hyperspectral imaging utilises a broadly tunable laser source to illuminate the scene with light at a range of wavelengths. While there are a number of illumination methods, the chosen configuration illuminates the scene by raster scanning the laser beam using a pair of galvanometric mirrors. The resulting backscattered light from the scene is collected by the same mirrors and focussed onto a suitable single-point detector, where the image is constructed pixel by pixel. The imaging instrument that was developed in this work is based around an IR optical parametric oscillator (OPO) source with broad tunability, operating in the 2.6 to 3.7 μm (MWIR) and 1.5 to 1.8 μm (shortwave IR, SWIR) spectral regions. The MWIR beam was primarily used as it addressed the fundamental absorption features of the target compounds compared to the overtone and combination bands in the SWIR region, which can be less intense by more than an order of magnitude. We show that a prototype NCI instrument was able to locate hydrocarbon materials at distances up to 15 metres.

  6. 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.

  7. Silicon nanowire arrays as learning chemical vapour classifiers.

    PubMed

    Niskanen, A O; Colli, A; White, R; Li, H W; Spigone, E; Kivioja, J M

    2011-07-22

    Nanowire field-effect transistors are a promising class of devices for various sensing applications. Apart from detecting individual chemical or biological analytes, it is especially interesting to use multiple selective sensors to look at their collective response in order to perform classification into predetermined categories. We show that non-functionalised silicon nanowire arrays can be used to robustly classify different chemical vapours using simple statistical machine learning methods. We were able to distinguish between acetone, ethanol and water with 100% accuracy while methanol, ethanol and 2-propanol were classified with 96% accuracy in ambient conditions. PMID:21673389

  8. Microscopic characterisation of suspended graphene grown by chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Bignardi, Luca; van Dorp, Willem F.; Gottardi, Stefano; Ivashenko, Oleksii; Dudin, Pavel; Barinov, Alexei; de Hosson, Jeff Th. M.; Stöhr, Meike; Rudolf, Petra

    2013-09-01

    We present a multi-technique characterisation of graphene grown by chemical vapour deposition (CVD) and thereafter transferred to and suspended on a grid for transmission electron microscopy (TEM). The properties of the electronic band structure are investigated by angle-resolved photoelectron spectromicroscopy, while the structural and crystalline properties are studied by TEM and Raman spectroscopy. We demonstrate that the suspended graphene membrane locally shows electronic properties comparable with those of samples prepared by micromechanical cleaving of graphite. Measurements show that the area of high quality suspended graphene is limited by the folding of the graphene during the transfer.

  9. Microscopic characterisation of suspended graphene grown by chemical vapour deposition.

    PubMed

    Bignardi, Luca; van Dorp, Willem F; Gottardi, Stefano; Ivashenko, Oleksii; Dudin, Pavel; Barinov, Alexei; De Hosson, Jeff Th M; Stöhr, Meike; Rudolf, Petra

    2013-10-01

    We present a multi-technique characterisation of graphene grown by chemical vapour deposition (CVD) and thereafter transferred to and suspended on a grid for transmission electron microscopy (TEM). The properties of the electronic band structure are investigated by angle-resolved photoelectron spectromicroscopy, while the structural and crystalline properties are studied by TEM and Raman spectroscopy. We demonstrate that the suspended graphene membrane locally shows electronic properties comparable with those of samples prepared by micromechanical cleaving of graphite. Measurements show that the area of high quality suspended graphene is limited by the folding of the graphene during the transfer. PMID:23945527

  10. 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.

  11. Chemical vapour deposition synthetic diamond: materials, technology and applications

    NASA Astrophysics Data System (ADS)

    Balmer, R. S.; Brandon, J. R.; Clewes, S. L.; Dhillon, H. K.; Dodson, J. M.; Friel, I.; Inglis, P. N.; Madgwick, T. D.; Markham, M. L.; Mollart, T. P.; Perkins, N.; Scarsbrook, G. A.; Twitchen, D. J.; Whitehead, A. J.; Wilman, J. J.; Woollard, S. M.

    2009-09-01

    Substantial developments have been achieved in the synthesis of chemical vapour deposition (CVD) diamond in recent years, providing engineers and designers with access to a large range of new diamond materials. CVD diamond has a number of outstanding material properties that can enable exceptional performance in applications as diverse as medical diagnostics, water treatment, radiation detection, high power electronics, consumer audio, magnetometry and novel lasers. Often the material is synthesized in planar form; however, non-planar geometries are also possible and enable a number of key applications. This paper reviews the material properties and characteristics of single crystal and polycrystalline CVD diamond, and how these can be utilized, focusing particularly on optics, electronics and electrochemistry. It also summarizes how CVD diamond can be tailored for specific applications, on the basis of the ability to synthesize a consistent and engineered high performance product.

  12. Chemical vapour deposition synthetic diamond: materials, technology and applications.

    PubMed

    Balmer, R S; Brandon, J R; Clewes, S L; Dhillon, H K; Dodson, J M; Friel, I; Inglis, P N; Madgwick, T D; Markham, M L; Mollart, T P; Perkins, N; Scarsbrook, G A; Twitchen, D J; Whitehead, A J; Wilman, J J; Woollard, S M

    2009-09-01

    Substantial developments have been achieved in the synthesis of chemical vapour deposition (CVD) diamond in recent years, providing engineers and designers with access to a large range of new diamond materials. CVD diamond has a number of outstanding material properties that can enable exceptional performance in applications as diverse as medical diagnostics, water treatment, radiation detection, high power electronics, consumer audio, magnetometry and novel lasers. Often the material is synthesized in planar form; however, non-planar geometries are also possible and enable a number of key applications. This paper reviews the material properties and characteristics of single crystal and polycrystalline CVD diamond, and how these can be utilized, focusing particularly on optics, electronics and electrochemistry. It also summarizes how CVD diamond can be tailored for specific applications, on the basis of the ability to synthesize a consistent and engineered high performance product. PMID:21832327

  13. 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

  14. 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

  15. 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

  16. Long distance spin communication in chemical vapour deposited graphene

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    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.

  17. 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.

  18. 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.

  19. Laser-induced etching of few-layer graphene synthesized by Rapid-Chemical Vapour Deposition on Cu thin films.

    PubMed

    Piazzi, Marco; Croin, Luca; Vittone, Ettore; Amato, Giampiero

    2012-12-01

    The outstanding electrical and mechanical properties of graphene make it very attractive for several applications, Nanoelectronics above all. However a reproducible and non destructive way to produce high quality, large-scale area, single layer graphene sheets is still lacking. Chemical Vapour Deposition of graphene on Cu catalytic thin films represents a promising method to reach this goal, because of the low temperatures (T < 950°C-1000°C) involved during the process and of the theoretically expected monolayer self-limiting growth. On the contrary such self-limiting growth is not commonly observed in experiments, thus making the development of techniques allowing for a better control of graphene growth highly desirable. Here we report about the local ablation effect, arising in Raman analysis, due to the heat transfer induced by the laser incident beam onto the graphene sample. PMID:23503582

  20. 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.

  1. 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.

  2. Surface melting of copper during graphene growth by chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Pakhnevich, A. A.; Golod, S. V.; Prinz, V. Ya

    2015-11-01

    Evidence for the presence of a liquid phase on a copper surface during graphene growth by chemical vapour deposition at temperatures of 1000 and 1050 °C has been experimentally obtained. It was established that, first, the liquid phase forms a groove structure and bubble-like nanoobjects on the copper surface. Second, the liquid phase promotes the propagation of the wavy relief of a growing graphene film to the adjacent copper, and, third, the surface flows of the liquid phase can influence the waviness and orientation of the graphene islands. From the obtained data, it was concluded that surface melting plays an important role in graphene formation by chemical vapour deposition at temperatures below the melting point of copper.

  3. Growth of graphene films by plasma enhanced chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Baraton, Laurent; Gangloff, Laurent; Xavier, Stéphane; Cojocaru, Costel S.; Huc, Vincent; Legagneux, Pierre; Lee, Young Hee; Pribat, Didier

    2009-08-01

    Since it was isolated in 2004, graphene, the first known 2D crystal, is the object of a growing interest, due to the range of its possible applications as well as its intrinsic properties. From large scale electronics and photovoltaics to spintronics and fundamental quantum phenomena, graphene films have attracted a large community of researchers. But bringing graphene to industrial applications will require a reliable, low cost and easily scalable synthesis process. In this paper we present a new growth process based on plasma enhanced chemical vapor deposition. Furthermore, we show that, when the substrate is an oxidized silicon wafer covered by a nickel thin film, graphene is formed not only on top of the nickel film, but also at the interface with the supporting SiO2 layer. The films grown using this method were characterized using classical methods (Raman spectroscopy, AFM, SEM) and their conductivity is found to be close to those reported by others.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Effect of process parameters on the chemical vapour synthesis of nanocrystalline titania

    NASA Astrophysics Data System (ADS)

    Md, Imteyaz Ahmad; Bhattacharya, S. S.

    2008-08-01

    In this investigation nanocrystalline titania powders were produced by the chemical vapour synthesis (CVS) route and characterized by standard techniques of XRD, HRTEM and BET. The effects of precursor/gas flow rates, hotwall temperature and system pressure on the particle size and distribution, as well as phase composition of the synthesized nanocrystalline titania powder, were studied. It was demonstrated that by suitably adjusting the process parameters during CVS it becomes possible to control the anatase crystallite size, specific surface area and the rutile content in the synthesized nanocrystalline titania powders.

  9. Large gauge factor of hot wire chemical vapour deposition in-situ boron doped polycrystalline silicon

    NASA Astrophysics Data System (ADS)

    Grech, David; Tarazona, Antulio; De Leon, Maria Theresa; Kiang, Kian S.; Zekonyte, Jurgita; Wood, Robert J. K.; Chong, Harold M. H.

    2016-04-01

    Polysilicon piezoresistors with a large longitudinal gauge factor (GF) of 44 have been achieved using in-situ boron doped hot-wire chemical vapour deposition (HWCVD). This GF is a consequence of a high quality p-type doped polysilicon with a crystal volume of 97% and an average grain size of 150 nm, estimated using Raman spectroscopy and atomic force microscopy (AFM) respectively. The measured minimum Hooge factor associated to the 1/f noise of the polysilicon piezoresistors is 1.4 × 10‑3. These results indicate that HWCVD polysilicon is a suitable piezoresistive material for micro-electro-mechanical systems (MEMS) applications.

  10. Giant spin Hall effect in graphene grown by chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Balakrishnan, Jayakumar; Koon, Gavin Kok Wai; Avsar, Ahmet; Ho, Yuda; Lee, Jong Hak; Jaiswal, Manu; Baeck, Seung-Jae; Ahn, Jong-Hyun; Ferreira, Aires; Cazalilla, Miguel A.; Neto, Antonio H. Castro; Özyilmaz, Barbaros

    2014-09-01

    Advances in large-area graphene synthesis via chemical vapour deposition on metals like copper were instrumental in the demonstration of graphene-based novel, wafer-scale electronic circuits and proof-of-concept applications such as flexible touch panels. Here, we show that graphene grown by chemical vapour deposition on copper is equally promising for spintronics applications. In contrast to natural graphene, our experiments demonstrate that chemically synthesized graphene has a strong spin-orbit coupling as high as 20 meV giving rise to a giant spin Hall effect. The exceptionally large spin Hall angle ~0.2 provides an important step towards graphene-based spintronics devices within existing complementary metal-oxide-semiconductor technology. Our microscopic model shows that unavoidable residual copper adatom clusters act as local spin-orbit scatterers and, in the resonant scattering limit, induce transverse spin currents with enhanced skew-scattering contribution. Our findings are confirmed independently by introducing metallic adatoms-copper, silver and gold on exfoliated graphene samples.

  11. Chemically assisted vapour transport for bulk ZnO crystal growth

    NASA Astrophysics Data System (ADS)

    Santailler, Jean-Louis; Audoin, Claire; Chichignoud, Guy; Obrecht, Rémy; Kaouache, Belkhiri; Marotel, Pascal; Pelenc, Denis; Brochen, Stéphane; Merlin, Jérémy; Bisotto, Isabelle; Granier, Carole; Feuillet, Guy; Levy, François

    2010-11-01

    A chemically assisted vapour phase transport (CVT) method is proposed for the growth of bulk ZnO crystals. Thermodynamic computations have confirmed the possibility of using CO as a sublimation activator for enhancing the sublimation rate of the feed material in a large range of pressures (10 -3 to 1 atm) and temperatures (800-1200 °C). Growth runs in a specific and patented design yielded single ZnO crystals up to 46 mm in diameter and 8 mm in thickness, with growth rates up to 400 μm/h. These values are compatible with an industrial production rate. N type ZnO crystals ( μ=182 cm 2/(V s) and n=7 10 15 cm -3) obtained by this CVT method (Chemical Vapour Transport) present a high level of purity (10-30 times better than hydrothermal ZnO crystals), which may be an advantage for obtaining p-type doped layers ([Li] and [Al] <10 +15 cm -3). Structural (HR-XRD), defect density (EPD), electrical (Hall measurements) and optical (photoluminescence) properties are presented.

  12. 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.

  13. Chemical vapour deposition diamond coating on tungsten carbide dental cutting tools

    NASA Astrophysics Data System (ADS)

    Sein, H.; Ahmed, W.; Rego, C. A.; Jones, A. N.; Amar, M.; Jackson, M.; Polini, R.

    2003-10-01

    Diamond coatings on Co cemented tungsten carbide (WC-Co) hard metal tools are widely used for cutting non-ferrous metals. It is difficult to deposit diamond onto cutting tools, which generally have a complex geometry, using a single step growth process. This paper focuses on the deposition of polycrystalline diamond films onto dental tools, which possess 3D complex or cylindrical shape, employing a novel single step chemical vapour deposition (CVD) growth process. The diamond deposition is carried out in a hot filament chemical vapour deposition (HFCVD) reactor with a modified filament arrangement. The filament is mounted vertically with the drill held concentrically in between the filament coils, as opposed to the commonly used horizontal arrangement. This is a simple and inexpensive filament arrangement. In addition, the problems associated with adhesion of diamond films on WC-Co substrates are amplified in dental tools due to the very sharp edges and unpredictable cutting forces. The presence of Co, used as a binder in hard metals, generally causes poor adhesion. The amount of metallic Co on the surface can be reduced using a two step pre-treatment employing Murakami etching followed by an acid treatment. Diamond films are examined in terms of their growth rate, morphology, adhesion and cutting efficiency. We found that in the diamond coated dental tool the wear rate was reduced by a factor of three as compared to the uncoated tool.

  14. Chemical vapour etching-based porous silicon and grooving: Application in silicon solar cells processing

    NASA Astrophysics Data System (ADS)

    Ben Rabha, M.; Boujmil, M. F.; Saadoun, M.; Bessaïs, B.

    2005-06-01

    Sponge like porous silicon (PS) was formed by a simple and low cost chemical vapour etching (CVE) method and applied in polycrystalline silicon (mc-Si) solar cells processing. The CVE method consists of exposing Si wafers to HNO3/HF vapours. It was shown that 8 min of HNO3/HF CVE (volume ratio = 1/7) is sufficient to form optimized PS layers on the emitter of mc-Si cells. The CVE-based PS can simultaneously passivate the Si surface and serves as an effective antireflection coating (ARC). As a result, the reflectivity decreases by about 60% of its initial value and the internal quantum efficiency is improved, particularly in the short wavelength region. For acid vapours rich in HNO3 (HNO3/HF >1/4), the CVE method favours the formation of a (NH4)2SiF6 powder, which is highly soluble in water. These findings let us achieve anisotropic grooving that enables to groove mc-Si wafers locally and in depth using an adequate anti-acid mask. The CVE - based grooving technique was used to form buried metallic contacts on the rear and frontal surface of the Si wafer in order to improve the current collection in mc-Si solar cells. No alteration of the spectral response in the long wavelength range was observed in mc-Si cells with rear-buried contacts. Adjustments of theoretical spectral responses to experimental ones show an increase in the effective electron diffusion length (Ln), which was attributed to Al gettering (passivation) at grain boundaries and to the reduction of the effective thickness of the base of the cells.

  15. Structural Evolution of SiC Films During Plasma-Assisted Chemical Vapour Deposition

    NASA Astrophysics Data System (ADS)

    Ding, Siye; Yan, Guanchao; Zhu, Xiaodong; Zhou, Haiyang

    2009-04-01

    Evolution of chemical bonding configurations for the films deposited from hexamethyldisiloxane (HMDSO) diluted with H2 during plasma assisted chemical vapour deposition is investigated. In the experiment a small amount of CH4 was added to adjust the plasma environment and modify the structure of the deposited films. The measurements of Raman spectroscopy and X-ray diffraction (XRD) revealed the production of 6H-SiC embedded in the amorphous matrix without the input of CH4. As CH4 was introduced into the deposition reaction, the transition of 6H-SiC to cubic SiC in the films took place, and also the film surfaces changed from a structure of ellipsoids to cauliflower-like shapes. With a further increase of CH4 in the flow ratio, the obtained films varied from Si-C bonding dominant to a sp2/sp3 carbon-rich composition.

  16. TOPICAL REVIEW Charged nanoparticles in thin film and nanostructure growth by chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Hwang, Nong-Moon; Lee, Dong-Kwon

    2010-12-01

    The critical role of charged nanoclusters and nanoparticles in the growth of thin films and nanostructures by chemical vapour deposition (CVD) is reviewed. Advanced nanoparticle detection techniques have shown that charged gas-phase nuclei tend to be formed under conventional processing conditions of thin films and nanostructures by thermal, hot-wire and plasma CVD. The relation between gas-phase nuclei and thin film and nanostructure growth has not been clearly understood. In this review it will be shown that many films and nanostructures, which have been believed to grow by individual atoms or molecules, actually grow by the building blocks of such charged nuclei. This new growth mechanism was revealed in an attempt to explain many puzzling phenomena involved in the gas-activated diamond CVD process. Therefore, detailed thermodynamic and kinetic analyses will be made to draw the conclusion that the well-known phenomenon of deposition of less stable diamond with simultaneous etching of stable graphite should be an indication of diamond growth exclusively by charged nuclei formed in the gas phase. A similar logic was applied to the phenomenon of simultaneous deposition and etching of silicon, which also leads to the conclusion that silicon films by CVD should grow mainly by the building blocks of charged nuclei. This new mechanism of crystal growth appears to be general in many CVD and some physical vapour deposition (PVD) processes. In plasma CVD, this new mechanism has already been utilized to open a new field of plasma-aided nanofabrication.

  17. 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

  18. Ferromagnetic resonance of patterned chromium dioxide thin films grown by selective area chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Durrant, C. J.; Jokubaitis, M.; Yu, W.; Mohamad, H.; Shelford, L. R.; Keatley, P. S.; Xiao, Gang; Hicken, R. J.

    2015-05-01

    A selective area chemical vapour deposition technique has been used to fabricate continuous and patterned epitaxial CrO2 thin films on (100)-oriented TiO2 substrates. Precessional magnetization dynamics were stimulated both electrically and optically, and probed by means of time-resolved Kerr microscopy and vector network analyser ferromagnetic resonance techniques. The dependence of the precession frequency and the effective damping parameter upon the static applied magnetic field were investigated. All films exhibited a large in-plane uniaxial anisotropy. The effective damping parameter was found to exhibit strong field dependence in the vicinity of the hard axis saturation field. However, continuous and patterned films were found to possess generally similar dynamic properties, confirming the suitability of the deposition technique for fabrication of future spintronic devices.

  19. High temperature stability of nanocrystalline anatase powders prepared by chemical vapour synthesis under varying process parameters

    NASA Astrophysics Data System (ADS)

    Ahmad, Md. Imteyaz; Fasel, Claudia; Mayer, Thomas; Bhattacharya, S. S.; Hahn, Horst

    2011-05-01

    Systematic variation in the high temperature stability of nanocrystalline anatase powders prepared by chemical vapour synthesis (CVS) using titanium (IV) isopropoxide under varying flow rates of oxygen and helium was obtained by progressively shifting the decomposition product from C 3H 6 to CO 2. The as-synthesised powders were characterised by high temperature X-ray diffraction (HTXRD), simultaneous thermo-gravimetric analyses (STA), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). It was observed that the anatase to rutile transformation temperature progressively increased for samples synthesised at higher O 2/He flow rate ratios. The improved anatase stability was attributed to the presence of incorporated carbon within the titania structure and confirmed by a high temperature carbon desorption peak.

  20. Chemical Vapour Deposition Graphene Radio-Frequency Field-Effect Transistors

    NASA Astrophysics Data System (ADS)

    Ma, Peng; Jin, Zhi; Guo, Jian-Nan; Pan, Hong-Liang; Liu, Xin-Yu; Ye, Tian-Chun; Wang, Hong; Wang, Guan-Zhong

    2012-05-01

    We report the dc and rf performance of graphene rf field-effect transistors, where the graphene films are grown on copper by using the chemical vapour deposition (CVD) method and transferred to SiO2/Si substrates. Composite materials, benzocyclobutene and atomic layer deposition Al2O3 are used as the gate dielectrics. The observation of n- and p-type transitions verifies the ambipolar characteristics in the graphene layers. While the intrinsic carrier mobility of CVD graphene is extracted to be 1200 cm2/V·s, the parasitic series resistances are demonstrated to have a serious impact on device performance. With a gate length of 1 μm and an extrinsic transconductance of 72 mS/mm, a cutoff frequency of 6.6 GHz and a maximum oscillation frequency of 8.8 GHz are measured for the transistors, illustrating the potential of the CVD graphene for rf applications.

  1. Elaboration of Bi 2Se 3 by metalorganic chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Giani, A.; Al Bayaz, A.; Foucaran, A.; Pascal-Delannoy, F.; Boyer, A.

    2002-03-01

    For the first time, Bi 2Se 3 thin films were elaborated by metalorganic chemical vapour deposition (MOCVD) using trimethylbismuth (TMBi) and diethylselenium (DESe) as metalorganic sources. The MOCVD elaboration of Bi 2Se 3 was carried out in a horizontal reactor for a substrate temperature ( Tg) varying from 450°C to 500°C, a total hydrogen flow rate DT=3 l min -1, RVI/V ratio >14 and TMBi partial pressure lower than 1.10 -4 atm. By X-ray diffraction and SEM observation, we noticed the polycrystalline structure of the layers typical preferential c-orientation and confirm the hexagonal structure. The microprobe data indicate that the best stoichiometry of Bi 2Se 3 was achieved. These films always displayed n-type conduction, and the maximum value of thermoelectric power α was found to be close to -120 μV/K.

  2. 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

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

    PubMed

    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

  4. 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

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

    NASA Astrophysics Data System (ADS)

    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

    2016-03-01

    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.

  6. Synthesis of Tin Nitride Sn x N y Nanowires by Chemical Vapour Deposition

    NASA Astrophysics Data System (ADS)

    Zervos, Matthew; Othonos, Andreas

    2009-09-01

    Tin nitride (Sn x N y ) 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 Sn x N y nanowires 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 NH3 is 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 NH3 and HCl which act as dispersants thereby enhancing the vapour pressure of Sn and the one-dimensional growth of Sn x N y nanowires. In addition to the action of dispersion, Sn reacts with HCl giving SnCl2 which in turn reacts with NH3 leading to the formation of Sn x N y NWs. A first estimate of the band-gap of the Sn x N y nanowires 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.

  7. Fluorinated carboxylic membranes deposited by plasma enhanced chemical vapour deposition for fuel cell applications

    NASA Astrophysics Data System (ADS)

    Thery, J.; Martin, S.; Faucheux, V.; Le Van Jodin, L.; Truffier-Boutry, D.; Martinent, A.; Laurent, J.-Y.

    Among the fuel cell technologies, the polymer electrolyte membrane fuel cells (PEMFCs) are particularly promising because they are energy-efficient, clean, and fuel-flexible (i.e., can use hydrogen or methanol). The great majority of PEM fuel cells rely on a polymer electrolyte from the family of perfluorosulfonic acid membranes, nevertheless alternative materials are currently being developed, mainly to offer the alternative workout techniques which are required for the portable energy sources. Plasma polymerization represents a good solution, as it offers the possibility to deposit thin layer with an accurate and homogeneous thickness, even on 3D surfaces. In this paper, we present the results for the growth of proton conductive fluoro carboxylic membranes elaborated by plasma enhanced chemical vapour deposition. These membranes present conductivity values of the same order than the one of Nafion ®. The properties of the membrane, such as the chemical composition, the ionic conductivity, the swelling behaviour and the permeability were correlated to the plasma process parameters. The membranes were integrated in fuel cells on porous substrates and we present here the results regarding the barrier effect and the power output. Barrier effect similar to those of 40 μm Nafion ® layers was reached for 10 μm thick carboxylic membranes. Power outputs around 3 mW cm -2 were measured. We discuss the results regarding the gas barrier effect and the power outputs.

  8. 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.

  9. 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.

  10. Control and characterization of individual grains and grain boundaries in graphene grown by chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Yu, Qingkai; Jauregui, Luis A.; Wu, Wei; Colby, Robert; Tian, Jifa; Su, Zhihua; Cao, Helin; Liu, Zhihong; Pandey, Deepak; Wei, Dongguang; Chung, Ting Fung; Peng, Peng; Guisinger, Nathan P.; Stach, Eric A.; Bao, Jiming; Pei, Shin-Shem; Chen, Yong P.

    2011-06-01

    The strong interest in graphene has motivated the scalable production of high-quality graphene and graphene devices. As the large-scale graphene films synthesized so far are typically polycrystalline, it is important to characterize and control grain boundaries, generally believed to degrade graphene quality. Here we study single-crystal graphene grains synthesized by ambient chemical vapour deposition on polycrystalline Cu, and show how individual boundaries between coalescing grains affect graphene’s electronic properties. The graphene grains show no definite epitaxial relationship with the Cu substrate, and can cross Cu grain boundaries. The edges of these grains are found to be predominantly parallel to zigzag directions. We show that grain boundaries give a significant Raman ‘D’ peak, impede electrical transport, and induce prominent weak localization indicative of intervalley scattering in graphene. Finally, we demonstrate an approach using pre-patterned growth seeds to control graphene nucleation, opening a route towards scalable fabrication of single-crystal graphene devices without grain boundaries.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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

  16. 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

  17. 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.

  18. Temporal Stability of Metal-Chloride-Doped Chemical-Vapour-Deposited Graphene.

    PubMed

    Kang, Moon H; Milne, William I; Cole, Matthew T

    2016-08-18

    Graphene has proven to be a promising material for transparent flexible electronics. In this study, we report the development of a transfer and doping scheme of large-area chemical vapour deposited (CVD) graphene. A technique to transfer the as-grown material onto mechanically flexible and optically transparent polymeric substrates using an ultraviolet adhesive (UVA) is outlined, along with the temporal stability of the sheet resistance and optical transparency following chemical doping with various metal chlorides (Mx Cly The sheet resistance (RS ) and 550 nm optical transparency (%T550 ) of the transferred un-doped graphene was 3.5 kΩ sq(-1) (±0.2 kΩ sq(-1) ) and 84.1 % (±2.9 %), respectively. Doping with AuCl3 showed a notable reduction in RS by some 71.4 % (to 0.93 kΩ sq(-1) ) with a corresponding %T550 of 77.0 %. After 200 h exposure to air at standard temperature and pressure, the increase in RS was found to be negligible (ΔRS AuCl3 =0.06 kΩ sq(-1) ), indicating that, of the considered Mx Cly species, AuCl3 doping offered the highest degree of time stability under ambient conditions. There appears a tendency of increasing RS with time for the remaining metal chlorides studied. We attribute the observed temporal shift to desorption of molecular dopants. We find that desorption was most significant in RhCl3 -doped samples whereas, in contrast, after 200 h in ambient conditions, AuCl3 -doped graphene showed only marginal desorption. The results of this study demonstrate that chemical doping of UVA-transferred graphene is a promising means for enhancing large-area CVD graphene in order to realise a viable platform for next-generation optically transparent and mechanically flexible electronics. PMID:27165783

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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

  4. Thin-Film Deposition of Metal Oxides by Aerosol-Assisted Chemical Vapour Deposition: Evaluation of Film Crystallinity

    NASA Astrophysics Data System (ADS)

    Takeuchi, Masahiro; Maki, Kunisuke

    2007-12-01

    Sn-doped In2O3 (ITO) thin films are deposited on glass substrates using 0.2 M aqueous and methanol solutions of InCl3(4H2O) with 5 mol % SnCl2(2H2O) by aerosol-assisted chemical vapour deposition under positive and negative temperature gradient conditions. The film crystallinity is evaluated by determining the film thickness dependence of X-ray diffraction peak height. When using aqueous solution, the ITO films grow with the same crystallinity during the deposition, but when using methanol solution, the preferred orientation of ITO changes during the deposition.

  5. 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

  6. 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

  7. Substrate patterning with NiOx nanoparticles and hot-wire chemical vapour deposition of WO3x and carbon nanostructures

    NASA Astrophysics Data System (ADS)

    Houweling, Z. S.

    2011-10-01

    The first part of the thesis treats the formation of nickel catalyst nanoparticles. First, a patterning technique using colloids is employed to create ordered distributions of monodisperse nanoparticles. Second, nickel films are thermally dewetted, which produces mobile species that self-arrange in non-ordered distributions of polydisperse particles. Third, the mobility of the nickel species is successfully reduced by the addition of air during the dewetting and the use of a special anchoring layer. Thus, non-ordered distributions of self-arranged monodisperse nickel oxide nanoparticles (82±10 nm x 16±2 nm) are made. Studies on nickel thickness, dewetting time and dewetting temperature are conducted. With these particle templates, graphitic carbon nanotubes are synthesised using catalytic hot-wire chemical vapour deposition (HWCVD), demonstrating the high-temperature processability of the nanoparticles. The second part of this thesis treats the non-catalytic HWCVD of tungsten oxides (WO3-x). Resistively heated tungsten filaments exposed to an air flow at subatmospheric pressures, produce tungsten oxide vapour species, which are collected on substrates and are subsequently characterised. First, a complete study on the process conditions is conducted, whereby the effects of filament radiation, filament temperature, process gas pressure and substrate temperature, are investigated. The thus controlled growth of nanogranular smooth amorphous and crystalline WO3-x thin films is presented for the first time. Partially crystalline smooth hydrous WO3-x thin films consisting of 20 nm grains can be deposited at very high rates. The synthesis of ultrafine powders with particle sizes of about 7 nm and very high specific surface areas of 121.7±0.4 m2·g-1 at ultrahigh deposition rates of 36 µm·min-1, is presented. Using substrate heating to 600°C or more, while using air pressures of 3·10-5 mbar to 0.1 mbar, leads to pronounced crystal structures, from nanowires, to

  8. 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. PMID:24817050

  9. Mosaic Structure Evolution in GaN Films with Annealing Time Grown by Metalorganic Chemical Vapour Deposition

    NASA Astrophysics Data System (ADS)

    Chen, Zhi-Tao; Xu, Ke; Guo, Li-Ping; Yang, Zhi-Jian; Pan, Yao-Bo; Su, Yue-Yong; Zhang, Han; Shen, Bo; Zhang, Guo-Yi

    2006-05-01

    We investigate mosaic structure evolution of GaN films annealed for a long time at 800°C grown on sapphire substrates by metalorganic chemical vapour deposition by high-resolution x-ray diffraction. The result show that residual stress in GaN films is relaxed by generating edge-type threading dislocations (TDs) instead of screw-type TDs. Compared to as-grown GaN films, the annealed ones have larger mean twist angles corresponding to higher density of edge-type TDs but smaller mean tilt angles corresponding to lower density of screw-type TDs films. Due to the increased edge-type TD density, the lateral coherence lengths of the annealed GaN films also decrease. The results obtained from chemical etching experiment and grazing-incidence x-ray diffraction (GIXRD) also support the proposed structure evolution.

  10. 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

  11. Growth of ZnO nanorods on stainless steel wire using chemical vapour deposition and their photocatalytic activity.

    PubMed

    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 I(uv)/I(vis) 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

  12. 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

  13. CATALYTIC CONVERSION OF HAZARDOUS AND TOXIC CHEMICALS: CATALYTIC HYDRODECHLORINATION OF POLYCHLORINATED PESTICIDES AND RELATED SUBSTANCES

    EPA Science Inventory

    A study has been undertaken of the catalytic conversion of chlorinated pesticides and other environmentally undesirable chlorinated materials into acceptable compounds. The results of this study show that chlorine can be catalytically removed and replaced by hydrogen to produce r...

  14. 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.

  15. 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.

  16. 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

  17. Growth of carbon nanotubes (CNTs) on metallic underlayers by diffusion plasma-enhanced chemical vapour deposition (DPECVD)

    NASA Astrophysics Data System (ADS)

    Kim, S. M.; Gangloff, L.

    2009-10-01

    Here, we demonstrate the low-temperature (480-612 °C) synthesis of carbon nanotubes (CNTs) on different metallic underlayers (i.e., NiV, Ir, Ag, Pt, W, and Ta) using diffusion (dc) plasma-enhanced (~20 W, -600 V) chemical vapour deposition (DPECVD). The catalyst used is bi-layered Fe/Al and the feedstock used is a mixture of C 2H 2 and NH 3 (1:4). The crucial component is the diffusion of radical ions and hydrogen generated such as H 2/H +/H 2+/NH 3+/CH 2+/C 2H 2+ (which are confirmed by in-situ mass spectroscopy) from the nozzle, where it is inserted for most effective plasma diffusion between a substrate and a gas distributor.

  18. Formation of a Si Si3N4 nanocomposite from plasma enhanced chemical vapour deposition multilayer structures

    NASA Astrophysics Data System (ADS)

    Scardera, G.; Bellet-Amalric, E.; Bellet, D.; Puzzer, T.; Pink, E.; Conibeer, G.

    2008-07-01

    This work reports on the crystallization of α-Si3N4, β-Si3N4, and silicon in plasma enhanced chemical vapour deposition silicon nitride films grown with SiH4 and NH3 at 400C and annealed at 1150C. Nanometric multilayer structures, composed of alternating layers of silicon nitride and silicon-rich nitride, were used as the starting material. The final product is a thin-film Si-Si3N4 nanocomposite. The formation of this composite is verified using glancing incidence X-ray diffraction, transmission electron microscopy and Fourier transform infra-red spectroscopy. Annealing investigations indicate that the multilayer structure plays a key role in the formation of this composite and for the relatively low temperature formation of α- and β-Si3N4 nanocrystals.

  19. 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.

  20. Properties of MgB2 films grown at various temperatures by hybrid physical chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Chen, Ke; Veldhorst, Menno; Lee, Che-Hui; Lamborn, Daniel R.; DeFrain, Raymond; Redwing, Joan M.; Li, Qi; Xi, X. X.

    2008-09-01

    A hybrid physical-chemical vapour deposition (HPCVD) system consisting of separately controlled Mg-source heater and substrate heater is used to grow MgB2 thin films and thick films at various temperatures. We are able to grow superconducting MgB2 thin films at temperatures as low as 350 °C with a Tc0 of 35.5 K. MgB2 films up to 4 µm in thickness grown at 550 °C have Jc over 106 A cm-2 at 5 K and zero applied field. The low deposition temperature of MgB2 films is desirable for all-MgB2 tunnel junctions and MgB2 thick films are important for applications in coated conductors.

  1. 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

  2. Growth of large size diamond single crystals by plasma assisted chemical vapour deposition: Recent achievements and remaining challenges

    NASA Astrophysics Data System (ADS)

    Tallaire, Alexandre; Achard, Jocelyn; Silva, François; Brinza, Ovidiu; Gicquel, Alix

    2013-02-01

    Diamond is a material with outstanding properties making it particularly suited for high added-value applications such as optical windows, power electronics, radiation detection, quantum information, bio-sensing and many others. Tremendous progresses in its synthesis by microwave plasma assisted chemical vapour deposition have allowed obtaining single crystal optical-grade material with thicknesses of up to a few millimetres. However the requirements in terms of size, purity and crystalline quality are getting more and more difficult to achieve with respect to the forecasted applications, thus pushing the synthesis method to its scientific and technological limits. In this paper, after a short description of the operating principles of the growth technique, the challenges of increasing crystal dimensions both laterally and vertically, decreasing and controlling point and extended defects as well as modulating crystal conductivity by an efficient doping will be detailed before offering some insights into ways to overcome them.

  3. 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.

  4. 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

  5. Chemical vapour deposition of undoped and spinel-doped cubic zirconia film using organometallic process

    NASA Astrophysics Data System (ADS)

    Takahashi, Yasutaka; Kawae, Takayuki; Nasu, Mineji

    1986-03-01

    Growth of undoped and spinel-doped ZrO 2 films on glass substrates by the vapour phase decomposition of zirconium t-butoxide (ZTB) was investigated. Undoped tetragonal and monoclinic ZrO 2 films were formed below and above 400°C, respectively. Cubic ZrO 2 films were grown when the ZrO 2 was doped with more than 5 mol% of spinel MgAl 2O 4. Magnesium aluminium isopropoxide MgAl 2 (O-i-Pr) 8 (MAI) was used as the dopant source of the spinel. The cubic films have a higher Vickers hardness than the monoclinic films by about 200-250 kg/mm 2, and are stable up to 800°C, above which they were transformed to the monoclinic phase. This is in contrast to the higher temperature stability of the spinel-doped zirconia powder with spinel content 6 mol% formed by hydrolysis of a isopropanol solution of mixed zirconium n-butoxide and MAI, where the tetragonal form of ZrO 2 was kept unchanged by annealing it up to about 1000°C. The difference is attributed to effect of surface energy control in the tetragonal powders which is absent in the cubic films produced by CVD.

  6. Well-controlled metal co-catalysts synthesised by chemical vapour impregnation for photocatalytic hydrogen production and water purification.

    PubMed

    Su, Ren; Forde, Michael M; He, Qian; Shen, Yanbin; Wang, Xueqin; Dimitratos, Nikolaos; Wendt, Stefan; Huang, Yudong; Iversen, Bo B; Kiely, Christopher J; Besenbacher, Flemming; Hutchings, Graham J

    2014-10-28

    As co-catalyst materials, metal nanoparticles (NPs) play crucial roles in heterogeneous photocatalysis. The photocatalytic performance strongly relies on the physical properties (i.e., composition, microstructure, and surface impurities) of the metal NPs. Here we report a convenient chemical vapour impregnation (CVI) approach for the deposition of monometallic-, alloyed, and core-shell structured metal co-catalysts onto the TiO2 photocatalyst. The as-synthesised metal NPs are highly dispersed on the support and show narrow size distributions, which suit photocatalysis applications. More importantly, the surfaces of the as-synthesised metal NPs are free of protecting ligands, enabling the photocatalysts to be ready to use without further treatment. The effect of the metal identity, the alloy chemical composition, and the microstructure on the photocatalytic performance has been investigated for hydrogen production and phenol decomposition. Whilst the photocatalytic H2 production performance can be greatly enhanced by using the core-shell structured co-catalyst (Pdshell-Aucore and Ptshell-Aucore), the Ptshell-Aucore modified TiO2 yields enhanced quantum efficiency but a reduced effective decomposition of phenol to CO2 compared to that of the monometallic counterparts. We consider the CVI approach provides a feasible and elegant process for the decoration of photocatalyst materials. PMID:24970298

  7. 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.

  8. 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

  9. Low-temperature synthesis and characterization of helical carbon fibers by one-step chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Jin, Yongzhong; Chen, Jian; Fu, Qingshan; Li, Binghong; Zhang, Huazhi; Gong, Yong

    2015-01-01

    Helical carbon fibers (HCNFs) were synthesized by one-step chemical vapour deposition using cupric tartrate as a catalyst at temperature below 500 °C. The bound rubber of natural rubber (NR)/HCNFs were also prepared in this study. The results of thermogravimetry-differential scanning calorimetry (TG/DSC) for cupric tartrate nanoparticles show that the transformation of C4H4CuO6 → Cu reaction occurs at ∼250-310 °C. The characterization of scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD) and Raman spectrum for the synthesized products confirms that the synthesis of HCNFs is highly temperature-dependent. The straight fibers with the fiber diameter of 100-400 nm are obtained at 280 °C and HCNFs can be synthesized at higher temperature, with the coil diameter of 0.5-1 μm and fiber diameter of 100-200 nm at 380 °C, and the coil diameter of ∼100 nm and fiber diameter of ∼80 nm at 480 °C. The maximum of the bound-rubber content (37%) can be obtained with the addition of 100 wt.% HCNFs in NR, which indicates that the coiled configuration of HCNFs makes a noticeable contribution to the reinforcement of NR/CB system.

  10. Structural and Compositional Study of Graphene grown on SrTiO3 by Chemical Vapour Deposition

    NASA Astrophysics Data System (ADS)

    Karamat, Shumaila; Celik, Umit; Oral, Ahmet

    Graphene, a monolayer of sp2 bonded carbon atom, is considered as one of the most promising candidate materials for future electronics. The most critical step in graphene research is its transfer from the growth catalyst to the dielectric substrate, many unavoidable issues in the transfer process are: contamination from etchants, photoresist residues, wrinkles, and mechanical breakage. The direct growth of graphene on the substrates without using catalyst offer new opportunities in device fabrication without any transfer process. But till now, the field of direct graphene growth on dielectrics or insulating substrates is not mature like growth on metallic catalysts using CVD. We used chemical vapour deposition to grow graphene on SrTiO3 (110) substrates. The growth was carried out in presence of methane, argon and hydrogen. Raman Spectrum clearly showed the D and G peaks which were absent in bare substrate. XPS was used to get information about the presence of necessary elements, their bonding with STO substrates. AFM imaging clearly showed graphene island formation on substrates.

  11. 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.

  12. 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

  13. Chemical vapour deposition enhanced by atmospheric microwave plasmas: a large-scale industrial process or the next nanomanufacturing tool?

    NASA Astrophysics Data System (ADS)

    Belmonte, T.; Gries, T.; Cardoso, R. P.; Arnoult, G.; Kosior, F.; Henrion, G.

    2011-04-01

    This paper describes several specific aspects of atmospheric plasma deposition carried out with a microwave resonant cavity. Deposition over a wide substrate is first studied. We show that high deposition rates (several hundreds of μm h-1) are due to localization of fluxes on the substrate by convection when slightly turbulent flows are used. Next, we describe possible routes to localize deposition over a nanometre-sized area. Scaling down atmospheric plasma deposition is possible and two strategies to reach nanometre scales are described. Finally, we study self-organization of SiO2 nanodots deposited by chemical vapour deposition at atmospheric pressure enhanced by an Ar-O2 micro-afterglow operating at high temperature (>1200 K). When the film being deposited is thin enough (~500 nm) nanodots are obtained and they can be assembled into threads to create patterned surfaces. When the coating becomes thicker (~1 µm), and for relatively high content in HMDSO, SiO2 walls forming hexagonal cells are obtained.

  14. Evaluation of freestanding boron-doped diamond grown by chemical vapour deposition as substrates for vertical power electronic devices

    NASA Astrophysics Data System (ADS)

    Issaoui, R.; Achard, J.; Tallaire, A.; Silva, F.; Gicquel, A.; Bisaro, R.; Servet, B.; Garry, G.; Barjon, J.

    2012-03-01

    In this study, 4 × 4 mm2 freestanding boron-doped diamond single crystals with thickness up to 260 μm have been fabricated by plasma assisted chemical vapour deposition. The boron concentrations measured by secondary ion mass spectroscopy were 1018 to 1020 cm-3 which is in a good agreement with the values calculated from Fourier transform infrared spectroscopy analysis, thus indicating that almost all incorporated boron is electrically active. The dependence of lattice parameters and crystal mosaicity on boron concentrations have also been extracted from high resolution x-ray diffraction experiments on (004) planes. The widths of x-ray rocking curves have globally shown the high quality of the material despite a substantial broadening of the peak, indicating a decrease of structural quality with increasing boron doping levels. Finally, the suitability of these crystals for the development of vertical power electronic devices has been confirmed by four-point probe measurements from which electrical resistivities as low as 0.26 Ω cm have been obtained.

  15. 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.

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

    DOE PAGESBeta

    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

  17. Chemical vapour deposition of group-VIB metal dichalcogenide monolayers: engineered substrates from amorphous to single crystalline.

    PubMed

    Ji, Qingqing; Zhang, Yu; Zhang, Yanfeng; Liu, Zhongfan

    2015-05-01

    As structural analogues of graphene but with a sizeable band gap, monolayers of group-VIB transition metal dichalcogenides (MX2, M = Mo, W; X = S, Se, Te, etc.) have emerged as the ideal two dimensional prototype for exploring fundamental issues in physics such as valley polarization, and for engineering a wide range of nanoelectronic, optoelectronic and photocatalytic applications. Recently, chemical vapour deposition (CVD) was introduced as a more efficient preparation method than traditional chemical or physical exfoliation options, and has allowed for the successful synthesis of large-area MX2 monolayers possessing a large domain size, high thickness uniformity and continuity, and satisfactory crystal quality. This tutorial review therefore focuses on introducing the more recent advances in the CVD growth of MX2 (MoS2, WS2, MoS2(1-x)Se2xetc.) monolayers via the sulphurisation/decomposition of pre-deposited metal-based precursors, or the one-step reaction and deposition of gaseous metal and chalcogen feedstocks. Differences in growth behaviour caused by commonly used amorphous SiO2/Si, and newly adopted insulating single crystal substrates such as sapphire, mica and SrTiO3, are also comparatively presented. Also discussed are the essential parameters that influence the growth of MX2, such as the temperature, the source-substrate distance and the composition of the carrier gas (Ar/H2). Finally, an assessment is provided for viable future pathways for fine-tuning of the domain size and orientation, thickness uniformity, and the bandgap of MX2 and its alloys. PMID:25256261

  18. 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.

  19. 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.

  20. 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

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

    PubMed Central

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

    2013-01-01

    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

  2. Plasma and ion beam enhanced chemical vapour deposition of diamond and diamond-like carbon

    NASA Astrophysics Data System (ADS)

    Tang, Yongji

    WC-Co cutting tools are widely used in the machining industry. The application of diamond coatings on the surfaces of the tools would prolong the cutting lifetime and improves the manufacturing efficiency. However, direct chemical vapor deposition (CVD) of diamond coatings on WC-Co suffer from severe premature adhesion failure due to interfacial graphitization induced by the binder phase Co. In this research, a combination of hydrochloric acid (HCl) and hydrogen (H2) plasma pretreatments and a novel double interlayer of carbide forming element (CFE)/Al were developed to enhance diamond nucleation and adhesion. The results showed that both the pretreatments and interlayers were effective in forming continuous and adhesive nanocrystalline diamond coatings. The method is a promising replacement of the hazardous Murakami's regent currently used in WC-Co pretreatment with a more environmental friendly approach. Apart from coatings, diamond can be fabricated into other forms of nanostructures, such as nanotips. In this work, it was demonstrated that oriented diamond nanotip arrays can be fabricated by ion beam etching of as-grown CVD diamond. The orientation of diamond nanotips can be controlled by adjusting the direction of incident ion beam. This method overcomes the limits of other techniques in producing nanotip arrays on large areas with controlled orientation. Oriented diamond nano-tip arrays have been used to produce anisotropic frictional surface, which is successfully used in ultra-precision positioning systems. Diamond-like carbon (DLC) has many properties comparable to diamond. In this thesis, the preparation of alpha-C:H thin films by end-Hall (EH) ion source and the effects of ion energy and nitrogen doping on the microstructure and mechanical properties of the as-deposited thin films were investigated. The results have demonstrated that smooth and uniform alpha-C:H and alpha-C:H:N films with large area and reasonably high hardness and Young's modulus can be

  3. 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

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

    PubMed

    Varghese, Sajnu; Elfakhri, Souad O; Sheel, David W; Sheel, Paul; Bolton, Frederick J Eric; Foster, Howard A

    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

  5. 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

  6. 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.

  7. Liquid-phase catalytic processing of biomass-derived oxygenated hydrocarbons to fuels and chemicals.

    PubMed

    Chheda, Juben N; Huber, George W; Dumesic, James A

    2007-01-01

    Biomass has the potential to serve as a sustainable source of energy and organic carbon for our industrialized society. The focus of this Review is to present an overview of chemical catalytic transformations of biomass-derived oxygenated feedstocks (primarily sugars and sugar-alcohols) in the liquid phase to value-added chemicals and fuels, with specific examples emphasizing the development of catalytic processes based on an understanding of the fundamental reaction chemistry. The key reactions involved in the processing of biomass are hydrolysis, dehydration, isomerization, aldol condensation, reforming, hydrogenation, and oxidation. Further, it is discussed how ideas based on fundamental chemical and catalytic concepts lead to strategies for the control of reaction pathways and process conditions to produce H(2)/CO(2) or H(2)/CO gas mixtures by aqueous-phase reforming, to produce furan compounds by selective dehydration of carbohydrates, and to produce liquid alkanes by the combination of aldol condensation and dehydration/hydrogenation processes. PMID:17659519

  8. 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.

  9. 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. PMID:27329206

  10. 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.

  11. Studies of coupled chemical and catalytic coal conversion methods

    SciTech Connect

    Stock, L.M.

    1989-01-01

    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.

  12. 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

  13. Alloyed Crystalline Au-Ag Hollow Nanostructures with High Chemical Stability and Catalytic Performance.

    PubMed

    Liu, Renxiao; Guo, Jianhua; Ma, Gang; Jiang, Peng; Zhang, Donghui; Li, Dexing; Chen, Lan; Guo, Yuting; Ge, Guanglu

    2016-07-01

    For bimetallic nanoparticles (NPs), the degree of alloying is beginning to be recognized as a significant factor affecting the NP properties. Here, we report an alloyed crystalline Au-Ag hollow nanostructure that exhibits a high catalytic performance, as well as structural and chemical stability. The Au-Ag alloyed hollow and porous nanoshell structures (HPNSs) with different morphologies and subnanoscale crystalline structures were synthesized by adjusting the size of the sacrificial Ag NPs via a galvanic replacement reaction. The catalytic activities of the nanomaterials were evaluated by the model reaction of the catalytic reduction of p-nitrophenol by NaBH4 to p-aminophenol. The experimental results show that the subnanoscale crystalline structure of the Au-Ag bimetallic HPNSs has much greater significance than the apparent morphology does in determining the catalytic ability of the nanostructures. The Au-Ag alloyed HPNSs with better surface crystalline alloying microstructures and open morphologies were found to exhibit much higher catalytic reaction rates and better cyclic usage efficiencies, probably because of the better dispersion of active Au atoms within these materials. These galvanic replacement-synthesized alloyed Au-Ag HPNSs, fabricated by a facile method that avoids Ag degradation, have potential applications in catalysis, nanomedicine (especially in drug/gene delivery and cancer theranostics), and biosensing. PMID:27268019

  14. Studies of coupled chemical and catalytic coal conversion methods

    SciTech Connect

    Stock, L.M.

    1988-01-01

    Liquefaction of coal by depolymerization in an organic solvent has been studied for several years. The liquefied coal extract which results from such a process is far more suitable for conversion into liquid fuel by hydrogenolysis than is the untreated coal. Investigations on the chemical structure and the reactive sites of coal can help to select useful reactions for the production of liquids from coal. Sternberg et al. demonstrated that the reductive alkylation method transforms bituminous coal into an enormously soluble substance, irrespective of the mild reaction conditions. The effectiveness of newly introduced alkyl groups for the disruption of intermolecular hydrogen bonds and pi-pi interactions between the aromatic sheets in coal macromolecules has been recognized. It has been reported by Ignasiak et al. that a C-alkylabon reaction using sodium or potassium amide in liquid ammonia can be used to introduce alkyl groups at acidic carbon sites. A method has been developed recently in this laboratory for the solubilization of high rank coals. In the previous reports it was shown that n-butyl lithium and potassium t-butoxide in refluxing heptane produced coal anions which could be alkylated with different alkyl halides. Such alkylated coals were soluble up to 92% in solvents like pyridine. Though the solubilization of coal depended very much on the length of the alkyl group, it also depended very much on the nature of the base used. Strong bases like n-butyl lithium (pKa=42) can cause proton abstraction from aromatic structures, if the more acidic benzylic protons are absent. The utility of this procedure, initially developed and used by Miyake and Stock, has now been tested with the high oxygen containing, low rank Illinois No. 6 and Wyodak coals.

  15. 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.

  16. 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.

  17. 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

  18. Optimization of growth temperature of multi-walled carbon nanotubes fabricated by chemical vapour deposition and their application for arsenic removal

    NASA Astrophysics Data System (ADS)

    Mageswari, S.; Kalaiselvan, S.; Syed Shabudeen, P. S.; Sivakumar, N.; Karthikeyan, S.

    2014-12-01

    Multi-walled carbon nanotubes have been synthesized at different temperatures ranging from 550 °C to 750 °C on silica supported Fe-Mo catalyst by chemical vapour deposition technique using Cymbopogen flexuous oil under nitrogen atmosphere. The as-grown MWNTs were characterized by scanning electron microscope (SEM), high resolution transmission electron microscope (HRTEM), X-ray diffraction analysis (XRD) and Raman spectral studies. The HRTEM and Raman spectroscopic studies confirmed the evolution of MWNTs with the outer diameter between 20 and 40 nm. The possibility of using as-grown MWNTs as an adsorbent for removal of As (V) ions from drinking water was studied. Adsorption isotherm data were interpreted by the Langmuir and Freundlich equations. Kinetic data were studied using Elovich, pseudo-first order and pseudo-second order equations in order to elucidate the reaction mechanism.

  19. 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.

  20. An investigation into the optimum thickness of titanium dioxide thin films synthesized by using atmospheric pressure chemical vapour deposition for use in photocatalytic water oxidation.

    PubMed

    Hyett, Geoffrey; Darr, Jawwad A; Mills, Andrew; Parkin, Ivan P

    2010-09-10

    Twenty eight films of titanium dioxide of varying thickness were synthesised by using atmospheric pressure chemical vapour deposition (CVD) of titanium(IV) chloride and ethyl acetate onto glass and titanium substrates. Fixed reaction conditions at a substrate temperature of 660 °C were used for all depositions, with varying deposition times of 5-60 seconds used to control the thickness of the samples. A sacrificial electron acceptor system composed of alkaline sodium persulfate was used to determine the rate at which these films could photo-oxidise water in the presence of 365 nm light. The results of this work showed that the optimum thickness for CVD films on titanium substrates for the purposes of water oxidation was ≈200 nm, and that a platinum coating on the reverse of such samples leads to a five-fold increase in the observed rate of water oxidation. PMID:20645333

  1. Catalytic activity of platinum on ruthenium electrodes with modified (electro)chemical states.

    PubMed

    Park, Kyung-Won; Sung, Yung-Eun

    2005-07-21

    Using Pt on Ru thin-film electrodes with various (electro)chemical states designed by the sputtering method, the effect of Ru states on the catalytic activity of Pt was investigated. The chemical and electrochemical properties of Pt/Ru thin-film samples were confirmed by X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry. In addition, Pt nanoparticles on Ru metal or oxide for an actual fuel cell system showed an effect of Ru states on the catalytic activity of Pt in methanol electrooxidation. Finally, it was concluded that such an enhancement of methanol electrooxidation on the Pt is responsible for Ru metallic and/or oxidation sites compared to pure Pt without any Ru state. PMID:16852701

  2. 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. PMID:26910271

  3. Chemical process for the catalytic oxidation of formaldehyde and other organic compounds

    SciTech Connect

    Murphy, A.P.

    1991-01-01

    The invention discusses a chemical process for the catalytic oxidation of formaldehyde and other organic compounds contained in a dilute aqueous solution, particularly waste water. The inventive feature resides in the use of a cobalt catalyst to increase the rate of oxidation of the organic compounds when hypochlorous acid is the oxidant. The latter may be provided by a chlorine compound, such as sodium hypochlorite, calcium hypochlorite or chlorine gas dissolved in water.

  4. 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

  5. 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.

  6. Identification of Catalytic Amino Acid Residues by Chemical Modification in Dextranase.

    PubMed

    Ko, Jin-A; Nam, Seung-Hee; Kim, Doman; Lee, Jun-Ho; Kim, Young-Min

    2016-05-28

    A novel endodextranase isolated from Paenibacillus sp. was found to produce isomaltotetraose and small amounts of cycloisomaltooligosaccharides with a degree of polymerization of 7-14 from dextran. To determine the active site, the enzyme was modified with 1-ethyl-3-[3- (dimethylamino)-propyl]-carbodiimide (EDC) and α-epoxyalkyl α-glucosides (EAGs), an affinity labeling reagent. The inactivation followed pseudo first-order kinetics. Kinetic analysis and chemical modification using EDC and EAGs indicated that carboxyl groups are essential for the enzymatic activity. Three Asp and one Glu residues were identified as candidate catalytic amino acids, since these residues are completely conserved across the GH family of 66 enzymes. Replacement of Asp189, Asp340, or Glu412 completely abolished the enzyme activity, indicating that these residues are essential for catalytic activity. PMID:26907761

  7. Growth of multiwalled carbon nanotube arrays by chemical vapour deposition over iron catalyst and the effect of growth parameters

    NASA Astrophysics Data System (ADS)

    Radhakrishnan, J. K.; Pandian, P. S.; Padaki, V. C.; Bhusan, H.; Rao, K. U. B.; Xie, J.; Abraham, J. K.; Varadan, V. K.

    2009-04-01

    Multiwalled carbon nanotube (CNT) arrays were grown by catalytic thermal decomposition of acetylene, over Fe-catalyst deposited on Si-wafer in the temperature range 700-750 °C. The growth parameters were optimized to obtain dense arrays of multiwalled CNTs of uniform diameter. The vertical cross-section of the grown nanotube arrays reveals a quasi-vertical alignment of the nanotubes. The effect of varying the thickness of the catalyst layer and the effect of increasing the growth duration on the morphology and distribution of the grown nanotubes were studied. A scotch-tape test to check the strength of adhesion of the grown CNTs to the Si-substrate surface reveals a strong adhesion between the grown nanotubes and the substrate surface. Transmission electron microscopy analysis of the grown CNTs shows that the grown CNTs are multiwalled nanotubes with a bamboo structure, and follow the base-growth mechanism.

  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. Physical, chemical, and catalytic properties of borided cobalt Fischer-Tropsch catalysts

    SciTech Connect

    Wang, J.

    1987-01-01

    Unsupported and alumina-supported borided cobalt catalysts were prepared by chemical reduction of anhydrous cobalt acetate at 25/sup 0/C using B/sub 2/H/sub 6//THF or NaBH/sub 4//diglyme solution as the reducing agent. These catalysts were further activated in H/sub 2/ at 250/sup 0/C prior to use. The physical and chemical properties of these catalysts were characterized by chemical analysis, BET surface area measurements, H/sub 2/ and CO adsorption measurements, X-ray Diffraction, and Temperature Programmed Desorption of CO. The catalytic properties of these catalysts for hydrogenation of CO to hydrocarbons were investigated at 160 - 300/sup 0/C, 1 and 10 atm, and H/sub 2//CO ratio of 2 in a differential conversion range of less than 8%. The data show that unsupported, Na-free, borided cobalt is much more active than Na-containing borided cobalt and pure cobalt on a site basis. Similarly, CoB/Al/sub 2/O/sub 3/ is more than an order of magnitude more active than Co/Al/sub 2/O/sub 3/ is more than an order of magnitude more active than Co/Al/sub 2/O/sub 3/ but has similar selectivity; its selectivity for C/sub 5//sup +/ hydrocarbons, however, is very high (> 75 wt%) at low reaction temperatures (e.g. 170/sup 0/C) or at low H/sub 2//CO ratios (e.g. less than or equal to 1). The observed changes in catalytic and adsorption behavior are consistent with an electron-donor model in which boron atoms donate electrons to cobalt. Na was found to lower catalytic activity of cobalt while increasing selectivity for light hydrocarbons, olefins, and CO/sub 2/ products.

  10. 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.

  11. 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. PMID:16980288

  12. 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.

  13. Rapid thermal low-pressure chemical vapour deposition of tungsten films onto InP using WF6 and H2

    NASA Astrophysics Data System (ADS)

    Katz, A.; Feingold, A.; El-Roy, A.; Pearton, S. J.; Lane, E.; Nakahara, S.; Geva, M.

    1992-11-01

    Tungsten (W) films were deposited onto InP in a cold wall, rapid thermal low-pressure chemical vapour deposition (RT-LPCVD) reactor, from a tungsten hexafluoride (WF6) gas reduced by hydrogen (H2). W films of thickness 50-450 nm were deposited in the temperature range 350-550 degrees C, pressure range 0.5-4.5 Torr at deposition rates up to 4 nm s-1 with an apparent activation energy of about 1.12 eV. The film stress varied depending upon the deposition pressure, from low compressive for deposition at 0.5 Torr to moderate tensile for deposition at about 4.5 Torr. The films were aged at temperatures as high as 300 degrees C for about 800 h and exhibited an excellent mechanical stability. Post-deposition sintering of the W films at temperatures up to 600 degrees C led to reduction of the resistivity with a minimum value of about 55 mu Omega cm as a result of heating at 500 degrees C. Conditions for both selective and blanket deposition were defined, and a dry etching process for further geometrical definitions of the films was developed, providing etch rates of 40-50 nm min-1. This report reflects the first attempt to deposit W films onto III-V semiconductor at a very high rate by means of RT-LPCVD.

  14. Fabrication of 160-nm T-gate metamorphic AlInAs/GaInAs HEMTs on GaAs substrates by metal organic chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Li, Hai-Ou; Huang, Wei; Tang Chak, Wah; Deng, Xiao-Fang; Lau Kei, May

    2011-06-01

    The fabrication and performance of 160-nm gate-length metamorphic AlInAs/GaInAs high electron mobility transistors (mHEMTs) grown on GaAs substrate by metal organic chemical vapour deposition (MOCVD) are reported. By using a novel combined optical and e-beam photolithography technology, submicron mHEMTs devices have been achieved. The devices exhibit good DC and RF performance. The maximum current density was 817 mA/mm and the maximum transconductance was 828 mS/mm. The non-alloyed Ohmic contact resistance Rc was as low as 0.02 Ω-mm. The unity current gain cut-off frequency (fT) and the maximum oscillation frequency (fmax) were 146 GHz and 189 GHz, respectively. This device has the highest fT yet reported for a 160-nm gate-length HEMTs grown by MOCVD. The output conductance is 28.9 mS/mm, which results in a large voltage gain of 28.6. Also, an input capacitance to gate-drain feedback capacitance ratio, Cgs/Cgd, of 4.3 is obtained in the device.

  15. 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

  16. 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

  17. Impact of Mo and Ce on growth of single-walled carbon nanotubes by chemical vapour deposition using MgO-supported Fe catalysts

    NASA Astrophysics Data System (ADS)

    El-Hendawy, Abdel-Nasser A.; Andrews, Robert J.; Alexander, Andrew J.

    2009-05-01

    A series of nine catalysts containing Ce/Fe and Mo/Fe at various loadings on MgO supports have been studied as catalysts for chemical vapour deposition (CVD) of single-walled carbon nanotubes (SWCNTs) using a methane carbon source. Our results show that the Ce/Fe system is very suitable as a catalyst that favours SWCNT growth, and we question the special importance that has been attributed to Mo as an additive to Fe-based catalysts for SWCNT growth, as it appears that Ce is equally effective. Our results indicate that dehydroaromatization (DHA) is not a defining step for the growth mechanism, as has been suggested for Mo/Fe systems previously, and show that Ce and Mo do not seriously perturb the well-known Fe/MgO system for growth of high quality SWCNT. Using Raman spectroscopy, we have shown that the Ce/Fe/MgO catalyst system favours growth of SWCNTs with a different distribution of chiralities compared to the analogous Mo/Fe/MgO system.

  18. Polyethylene Oxide Films Polymerized by Radio Frequency Plasma-Enhanced Chemical Vapour Phase Deposition and Its Adsorption Behaviour of Platelet-Rich Plasma

    NASA Astrophysics Data System (ADS)

    Hu, Wen-Juan; Xie, Fen-Yan; Chen, Qiang; Weng, Jing

    2008-10-01

    We present polyethylene oxide (PEO) functional films polymerized by rf plasma-enhanced vapour chemical deposition (rf-PECVD) on p-Si (100) surface with precursor ethylene glycol dimethyl ether (EGDME) and diluted Ar in pulsed plasma mode. The influences of discharge parameters on the film properties and compounds are investigated. The film structure is analysed by Fourier transform infrared (FTIR) spectroscopy. The water contact angle measurement and atomic force microscope (AFM) are employed to examine the surface polarity and to detect surface morphology, respectively. It is concluded that the smaller duty cycle in pulsed plasma mode contributes to the rich C-O-C (EO) group on the surfaces. As an application, the adsorption behaviour of platelet-rich plasma on plasma polymerization films performed in-vitro is explored. The shapes of attached cells are studied in detail by an optic invert microscope, which clarifies that high-density C-O-C groups on surfaces are responsible for non-fouling adsorption behaviour of the PEO films.

  19. Reactive Chemical Vapour Deposition of Titanium Carbide from H2-TiCl4 Gas Mixture on Pyrocarbon: A Comprehensive Study

    NASA Astrophysics Data System (ADS)

    Ledain, O.; Woelffel, W.; Roger, J.; Vignoles, G.; Maillé, L.; Jacques, S.

    In Reactive Chemical Vapour Deposition (RCVD), the absence of one element of the deposited carbide in the initial gas phase involves the consumption/conversion of the solid substrate. In this way, the growth of a continuous carbide layer on the substrate requires solid-phase diffusion of the reagent. In this work, a parametric study of the RCVD of titanium carbide from pyrocarbon (PyC) and an H2-TiCl4 mixture has been carried out. Conversion ratio, PyC consumption and carbide layer growth kinetics have been determined at 1000̊C. The influence of the H2/TiCl4 dilution ratio has been also investigated. The apparent inter-diffusion coefficient of the carbon through the TiC deposited layer and the direct apparent reaction rate were determined from a comparison between simulations based on a Deal-Grove-type model and the experimental results. The study has been completed with FTIR spectrometry analyses of the gases.

  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. A chemical assessment of the suitability of allyl- iso-propyltelluride as a Te precursor for metal organic vapour phase epitaxy

    NASA Astrophysics Data System (ADS)

    Hails, Janet E.; Cole-Hamilton, David J.; Stevenson, John; Bell, William; Foster, Douglas F.; Ellis, David

    2001-04-01

    The chemical studies, which led to the testing of allyl- iso-propyltelluride (allylTePr i) as a Te precursor in metal organic vapour phase epitaxy are presented. The pyrolysis in hydrogen of allylTePr i gave products including 1,5-hexadiene, propane and propene. Co-pyrolysis of dimethylcadmium (Me 2Cd) and allylTePr i gave the hydrocarbons expected from the pyrolysis of the individual precursors plus additional hydrocarbons including 2-methylpropane and 1-butene. Plots of percentage decomposition versus temperature, which proved extremely useful in determining the likely growth temperatures for both CdTe and HgTe, showed that allylTePr i is less stable than both Pr 2iTe (di- iso-propyltelluride) and Me 2Cd. The possible role of Hg in the growth of CdTe is also discussed. The chemistry of allylTePr i is well suited for use as an efficient precursor for epitaxial growth of tellurium containing semiconductors since there is very little formation of other organotellurium compounds on pyrolysis.

  2. Chemical and physical properties of ultrafine diesel exhaust particles sampled downstream of a catalytic trap.

    PubMed

    Grose, Melissa; Sakurai, Hiromu; Savstrom, Jake; Stolzenburg, Mark R; Watts, Winthrop F; Morgan, Christopher G; Murray, Ian P; Twigg, Martyn V; Kittelson, David B; McMurry, Peter H

    2006-09-01

    The chemical and physical properties of exhaust particles produced by a Caterpillar 3176 C-12 heavy duty diesel engine equipped with a catalytic trap (CRT) are reported. The engine was operated at 600 Nm and 1500 rpm, using fuels containing 15 and 49 ppm sulfur. A two-stage dilution tunnel designed to simulate the reactions that occur when hot combustion products mix with cooler atmospheric air was used. Particle size distributions were measured using a scanning mobility particle sizer (SMPS) and nano-scanning mobility particle sizer (nano SMPS); a nanomicro-orifice uniform deposit impactor (nano MOUDI) collected size-resolved samples for gravimetric and chemical analysis. A nanometer tandem differential mobility analyzer (nano TDMA) was used to measure the volatility and hygroscopicity of 4-15 nm particles. These measurements confirm that the particles consisted primarily of sulfates. PMID:16999131

  3. 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.

  4. Formation of low pressure chemically vapour deposited W thin film on silicon dioxide for gate electrode application

    NASA Astrophysics Data System (ADS)

    Sone, Jae Hyun; Kim, Sun-Oo; Kim, Ki-Joon; Kim, Hyoung Sub; Kim, Hyeong Joon

    1994-12-01

    We have investigated the feasibility that low pressure chemically vapor deposited W can be used as a gate electrode material of metal-oxide-semiconductor (MOS) field effect transistors. We improved adhesion of the W film to SiO2 by using a pulsing injection of source gas. The pulsing injection of the reactant gas enhances the desorption of byproduct gases from the surface of the growing film and thus more W nuclei formed on SiO2. Tungsten thin films were deposited on the SiO2/Si with a deposition rate of 1000-2000 A/min. The deposition was carried out at various temperatures of 300-750 C and various SiH4:WF6 ratios of 0.6-1.5. The higher adhesion strength and resistivity of W thin films were achieved at the higher SiH4:WF6 ratio and higher deposition temperature. X-ray diffraction analysis showed that the crystal structure of all W films, deposited at various temperatures, was alpha-W in spite of either high reactant gas ratio or high temperature. Since W thin films had good adhesion to SiO2, MOS structure capacitors were fabricated with a W electrode via wet chemical processes and their electrical properties were also characterized. The extreme value distribution function of dielectric breakdown strength indicates that the thin SiO2 layer was significantly degraded by the diffused F ions. However, the stacked gate dielectric of SiO2 and Si3N4 layers instead of the single SiO2 layer was not degraded by the W gate electrode, since the Si3N4 layer protected SiO2 from chemical attack or restricted the F diffusion during deposition of the W gate electrode.

  5. 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.

  6. The top 50 commodity chemicals: Impact of catalytic process limitations on energy, environment, and economics

    SciTech Connect

    Tonkovich, A.L.Y.; Gerber, M.A.

    1995-08-01

    The production processes for the top 50 U.S. commodity chemicals waste energy, generate unwanted byproducts, and require more than a stoichiometric amount of feedstocks. Pacific Northwest Laboratory has quantified this impact on energy, environment, and economics for the catalytically produced commodity chemicals. An excess of 0.83 quads of energy per year in combined process and feedstock energy is required. The major component, approximately 54%, results from low per-pass yields and the subsequent separation and recycle of unreacted feedstocks. Furthermore, the production processes, either directly or through downstream waste treatment steps, release more than 20 billion pounds of carbon dioxide per year to the environment. The cost of the wasted feedstock exceeds 2 billion dollars per year. Process limitations resulting from unselective catalysis and unfavorable reaction thermodynamic constraints are the major contributors to this waste. Advanced process concepts that address these problems in an integrated manner are needed to improve process efficiency, which would reduce energy and raw material consumption, and the generation of unwanted byproducts. Many commodity chemicals are used to produce large volume polymer products. Of the energy and feedstock wasted during the production of the commodity chemicals, nearly one-third and one-half, respectively, represents chemicals used as polymer precursors. Approximately 38% of the carbon dioxide emissions are generated producing polymer feedstocks.

  7. Growth of complex SiGe/Ge superlattices by reduced pressure chemical vapour deposition at low temperature

    NASA Astrophysics Data System (ADS)

    Halpin, John E.; Rhead, Stephen D.; Sanchez, Ana M.; Myronov, Maksym; Leadley, David R.

    2015-11-01

    In this work the growth of complex n-type, high Ge content superlattice structures by reduced pressure chemical vapor deposition is presented. The structures feature 50 repeats of a 14 layer period, which includes a main quantum well that is between 13 and 21 nm wide. The total epitaxy thickness is approximately 8 μm. Diffusion and segregation in the structures was minimized by using a low growth temperature. Materials characterization shows the structures to be of good crystalline quality, with the thickness of all layers close to the design, abrupt interfaces, and uniformity throughout the structures. High angle annular dark field scanning transmission electron microscopy is shown to be an ideal technique for measuring layer thickness and interface quality in these structures.

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

    SciTech Connect

    Prengle, Jr, H W; 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.

  9. 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.

  10. [Studies on photo-electron-chemical catalytic degradation of the malachite green].

    PubMed

    Li, Ming-yu; Diao, Zeng-hui; Song, Lin; Wang, Xin-le; Zhang, Yuan-ming

    2010-07-01

    A novel two-compartment photo-electro-chemical catalytic reactor was designed. The TiO2/Ti thin film electrode thermally formed was used as photo-anode, and graphite as cathode and a saturated calomel electrode (SCE) as the reference electrode in the reactor. The anode compartment and cathode compartment were connected with the ionic exchange membrane in this reactor. Effects of initial pH, initial concentration of malachite green and connective modes between the anode compartment and cathode compartment on the decolorization efficiency of malachite green were investigated. The degradation dynamics of malachite green was studied. Based on the change of UV-visible light spectrum, the degradation process of malachite green was discussed. The experimental results showed that, during the time of 120 min, the decolouring ratio of the malachite green was 97.7% when initial concentration of malachite green is 30 mg x L(-1) and initial pH is 3.0. The catalytic degradation of malachite green was a pseudo-first order reaction. In the degradation process of malachite green the azo bond cleavage and the conjugated system of malachite green were attacked by hydroxyl radical. Simultaneity, the aromatic ring was oxidized. Finally, malachite green was degraded into other small molecular compounds. PMID:20825023

  11. Review of Catalytic Hydrogen Generation in the DWPF Chemical Processing Cell, Part II

    SciTech Connect

    Koopman, David C.; Lambert, Daniel P.; Baich, Mark A.

    2005-08-01

    The Savannah River National Laboratory is in the process of investigating factors suspected of impacting catalytic hydrogen generation in the Defense Waste Processing Facility, DWPF, Chemical Process Cell, CPC. Noble metal catalyzed hydrogen generation in simulation work constrains the allowable acid addition operating window in DWPF. This constraint potentially impacts washing strategies during sludge batch preparation. It can also influence decisions related to the addition of secondary waste streams to a sludge batch. Catalytic hydrogen generation data from 2002-2005 were reviewed. The data came from process simulations of the DWPF Sludge Receipt and Adjustment Tank, SRAT, and Slurry Mix Evaporator, SME. Most of the data was from the development work for the Sludge Batch 3 process flowsheet. This included simulant and radioactive waste testing. Preliminary Sludge Batch 4 data were also reviewed. A statistical analysis of SB3 simulant hydrogen generation data was performed. One factor considered in the statistical analysis was excess acid. Excess acid was determined experimentally as the acid added beyond that required to achieve satisfactory nitrite destruction.

  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 dilute Cu(Ni) alloy for synthesis of large-area Bernal stacked bilayer graphene using atmospheric pressure chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Madito, M. J.; Bello, A.; Dangbegnon, J. K.; Oliphant, C. J.; Jordaan, W. A.; Momodu, D. Y.; Masikhwa, T. M.; Barzegar, F.; Fabiane, M.; Manyala, N.

    2016-01-01

    A bilayer graphene film obtained on copper (Cu) foil is known to have a significant fraction of non-Bernal (AB) stacking and on copper/nickel (Cu/Ni) thin films is known to grow over a large-area with AB stacking. In this study, annealed Cu foils for graphene growth were doped with small concentrations of Ni to obtain dilute Cu(Ni) alloys in which the hydrocarbon decomposition rate of Cu will be enhanced by Ni during synthesis of large-area AB-stacked bilayer graphene using atmospheric pressure chemical vapour deposition. The Ni doped concentration and the Ni homogeneous distribution in Cu foil were confirmed with inductively coupled plasma optical emission spectrometry and proton-induced X-ray emission. An electron backscatter diffraction map showed that Cu foils have a single (001) surface orientation which leads to a uniform growth rate on Cu surface in early stages of graphene growth and also leads to a uniform Ni surface concentration distribution through segregation kinetics. The increase in Ni surface concentration in foils was investigated with time-of-flight secondary ion mass spectrometry. The quality of graphene, the number of graphene layers, and the layers stacking order in synthesized bilayer graphene films were confirmed by Raman and electron diffraction measurements. A four point probe station was used to measure the sheet resistance of graphene films. As compared to Cu foil, the prepared dilute Cu(Ni) alloy demonstrated the good capability of growing large-area AB-stacked bilayer graphene film by increasing Ni content in Cu surface layer.

  14. Catalytic activity of noble metals for metal-assisted chemical etching of silicon

    PubMed Central

    2012-01-01

    Metal-assisted chemical etching of silicon is an electroless method that can produce porous silicon by immersing metal-modified silicon in a hydrofluoric acid solution without electrical bias. We have been studying the metal-assisted hydrofluoric acid etching of silicon using dissolved oxygen as an oxidizing agent. Three major factors control the etching reaction and the porous silicon structure: photoillumination during etching, oxidizing agents, and metal particles. In this study, the influence of noble metal particles, silver, gold, platinum, and rhodium, on this etching is investigated under dark conditions: the absence of photogenerated charges in the silicon. The silicon dissolution is localized under the particles, and nanopores are formed whose diameters resemble the size of the metal nanoparticles. The etching rate of the silicon and the catalytic activity of the metals for the cathodic reduction of oxygen in the hydrofluoric acid solution increase in the order of silver, gold, platinum, and rhodium. PMID:22738277

  15. Pretreatment of empty palm fruit bunch for production of chemicals via catalytic pyrolysis.

    PubMed

    Misson, Mailin; Haron, Roslindawati; Kamaroddin, Mohd Fadhzir Ahmad; Amin, Nor Aishah Saidina

    2009-06-01

    The effect of chemical pretreatments using NaOH, H(2)O(2), and Ca(OH)(2) on Empty Palm Fruit Bunches (EPFB) to degrade EPFB lignin before pyrolysis was investigated. Spectrophotometer analysis proved consecutive addition of NaOH and H(2)O(2) decomposed almost 100% of EPFB lignin compared to 44% for the Ca(OH)(2), H(2)O(2) system while NaOH and Ca(OH)(2) used exclusively could not alter lignin much. Next, the pretreated EPFB was catalytically pyrolyzed. Experimental results indicated the phenolic yields over Al-MCM-41 and HZSM-5 catalysts were 90 wt% and 80 wt%, respectively compared to 67 wt% yield for the untreated sample under the same set of conditions. Meanwhile, the experiments with HY zeolite yielded 70 wt% phenols. PMID:19232488

  16. Catalytic activity of noble metals for metal-assisted chemical etching of silicon

    NASA Astrophysics Data System (ADS)

    Yae, Shinji; Morii, Yuma; Fukumuro, Naoki; Matsuda, Hitoshi

    2012-06-01

    Metal-assisted chemical etching of silicon is an electroless method that can produce porous silicon by immersing metal-modified silicon in a hydrofluoric acid solution without electrical bias. We have been studying the metal-assisted hydrofluoric acid etching of silicon using dissolved oxygen as an oxidizing agent. Three major factors control the etching reaction and the porous silicon structure: photoillumination during etching, oxidizing agents, and metal particles. In this study, the influence of noble metal particles, silver, gold, platinum, and rhodium, on this etching is investigated under dark conditions: the absence of photogenerated charges in the silicon. The silicon dissolution is localized under the particles, and nanopores are formed whose diameters resemble the size of the metal nanoparticles. The etching rate of the silicon and the catalytic activity of the metals for the cathodic reduction of oxygen in the hydrofluoric acid solution increase in the order of silver, gold, platinum, and rhodium.

  17. 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

  18. 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...

  19. Role of support-nanoalloy interactions in the atomic-scale structural and chemical ordering for tuning catalytic sites

    SciTech Connect

    Yang, Lefu; Shan, Shiyao; Loukrakpam, Rameshwori; Petkov, Valeri; Ren, Yang; Wanjala, Bridgid N.; Engelhard, Mark H.; Luo, Jin; Yin, Jun; Chen, Yongsheng; Zhong, Chuan-Jian

    2012-09-12

    The understanding of the atomic-scale structural and chemical ordering in supported nanosized alloy particles is fundamental for achieving active catalysts by design. This report shows how such knowledge can be obtained by a combination of techniques including x-ray photoelectron spectroscopy and synchrotron radiation based x-ray fine structure absorption spectroscopy and high-energy x-ray diffraction coupled to atomic pair distribution function analysis, and how the support-nanoalloy interaction influences the catalytic activity of a ternary nanoalloy (platinum-nickel-cobalt) particles on three different supports: carbon, silica and titania. The reaction of carbon monoxide with oxygen is employed as a probe of the catalytic activity. This ternary composition, in combination with the different support materials, is demonstrated to be capable of fine-tuning the catalytic activity and stability. The support-nanoalloy interaction is shown to influence structural and chemical ordering in the nanoparticles, leading to support-tunable active sites on the nanoalloys for oxygen activation in the catalytic oxidation of carbon monoxide. A nickel/cobalt-tuned catalytic site on the surface of nanoalloy was revealed for oxygen activation, which differs from the traditional oxygen-activation sites known for oxide-supported noble metal catalysts. The discovery of such support-nanoalloy interaction enabled oxygen-activation sites introduces a very promising strategy for designing active catalysts in heterogeneous catalysis.

  20. 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

  1. 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

  2. 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

  3. Catalytic Conversion of Carbon-Containing Compounds into Valuable Chemicals and Fuels

    NASA Astrophysics Data System (ADS)

    Cheng, Zhuo

    Conversion of carbon-containing compounds, especially C1 compounds such as carbon dioxide and methane, to valuable chemicals and fuels will hopefully address concerns over decreasing supplies of fossil fuels and mitigate the eects of greenhouse gas emissions on global climate change. Many challenges, however, remain to be addressed before these technologies may be adopted on an industrial scale. Chiefly, catalysts must be developed to activate carbon-containing compounds from their thermodynamically stable ground states, using hydrogen, electrons, or heat as energy sources. We chose as model catalytic systems: 1) Metathesis of ethene and 2-butene; 2) Methane dehydrogenation and carbon dioxide hydrogenation. We developed three computational methodologies to study these processes across a range of length and time scales. First, we investigated how electronic structure affects the properties and reactivity of these catalyst systems; by computing the partial electronic density of states, electronic localization function, and excess spin density, we showed how redox supports, such as ceria, promote electron transfer reactions. We applied this to the studies of methane activation and carbon dioxide activation. Second, we developed a non-equilibrium thermodynamics approach to calculate energies of activation at nite temperatures, based on the Bronsted-Evans-Polanyi principle and the Nudged Elastic Band method. Third, we developed an approach to numerically compute heat capacities and other thermodynamic properties on extended catalytic systems that are comparable in accuracy and precision to methods that have been well-developed for gas-phase molecules. We applied these to the studies of metathesis propagation and carbon dioxide hydrogenation. We gained mechanistic, thermodynamic, and kinetic insight into the elementary steps that comprise larger reaction networks of interest to the broader catalysis community. Ultimately, these theoretical and computational predictions

  4. 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.

  5. 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

  6. 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

  7. 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

  8. Growth and morphology of carbon nanostructures on nickel oxide nanoparticles in catalytic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Jana, M.; Sil, A.; Ray, S.

    2014-07-01

    The present study explores the conditions favorable for the growth of cylindrical carbon nanostructures such as multi-walled carbon nanotube (MWCNT) and carbon nanofiber by catalytic chemical vapor deposition (CCVD) method using nickel oxide-based catalyst nanoparticles of different average sizes as well as different levels of doping by copper oxide. The role of doping and the average size have been related to the observed melting behavior of nanoparticles of nickel oxide by thermal and diffraction analysis, and the importance of melting has been highlighted in the context of growth of cylindrical nanostructures. In the reducing environment prevailing in the CCVD chamber due to decomposition of flowing acetylene gas at elevated temperature, there is extensive reduction of oxide nanoparticles. Lack of melting and faster flow of carbon-bearing gases favor the formation of a carbon deposit cover over the catalyst nanoparticles giving rise to the formation of nanobeads. Melting allows rapid diffusion of carbon from the surface to inside catalyst particles, and reduced flow of gas lowers the rate of carbon deposit, both creating conditions favorable for the formation of cylindrical nanostructures, which grows around the catalyst particles. Smaller particle size and lower doping favor growth of MWCNT, while growth of fiber is commonly observed on larger particles having relatively higher level of doping.

  9. 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.

  10. Tip-growth of aligned carbon nanotubes on cobalt catalyst supported by alumina using alcohol catalytic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Bistamam, Mohd Shahril Amin; Azam, Mohd Asyadi

    Metal oxide layer helps to support carbon nanotubes (CNTs) aligned perpendicular as well as preventing the tip-growth which takes place due to the strong adhesion force between the catalyst and metal oxide. However, in this work we discovered tip-growth of aligned CNTs with Co as catalyst on thermally oxidized Al/SiO2/Si substrate system using simple alcohol catalytic chemical vapor deposition technique.

  11. 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).

  12. 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

  13. 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. PMID:26569475

  14. 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.

  15. Effect of crystallization time on the physico-chemical and catalytic properties of the hierarchical porous materials

    SciTech Connect

    Xu, Ling; Ma, Yuanyuan; Ding, Wenli; Guan, Jingqi; Wu, Shujie; Kan, Qiubin

    2010-09-15

    A series of hierarchical porous materials were prepared by a dual template method. The effect of different crystallization time on the channel architecture, morphology, acid performance of the hierarchical porous materials was investigated. X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, nitrogen adsorption and {sup 27}Al nuclear magnetic resonance were performed to obtain information on the physico-chemical properties of the materials. It was shown that the change in crystallization time could influence the structure/texture and surface acid properties of the hierarchical porous materials. In addition, alkylation of phenol with tert-butanol reaction was carried out to investigate the catalytic performance of the hierarchical porous materials. The results showed that the catalytic activity of the hierarchical porous materials and the selectivity to the bulkly product 2,4-di-tert-butyl-phenol decreased with processing time.

  16. 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.

  17. Review of Catalytic Hydrogen Generation in the Defense Waste Processing Facility (DWPF) Chemical Processing Cell

    SciTech Connect

    Koopman, D. C.

    2004-12-31

    This report was prepared to fulfill the Phase I deliverable for HLW/DWPF/TTR-98-0018, Rev. 2, ''Hydrogen Generation in the DWPF Chemical Processing Cell'', 6/4/2001. The primary objective for the preliminary phase of the hydrogen generation study was to complete a review of past data on hydrogen generation and to prepare a summary of the findings. The understanding was that the focus should be on catalytic hydrogen generation, not on hydrogen generation by radiolysis. The secondary objective was to develop scope for follow-up experimental and analytical work. The majority of this report provides a summary of past hydrogen generation work with radioactive and simulated Savannah River Site (SRS) waste sludges. The report also includes some work done with Hanford waste sludges and simulants. The review extends to idealized systems containing no sludge, such as solutions of sodium formate and formic acid doped with a noble metal catalyst. This includes general information from the literature, as well as the focused study done by the University of Georgia for the SRS. The various studies had a number of points of universal agreement. For example, noble metals, such as Pd, Rh, and Ru, catalyze hydrogen generation from formic acid and formate ions, and more acid leads to more hydrogen generation. There were also some points of disagreement between different sources on a few topics such as the impact of mercury on the noble metal catalysts and the identity of the most active catalyst species. Finally, there were some issues of potential interest to SRS that apparently have not been systematically studied, e.g. the role of nitrite ion in catalyst activation and reactivity. The review includes studies covering the period from about 1924-2002, or from before the discovery of hydrogen generation during simulant sludge processing in 1988 through the Shielded Cells qualification testing for Sludge Batch 2. The review of prior studies is followed by a discussion of proposed

  18. 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.

  19. 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.

  20. 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?

    NASA Astrophysics Data System (ADS)

    Podhorodecki, A.; Golacki, L. W.; Zatryb, G.; Misiewicz, J.; Wang, J.; Jadwisienczak, W.; Fedus, K.; Wojcik, J.; Wilson, P. R. J.; Mascher, P.

    2014-04-01

    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.

  1. Modeling of the Process of Three-Isotope (H, D, T) Exchange Between Hydrogen Gas and Water Vapour on Pt-SDBC Catalyst over a Wide Range of Deuterium Concentration

    SciTech Connect

    Fedorchenko, O.A.; Alekseev, I.A.; Tchijov, A.S.; Uborsky, V.V.

    2005-07-15

    The large scale studies of Combined Electrolysis and Catalytic Exchange (CECE) process in Petersburg Nuclear Physics Institute showed a complicated influence of various factors on the process caused by the presence of two simultaneous isotope exchange sub processes: counter-current phase exchange (between liquid water and water vapour) and co-current catalytic exchange (between hydrogen gas and water vapour). A laboratory scale set-up of glass made apparatuses was established in such a way that it allows us to study phase and catalytic exchange apart. A computer model of the set-up has been developed.The catalytic isotope exchange model formulation is presented. A collection of reversible chemical reactions is accompanied by diffusion of the gaseous reactants and reaction products in the pores of catalyst carrier. This has some interesting features that are demonstrated. Thus it was noted that the flow rates ratio (gas to vapour - {lambda} = G/V) as well as the concentrations of reactants exert influence on the process efficiency.

  2. Transient and sustained elementary flux mode networks on a catalytic string-based chemical evolution model.

    PubMed

    Pereira, José A

    2014-08-01

    Theoretical models designed to test the metabolism-first hypothesis for prebiotic evolution have yield strong indications about the hypothesis validity but could sometimes use a more extensive identification between model objects and real objects towards a more meaningful interpretation of results. In an attempt to go in that direction, the string-based model SSE ("steady state evolution") was developed, where abstract molecules (strings) and catalytic interaction rules are based on some of the most important features of carbon compounds in biological chemistry. The system is open with a random inflow and outflow of strings but also with a permanent string food source. Although specific catalysis is a key aspect of the model, used to define reaction rules, the focus is on energetics rather than kinetics. Standard energy change tables were constructed and used with standard formation reactions to track energy flows through the interpretation of equilibrium constant values. Detection of metabolic networks on the reaction system was done with elementary flux mode (EFM) analysis. The combination of these model design and analysis options enabled obtaining metabolic and catalytic networks showing several central features of biological metabolism, some more clearly than in previous models: metabolic networks with stepwise synthesis, energy coupling, catalysts regulation, SN2 coupling, redox coupling, intermediate cycling, coupled inverse pathways (metabolic cycling), autocatalytic cycles and catalytic cascades. The results strongly suggest that the main biological metabolism features, including the genotype-phenotype interpretation, are caused by the principles of catalytic systems and are prior to modern genetic systems principles. It also gives further theoretical support to the thesis that the basic features of biologic metabolism are a consequence of the time evolution of a random catalyst search working on an open system with a permanent food source. The importance

  3. Carbon Dioxide Conversion to Valuable Chemical Products over Composite Catalytic Systems

    SciTech Connect

    Dagle, Robert A.; Hu, Jianli; Jones, Susanne B.; Wilcox, Wayne A.; Frye, John G.; White, J. F.; Jiang, Juyuan; Wang, Yong

    2013-05-01

    Presented is an experimental study on catalytic conversion of carbon dioxide into methanol, ethanol and acetic acid. Catalysts having different catalytic functions were synthesized and combined in different ways to enhance selectivity to desired products. The combined catalyst system possessed the following functions: methanol synthesis, Fischer-Tropsch synthesis, water-gas-shift and hydrogenation. Results showed that the methods of integrating these catalytic functions played important role in achieving desired product selectivity. It was speculated that if methanol synthesis sites were located adjacent to the C-C chain growth sites, the formation rate of C2 oxygenates would be enhanced. The advantage of using high temperature methanol catalyst PdZnAl in the combined catalyst system was demonstrated. In the presence of PdZnAl catalyst, the combined catalyst system was stable at temperature of 380oC. It was observed that, at high temperature, kinetics favored oxygenate formation. Results implied that the process can be intensified by operating at high temperature using Pd-based methanol synthesis catalyst. Steam reforming of the byproduct organics was demonstrated as a means to provide supplemental hydrogen. Preliminary process design, simulation, and economic analysis of the proposed CO2 conversion process were carried out. Economic analysis indicates how ethanol production cost was affected by the price of CO2 and hydrogen.

  4. 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...

  5. 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

  6. 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. PMID:18537227

  7. 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.

  8. 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.

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

    DOE PAGESBeta

    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. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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

  16. 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

  17. 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.

  18. Epitaxial growth of antiphase boundary free GaAs layer on 300 mm Si(001) substrate by metalorganic chemical vapour deposition with high mobility

    NASA Astrophysics Data System (ADS)

    Alcotte, R.; Martin, M.; Moeyaert, J.; Cipro, R.; David, S.; Bassani, F.; Ducroquet, F.; Bogumilowicz, Y.; Sanchez, E.; Ye, Z.; Bao, X. Y.; Pin, J. B.; Baron, T.

    2016-04-01

    Metal organic chemical vapor deposition of GaAs on standard nominal 300 mm Si(001) wafers was studied. Antiphase boundary (APB) free epitaxial GaAs films as thin as 150 nm were obtained. The APB-free films exhibit an improvement of the room temperature photoluminescence signal with an increase of the intensity of almost a factor 2.5. Hall effect measurements show an electron mobility enhancement from 200 to 2000 cm2/V s. The GaAs layers directly grown on industrial platform with no APBs are perfect candidates for being integrated as active layers for nanoelectronic as well as optoelectronic devices in a CMOS environment.

  19. Catalytically enhanced thermal decomposition of chemically grown silicon oxide layers on Si(001)

    NASA Astrophysics Data System (ADS)

    Leroy, F.; Passanante, T.; Cheynis, F.; Curiotto, S.; Bussmann, E. B.; Müller, P.

    2016-03-01

    The thermal decomposition of Si dioxide layers formed by wet chemical treatment on Si(001) has been studied by low-energy electron microscopy. Independent nucleations of voids occur into the Si oxide layers that open by reaction at the void periphery. Depending on the voids, the reaction rates exhibit large differences via the occurrence of a nonlinear growth of the void radius. This non-steady state regime is attributed to the accumulation of defects and silicon hydroxyl species at the SiO2/Si interface that enhances the silicon oxide decomposition at the void periphery.

  20. 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. PMID:25056451

  1. 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.

  2. Structural and chemical transformations in the products of the interaction of silica gel with vapours of TiCl4 and H2O

    NASA Astrophysics Data System (ADS)

    Koshtyal, Yury M.; Malkov, Anatoly A.; Taulemesse, Jean-Marie; Petrov, Sergey N.; Krasilin, Andrei A.; Malygin, Anatoly A.

    2014-01-01

    Titanium oxide structures were synthesised by a molecular layering method on the surface of silica (ShSKG, SBET = 270 m2/g, V = 0.94 cm3/g, d = 14 nm). The change in the mass of the sample during the deposition was measured in situ. The samples were characterised by elemental analysis of Ti (photocolorimetry) and Cl (mercurimetry), scanning electron microscopy, and energy-dispersive X-ray spectroscopy. In this study, the effect of the temperature (200 °C, 500 °C) and number of synthesis cycles (1-4) on the distribution of titanium oxide structures over a cross-section of silica was investigated, along with the chemical composition and the microstructure of the modified silica samples.

  3. 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.

  4. 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

  5. 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

  6. 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. PMID:27047384

  7. 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

  8. 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

  9. Studies of coupled chemical and catalytic coal conversion methods. Fifth quarterly report, October--December 1988

    SciTech Connect

    Stock, L.M.

    1988-12-31

    Liquefaction of coal by depolymerization in an organic solvent has been studied for several years. The liquefied coal extract which results from such a process is far more suitable for conversion into liquid fuel by hydrogenolysis than is the untreated coal. Investigations on the chemical structure and the reactive sites of coal can help to select useful reactions for the production of liquids from coal. Sternberg et al. demonstrated that the reductive alkylation method transforms bituminous coal into an enormously soluble substance, irrespective of the mild reaction conditions. The effectiveness of newly introduced alkyl groups for the disruption of intermolecular hydrogen bonds and pi-pi interactions between the aromatic sheets in coal macromolecules has been recognized. It has been reported by Ignasiak et al. that a C-alkylabon reaction using sodium or potassium amide in liquid ammonia can be used to introduce alkyl groups at acidic carbon sites. A method has been developed recently in this laboratory for the solubilization of high rank coals. In the previous reports it was shown that n-butyl lithium and potassium t-butoxide in refluxing heptane produced coal anions which could be alkylated with different alkyl halides. Such alkylated coals were soluble up to 92% in solvents like pyridine. Though the solubilization of coal depended very much on the length of the alkyl group, it also depended very much on the nature of the base used. Strong bases like n-butyl lithium (pKa=42) can cause proton abstraction from aromatic structures, if the more acidic benzylic protons are absent. The utility of this procedure, initially developed and used by Miyake and Stock, has now been tested with the high oxygen containing, low rank Illinois No. 6 and Wyodak coals.

  10. 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

  11. A eutectic gold vapour laser

    NASA Astrophysics Data System (ADS)

    Tou, T. Y.; Cheak, K. E.; Low, K. S.

    This paper presents a eutectic gold vapour laser (EGVL) which uses the eutectic alloy of gold and silicon, Au/3.15Si, as the lasant. It was observed that, at low input power operation, the presence of the silicon vapour could increase the output of the 627.8 nm laser line by (50-60)% when compared with a gold vapour laser (GVL) which uses pure gold as the lasant. The improved laser output for the EGVL may be explained by an increased electron density, as a result of Penning ionization of silicon atoms. However, for higher input power operation, the EGVL showed a slower rate of increase in its laser output power and was overtaken by GVLs at a tube operating temperature of around 1650°C. This may be explained by a lowering of the electron temperature owing to increasing inelastic collisions between the electrons and silicon atoms which, although excited, may not produce additional electrons.

  12. 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.

  13. 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...

  14. Bimetallic catalyst for synthesizing quasi-aligned, well-graphitized multiwalled carbon nanotube bundles on a large scale by the catalytic chemical vapor deposition method.

    PubMed

    Mukhopadhyay, Kingsuk; Mathur, Gyanesh Narayan

    2002-04-01

    An effective method of growth by catalytic chemical vapor deposition (CCVD) to get a large-scale yield of carbon nanotubes is reported. In this method, acetylene is decomposed catalytically over well-dispersed metal particles (Co-Fe and Co-Ni) embedded in commercially available zeolite at a lower temperature (600-700 degrees C). The two binary-metal catalysts (Co-Fe and Co-Ni) used are compared by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Crucial reaction parameters, such as reaction time, temperature, and the effect of purity of gas to obtain optimum production of the nanotubes, both qualitatively and quantitatively, are also reported. PMID:12908309

  15. Catalytic reactor

    DOEpatents

    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.

  16. 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. PMID:27038784

  17. 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

  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. Electron Transport in Water Vapour

    NASA Astrophysics Data System (ADS)

    Kawaguchi, Satoru; Satoh, Kohki; Itoh, Hidenori

    2015-09-01

    Sets of electron collision cross sections for water vapour previously reported are examined by comparing calculated electron swarm parameters with measured parameters. Further, reliable cross section set of water vapour is estimated by the electron swarm method using Monte Carlo simulation to ensure the accuracy of the swarm parameter calculation. The values of an electron drift velocity, a longitudinal diffusion coefficient, and an effective ionisation coefficient calculated from Yousfi and Benabdessadok's set and those calculated from Itikawa and Mason's set do not necessarily agree with measured data. A new cross section set of water vapour, which consists of three kinds of rotational excitation, two kinds of vibrational excitation, three kinds of electron attachment, twenty-six kinds of electronic excitation, and six kinds of ionisation cross sections, and an elastic collision cross section, is estimated, and an anisotropic electron scattering for elastic and rotational excitation collision is considered. The swarm parameters calculated from the estimated cross section set is in good agreement with measured data in a wide range of reduced electric field.

  20. 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...

  1. 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...

  2. 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.

  3. Heterogeneous adsorption and catalytic oxidation of benzene, toluene and xylene over spent and chemically regenerated platinum catalyst supported on activated carbon

    NASA Astrophysics Data System (ADS)

    Shim, Wang Geun; Kim, Sang Chai

    2010-06-01

    The heterogeneous adsorption and catalytic oxidation of benzene, toluene and o-xylene (BTX) over the spent platinum catalyst supported on activated carbon (Pt/AC) as well as the chemically treated spent catalysts were studied to understand their catalytic and adsorption activities. Sulfuric aqueous acid solution (0.1N, H 2SO 4) was used to regenerate the spent Pt/AC catalyst. The physico-chemical properties of the catalysts in the spent and chemically treated states were analyzed by using nitrogen adsorption-desorption isotherm and elemental analysis (EDX). The gravimetric adsorption and the light-off curve analysis were employed to study the BTX adsorption and oxidation on the spent catalyst and its modified Pt/AC catalysts. The experimental results indicate that the spent Pt/AC catalyst treated with the H 2SO 4 aqueous solution has a higher toluene adsorption and conversion ability than that of the spent Pt/AC catalyst. A further studies of H 2SO 4 treated Pt/AC catalyst on their catalytic and heterogeneous adsorption behaviours for BTX revealed that the activity of the H 2SO 4 treated Pt/AC catalyst follows the sequence of benzene > toluene > o-xylene. The adsorption equilibrium isotherms of BTX on the H 2SO 4 treated Pt/AC were measured at different temperatures ranging from 120 to 180 °C. To correlate the equilibrium data and evaluate their adsorption affinity for BTX, the two sites localized Langmuir (L2m) isotherm model was employed. The heterogeneous surface feature of the H 2SO 4 treated Pt/AC was described in detail with the information obtained from the results of isosteric enthalpy of adsorption and adsorption energy distributions. Furthermore, the activity of H 2SO 4 treated Pt/AC about BTX was found to be directly related to the Henry's constant, isosteric enthalpy of adsorption and adsorption energy distribution functions.

  4. 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. PMID:16792361

  5. 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

  6. 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

  7. 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

  8. Quantum chemical investigation on the catalytic mechanism of vanadium iodoperoxidase and the iodination of common organic compounds

    NASA Astrophysics Data System (ADS)

    Gálvez, Óscar; Pacios, Luis F.

    2010-05-01

    Atmospheric iodine has received considerable attention in the two past decades due to both its potential role in the catalytic destruction of ozone (1) and its contribution to the formation of cloud condensation nuclei (2). It is generally assumed that iodine in the atmosphere has a natural origin since no anthropogenic sources are known. Seaweeds and marine phytoplankton release iodocarbons. In addition, IO and even I2, a major source of particle formation in coastal areas, are also detectable in the atmosphere above kelp beds. However, the reasons why iodocarbons are released by seaweeds and the mechanisms involved in their production remain largely unknown. It is currently well established that the general catalytic role of halide oxidation in marine algae is actually played by vanadium-dependent haloperoxidases enzymes, although relevant details such as protonation states of the vanadate cofactor or even key steps in the mechanism are still unknown. In this contribution, we focus on the iodoperoxidase VIPO enzyme. Quantum calculations on the vanadate cofactor were combined with structural analyses on a reliable three-dimensional model of the VIPO protein to investigate the steps along the catalytic mechanism that lead to the release of halide oxidation products. In addition, iodination reactions of several common organic compounds selected to account for representative volatile and non-volatile iodocarbons were thermodynamically studied by means of high-level ab initio correlated calculations. Free energies of reactions with the three possible iodinating species produced by the enzyme, namely HOI, I2, and I3- were calculated. Our results show that only hypoiodous acid give rise to clearly exoergonic iodination of organic substrates. (1) Saiz-Lopez, A.; Mahajan, A.S.; Salmon, R.A.; Bauguitte, J.B.; Jones, A.E.; Roscoe, H.K.; Plane, J.M.C. Science 2007, 317, 348-351 (2) O'Dowd, C.D.; Jimenez, J.L.; Bahreini, R.; Flagan, R.C.; Seinfeld, J.H.; Hämeri, K.; Pirjola

  9. 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.

  10. Encapsulating Pd Nanoparticles in Double-Shelled Graphene@Carbon Hollow Spheres for Excellent Chemical Catalytic Property

    NASA Astrophysics Data System (ADS)

    Zhang, Zheye; Xiao, Fei; Xi, Jiangbo; Sun, Tai; Xiao, Shuang; Wang, Hairong; Wang, Shuai; Liu, Yunqi

    2014-02-01

    Double-shelled hollow carbon spheres with reduced graphene oxide (RGO) as inner shell and carbon (C) layer as outer shell have been successfully designed and prepared. This tailor-making structure acts as an excellent capsule for encapsulating with ultrafine Pd nanoparticles (Pd NPs), which could effectively prevent Pd NPs from aggregation and leaching. As a result, the as-obtained RGO@Pd@C nanohybid exhibits superior and stable catalytic performance. With the aid of RGO@Pd@C, the reduction reaction of 4-nitrophenol (4-NP) to 4-aminophenol with NaBH4 as reducing agent can be finished within only 30 s, even the content of Pd is as low as 0.28 wt%. As far as we know, RGO@Pd@C is one of the most effective catalyst for 4-NP reducing reaction up to now.

  11. Encapsulating Pd Nanoparticles in Double-Shelled Graphene@Carbon Hollow Spheres for Excellent Chemical Catalytic Property

    PubMed Central

    Zhang, Zheye; Xiao, Fei; Xi, Jiangbo; Sun, Tai; Xiao, Shuang; Wang, Hairong; Wang, Shuai; Liu, Yunqi

    2014-01-01

    Double-shelled hollow carbon spheres with reduced graphene oxide (RGO) as inner shell and carbon (C) layer as outer shell have been successfully designed and prepared. This tailor-making structure acts as an excellent capsule for encapsulating with ultrafine Pd nanoparticles (Pd NPs), which could effectively prevent Pd NPs from aggregation and leaching. As a result, the as-obtained RGO@Pd@C nanohybid exhibits superior and stable catalytic performance. With the aid of RGO@Pd@C, the reduction reaction of 4-nitrophenol (4-NP) to 4-aminophenol with NaBH4 as reducing agent can be finished within only 30 s, even the content of Pd is as low as 0.28 wt%. As far as we know, RGO@Pd@C is one of the most effective catalyst for 4-NP reducing reaction up to now. PMID:24514577

  12. 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%.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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

  19. 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

  20. Physical properties of vapour grown indium monotelluride platelets

    NASA Astrophysics Data System (ADS)

    Kunjomana, A. G.; Chandrasekharan, K. A.; Teena, M.

    2015-02-01

    Indium monotelluride (InTe) crystals were grown from vapour phase under different temperature gradients by employing physical vapour deposition (PVD) method. The morphology of these crystals such as whiskers, needles, platelets etc., strongly depends on the temperature distribution in the horizontal dual zone furnace. InTe platelets were deposited by setting the temperature of the charge (TC) and growth (TS) zones at 1073 K and 773 K (ΔT=300 K), respectively, for different growth periods (24 h, 48 h, 72 h and 96 h). The surface growth features have been analyzed by scanning electron microscopes, which indicate layer growth mechanism for all the crystals. Various crystals grown under ΔT=200 K and 300 K (retaining TS invariant) were examined by X-ray diffraction and elemental analysis. InTe samples exhibited consistent lattice parameters, density and atomic percentage, establishing stoichiometry and chemical homogeneity. The results obtained for Seebeck coefficient, electrical conductivity, power factor, dislocation density and microhardness are found to be reproducible as well. The vapour deposited InTe platelets are mechanically stable and possess high value of TEP, which ensure their practical application in thermoelectric power generation.

  1. 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

  2. A novel approach for enhancing the catalytic efficiency of a protease at low temperature: reduction in substrate inhibition by chemical modification.

    PubMed

    Siddiqui, Khawar Sohail; Parkin, Don M; Curmi, Paul M G; De Francisci, Davide; Poljak, Anne; Barrow, Kevin; Noble, Malcolm H; Trewhella, Jill; Cavicchioli, Ricardo

    2009-07-01

    The alkaline protease, savinase was chemically modified to enhance the productivity of the enzyme at low temperatures on a complex polymeric protein (azocasein) substrate. At 5 and 15 degrees C, savinase modified with ficol or dextran hydrolyzed fivefold more azocasein than the unmodified savinase. Kinetic studies showed that the catalytic improvements are associated with changes in uncompetitive substrate inhibition with K(i) values of modified savinases sixfold higher than the unmodified savinase. Modeling of small-angle scattering data indicates that two substrate molecules bind on opposing sides of the enzyme. The combined kinetic and structural data indicate that the polysaccharide modifier sterically blocks the allosteric site and reduces substrate inhibition. In contrast to the properties of cold-active enzymes that generally manifest as low activation enthalpy and high flexibility, this study shows that increased activity and productivity at low temperature can be achieved by reducing uncompetitive substrate inhibition, and that this can be achieved using chemical modification with an enzyme in a commercial enzyme-formulation. PMID:19288442

  3. Characterization of interface abruptness and material properties in catalytically grown III-V nanowires: exploiting plasmon chemical shift

    NASA Astrophysics Data System (ADS)

    Tizei, L. H. G.; Chiaramonte, T.; Cotta, M. A.; Ugarte, D.

    2010-07-01

    We have studied the assessment of chemical composition changes in III-V heterostructured semiconductor nanowires (NWs) with nanometric spatial resolution using transmission electron microscopy methods. These materials represent a challenge for conventional spectroscopy techniques due to their high sensitivity to electron beam irradiation. Radiation damage strongly limits the exposure time to a few (5-10) s, which reduces the sensitivity of the traditionally used x-ray spectroscopy. The rather low counting statistics results in significant errors bars for EDS chemical quantification (5-10%) and interface width determination (few nanometers). Plasmon chemical shift is ideal in this situation, as its measurement requires very short exposure times (~100 ms) and the plasmon peak energy can be measured with high precision (~20 meV in this work). This high sensitivity allows the detection of subtle changes (1-2%) in composition or even the detection of a small plasmon energy (33 ± 7) meV change along usually assumed pure and homogeneous InAs segments. We have applied this approach to measure interface widths in heterostructure InAs/InP NWs grown using metal catalysts and also to determine the timescale (~10 s) in which beam irradiation induces material damage in these wires. In particular, we have detected small As concentrations (4.4 ± 0.5)% in the final InP segment close to the Au catalyst, which leads to the conclusion that As diffuses through the metal nanoparticle during growth.

  4. Characterization of interface abruptness and material properties in catalytically grown III-V nanowires: exploiting plasmon chemical shift.

    PubMed

    Tizei, L H G; Chiaramonte, T; Cotta, M A; Ugarte, D

    2010-07-23

    We have studied the assessment of chemical composition changes in III-V heterostructured semiconductor nanowires (NWs) with nanometric spatial resolution using transmission electron microscopy methods. These materials represent a challenge for conventional spectroscopy techniques due to their high sensitivity to electron beam irradiation. Radiation damage strongly limits the exposure time to a few (5-10) s, which reduces the sensitivity of the traditionally used x-ray spectroscopy. The rather low counting statistics results in significant errors bars for EDS chemical quantification (5-10%) and interface width determination (few nanometers). Plasmon chemical shift is ideal in this situation, as its measurement requires very short exposure times (approximately 100 ms) and the plasmon peak energy can be measured with high precision (approximately 20 meV in this work). This high sensitivity allows the detection of subtle changes (1-2%) in composition or even the detection of a small plasmon energy (33 +/- 7) meV change along usually assumed pure and homogeneous InAs segments. We have applied this approach to measure interface widths in heterostructure InAs/InP NWs grown using metal catalysts and also to determine the timescale (approximately 10 s) in which beam irradiation induces material damage in these wires. In particular, we have detected small As concentrations (4.4 +/- 0.5)% in the final InP segment close to the Au catalyst, which leads to the conclusion that As diffuses through the metal nanoparticle during growth. PMID:20585172

  5. 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

  6. 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

  7. 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.

  8. 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

  9. 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.

  10. 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.