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Sample records for deposition methanol oxidation

  1. Smart methanol sensor based on silver oxide-doped zinc oxide nanoparticles deposited on microchips

    International Nuclear Information System (INIS)

    Rahman, Mohammed M.; Khan, Sher Bahadar; Asiri, Abdullah M.

    2014-01-01

    We have prepared calcined silver oxide-doped zinc oxide nanoparticles (NPs) by a hydrothermal method using reducing agents in alkaline medium. The doped NPs were characterized by UV/vis, FTIR, and X-ray photoelectron spectroscopy, and by X-ray powder diffraction and field-emission scanning electron microscopy. The NPs were deposited on microchips to result in a sensor that has a fast response to methanol in the liquid phase. Features include high sensitivity, low-sample volume, reliability, reproducibility, ease of integration, long-term stability, and enhanced electrochemical responses. The calibration plot is linear (r 2  = 0.9981) over the 0.25 mmolL −1 to 0.25 molL −1 methanol concentration range. The sensitivity is ∼7.917 μA cm −2 mmolL −2 , and the detection limit is 71.0 ± 0.5 μmolL −1 at a signal-to-noise-ratio of 3. (author)

  2. Enhanced methanol electro-oxidation activity of Pt/MWCNTs electro-catalyst using manganese oxide deposited on MWCNTs

    International Nuclear Information System (INIS)

    Nouralishahi, Amideddin; Khodadadi, Abbas Ali; Mortazavi, Yadollah; Rashidi, Alimorad; Choolaei, Mohammadmehdi

    2014-01-01

    Highlights: • Promoting effects of manganese oxide (MnO x ) on methanol electro-oxidation over Pt/MWCNTs are studied. • 3.3 times higher activity and improved stability are observed on Pt/MnO x -MWCNTs in MOR. • Both hydrogen spill over and bi-functional mechanism are facilitated in presence of MnO x . • MnO x significantly enhances electrochemical active surface area and dispersion of Pt nanoparticles. • Proton conductivity of electrocatalyst layer is improved upon MnO x incorporation. - Abstract: Electro-oxidation of methanol on platinum nanoparticles supported on a nanocomposite of manganese oxide (MnO x ) and multi-wall carbon nanotubes (MWCNTs) is investigated. The morphology, structure, and chemical composition of the electro-catalysts are characterized by TEM, XRD, EDS, TGA, and H 2 -TPR. The electro-catalytic properties of electrodes are examined by cyclic voltammetry, CO-stripping, electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV). Compared to Pt/MWCNTs, the Pt/MnO x -MWCNTs electro-catalyst exhibits about 3.3 times higher forward peak current density, during cyclic voltammetry, and 4.6 times higher exchange current density in methanol electro-oxidation reaction. In addition, deposition of manganese oxide onto MWCNTs dramatically increases the electrochemical active surface area from 29.7 for Pt/MWCNTs to 89.4 m 2 g −1 Pt for Pt/MnO x -MWCNTs. The results of long-term cyclic voltammetry show superior stability of Pt nanoparticles upon addition of manganese oxide to the support. Furthermore, the kinetics of formation of the chemisorbed OH groups improves upon manganese oxide incorporation. This leads to a lower onset potential of CO ads oxidation on Pt/MnO x -MWCNTs than on Pt/MWCNTs

  3. Effect of glassy carbon properties on the electrochemical deposition of platinum nano-catalyst and its activity for methanol oxidation

    Directory of Open Access Journals (Sweden)

    SANJA TERZIC

    2007-02-01

    Full Text Available The effects of the properties of glassy carbon on the deposition of platinum particles and the electrocatalytic activity of platinum supported on glassy carbon (GC/Pt for methanol oxidation in alkaline and acidic solutions were studied. Platinum was potentiostatically deposited on two glassy carbon samples, thermally treated at different temperatures, which were either polished or anodicaly polarised in acid (GCOX-AC/Pt and in alkali (GCOX-AL/Pt. Anodic polarisation of glassy carbon, either in alkaline or acidic solution, enhances the activity of both types of GC/Pt electrodes for methanol oxidation. The activity of the catalysts follows the change in the properties of the glassy carbon support upon anodic treatment. The specific activity of the GCOX-AL/Pt electrode for this reaction in alkali is increased only a few times in comparison with the activity of the GC/Pt one. On the other hand, the specific activity of the GCOX-AC/Pt electrode for methanol oxidation in acid is about one order of magnitude higher than that of the GC/Pt electrode. The role of the substrate on the properties of catalyst is discussed in detail.

  4. Role of Platinum Deposited on TiO2 in Photocatalytic Methanol Oxidation and Dehydrogenation Reactions

    Directory of Open Access Journals (Sweden)

    Luma M. Ahmed

    2014-01-01

    Full Text Available Titania modified nanoparticles have been prepared by the photodeposition method employing platinum particles on the commercially available titanium dioxide (Hombikat UV 100. The properties of the prepared photocatalysts were investigated by means of the Fourier transform infrared spectroscopy (FTIR, X-ray diffraction (XRD, atomic force microscopy (AFM, and UV-visible diffuse spectrophotometry (UV-Vis. XRD was employed to determine the crystallographic phase and particle size of both bare and platinised titanium dioxide. The results indicated that the particle size was decreased with the increasing of platinum loading. AFM analysis showed that one particle consists of about 9 to 11 crystals. UV-vis absorbance analysis showed that the absorption edge shifted to longer wavelength for 0.5% Pt loading compared with bare titanium dioxide. The photocatalytic activity of pure and Pt-loaded TiO2 was investigated employing the photocatalytic oxidation and dehydrogenation of methanol. The results of the photocatalytic activity indicate that the platinized titanium dioxide samples are always more active than the corresponding bare TiO2 for both methanol oxidation and dehydrogenation processes. The loading with various platinum amounts resulted in a significant improvement of the photocatalytic activity of TiO2. This beneficial effect was attributed to an increased separation of the photogenerated electron-hole charge carriers.

  5. Bimetallic Nickel/Ruthenium Catalysts Synthesized by Atomic Layer Deposition for Low-Temperature Direct Methanol Solid Oxide Fuel Cells.

    Science.gov (United States)

    Jeong, Heonjae; Kim, Jun Woo; Park, Joonsuk; An, Jihwan; Lee, Tonghun; Prinz, Fritz B; Shim, Joon Hyung

    2016-11-09

    Nickel and ruthenium bimetallic catalysts were heterogeneously synthesized via atomic layer deposition (ALD) for use as the anode of direct methanol solid oxide fuel cells (DMSOFCs) operating in a low-temperature range. The presence of highly dispersed ALD Ru islands over a porous Ni mesh was confirmed, and the Ni/ALD Ru anode microstructure was observed. Fuel cell tests were conducted using Ni-only and Ni/ALD Ru anodes with approximately 350 μm thick gadolinium-doped ceria electrolytes and platinum cathodes. The performance of fuel cells was assessed using pure methanol at operating temperatures of 300-400 °C. Micromorphological changes of the anode after cell operation were investigated, and the content of adsorbed carbon on the anode side of the operated samples was measured. The difference in the maximum power density between samples utilizing Ni/ALD Ru and Pt/ALD Ru, the latter being the best catalyst for direct methanol fuel cells, was observed to be less than 7% at 300 °C and 30% at 350 °C. The improved electrochemical activity of the Ni/ALD Ru anode compared to that of the Ni-only anode, along with the reduction of the number of catalytically active sites due to agglomeration of Ni and carbon formation on the Ni surface as compared to Pt, explains this decent performance.

  6. Novel Pt-Ru nanoparticles formed by vapour deposition as efficient electrocatalyst for methanol oxidation

    International Nuclear Information System (INIS)

    Sivakumar, Pasupathi; Ishak, Randa; Tricoli, Vincenzo

    2005-01-01

    Bimetallic Pt-Ru nanoparticles supported on carbon substrates have been prepared reproducibly by a simple method that utilizes commercially available metal-organic precursors at low temperature in vacuum. Particles morphology, composition and structure have been investigated using HRTEM, EDX, selected area electron diffraction (SAED) and powder XRD analysis. TEM shows that the obtained nanoparticles are homogeneously dispersed on the substrate surface and exhibit narrow size distribution, the average diameter being ca. 2 nm. Point resolved EDX analysis demonstrates co-presence of both Pt and Ru in each particle, thereby indicating that truly bimetallic nanoparticles have been obtained. Moreover, EDX performed on several areas of the sample evidences uniform particles composition. The latter can be controlled very easily and effectively by regulating the operation temperature during particles preparation. HRTEM imaging shows that the particles possess crystalline structure. Both SAED and XRD analyses indicate presence of nanoparticles exhibiting structure consistent with that of an f.c.c. Pt-Ru alloy. Besides the f.c.c. alloy, an additional crystalline phase might also be present as noticed by SAED. These nanoparticles display electrocatalytic activity with regard to methanol oxidation as evidenced by cyclic voltammetry (CV)

  7. Novel Pt-Ru nanoparticles formed by vapour deposition as efficient electrocatalyst for methanol oxidation

    International Nuclear Information System (INIS)

    Sivakumar, Pasupathi; Tricoli, Vincenzo

    2006-01-01

    The methods developed and described in paper-part I are employed to prepare nanometer size Pt-Ru particles on a Vulcan[reg] XC72R substrate with controlled metal loading. Transmission Electron Microscopy (TEM) confirmed uniform particles size (average diameter 2 nm) and homogeneous dispersion of the particles over the substrate. Energy Dispersive X-ray absorption (EDX) analysis confirmed the compositional homogeneity. The catalytic activity of these supported nanoparticles with regard to methanol electrooxidation is investigated using cyclic voltammetry (CV), chronoamperometry (CA) and CO-stripping voltammetry techniques at temperatures between 25 and 60 deg. C. Such investigation concerns supported catalysts prepared with ca. 10 and 18 wt.% overall metal loading (Pt + Ru) onto the Vulca[reg] XC72R substrate. Comparative testing of our catalysts and a commercial Pt-Ru/Vulcan reveals markedly superior activity for our catalysts. In fact, we observe for the latter a five-fold increase of the oxidation current as compared to a commercial Pt-Ru/Vulcan with equal metal loading. One of the reasons for the greater activity is found to be the very high dispersion of the metals over the substrate, i.e. the large surface area of the active phase. Other reasons are plausibly ascribable to the varied Pt/Ru composition and/or reduced presence of contaminants at the catalyst surface

  8. Sputter deposition on gas diffusion electrodes of Pt-Au nanoclusters for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Giorgi, L.; Giorgi, R.; Gagliardi, S.; Serra, E. [ENEA Casaccia Research Center, Rome (Italy). Physics Technologies and New Materials; Alvisi, M.; Signore, M.A. [ENEA Brindisi Research Center, Brindisi (Italy). Physics Technologies and New Materials

    2008-07-01

    Polymer electrolyte fuel cells (PEFCs) are suited for use in commercial electrical vehicle and electric power applications. The gas diffusion electrodes of PEFCs are catalyzed by the deposition of platinum (Pt) nanoparticles on carbon powder. The particles must be localized on the electrode surface in order to achieve high electrocatalyst utilization. This study discussed a method of preparing PEFC electrodes using sputter deposition of a Pt-gold (Au) alloy nanoparticles on carbon powders. The method was designed to improve electrode performance and catalyst utilization. The nano-sized alloy clusters were deposited on a gas diffusion electrode at room temperature. The deposits were then characterized using field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) in order to examine the effect of the deposition technique on the nano-morphology and electrocatalytic performance of the electrode. Results of the study showed that the technique can be used in the large-scale manufacture of fuel cell electrodes. 3 refs., 1 fig.

  9. Methanol electro-oxidation catalyzed by platinum deposited on various substrates using Electrochemical Atomic Layer Deposition (ECALD)

    CSIR Research Space (South Africa)

    Louw, EK

    2013-12-01

    Full Text Available Direct carbon fuel cell Several different 700-850 80 % 70 % Commercial / Research Direct formic acid fuel cell (DFAFC) Polymer membrane (ionomer) < 50 W < 40 Commercial / Research Direct methanol fuel cell Polymer membrane... (ionomer) 100 mW – 1 kW 90–120 20–30 % 10–20 % Commercial / Research Direct- ethanol fuel cell Polymer membrane (ionomer) < 140 mW/cm² 90–120 Research Molten carbonate fuel cell Molten alkaline carbonate 100 MW 600-650 55 % 47...

  10. Electro-oxidation of methanol diffused through proton exchange membrane on Pt surface: crossover rate of methanol

    International Nuclear Information System (INIS)

    Jung, Inhwa; Kim, Doyeon; Yun, Yongsik; Chung, Suengyoung; Lee, Jaeyoung; Tak, Yongsug

    2004-01-01

    Methanol crossover rate through proton exchange membrane (Nafion 117) was investigated with a newly designed electrochemical stripping cell. Nanosize Pt electrode was prepared by the electroless deposition. Distinct electrocatalytic oxidation behaviors of methanol inside membrane were similar to the methanol oxidation in aqueous electrolyte, except adsorption/desorption of hydrogen. The amount of methanol diffused through membrane was calculated from the charge of methanol oxidation during repetitive cyclic voltammetry (CV) and methanol crossover rate was estimated to be 0.69 nmol/s

  11. Methanol Oxidation on Pt3Sn(111) for Direct Methanol Fuel Cells: Methanol Decomposition.

    Science.gov (United States)

    Lu, Xiaoqing; Deng, Zhigang; Guo, Chen; Wang, Weili; Wei, Shuxian; Ng, Siu-Pang; Chen, Xiangfeng; Ding, Ning; Guo, Wenyue; Wu, Chi-Man Lawrence

    2016-05-18

    PtSn alloy, which is a potential material for use in direct methanol fuel cells, can efficiently promote methanol oxidation and alleviate the CO poisoning problem. Herein, methanol decomposition on Pt3Sn(111) was systematically investigated using periodic density functional theory and microkinetic modeling. The geometries and energies of all of the involved species were analyzed, and the decomposition network was mapped out to elaborate the reaction mechanisms. Our results indicated that methanol and formaldehyde were weakly adsorbed, and the other derivatives (CHxOHy, x = 1-3, y = 0-1) were strongly adsorbed and preferred decomposition rather than desorption on Pt3Sn(111). The competitive methanol decomposition started with the initial O-H bond scission followed by successive C-H bond scissions, (i.e., CH3OH → CH3O → CH2O → CHO → CO). The Brønsted-Evans-Polanyi relations and energy barrier decomposition analyses identified the C-H and O-H bond scissions as being more competitive than the C-O bond scission. Microkinetic modeling confirmed that the vast majority of the intermediates and products from methanol decomposition would escape from the Pt3Sn(111) surface at a relatively low temperature, and the coverage of the CO residue decreased with an increase in the temperature and decrease in partial methanol pressure.

  12. Nickel as a catalyst for the electro-oxidation of methanol in alkaline medium

    Science.gov (United States)

    Abdel Rahim, M. A.; Abdel Hameed, R. M.; Khalil, M. W.

    The use of Ni as a catalyst for the electro-oxidation of methanol in alkaline medium was studied by cyclic voltammetry. It was found that only Ni dispersed on graphite shows a catalytic activity towards methanol oxidation but massive Ni does not. Ni was dispersed on graphite by the electro-deposition from acidic NiSO 4 solution using potentiostatic and galvanostatic techniques. The catalytic activity of the C/Ni electrodes towards methanol oxidation was found to vary with the amount of electro-deposited Ni. The dependence of the oxidation current on methanol concentration and scan rate was discussed. It was concluded from the electro-chemical measurements and SEM analysis that methanol oxidation starts as Ni-oxide is formed on the electrode surface.

  13. Atmospheric deposition of methanol over the Atlantic Ocean

    Science.gov (United States)

    Yang, Mingxi; Nightingale, Philip D.; Beale, Rachael; Liss, Peter S.; Blomquist, Byron; Fairall, Christopher

    2013-01-01

    In the troposphere, methanol (CH3OH) is present ubiquitously and second in abundance among organic gases after methane. In the surface ocean, methanol represents a supply of energy and carbon for marine microbes. Here we report direct measurements of air–sea methanol transfer along a ∼10,000-km north–south transect of the Atlantic. The flux of methanol was consistently from the atmosphere to the ocean. Constrained by the aerodynamic limit and measured rate of air–sea sensible heat exchange, methanol transfer resembles a one-way depositional process, which suggests dissolved methanol concentrations near the water surface that are lower than what were measured at ∼5 m depth, for reasons currently unknown. We estimate the global oceanic uptake of methanol and examine the lifetimes of this compound in the lower atmosphere and upper ocean with respect to gas exchange. We also constrain the molecular diffusional resistance above the ocean surface—an important term for improving air–sea gas exchange models. PMID:24277830

  14. FORMALDEHYDE DISMUTASE ACTIVITIES IN GRAM-POSITIVE BACTERIA OXIDIZING METHANOL

    NARCIS (Netherlands)

    BYSTRYKH, LV; GOVORUKHINA, NI; VANOPHEM, PW; HEKTOR, HJ; DIJKHUIZEN, L; DUINE, JA; Govorukhina, Natalya; Ophem, Peter W. van; Duine, Johannis A.

    Extracts of methanol-grown cells of Amycolatopsis methanolica and Mycobacterium gastri oxidized methanol and ethanol with concomitant reduction of N,N'-dimethyl-4-nitrosoaniline (NDMA). Anion-exchange chromatography revealed the presence of a single enzyme able to catalyse this activity in methanol-

  15. Electrochemical characterization of Pt-Ru-Pd catalysts for methanol oxidation reaction in direct methanol fuel cells.

    Science.gov (United States)

    Choi, M; Han, C; Kim, I T; An, J C; Lee, J J; Lee, H K; Shim, J

    2011-01-01

    PtRuPd nanoparticles on carbon black were prepared and characterized as electrocatalysts for methanol oxidation reaction in direct methanol fuel cells. Nano-sized Pd (2-4 nm) particles were deposited on Pt/C and PtRu/C (commercial products) by a simple chemical reduction process. The structural and physical information of the PtRuPd/C were confirmed by TEM and XRD, and their electrocatalytic activities were measured by cyclic voltammetry and linear sweep voltammetry. The catalysts containing Pd showed higher electrocatalytic activity for methanol oxidation reaction than the other catalysts. This might be attributed to an increase in the electrochemical surface area of Pt, which is caused by the addition of Pd; this results in increased catalyst utilization.

  16. Methanol decomposition and oxidation on Ir(111)

    NARCIS (Netherlands)

    Weststrate, C.J.; Ludwig, W.; Bakker, J.W.; Gluhoi, A.C.; Nieuwenhuys, B.E.

    2007-01-01

    The adsorption, decompn., and oxidn. of methanol (CH3OH) has been studied on Ir(111) using temp.-programmed desorption and high-energy resoln. fast XPS. Mol. methanol desorption from a methanol-satd. surface at low temp. shows three desorption peaks, around 150 K (alpha ), around 170 K (beta 1), and

  17. Platinized titanium dioxide electrodes for methanol oxidation and photo-oxidation

    Directory of Open Access Journals (Sweden)

    IOANNIS POULIOS

    2012-11-01

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

  18. Kinetics of Photoelectrochemical Oxidation of Methanol on Hematite Photoanodes

    Science.gov (United States)

    2017-01-01

    The kinetics of photoelectrochemical (PEC) oxidation of methanol, as a model organic substrate, on α-Fe2O3 photoanodes are studied using photoinduced absorption spectroscopy and transient photocurrent measurements. Methanol is oxidized on α-Fe2O3 to formaldehyde with near unity Faradaic efficiency. A rate law analysis under quasi-steady-state conditions of PEC methanol oxidation indicates that rate of reaction is second order in the density of surface holes on hematite and independent of the applied potential. Analogous data on anatase TiO2 photoanodes indicate similar second-order kinetics for methanol oxidation with a second-order rate constant 2 orders of magnitude higher than that on α-Fe2O3. Kinetic isotope effect studies determine that the rate constant for methanol oxidation on α-Fe2O3 is retarded ∼20-fold by H/D substitution. Employing these data, we propose a mechanism for methanol oxidation under 1 sun irradiation on these metal oxide surfaces and discuss the implications for the efficient PEC methanol oxidation to formaldehyde and concomitant hydrogen evolution. PMID:28735533

  19. Methanol Oxidation on Model Elemental and Bimetallic Transition Metal Surfaces

    DEFF Research Database (Denmark)

    Tritsaris, G. A.; Rossmeisl, J.

    2012-01-01

    Direct methanol fuel cells are a key enabling technology for clean energy conversion. Using density functional theory calculations, we study the methanol oxidation reaction on model electrodes. We discuss trends in reactivity for a set of monometallic and bimetallic transition metal surfaces, flat...... sites on the surface and to screen for novel bimetallic surfaces of enhanced activity. We suggest platinum copper surfaces as promising anode catalysts for direct methanol fuel cells....

  20. Characterization and methanol electrooxidation studies of Pt(111)/Os surfaces prepared by spontaneous deposition.

    Science.gov (United States)

    Johnston, Christina M; Strbac, Svetlana; Lewera, Adam; Sibert, Eric; Wieckowski, Andrzej

    2006-09-12

    Catalytic activity of the Pt(111)/Os surface toward methanol electrooxidation was optimized by exploring a wide range of Os coverage. Various methods of surface analyses were used, including electroanalytical, STM, and XPS methods. The Pt(111) surface was decorated with nanosized Os islands by spontaneous deposition, and the Os coverage was controlled by changing the exposure time to the Os-containing electrolyte. The structure of Os deposits on Pt(111) was characterized and quantified by in situ STM and stripping voltammetry. We found that the optimal Os surface coverage of Pt(111) for methanol electrooxidation was 0.7 +/- 0.1 ML, close to 1.0 +/- 0.1 Os packing density. Apparently, the high osmium coverage Pt(111)/Os surface provides more of the necessary oxygen-containing species (e.g., Os-OH) for effective methanol electrooxidation than the Pt(111)/Os surfaces with lower Os coverage (vs e.g., Ru-OH). Supporting evidence for this conjecture comes from the CO electrooxidation data, which show that the onset potential for CO stripping is lowered from 0.53 to 0.45 V when the Os coverage is increased from 0.2 to 0.7 ML. However, the activity of Pt(111)/Os for methanol electrooxidation decreases when the Os coverage is higher than 0.7 +/- 0.1 ML, indicating that Pt sites uncovered by Os are necessary for sustaining significant methanol oxidation rates. Furthermore, osmium is inactive for methanol electrooxidation when the platinum substrate is absent: Os deposits on Au(111), a bulk Os ingot, and thick films of electrodeposited Os on Pt(111), all compare poorly to Pt(111)/Os. We conclude that a bifunctional mechanism applies to the methanol electrooxidation similarly to Pt(111)/Ru, although with fewer available Pt sites. Finally, the potential window for methanol electrooxidation on Pt(111)/Os was observed to shift positively versus Pt(111)/Ru. Because of the difference in the Os and Ru oxophilicity under electrochemical conditions, the Os deposit provides fewer

  1. Methanol Oxidation Using Ozone on Titania-Supported Vanadium Catalyst

    Science.gov (United States)

    Ozone-enhanced catalytic oxidation of methanol has been conducted at mild temperatures of 100 to 250NC using V2O5/TiO2 catalyst prepared by the sol-gel method. The catalyst was characterized using XRD, surface area measurements, and temperature-programmed desorption of methanol. ...

  2. Kinetic and reaction pathways of methanol oxidation on platinum

    International Nuclear Information System (INIS)

    McCabe, R.W.; McCready, D.F.

    1986-01-01

    Methanol oxidation kinetics were measured on Pt wires in a flow reactor at pressures between 30 and 130 Pa. The kinetics were measured as a function of oxygen-to-methanol equivalence ratio phi and wire temperature. In methanol-lean feeds (phi 2 CO, CO 2 , and H 2 O were the only products; in methanol-rich feeds (phi > 1), CO, H 2 , H 2 CO, CO 2 , and H 2 O were observed. Experiments with 18 O 2 showed that the principal methanol oxidation pathway does not involve C-O bond dissociation. However, the 18 O 2 experiments, together with other features of the methanol oxidation data, also provided evidence for a minor oxidation pathway (accounting for less than 1% of the product CO 2 ) which proceeds through a carbon intermediate. A mathematical model is presented which describes the principal CH 3 OH oxidation pathway as a series reaction involving adsorbed H 2 CO and CO intermediates. Consistent with experimental results, the model predicts that inhibition by adsorbed CO should be weaker for CH 3 OH and H 2 CO oxidation than for CO oxidation. 34 references, 10 figures, 2 tables

  3. Oxidation stability of biodiesel fuel as prepared by supercritical methanol

    Energy Technology Data Exchange (ETDEWEB)

    Jiayu Xin; Hiroaki Imahara; Shiro Saka [Kyoto University, Kyoto (Japan). Department of Socio-Environmental Energy Science, Graduate School of Energy Science

    2008-08-15

    A non-catalytic supercritical methanol method is an attractive process to convert various oils/fats efficiently into biodiesel. To evaluate oxidation stability of biodiesel, biodiesel produced by alkali-catalyzed method was exposed to supercritical methanol at several temperatures for 30 min. As a result, it was found that the tocopherol in biodiesel is not stable at a temperature higher than 300{sup o}C. After the supercritical methanol treatment, hydroperoxides were greatly reduced for biodiesel with initially high in peroxide value, while the tocopherol slightly decreased in its content. As a result, the biodiesel prepared by the supercritical methanol method was enhanced for oxidation stability when compared with that prepared by alkali-catalyzed method from waste oil. Therefore, supercritical methanol method is useful especially for oils/fats having higher peroxide values. 32 refs., 8 figs., 3 tabs.

  4. Advances in direct oxidation methanol fuel cells

    Science.gov (United States)

    Surampudi, S.; Narayanan, S. R.; Vamos, E.; Frank, H.; Halpert, G.; Laconti, Anthony B.; Kosek, J.; Prakash, G. K. Surya; Olah, G. A.

    1993-01-01

    Fuel cells that can operate directly on fuels such as methanol are attractive for low to medium power applications in view of their low weight and volume relative to other power sources. A liquid feed direct methanol fuel cell has been developed based on a proton exchange membrane electrolyte and Pt/Ru and Pt catalyzed fuel and air/O2 electrodes, respectively. The cell has been shown to deliver significant power outputs at temperatures of 60 to 90 C. The cell voltage is near 0.5 V at 300 mA/cm(exp 2) current density and an operating temperature of 90 C. A deterrent to performance appears to be methanol crossover through the membrane to the oxygen electrode. Further improvements in performance appear possible by minimizing the methanol crossover rate.

  5. Sequential Electrodeposition of Platinum-Ruthenium at Boron-Doped Diamond Electrodes for Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Ileana González-González

    2011-01-01

    Full Text Available Sequential electrodeposition of Pt and Ru on boron-doped diamond (BDD films, in 0.5 M H2SO4 by cyclic voltammetry, has been prepared. The potential cycling, in the aqueous solutions of the respective metals, was between 0.00 and 1.00 V versus Ag/AgCl. The catalyst composites, Pt and PtRu, deposited on BDD film substrates, were tested for methanol oxidation. The modified diamond surfaces were also characterized by scanning electron microscopy-X-ray fluorescence-energy dispersive spectroscopy, X-ray photoelectron spectroscopy, and Auger electron spectroscopy. The scanning Auger electron spectroscopy mapping showed the ruthenium signal only in areas where platinum was electrodeposited. Ruthenium does not deposit on the oxidized diamond surface of the boron-doped diamond. Particles with 5–10% of ruthenium with respect to platinum exhibited better performance for methanol oxidation in terms of methanol oxidation peak current and chronoamperometric current stability. The electrogenerated •OH radicals on BDD may interact with Pt surface, participating in the methanol oxidation as shown in oxidation current and the shift in the peak position. The conductive diamond surface is a good candidate as the support for the platinum electrocatalyst, because it ensures catalytic activity, which compares with the used carbon, and higher stability under severe anodic and cathodic conditions.

  6. Electrochemical oxidation of methanol on Pt3Co bulk alloy

    Directory of Open Access Journals (Sweden)

    S. LJ. GOJKOVIC

    2003-11-01

    Full Text Available The electrochemical oxidation of methanol was investigated on a Pt3Co bulk alloy in acid solutions. Kinetic parameters such as transfer coefficient, reaction orders with respect to methanol and H+ ions and energy of activation were determined. It was found that the rate of methanol oxidation is significantly diminished by rotation of the electrode. This effect was attributed to the diffusion of formaldehyde and formic acid from the electrode surface. Stirring of the electrolyte also influenced the kinetic parameters of the reaction. It was speculated that the predominant reaction pathway and rate determining step are different in the quiescent and in the stirred electrolyte. Cobalt did not show a promoting effect on the rate of methanol oxidation on the Pt3Co bulk alloy with respect to a pure Pt surface.

  7. Electro-oxidation of methanol and formic acid on platinum nanoparticles with different oxidation levels

    International Nuclear Information System (INIS)

    Hsieh, Chien-Te; Hsiao, Han-Tsung; Tzou, Dong-Ying; Yu, Po-Yuan; Chen, Po-Yen; Jang, Bi-Sheng

    2015-01-01

    Herein reported is an atomic layer deposition (ALD) process of platinum (Pt) from (methylcyclopentadienyl) trimethylplatinum (MeCpPtMe 3 ) and oxygen (O 2 ) for synthesizing the Pt electrocatalysts toward methanol and formic acid oxidation. The as-synthesized Pt catalysts are thermally reduced in 5 vol% H 2 within temperature window of 150–450 °C. The reduction treatment induces a decrease in amount of Pt oxide (Pt–O) species, e.g., PtO and PtO 2 . The presence of Pt–O species not only enhances catalytic activity but also improves anti-poisoning ability toward the oxidation of methanol and formic acid. The improved activity originates from the fact that the Pt–O species, formed by the ALD route, creates a large number of active sites (e.g., Pt–O ads and Pt–(OH) ads ) to strip the CO-adsorbed sites, leading to a high-level of CO tolerance. This work also proposes a stepwise reaction steps to shed some lights on how the Pt–O species promote the catalytic activity. - Highlights: • This study adopts atomic layer deposition (ALD) to grow metallic Pt nanoparticles. • The Pt catalysts show catalytic activity toward methanol and formic acid oxidation. • The reduction treatment induces a decrease in amount of Pt oxide (Pt–O) species. • The Pt–O species creates a number of active sites to strip the CO-adsorbed sites. • A stepwise reaction step concerning the promoted catalytic activity is proposed

  8. Electro-oxidation of methanol and formic acid on platinum nanoparticles with different oxidation levels

    Energy Technology Data Exchange (ETDEWEB)

    Hsieh, Chien-Te, E-mail: cthsieh@saturn.yzu.edu.tw [Department of Chemical Engineering and Materials Science, Yuan Ze University, Taoyuan 320, Taiwan (China); Hsiao, Han-Tsung; Tzou, Dong-Ying; Yu, Po-Yuan [Department of Chemical Engineering and Materials Science, Yuan Ze University, Taoyuan 320, Taiwan (China); Chen, Po-Yen; Jang, Bi-Sheng [Materials and Electro-Optics Research Division, National Chung-Shan Institute of Science and Technology, Taoyuan 325, Taiwan (China)

    2015-01-15

    Herein reported is an atomic layer deposition (ALD) process of platinum (Pt) from (methylcyclopentadienyl) trimethylplatinum (MeCpPtMe{sub 3}) and oxygen (O{sub 2}) for synthesizing the Pt electrocatalysts toward methanol and formic acid oxidation. The as-synthesized Pt catalysts are thermally reduced in 5 vol% H{sub 2} within temperature window of 150–450 °C. The reduction treatment induces a decrease in amount of Pt oxide (Pt–O) species, e.g., PtO and PtO{sub 2}. The presence of Pt–O species not only enhances catalytic activity but also improves anti-poisoning ability toward the oxidation of methanol and formic acid. The improved activity originates from the fact that the Pt–O species, formed by the ALD route, creates a large number of active sites (e.g., Pt–O{sub ads} and Pt–(OH){sub ads}) to strip the CO-adsorbed sites, leading to a high-level of CO tolerance. This work also proposes a stepwise reaction steps to shed some lights on how the Pt–O species promote the catalytic activity. - Highlights: • This study adopts atomic layer deposition (ALD) to grow metallic Pt nanoparticles. • The Pt catalysts show catalytic activity toward methanol and formic acid oxidation. • The reduction treatment induces a decrease in amount of Pt oxide (Pt–O) species. • The Pt–O species creates a number of active sites to strip the CO-adsorbed sites. • A stepwise reaction step concerning the promoted catalytic activity is proposed.

  9. Methanol from biomass by partial oxidation

    International Nuclear Information System (INIS)

    Anon.

    1989-01-01

    The advantages of methanol should grow when petroleum again becomes scarce and expensive. An active program should be continued to develop technology and resolve outstanding questions. Some of the elements of this program included in this paper are: Make design studies and more accurate cost estimates for the largest plant. The increased size of this plant over the small plant studied by S and W should result in improved methanol yield and better energy efficiency. Continue development of the SERI biomass gasifier for a better understanding of design and operating parameters, for design of larger units, for higher operating pressures, and for gasification of Hawaiian woods and agricultural wastes. An earlier gasifier test bed in Hawaii is very desirable. Develop a plan to build successfully larger methanol plants in Hawaii to provide the basis for a large plant. Develop a plan for large-scale production of biomass in the islands. Elements of the plan might include technical (types of trees, maximizing wood per acre, and harvesting processes), economic (price to be paid for the biomass), social, cultural, and political factors. Develop a plan to convert liquid fuel users to methanol and begin implementing the plan as the initial small plants supply methanol. Develop an overall plant to integrate the various parts of the program covered above

  10. Structural Study of Reduced Graphene Oxide/ Polypyrrole Composite as Methanol Sensor in Direct Methanol Fuel Cell

    International Nuclear Information System (INIS)

    Mumtazah Atiqah Hassan; Siti Kartom Kamarudin; Siti Kartom Kamarudin

    2016-01-01

    Density functional theory (DFT) computations were performed on the optimized geometric and electronic properties of reduced graphene oxide/polypyrole (rGO/ PPy) composite in comparison with pure graphene and graphene oxide structures. Incorporation of both reduced GO (rGO) and PPy will form a good composite which have advantages from both materials such as good mechanical strength and excellent electrical conductivity. These composite would be very suitable in fabrication of methanol sensor in direct methanol fuel cell (DMFC). The HOMO-LUMO energy (eV) was also calculated. These computations provide a theoretical explanation for the good performance of rGO/ PPy composite as electrode materials in methanol sensor. (author)

  11. Studies of Deactivation of Methanol to Formaldehyde Selective Oxidation Catalyst

    DEFF Research Database (Denmark)

    Raun, Kristian Viegaard; Schumann, Max; Høj, Martin

    This work presents a study of the deactivation behavior of Fe-Mo oxide catalyst during selective oxidation of methanol to formaldehyde in a period of 5 days. The structural changes in the catalyst have been investigated in situ for the initial 10 h by Raman spectroscopy, and the structure after 5...

  12. Controllable pt nanoparticle deposition on carbon nanotubes as an anode catalyst for direct methanol fuel cells.

    Science.gov (United States)

    Mu, Yongyan; Liang, Hanpu; Hu, Jinsong; Jiang, Li; Wan, Lijun

    2005-12-01

    We report a novel process to prepare well-dispersed Pt nanoparticles on CNTs. Pt nanoparticles, which were modified by the organic molecule triphenylphosphine, were deposited on multiwalled carbon nanotubes by the organic molecule, which acts as a cross linker. By manipulating the relative ratio of Pt nanoparticles and multiwalled carbon nanotubes in solution, Pt/CNT composites with different Pt content were achieved. The so-prepared Pt/CNT composite materials show higher electrocatalytic activity and better tolerance to poisoning species in methanol oxidation than the commercial E-TEK catalyst, which can be ascribed to the high dispersion of Pt nanoparticles on the multiwalled carbon nanotube surface.

  13. Petroleum Refinery Effluents Treatment by Advanced Oxidation Process with Methanol

    Energy Technology Data Exchange (ETDEWEB)

    Shoucheng, Wen [Yangtze Univ., HuBei Jingzhou (China)

    2014-02-15

    Petroleum refinery effluents are waste originating from industries primarily engaged in refining crude oil. It is a very complex compound of various oily wastes, water, heavy metals and so on. Conventional processes are unable to effectively remove the chemical oxygen demand (COD) of petroleum refinery effluents. Supercritical water oxidation (SCWO) was proposed to treat petroleum refinery effluents. In this paper, methanol was used to investigate co-oxidative effect of methanol on petroleum refinery effluents treatment. The results indicated that supercritical water oxidation is an effective process for petroleum refinery effluents treatment. Adding methanol caused an increase in COD removal. When reaction temperature is 440 .deg. C, residence time is 20 min, OE is 0.5 and initial COD is 40000 mg/L, and COD removal increases 8.5%.

  14. Petroleum Refinery Effluents Treatment by Advanced Oxidation Process with Methanol

    International Nuclear Information System (INIS)

    Shoucheng, Wen

    2014-01-01

    Petroleum refinery effluents are waste originating from industries primarily engaged in refining crude oil. It is a very complex compound of various oily wastes, water, heavy metals and so on. Conventional processes are unable to effectively remove the chemical oxygen demand (COD) of petroleum refinery effluents. Supercritical water oxidation (SCWO) was proposed to treat petroleum refinery effluents. In this paper, methanol was used to investigate co-oxidative effect of methanol on petroleum refinery effluents treatment. The results indicated that supercritical water oxidation is an effective process for petroleum refinery effluents treatment. Adding methanol caused an increase in COD removal. When reaction temperature is 440 .deg. C, residence time is 20 min, OE is 0.5 and initial COD is 40000 mg/L, and COD removal increases 8.5%

  15. Influence of surface morphology on methanol oxidation at a glassy carbon-supported Pt catalyst

    Directory of Open Access Journals (Sweden)

    S. STEVANOVIC

    2008-08-01

    Full Text Available Platinum supported on glassy carbon (GC was used as a model system for studying the influence of the surface morphology of a Pt catalyst on methanol oxidation in alkaline and acidic solutions. Platinum was deposited by the potential step method on GC samples from H2SO4 + H2PtCl6 solution under the same conditions with loadings from 10 to 80 mg cm-2. AFM and STM images of the GC/Pt electrodes showed that the Pt was deposited in the form of 3D agglomerates composed of spherical particles. Longer deposition times resulted in increased growth of Pt forms and a decrease in the specific area of the Pt. The real surface area of Pt increased with loading but the changes were almost negligible at higher loadings. Nevertheless, both the specific and mass activity of platinum supported on glassy carbon for methanol oxidation in acidic and in alkaline solutions exhibit a volcanic dependence with respect to the platinum loading. The increase in the activity can be explained by the increasing the particle size with the loading and thus an increase in the contiguous Pt sites available for adsorption and decomposition of methanol. However, the decrease in the activity of the catalyst with further increase of loading and particle size after reaching the maximum is related to the decrease of active sites available for methanol adsorption and their accessibility as a result of more close proximity and pronounced coalescence of the Pt particles.

  16. A nanogravimmetric investigation of the charging processes on ruthenium oxide thin films and their effect on methanol oxidation

    International Nuclear Information System (INIS)

    Santos, M.C.; Cogo, L.; Tanimoto, S.T.; Calegaro, M.L.; Bulhoes, L.O.S

    2006-01-01

    The charging processes and methanol oxidation that occur during the oxidation-reduction cycles in a ruthenium oxide thin film electrode (deposited by the sol-gel method on Pt covered quartz crystals) were investigated by using cyclic voltammetry, chronoamperometry and electrochemical quartz crystal nanobalance techniques. The ruthenium oxide rutile phase structure was determined by X-ray diffraction analysis. The results obtained during the charging of rutile ruthenium oxide films indicate that in the anodic sweep the transition from Ru(II) to Ru(VI) occurs followed by proton de-intercalation. In the cathodic sweep, electron injection occurs followed by proton intercalation, leading to Ru(II). The proton intercalation/de-intercalation processes can be inferred from the mass/charge relationship which gives a slope close to 1 g mol -1 (multiplied by the Faraday constant) corresponding to the molar mass of hydrogen. From the chronoamperometric measurements, charge and mass saturation of the RuO 2 thin films was observed (440 ng cm -2 ) during the charging processes, which is related to the total number of active sites in these films. Using the electrochemical quartz crystal nanobalance technique to study the methanol oxidation reaction at these films was possible to demonstrate that bulk oxidation occurs without the formation of strongly adsorbed intermediates such as CO ads , demonstrating that Pt electrodes modified by ruthenium oxide particles can be promising catalysts for the methanol oxidation as already shown in the literature

  17. Simplified kinetic models of methanol oxidation on silver

    DEFF Research Database (Denmark)

    Andreasen, A.; Lynggaard, H.; Stegelmann, C.

    2005-01-01

    Recently the authors developed a microkinetic model of methanol oxidation on silver [A. Andreasen, H. Lynggaard, C. Stegelmann, P. Stoltze, Surf. Sci. 544 (2003) 5-23]. The model successfully explains both surface science experiments and kinetic experiments at industrial conditions applying...

  18. Biodiesel from sunflower oil in supercritical methanol with calcium oxide

    International Nuclear Information System (INIS)

    Demirbas, Ayhan

    2007-01-01

    In this study, sunflower seed oil was subjected to the transesterification reaction with calcium oxide (CaO) in supercritical methanol for obtaining biodiesel. Methanol is used most frequently as the alcohol in the transesterification process. Calcium oxide (CaO) can considerably improve the transesterification reaction of sunflower seed oil in supercritical methanol. The variables affecting the methyl ester yield during the transesterification reaction, such as the catalyst content, reaction temperature and the molar ratio of soybean oil to alcohol, were investigated and compared with those of non-catalyst runs. The catalytic transesterification ability of CaO is quite weak under ambient temperature. At a temperature of 335 K, the yield of methyl ester is only about 5% in 3 h. When CaO was added from 1.0% to 3.0%, the transesterification speed increased evidently, while when the catalyst content was further enhanced to 5%, the yield of methyl ester slowly reached to a plateau. It was observed that increasing the reaction temperature had a favorable influence on the methyl ester yield. In addition, for molar ratios ranging from 1 to 41, as the higher molar ratios of methanol to oil were charged, the greater transesterification speed was obtained. When the temperature was increased to 525 K, the transesterification reaction was essentially completed within 6 min with 3 wt% CaO and 41:1 methanol/oil molar ratio

  19. New Catalysts for Direct Methanol Oxidation Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Adzic, Radoslav

    1998-08-01

    A new class of efficient electrocatalytic materials based on platinum - metal oxide systems has been synthetized and characterized by several techniques. Best activity was found with NiWO{sub 4}-, CoWO{sub 4}-, and RuO{sub 2}- sr¡pported platinum catalysts. A very similar activity at room temperature was observed with the electrodes prepared with the catalyst obtained from International Fuel Cells Inc. for the same Pt loading. Surprisingly, the two tungstates per se show a small activity for methanol oxidation without any Pt loading. Synthesis of NiWO{sub 4} and CoWO{sub 4} were carried out by solid-state reactions. FTIR spectroscopy shows that the tungstates contain a certain amount of physically adsorbed water even after heating samples at 200{degrees}C. A direct relationship between the activity for methanol oxidation and the amount of adsorbed water on those oxides has been found. The Ru(0001) single crystal shows a very small activity for CO adsorption and oxidation, in contrast to the behavior of polycrystalline Ru. In situ extended x-ray absorption fine structure spectroscopy (EXAFS) and x-ray absorption near edge spectroscopy (XANES) showed that the OH adsorption on Ru in the Pt-Ru alloy appears to be the limiting step in methanol oxidation. This does not occur for Pt-RuO{SUB 2} electrocatalyst, which explains its advantages over the Pt-Ru alloys. The IFCC electrocatalyst has the properties of the Pt-Ru alloy.

  20. Co-deposition of Pt and ceria anode catalyst in supercritical carbon dioxide for direct methanol fuel cell applications

    International Nuclear Information System (INIS)

    You, Eunyoung; Guzmán-Blas, Rolando; Nicolau, Eduardo; Aulice Scibioh, M.; Karanikas, Christos F.; Watkins, James J.; Cabrera, Carlos R.

    2012-01-01

    Pt and mixed Pt-ceria catalysts were deposited onto gas diffusion layers using supercritical fluid deposition (SFD) to fabricate thin layer electrodes for direct methanol fuel cells. Dimethyl (1,5-cyclooctadiene) platinum (II) (CODPtMe 2 ) and tetrakis (2,2,6,6-tetramethyl 3,5-heptanedionato) cerium (IV) (Ce(tmhd) 4 ) were used as precursors. Hydrogen-assisted Pt deposition was performed in compressed carbon dioxide at 60 °C and 17.2 MPa to yield high purity Pt on carbon-black based gas diffusion layers. During the preparation of the mixed Pt-ceria catalyst, hydrogen reduction of CODPtMe 2 to yield Pt catalyzed the deposition of ceria from Ce(tmhd) 4 enabling co-deposition at 150 °C. The catalyst layers were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscope-energy dispersive spectral (SEM-EDS) analyses. Their electrochemical performance toward methanol oxidation was examined in half cell mode using a three electrode assembly as well as in fuel cell mode. The thin layer electrodes formed via SFD exhibited higher performance in fuel cell operations compared to those prepared by the conventional brush-paint method. Furthermore, the Pt-ceria catalyst with an optimized composition exhibited greater methanol oxidation activity than pure platinum.

  1. Electro-oxidation of methanol on copper in alkaline solution

    International Nuclear Information System (INIS)

    Heli, H.; Jafarian, M.; Mahjani, M.G.; Gobal, F.

    2004-01-01

    The electro-oxidation of methanol on copper in alkaline solutions has been studied by the methods of cyclic voltammetry, quasi-steady state polarization and chronoamperometry. It has been found that in the course of an anodic potential sweep the electro-oxidation of methanol follows the formation of Cu III and is catalysed by this species through a mediated electron transfer mechanism. The reaction also continues in the early stages of the reversed cycle until it is stopped by the prohibitively negative potentials. The process is diffusion controlled and the current-time responses follow Cottrellian behavior. The rate constants, turnover frequency, anodic transfer coefficient and the apparent activation energy of the electro-oxidation reaction are reported

  2. Electrodeposition of a Pt-PrO{sub 2-x} electrocatalyst on diamond electrodes for the oxidation of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Liang; Hu, Jingping; Foord, John S. [Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford OX1 3TA (United Kingdom)

    2012-09-15

    The electrodeposition of Pt-PrO{sub 2-x} nanostructures on boron-doped diamond electrodes was explored by decorating platinum nanoparticles with praseodymium oxide, for application as an electrocatalyst in the electrooxidation of methanol in direct methanol fuel cells. A high loading of platinum with good stability was deposited by adopting a two-stage protocol, which involved a stepped potential route and a chronoamperometric approach. Praseodymium oxide was then coated on the platinum particles from solutions containing praseodymium nitrate and hydrogen peroxide. The porous microstructure of the resulting catalyst was characterized by X-ray photoelectron spectroscopy and scanning electron microscope, along with electrochemical measurement. The addition of praseodymium oxide to the Pt resulted in a higher catalytic activity profile for methanol oxidation along with an improved resistance to poisoning effects caused by incompletely oxidized carbonaceous species. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  3. Studies of Deactivation of Methanol to Formaldehyde Selective Oxidation Catalyst

    DEFF Research Database (Denmark)

    Raun, Kristian Viegaard; Schumann, Max; Høj, Martin

    Formaldehyde (CH2O) may be synthesized industrially by selective oxidation of methanol over an iron-molybdate (Fe-Mo) oxide catalyst according to: CH3OH + ½O2 →CH2O + H2O. The reaction is normally carried out in a multitubular reactor with excess of air at 250-400 °C (yield = 90-95 %), known...... the activity of the catalyst [2]. Pure MoO3 in itself has low activity. Literature from the last decades agrees that the major reason for the deactivation is loss of molybdenum from the catalyst. Molybdenum forms volatile species with methanol, which can leave behind Mo poor zones. The catalyst is usually...

  4. Highly sensitive methanol chemical sensor based on undoped silver oxide nanoparticles prepared by a solution method

    International Nuclear Information System (INIS)

    Rahman, M.M.; Khan, S.B.; Asiri, A.M.; Jamal, A.; Faisal, M.

    2012-01-01

    We have prepared silver oxide nanoparticles (NPs) by a simple solution method using reducing agents in alkaline medium. The resulting NPs were characterized by UV-vis and FT-IR spectroscopy, X-ray powder diffraction, and field-emission scanning electron microscopy. They were deposited on a glassy carbon electrode to give a sensor with a fast response towards methanol in liquid phase. The sensor also displays good sensitivity and long-term stability, and enhanced electrochemical response. The calibration plot is linear (r 2 = 0.8294) over the 0.12 mM to 0.12 M methanol concentration range. The sensitivity is ∼ 2.65 μAcm -2 mM -1 , and the detection limit is 36.0 μM (at a SNR of 3). We also discuss possible future prospective uses of this metal oxide semiconductor nanomaterial in terms of chemical sensing. (author)

  5. Methanol electrocatalytic oxidation on Pt nanoparticles on nitrogen doped graphene prepared by the hydrothermal reaction of graphene oxide with urea

    International Nuclear Information System (INIS)

    Xu, Xiao; Zhou, Yingke; Yuan, Tao; Li, Yawei

    2013-01-01

    A facile hydrothermal reaction of graphene oxide with urea was used to produce nitrogen doped graphene, and Pt nanoparticles were deposited on the obtained nitrogen doped graphene by the NaBH 4 reduction route. The morphology and microstructure of the synthesized catalysts were characterized by transmission electron microscopy, X-ray powder diffraction and X-ray photoelectron spectroscopy, while the functional groups on the surface of the catalysts were investigated by the Fourier transform infrared spectroscopy and ultraviolet-visible absorption spectra. Cyclic voltammetry, chronoamperometry and electrochemical impedance techniques were carried out to evaluate the methanol electrocatalytic oxidation activity and durability of Pt catalysts supported on the nitrogen doped graphene. The results showed that nitrogen doping and reduction of GO were achieved simultaneously by the facile hydrothermal reaction, which had beneficial effects for the deposition process and electrocatalytic activity of Pt nanoparticles. The Pt catalysts supported on the nitrogen doped graphene substrate presented excellent activity and durability of methanol oxidation reaction, which might be promising for application in direct methanol fuel cells

  6. Vanadium oxide monolayer catalysts : The vapor-phase oxidation of methanol

    NARCIS (Netherlands)

    Roozeboom, Fred; Cordingley, Peter D.; Gellings, P.J.

    1981-01-01

    The oxidation of methanol over vanadium oxide, unsupported and applied as a monolayer on γ-Al2O3, CeO2, TiO2, and ZrO2, was studied between 100 and 400 °C in a continuous-flow reactor. At temperatures from 150 to about 250 °C two main reactions take place, (a) dehydration of methanol to dimethyl

  7. Synthesis of dimethyl carbonate by oxidative carbonylation of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Lee, B.G.; Han, M.S.; Kim, H.S.; Ahn, B.S.; Park, K.Y.

    1999-07-01

    Dimethyl carbonate (DMC) synthesis reaction by oxidative carbonylation of methanol has been studied using vapor phase flow reaction system in the presence of Cu-based catalysts. A series of Cu-based catalysts were prepared by the conventional impregnation method using activated carbon (AC) as support. The effect of various promoters and reaction conditions on the catalytic reactivities was intensively evaluated in terms of methanol conversion and DMC selectivity. The morphological change of catalysts during the reaction was also compared by X-ray diffraction and SEM analysis. Regardless of catalyst compositions, the optimal reaction temperature for oxidative carbonylation of methanol was found to be around 120--130 C. The reaction rate was too slow below 100 C, while too many by-products were produced above 150 C. Among the various catalysts employed, CuCl{sub 2}/NaOH/AC catalyst with the mole ratio of OH/Cu = 0.5--1.0 has shown the best catalytic performance, which appears to have a strong relationship with the formation of intermediate species, Cu{sub 2}(OH){sub 3}Cl.

  8. Preparation and characterization of nickel oxide nanoparticles and their application in glucose and methanol sensing

    Directory of Open Access Journals (Sweden)

    Mahsa Hasanzadeh

    2015-03-01

    Full Text Available In this work, a low cost glucose and methanol nonenzymatic sensor was prepared using nickel oxide (NiO nanofilm electrodeposited on a bare Cu electrode. Electrochemical deposition was assisted with cetyl trimethylammonium bromide (CTAB as a template. Scanning electron microscopy (SEM was applied to observe the surface morphology of the modified electrode. Cyclic voltammetry (CV and amperometry techniques were used to study the electrocatalytic behavior of NiO porous film in glucose and methanol detection. For glucose sensing, the electrode showed a linear relationship in the concentration range of 0.01-2.14 mM with a low limit of detection (LOD 1.7 µM (signal/noise ratio (S/N=3. Moreover, high sensitivities of 4.02 mA mM−1 cm−2 and 0.38 mA mM−1 cm−2 respectively in glucose and methanol monitoring suggested the modified electrode as an excellent sensor. The NiO-Cu modified electrode was relatively insensitive to common biological interferers. This sensor possessed good poison resistance towards chloride ions, and long term stability and significant selectivity towards glucose and methanol. Finally the proposed sensor was successfully applied for determination of glucose in human blood serum samples.

  9. A microkinetic model of the methanol oxidation over silver

    DEFF Research Database (Denmark)

    Andreasen, A.; Lynggaard, H.; Stegelmann, C.

    2003-01-01

    A simple microkinetic model for the oxidation of methanol on silver based on surface science studies at UHV and low temperatures has been formulated. The reaction mechanism is a simple Langmuir-Hinshelwood mechanism, with one type of active oxygen and one route to formaldehyde and carbon dioxide......, respectively. The model explains observed reaction orders, selectivity, apparent activation enthalpies and the choice of industrial reaction conditions. More interesting the model disproves the notion that the mechanism deduced from surface science in UHV cannot be responsible for formaldehyde synthesis...

  10. Oxidation of Glycerol and Propanediols in Methanol over Heterogeneous Gold Catalysts

    DEFF Research Database (Denmark)

    Taarning, Esben; Madsen, Anders Theilgaard; Marchetti, Jorge

    2008-01-01

    Aerobic oxidation of glycerol over metal oxide supported gold nanoparticles in methanol results in the formation of dimethyl mesoxalate in selectivities up to 89% at full conversion. The oxidative esterification takes place in methanol, acting both as solvent and reactant, and in the presence of ...

  11. Methanol oxidation on stepped Pt[n(111) x (110)] electrodes: a chronoamperometric study

    NARCIS (Netherlands)

    Housmans, T.H.M.; Koper, M.T.M.

    2003-01-01

    The methanol oxidation reaction has been studied on Pt[n(111) × (110)]-type electrodes in a 0.5 M sulfuric acid and 0.025 M methanol solution, using cyclic voltammetry and chronoamperometry. The voltammetric behavior of methanol on the three electrodes under investigation [Pt(111), Pt(554), and

  12. Electrocatalytic oxidation of methanol: study with Pt:Mo dispersed catalysts

    Directory of Open Access Journals (Sweden)

    Oliveira Neto Almir

    2000-01-01

    Full Text Available The electrocatalytic oxidation of methanol on Pt:Mo dispersed on carbon prepared using an alternative method recently developed in this laboratory was investigated. The EDX analysis confirmed that the simultaneous reduction of the precursor salts of Pt and Mo leads to the presence of these materials at the nominal composition initially calculated. The addition of Mo to Pt causes an increase of the oxidation currents, but does not improve the catalytic effect for methanol oxidation. Tafel plots for various methanol concentrations showed the presence of two slopes. On line differential electrochemical mass spectrometry (DEMS was used to investigate the distribution of products and intermediates in methanol oxidation.

  13. Enhanced electrochemical oxidation of methanol on copper electrodes modified by electrocorrosion and electrodeposition

    Energy Technology Data Exchange (ETDEWEB)

    Carugno, Sofía [INQUIMAE – DQIAQF, Facultad de Ciencias, Exactas y Naturales, Universidad de Buenos Aires, Consejo Nacional de Investigaciones Científicas y Técnicas, 1428 Buenos Aires (Argentina); Chassaing, Elisabeth [IRDEP (UMR7174), EDF R and D, 6 Quai Watier, 78401 Chatou (France); Rosso, Michel [LPMC (UMR7643), CNRS, Ecole Polytechnique, F91128 Palaiseau Cedex (France); González, Graciela A., E-mail: graciela@qi.fcen.uba.ar [INQUIMAE – DQIAQF, Facultad de Ciencias, Exactas y Naturales, Universidad de Buenos Aires, Consejo Nacional de Investigaciones Científicas y Técnicas, 1428 Buenos Aires (Argentina)

    2014-02-14

    In this paper, we report a study of electrocatalytic oxidation of methanol on copper electrodes subjected to different surface treatments, either electrocorrosion or electrodeposition in the absence of strong hydrogen co-deposition. The surface morphology of treated electrodes was examined by Field Emission Scanning Electron Microscopy (FE-SEM). The effect of different treatment conditions and the methanol concentration dependence were evaluated by cyclic voltammetric technique. The results indicate that the oxidation of methanol can be enhanced by a suitable micro and nano structure generated by these treatments. This enhanced electrode activity is related to an increase of the effective surface area and/or to an increase of the surface concentration of electroactive molecules or intermediates. - Highlights: • We presented simple treatments to increase the response of copper electrodes. • Copper electrodes were modified by electrocorrosion and electrodeposition. • Scanning Electron Microscopy images reveal the effects of the different treatments. • The response is enhanced by an area increase and/or intermediates concentration. • For each treatment the concentration range of the diffusion control is analyzed.

  14. Preparation and charaterization of Pt/functionalized graphene and its electrocatalysis for methanol oxidation

    International Nuclear Information System (INIS)

    Liang, Qingsheng; Zhang, Li; Cai, Maolin; Li, Yong; Jiang, Kun; Zhang, Xin; Shen, Pei Kang

    2013-01-01

    Water-dispersible 8-hydroxy-1,3,6-pyrene trisulfonic acid trisodium salt (PyS)-functionalized graphene (PyS-graphene) sheets were prepared by a π–π interaction method, in which the aromatic organic molecules of PyS were reacted with graphene. The PyS-graphene sheets were used as Pt nanoparticle support to prepare a Pt/PyS-graphene catalyst for direct methanol fuel cells. The prepared materials were characterized by ultraviolet spectrometry (UV–vis), Fourier transform infrared spectrometry (FT-IR), atomic force microscopy (AFM), X-ray diffraction (XRD), Raman spectroscopy (SERS), and transmission electron microscopy (TEM). The electrocatalytic properties of the catalysts for methanol oxidation were evaluated by cyclic voltammetry (CV). The Pt/PyS-graphene catalysts were found to have higher electrocatalytic activity for methanol oxidation than Pt/graphene catalyst. This finding can be attributed to the introduction of negative sulfonic (SO 3 − ) groups to the graphene sheet surface, which makes the graphene sheets dispersible in water. Consequently, the Pt nanoparticles were uniformly and securely deposited onto the graphene sheet surface. These results suggested that the sulfonic group-modified water-dispersible graphene sheets can be used to improve the electrocatalytic activity of catalysts for fuel cells

  15. Silver nanoparticles anchored reduced graphene oxide for enhanced electrocatalytic activity towards methanol oxidation

    Science.gov (United States)

    Kumar, Sanjeev; Mahajan, Mani; Singh, Rajinder; Mahajan, Aman

    2018-02-01

    In this report, silver nanoparticles (Ag NPs) anchored reduced graphene oxide (rGO) sheets (rGO/Ag) nanohybrid has been explored as anode material in direct methanol fuel cells (DMFCs). The synthesized rGO/Ag nanohybrid is characterized by XRD, XPS, FTIR spectroscopy and HRTEM techniques. Cyclic voltammograms demonstrate that the rGO/Ag nanohybrid exhibits higher electrocatalytic activity in comparison to rGO sheets for methanol oxidation reaction (MOR). This enhancement is attributed to the synergetic effect produced by the presence of more active sites provided by Ag NPs anchored on a conducting network of large surface area rGO sheets.

  16. Porous platinum mesoflowers with enhanced activity for methanol oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhuang Lina; Wang Wenjin; Hong Feng [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi' an Jiaotong University, Xi' an 710049 (China); Yang Shengchun, E-mail: ysch1209@mail.xjtu.edu.cn [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi' an Jiaotong University, Xi' an 710049 (China); You Hongjun, E-mail: hjyou@mail.xjtu.edu.cn [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi' an Jiaotong University, Xi' an 710049 (China); Fang Jixiang; Ding Bingjun [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi' an Jiaotong University, Xi' an 710049 (China)

    2012-07-15

    Porous Pt and Pt-Ag alloy mesoflowers (MFs) with about 2 {mu}m in diameter and high porosity were synthesized using Ag mesoflowers as sacrificial template by galvanic reaction. The silver content in Pt-Ag alloys can be facilely controlled by nitric acid treatment. And the pure Pt MFs can be obtained by selective removal of silver element from Pt{sub 72}Ag{sub 28} MFs electrochemically. Both Pt{sub 45}Ag{sub 55}, Pt{sub 72}Ag{sub 28} and pure Pt show a high catalytic performance in methanol oxidation reaction (MOR). Especially, pure Pt MFs exhibited a 2 to 3 times current density enhancement in MOR compared with the commercial used Pt black, which can be attributed to their porous nanostructure with 3-dimentional nature and small crystal sizes. - Graphical Abstract: The CVs of MOR on Pt (red) and Pt black (green) catalysts in 0.1 M HClO{sub 4} and 0.5 M CH{sub 3}OH for specific mass current. The insert shows the SEM images of two porous Pt MFs. Platinum mesoflowers (MFs) with about 2 {mu}m in diameter and high porosity were synthesised with Ag mesoflowers as sacrificial template by galvanic replacement. The porous Pt MFs exhibited a more than 3 times enhancement in electrocatalytic performance for methanol oxidation reaction compared the commercial used Pt black. Highlights: Black-Right-Pointing-Pointer Porous Pt and Pt-Ag mesoflowers (MFs) were synthesized using Ag MFs sacrifical template. Black-Right-Pointing-Pointer Pt MFs presents an improved catalytic activity in MOR compared with Pt black. Black-Right-Pointing-Pointer We provided a facile approach for the development of high performance Pt electrocatalysts for fuel cells.

  17. Te/Pt nanonetwork modified carbon fiber microelectrodes for methanol oxidation

    International Nuclear Information System (INIS)

    Tsai, Hsiang-Yu; Shih, Zih-Yu; Lin, Zong-Hong; Chang, Huan-Tsung

    2013-01-01

    Te/Pt nanonetwork-decorated carbon fiber microelectrodes (CFMEs) have been fabricated and employed as anodic catalysts in a direct methanol fuel cell (DMFC). Te nanowires were prepared from tellurite ions (TeO 3 2− ) through a seed-mediated growth process and were deposited onto CFMEs to form three-dimensional Te nanonetworks. The Te nanonetworks then acted as a framework and reducing agent to reduce PtCl 6 2− ions to form Te/Pt through a galvanic replacement reaction, leading to the formation of Te/PtCFMEs. By controlling the reaction time, the amount of Pt and morphology of Te/Pt nanonetworks were controlled, leading to various degrees of electrocatalytic activity. The Te/PtCFMEs provide a high electrochemical active surface area (129.2 m 2 g −1 ), good catalytic activity (1.2 A mg −1 ), high current density (20.0 mA cm −2 ), long durability, and tolerance toward the poisoning species for methanol oxidation in 0.5 M sulfuric acid containing 1 M methanol. We have further demonstrated an enhanced current density by separately using 3 and 5 Te/PtCFMEs. Our results show that the low-cost, stable, and effective Te/PtCFMEs have great potential in the fabrication of cost-effective fuel cells. (paper)

  18. Study of catalysis for solid oxide fuel cells and direct methanol fuel cells

    Science.gov (United States)

    Jiang, Xirong

    Fuel cells offer the enticing promise of cleaner electricity with lower environmental impact than traditional energy conversion technologies. Driven by the interest in power sources for portable electronics, and distributed generation and automotive propulsion markets, active development efforts in the technologies of both solid oxide fuel cell (SOFC) and direct methanol fuel cell (DMFC) devices have achieved significant progress. However, current catalysts for fuel cells are either of low catalytic activity or extremely expensive, presenting a key barrier toward the widespread commercialization of fuel cell devices. In this thesis work, atomic layer deposition (ALD), a novel thin film deposition technique, was employed to apply catalytic Pt to SOFC, and investigate both Pt skin catalysts and Pt-Ru catalysts for methanol oxidation, a very important reaction for DMFC, to increase the activity and utilization levels of the catalysts while simultaneously reducing the catalyst loading. For SOFCs, we explored the use of ALD for the fabrication of electrode components, including an ultra-thin Pt film for use as the electrocatalyst, and a Pt mesh structure for a current collector for SOFCs, aiming for precise control over the catalyst loading and catalyst geometry, and enhancement in the current collect efficiency. We choose Pt since it has high chemical stability and excellent catalytic activity for the O2 reduction reaction and the H2 oxidation reaction even at low operating temperatures. Working SOFC fuel cells were fabricated with ALD-deposited Pt thin films as an electrode/catalyst layer. The measured fuel cell performance reveals that comparable peak power densities were achieved for ALD-deposited Pt anodes with only one-fifth of the Pt loading relative to a DC-sputtered counterpart. In addition to the continuous electrocatalyst layer, a micro-patterned Pt structure was developed via the technique of area selective ALD. By coating yttria-stabilized zirconia, a

  19. Titanium Oxide/Platinum Catalysis: Charge Transfer from a Titanium Oxide Support Controls Activity and Selectivity in Methanol Oxidation on Platinum

    KAUST Repository

    Hervier, Antoine

    2011-11-24

    Platinum films of 1 nm thickness were deposited by electron beam evaporation onto 100 nm thick titanium oxide films (TiOx) with variable oxygen vacancy concentrations and fluorine (F) doping. Methanol oxidation on the platinum films produced formaldehyde, methyl formate, and carbon dioxide. F-doped samples demonstrated significantly higher activity for methanol oxidation when the TiOx was stoichiometric (TiO 2), but lower activity when it was nonstoichiometric (TiO 1.7 and TiO1.9). These results correlate with the chemical behavior of the same types of catalysts in CO oxidation. Fluorine doping of stoichiometric TiO2 also increased selectivity toward partial oxidation of methanol to formaldehyde and methyl formate, but had an opposite effect in the case of nonstoichiometric TiOx. Introduction of oxygen vacancies and fluorine doping both increased the conductivity of the TiO x film. For oxygen vacancies, this occurred by the formation of a conduction channel in the band gap, whereas in the case of fluorine doping, F acted as an n-type donor, forming a conduction channel at the bottom of the conduction band, about 0.5-1.0 eV higher in energy. The higher energy electrons in F-doped stoichiometric TiOx led to higher turnover rates and increased selectivity toward partial oxidation of methanol. This correlation between electronic structure and turnover rate and selectivity indicates that the ability of the support to transfer charges to surface species controls in part the activity and selectivity of the reaction. © 2011 American Chemical Society.

  20. Titania and zirconia binary oxides as catalysts for total oxidation of ethyl acetate and methanol decomposition

    Czech Academy of Sciences Publication Activity Database

    Tsoncheva, T.; Mileva, A.; Issa, G.; Dimitrov, M.; Kovacheva, D.; Henych, Jiří; Kormunda, M.; Scotti, N.; Slušná, Michaela; Tolasz, Jakub; Štengl, Václav

    2018-01-01

    Roč. 6, č. 2 (2018), s. 2540-2550 ISSN 2213-3437 Grant - others:AV ČR(CZ) BAS-17-13 Program:Bilaterální spolupráce Institutional support: RVO:61388980 Keywords : Effect of preparation procedure * Ethyl acetate oxidation * Methanol decomposition * Titania-zirconia binary oxides Subject RIV: CA - Inorganic Chemistry OBOR OECD: Inorganic and nuclear chemistry

  1. Methanol electro-oxidation on platinum modified tungsten carbides in direct methanol fuel cells: a DFT study.

    Science.gov (United States)

    Sheng, Tian; Lin, Xiao; Chen, Zhao-Yang; Hu, P; Sun, Shi-Gang; Chu, You-Qun; Ma, Chun-An; Lin, Wen-Feng

    2015-10-14

    In exploration of low-cost electrocatalysts for direct methanol fuel cells (DMFCs), Pt modified tungsten carbide (WC) materials are found to be great potential candidates for decreasing Pt usage whilst exhibiting satisfactory reactivity. In this work, the mechanisms, onset potentials and activity for electrooxidation of methanol were studied on a series of Pt-modified WC catalysts where the bare W-terminated WC(0001) substrate was employed. In the surface energy calculations of a series of Pt-modified WC models, we found that the feasible structures are mono- and bi-layer Pt-modified WCs. The tri-layer Pt-modified WC model is not thermodynamically stable where the top layer Pt atoms tend to accumulate and form particles or clusters rather than being dispersed as a layer. We further calculated the mechanisms of methanol oxidation on the feasible models via methanol dehydrogenation to CO involving C-H and O-H bonds dissociating subsequently, and further CO oxidation with the C-O bond association. The onset potentials for the oxidation reactions over the Pt-modified WC catalysts were determined thermodynamically by water dissociation to surface OH* species. The activities of these Pt-modified WC catalysts were estimated from the calculated kinetic data. It has been found that the bi-layer Pt-modified WC catalysts may provide a good reactivity and an onset oxidation potential comparable to pure Pt and serve as promising electrocatalysts for DMFCs with a significant decrease in Pt usage.

  2. Synergistic effect of graphene oxide on the methanol oxidation for fuel cell application

    Science.gov (United States)

    Siwal, Samarjeet; Ghosh, Sarit; Nandi, Debkumar; Devi, Nishu; Perla, Venkata K.; Barik, Rasmita; Mallick, Kaushik

    2017-09-01

    Aromatic polypyrene was synthesized by the oxidative polymerization of pyrene with potassium tetrachloropalladate (II), as oxidant. During the polymerization process the palladium salt was reduced to metallic palladium and forms the metal-polymer composite material. Polypyrene stabilized palladium nanoparticles showed electrocatalytic activity toward the oxidation of methanol. The performance of the electrocatalytic activity was substantially improved with the incorporation of graphene oxide to the palladium-polypyrene composite and the synergistic performance was attributed to the electronic and structural properties of the system.

  3. Selectivity and Activity of Iron Molybdate Catalysts in Oxidation of Methanol

    OpenAIRE

    Khalid Khazzal Hummadi; Karim H. Hassan; Phillip C.H. Mitchell

    2009-01-01

    The selectivity and activity of iron molybdate catalysts prepared by different methods are compared with those of a commercial catalyst in the oxidation of methanol to formaldehyde in a continuous tubular bed reactor at 200-350 oC (473-623 oK), 10 atm (1013 kPa), with a methanol-oxygen mixture fixed at 5.5% by volume methanol: air ratio. The iron(III) molybdate catalyst prepared by co-precipitation and filtration had a selectivity towards formaldehyde in methanol oxidation comparable with a c...

  4. Methanol electro-oxidation and direct methanol fuel cell using Pt/Rh and Pt/Ru/Rh alloy catalysts

    International Nuclear Information System (INIS)

    Choi, Jong-Ho; Park, Kyung-Won; Park, In-Su; Nam, Woo-Hyun; Sung, Yung-Eun

    2004-01-01

    Pt-based binary or ternary catalysts containing Rh for use as anodes in direct methanol fuel cells (DMFC) were synthesized by borohydride reduction method combined with freeze-drying. The resulting catalysts had a specific surface area of approximately 65-75 m 2 /g. X-ray diffraction (XRD) patterns indicated that the catalysts were well alloyed and the average size of alloy catalysts was confirmed by transmission electron microscopy (TEM). The Pt/Rh (2:1) and Pt/Ru/Rh (5:4:1) alloy catalysts showed better catalytic activities for methanol electro-oxidation than Pt or Pt/Ru (1:1), respectively

  5. A study of the electro-catalytic oxidation of methanol on a cobalt hydroxide modified glassy carbon electrode

    International Nuclear Information System (INIS)

    Jafarian, M.; Mahjani, M.G.; Heli, H.; Gobal, F.; Khajehsharifi, H.; Hamedi, M.H.

    2003-01-01

    Cobalt hydroxide modified glassy carbon electrodes (CHM/GC) prepared by the anodic deposition in presence of tartrate ions have been used for the electro-catalytic oxidation of methanol in alkaline solutions where the methods of cyclic voltammetery (CV), chronoamperometry (CA) and impedance spectroscopy (IS) have been employed. In CV studies, in the presence of methanol the peak current of the oxidation of cobalt hydroxide increase is followed by a decrease in the corresponding cathodic current. This suggests that the oxidation of methanol is being catalysed through the mediated electron transfer across the cobalt hydroxide layer comprising of cobalt ions of various valence states. A mechanism based on the electro-chemical generation of Co(IV) active sites and their subsequent consumptions by methanol have been discussed and the corresponding rate law under the control of charge transfer has been developed and kinetic parameters have been derived. In this context the charge transfer resistance accessible both theoretically and through the IS studies have been used as a criteria. Under the CA regimes the reaction followed a Cottrellian behaviour

  6. C1 Metabolism in Corynebacterium glutamicum: an Endogenous Pathway for Oxidation of Methanol to Carbon Dioxide

    Science.gov (United States)

    Witthoff, Sabrina; Mühlroth, Alice

    2013-01-01

    Methanol is considered an interesting carbon source in “bio-based” microbial production processes. Since Corynebacterium glutamicum is an important host in industrial biotechnology, in particular for amino acid production, we performed studies of the response of this organism to methanol. The C. glutamicum wild type was able to convert 13C-labeled methanol to 13CO2. Analysis of global gene expression in the presence of methanol revealed several genes of ethanol catabolism to be upregulated, indicating that some of the corresponding enzymes are involved in methanol oxidation. Indeed, a mutant lacking the alcohol dehydrogenase gene adhA showed a 62% reduced methanol consumption rate, indicating that AdhA is mainly responsible for methanol oxidation to formaldehyde. Further studies revealed that oxidation of formaldehyde to formate is catalyzed predominantly by two enzymes, the acetaldehyde dehydrogenase Ald and the mycothiol-dependent formaldehyde dehydrogenase AdhE. The Δald ΔadhE and Δald ΔmshC deletion mutants were severely impaired in their ability to oxidize formaldehyde, but residual methanol oxidation to CO2 was still possible. The oxidation of formate to CO2 is catalyzed by the formate dehydrogenase FdhF, recently identified by us. Similar to the case with ethanol, methanol catabolism is subject to carbon catabolite repression in the presence of glucose and is dependent on the transcriptional regulator RamA, which was previously shown to be essential for expression of adhA and ald. In conclusion, we were able to show that C. glutamicum possesses an endogenous pathway for methanol oxidation to CO2 and to identify the enzymes and a transcriptional regulator involved in this pathway. PMID:24014532

  7. An Electrochemical Investigation of Methanol Oxidation on Nickel ...

    African Journals Online (AJOL)

    NICO

    Cyclic voltammetry, electrooxidation, glassy carbon electrode, methanol, nickel hydroxide nanoparticles. 1. ... substrate at room temperature without templates. Recently, we ... placed in ethanol and sonicated to remove adsorbed particles.

  8. High Electrocatalytic Performance of CuCoNi@CNTs Modified Glassy Carbon Electrode towards Methanol Oxidation in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Amina A. Hamza

    2017-01-01

    Full Text Available A novel non-precious multiwalled carbon nanotubes (CNTs—supported metal oxide electrocatalyst was developed for methanol electrooxidation in alkaline medium. The catalyst was fabricated by simultaneous electrodeposition of copper-cobalt-nickel ternary nanostructures (CuCoNi on a glassy carbon electrode (GCE modified with CNTs. The proposed electrode was characterized using X-ray diffraction (XRD, energy dispersive X-ray (EDX, and scanning electron microscopy (SEM. The electrochemical behavior and the electrocatalytic performance of the suggested electrode towards the oxidation of methanol were evaluated by cyclic voltammetry (CV, linear sweep voltammetry (LSV, and chronoamperometry (CA in alkaline medium. Several parameters were investigated, e.g., deposition time, potential scan rate, etc. Compared to Cu, Co, or Ni mono electrocatalysts, the electrode based on ternary-metals exhibited superior electrocatalytic activity and stability towards methanol electrooxidation. For instance, CuCoNi@CNTs/GCE has shown at least 2.5 times electrocatalytic activity and stability compared to the mono eletrocatalysts. Moreover, the present study found that the optimized loading level is 1500 s of simultaneous electrodeposition. At this loading level, it was found that the relation between the Ip/ν1/2 function and scan rate gives the characteristic features of a catalytic process. The enhanced activity and stability of CuCoNi@CNTs/GCE was attributed to (i a synergism between three metal oxides coexisting in the same structure; (ii the presence of CNTs as a support for the metal oxides, that offers high surface area for the deposited tertiary alloy and suppresses the aggregation and sintering of the metals oxide with time; as well as (iii the increase of the conductivity of the deposited semiconducting metal oxides.

  9. Methanol oxidation at platinized copper particles prepared by galvanic replacement

    Directory of Open Access Journals (Sweden)

    Ioanna Mintsouli

    2016-04-01

    Full Text Available Bimetallic Pt-Cu particles have been prepared by galvanic replacement of Cu precursor nanoparticles, upon the treatment of the latter with a chloro-platinate acidic solution. The resulting particles, typically a few tens of nm large, were supported on high surface area carbon (Vulcan® XC–72R, Cabot and tested as electrodes. Surface electrochemistry in deaerated acid solutions was similar to that of pure Pt, indicating the existence of a Pt shell (hence the particles are denoted as Pt(Cu. Pt(Cu/C supported catalysts exhibit superior carbon monoxide and methanol oxidation activity with respect to their Pt/C analogues when compared on a per electroactive surface area basis, due to the modification of Pt activity by Cu residing in the particle core. However, as a result of large particle size and agglomeration phenomena, Pt(Cu/C are still inferior to Pt/C when compared on a mass specific activity basis.

  10. Electro-oxidation of methanol at multi-walled carbon nanotubes decorated with metal nanoparticles

    CSIR Research Space (South Africa)

    Maxakato, NW

    2008-01-01

    Full Text Available Fuel Cells (FC) employing methanol are extremely attractive as power sources for portable applications. One of the keys to the development of FC is to find a new and improved electrocatalyst. During methanol electro-oxidation on platinum (Pt...

  11. Kinetics of the partial oxidation of methanol over a Fe-Mo catalyst

    NARCIS (Netherlands)

    Deshmukh, S.A.R.K.; Sint Annaland, van M.; Kuipers, J.A.M.

    2005-01-01

    The intrinsic steady-state kinetics of the partial oxidation of methanol to formaldehyde over a commercial Fe-Mo catalyst has been studied experimentally in a differentially operated reactor at temperatures of 230–260 °C, over a wide range of methanol and oxygen concentrations. The principal

  12. Kinetics of the partial oxidation of methanol over a Fe-Mo catalyst

    NARCIS (Netherlands)

    Deshmukh, S.A.R.K.; van Sint Annaland, M.; Kuipers, J.A.M.

    2005-01-01

    The intrinsic steady-state kinetics of the partial oxidation of methanol to formaldehyde over a commercial Fe-Mo catalyst has been studied experimentally in a differentially operated reactor at temperatures of 230¿260 °C, over a wide range of methanol and oxygen concentrations. The principal

  13. Solvation of graphite oxide in water-methanol binary polar solvents

    Energy Technology Data Exchange (ETDEWEB)

    You, Shujie; Yu, Junchun; Sundqvist, Bertil; Talyzin, Alexandr V. [Department of Physics, Umeaa University, SE-901 87 Umeaa (Sweden)

    2012-12-15

    The phase transition between two solvated phases was studied by DSC for graphite oxide (GO) powders immersed in water-methanol mixtures of various compositions. GO forms solid solvates with two different compositions when immersed in methanol. Reversible phase transition between two solvate states due to insertion/desertion of methanol monolayer occurs upon temperature variations. The temperature point and the enthalpy ({Delta}H) of the phase transition are maximal for pure methanol and decrease linearly with increase of water fraction up to 30%. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Ammonia release method for depositing metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Silver, G.L.; Martin, F.S.

    1993-12-31

    A method of depositing metal oxides on substrates which is indifferent to the electrochemical properties of the substrates and which comprises forming ammine complexes containing metal ions and thereafter effecting removal of ammonia from the ammine complexes so as to permit slow precipitation and deposition of metal oxide on the substrates.

  15. Studies of the role of water in the electrocatalysis of methanol oxidation

    Science.gov (United States)

    Lin, Andrew S.; Kowalak, Albert D.; O'Grady, William E.

    The oxidation of methanol has been carried out on electrodes prepared by evaporating Pt directly onto a Nafion membrane and then introducing the methanol either in the gas-fed mode or directly from the electrolyte in the electrolyte-fed mode. It was found that the oxidation carried out using a gas-fed electrode was shifted 100-150 mV more cathodic than the electrolyte-fed electrode. A similar set of experiments was carried out using hydrophobic gas-diffusion electrodes and similar results were obtained. These results suggest that the mechanism of the methanol oxidation reaction depends on the nature of the surroundings and the orientation of the methanol with respect to the electrode surface. In the electrolyte-fed configuration the methanol will be in a hydrogen-bonded water cluster allowing the carbon end of the molecule to more readily approach the catalyst surface. While in the gas-fed configuration the methanol will interact with the water or oxidic surface through the hydroxyl end of the molecule. Clearly, these two possible mechanisms will lead to different products and one may enhance the rate of the direct oxidation of methanol as observed in this work.

  16. Lanthanide-Dependent Regulation of Methanol Oxidation Systems in Methylobacterium extorquens AM1 and Their Contribution to Methanol Growth.

    Science.gov (United States)

    Vu, Huong N; Subuyuj, Gabriel A; Vijayakumar, Srividhya; Good, Nathan M; Martinez-Gomez, N Cecilia; Skovran, Elizabeth

    2016-04-01

    Methylobacterium extorquens AM1 has two distinct types of methanol dehydrogenase (MeDH) enzymes that catalyze the oxidation of methanol to formaldehyde. MxaFI-MeDH requires pyrroloquinoline quinone (PQQ) and Ca in its active site, while XoxF-MeDH requires PQQ and lanthanides, such as Ce and La. Using MeDH mutant strains to conduct growth analysis and MeDH activity assays, we demonstrate that M. extorquens AM1 has at least one additional lanthanide-dependent methanol oxidation system contributing to methanol growth. Additionally, the abilities of different lanthanides to support growth were tested and strongly suggest that both XoxF and the unknown methanol oxidation system are able to use La, Ce, Pr, Nd, and, to some extent, Sm. Further, growth analysis using increasing La concentrations showed that maximum growth rate and yield were achieved at and above 1 μM La, while concentrations as low as 2.5 nM allowed growth at a reduced rate. Contrary to published data, we show that addition of exogenous lanthanides results in differential expression from the xox1 and mxa promoters, upregulating genes in the xox1 operon and repressing genes in the mxa operon. Using transcriptional reporter fusions, intermediate expression from both the mxa and xox1 promoters was detected when 50 to 100 nM La was added to the growth medium, suggesting that a condition may exist under which M. extorquens AM1 is able to utilize both enzymes simultaneously. Together, these results suggest that M. extorquens AM1 actively senses and responds to lanthanide availability, preferentially utilizing the lanthanide-dependent MeDHs when possible. The biological role of lanthanides is a nascent field of study with tremendous potential to impact many areas in biology. Our studies demonstrate that there is at least one additional lanthanide-dependent methanol oxidation system, distinct from the MxaFI and XoxF MeDHs, that may aid in classifying additional environmental organisms as methylotrophs. Further

  17. METHANOL OXIDATION OVER AU/ γ -AL 2O3 CATALYSTS 149

    African Journals Online (AJOL)

    DR. AMINU

    catalysts were used to catalyze the oxidation of methanol and characterised using X-ray ... As the concentration of methoxy diminishes, so the mechanism reverts to a decomposition pathway ..... Catalysis Reviews: Science and Engineering 41.

  18. High activity of novel Pd/TiO2 nanotube catalysts for methanol electro-oxidation

    International Nuclear Information System (INIS)

    Wang Mei; Guo Daojun; Li Hulin

    2005-01-01

    Electro-oxidation of methanol in sulfuric acid solution was studied using palladium well-dispersed on titanium nanotubes, in relation to methanol oxidation processes in the direct oxidation methanol fuel cell. Pd dispersed on titania nanotubes, which leads to high surface area substrates, showed excellent catalytic activities compared to those of pure Pd and Pd-TiO 2 nanoparticles. TEM results show a narrow distribution of TiO 2 nanoparticles whose particle size is about 10nm, and uniform nano-sized TiO 2 nanotubes with 10nm in diameters are seen from HRTEM . A homogeneous structure in the composite nanomaterials is indicated by XRD analysis. The composite electrode activities were measured by cyclic voltammetry (CV) and at 25 deg. C it was found that 3wt% Pd in titania nanotubes had the best activity for methanol oxidation

  19. Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

    KAUST Repository

    Nagaraju, Doddahalli H.; Devaraj, Sappani; Balaya, Palani

    2014-01-01

    nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient

  20. One-pot synthesis of graphene supported platinum–cobalt nanoparticles as electrocatalysts for methanol oxidation

    International Nuclear Information System (INIS)

    Kepenienė, V.; Tamašauskaitė-Tamašiūnaitė, L.; Jablonskienė, J.; Semaško, M.; Vaičiūnienė, J.; Vaitkus, R.; Norkus, E.

    2016-01-01

    In the present study the graphene supported platinum–cobalt nanoparticles were prepared via microwave synthesis. The composition of prepared catalysts was examined by Inductively Coupled Plasma Optical Emission Spectroscopy. The shape and size of catalyst particles were determined by Transmission Electron Microscopy. The electrocatalytic activity of the graphene supported platinum–cobalt nanoparticles was investigated towards the electro-oxidation of methanol in an alkaline medium. It has been found that the graphene supported platinum–cobalt nanoparticles having the Pt:Co molar ratio 1:7 show the highest activity towards the electro-oxidation of methanol among the catalysts with the Pt:Co molar ratios equal to 1:1 and 1:44, graphene supported bare Co and Pt/C catalysts. - Highlights: • Preparation of graphene supported Pt-Co nanoparticles by microwave synthesis. • Electrocatalysts for oxidation of methanol. • Higher activity of PtCo/graphene towards methanol oxidation.

  1. One-pot synthesis of graphene supported platinum–cobalt nanoparticles as electrocatalysts for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Kepenienė, V., E-mail: virginalisk@gmail.com [Department of Catalysis, Center for Physical Sciences and Technology, Vilnius LT 01108 (Lithuania); Tamašauskaitė-Tamašiūnaitė, L.; Jablonskienė, J.; Semaško, M.; Vaičiūnienė, J. [Department of Catalysis, Center for Physical Sciences and Technology, Vilnius LT 01108 (Lithuania); Vaitkus, R. [Faculty of Chemistry, Vilnius University, Vilnius LT 03225 (Lithuania); Norkus, E. [Department of Catalysis, Center for Physical Sciences and Technology, Vilnius LT 01108 (Lithuania)

    2016-03-01

    In the present study the graphene supported platinum–cobalt nanoparticles were prepared via microwave synthesis. The composition of prepared catalysts was examined by Inductively Coupled Plasma Optical Emission Spectroscopy. The shape and size of catalyst particles were determined by Transmission Electron Microscopy. The electrocatalytic activity of the graphene supported platinum–cobalt nanoparticles was investigated towards the electro-oxidation of methanol in an alkaline medium. It has been found that the graphene supported platinum–cobalt nanoparticles having the Pt:Co molar ratio 1:7 show the highest activity towards the electro-oxidation of methanol among the catalysts with the Pt:Co molar ratios equal to 1:1 and 1:44, graphene supported bare Co and Pt/C catalysts. - Highlights: • Preparation of graphene supported Pt-Co nanoparticles by microwave synthesis. • Electrocatalysts for oxidation of methanol. • Higher activity of PtCo/graphene towards methanol oxidation.

  2. Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal-Organic Framework.

    Science.gov (United States)

    Ikuno, Takaaki; Zheng, Jian; Vjunov, Aleksei; Sanchez-Sanchez, Maricruz; Ortuño, Manuel A; Pahls, Dale R; Fulton, John L; Camaioni, Donald M; Li, Zhanyong; Ray, Debmalya; Mehdi, B Layla; Browning, Nigel D; Farha, Omar K; Hupp, Joseph T; Cramer, Christopher J; Gagliardi, Laura; Lercher, Johannes A

    2017-08-02

    Copper oxide clusters synthesized via atomic layer deposition on the nodes of the metal-organic framework (MOF) NU-1000 are active for oxidation of methane to methanol under mild reaction conditions. Analysis of chemical reactivity, in situ X-ray absorption spectroscopy, and density functional theory calculations are used to determine structure/activity relations in the Cu-NU-1000 catalytic system. The Cu-loaded MOF contained Cu-oxo clusters of a few Cu atoms. The Cu was present under ambient conditions as a mixture of ∼15% Cu + and ∼85% Cu 2+ . The oxidation of methane on Cu-NU-1000 was accompanied by the reduction of 9% of the Cu in the catalyst from Cu 2+ to Cu + . The products, methanol, dimethyl ether, and CO 2 , were desorbed with the passage of 10% water/He at 135 °C, giving a carbon selectivity for methane to methanol of 45-60%. Cu oxo clusters stabilized in NU-1000 provide an active, first generation MOF-based, selective methane oxidation catalyst.

  3. Low Pt content Pt-Ru-Ir-Sn quaternary catalysts for anodic methanol oxidation in DMFC

    Energy Technology Data Exchange (ETDEWEB)

    Neburchilov, Vladimir; Wang, Haijiang; Zhang, Jiujun [Institute for Fuel Cell Innovation, National Research Council (Canada)

    2007-07-15

    In this communication we report our research work on low Pt content Pt-Ru-Ir-Sn quaternary catalysts for use in DMFC anodes. The carbon-supported quaternary metal alloy catalyst was synthesized according to the solution reduction method and was deposited onto a carbon fiber paper or a carbon aerogel nanofoam to form the anode for direct methanol fuel cells. The Pt loading of the electrode is 0.1 mg/cm{sup 2}. The testing results from a three-electrode electrochemical cell show that the simultaneous use of higher Ir (25-35 wt.%) and Sn (10 wt.%) content gives satisfactory stability and higher activity for methanol oxidation than the commercially available E-TEK anode (80%[0.5Pt 0.5Ru]/C on carbon cloth). Energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), scanning electron microscope (SEM), and Bruner-Emmett-Teller method (BET) measurements were carried out to characterize the composition, structure, morphology, and surface area of the developed catalysts. (author)

  4. Electrocatalytic oxidation of methanol on (Pb) lead modified by Pt, Pt-Ru and Pt-Sn microparticles dispersed into poly(o-phenylenediamine) film

    Energy Technology Data Exchange (ETDEWEB)

    Golikand, Ahmad Nozad; Maragheh, Mohammad Ghannadi; Irannejad, Leila [Jaber Ibn Hayan Research Lab., Atomic Energy Organization of Iran (AEOI), Tehran (Iran); Golabi, Seyed Mehdi [Electroanalytical Chemistry Lab., Faculty of Chemistry, University of Tabriz, Tabriz (Iran)

    2005-08-18

    The electrocatalytic oxidation of methanol at a (Pb) lead electrode modified by Pt, Pt-Ru and Pt-Sn microparticles dispersed into poly(o-phenylenediamine) (PoPD) film has been investigated using cyclic voltammetry as analytical technique and 0.5M sulfuric acid as supporting electrolyte. It has been shown that the presence of PoPD film increases considerably the efficiency of deposited Pt and Pt alloys microparticles toward the electrocatalytic oxidation of methanol. The catalytic activity of Pt particles is further enhanced when Ru and especially Sn, is co-deposited in the polymer film. The effects of various parameters such as concentration of methanol, medium temperature as well as the long term stability of modified electrodes have also been investigated. (author)

  5. Electrostatic layer-by-layer a of platinum-loaded multiwall carbon nanotube multilayer: A tunable catalyst film for anodic methanol oxidation

    International Nuclear Information System (INIS)

    Yuan Junhua; Wang Zhijuan; Zhang Yuanjian; Shen Yanfei; Han Dongxue; Zhang Qixian; Xu Xiaoyu; Niu Li

    2008-01-01

    A simple layer-by-layer (LBL) electrostatic adsorption technique was developed for deposition of films composed of alternating layers of positively charged poly(diallyldimethylammonium chloride) (PDDA) and negatively charged multiwall carbon nanotubes bearing platinum nanoparticles (Pt-CNTs). PDDA/Pt-CNT film structure and morphology up to six layers were characterized by scanning electron microscopy and ultraviolet-visible spectroscopy, showing the Pt-CNT layers to be porous and uniformly deposited within the multilayer films. Electrochemical properties of the PDDA/Pt-CNT films, as well as electrocatalytic activity toward methanol oxidation, were investigated with cyclic voltammetry. Significant activity toward anodic methanol oxidation was observed and is readily tunable through changing film thickness and/or platinum-nanoparticle loading. Overall, the observed properties of these PDDA/Pt-CNT multilayer films indicated unique potential for application in direct methanol fuel cell

  6. Oxide cathodes produced by plasma deposition

    International Nuclear Information System (INIS)

    Scheitrum, G.; Caryotakis, G.; Pi, T.; Umstattd, R.; Brown, I.; Montiero, O.

    1997-01-01

    These are two distinct applications for high-current-density, long-life thermionic cathodes. The first application is as a substitute for explosive emission cathodes used in high-power microwave (HPM) devices being developed for Air Force programs. The second application is in SLAC's X-band klystrons for the Next Linear Collider (NLC). SLAC, UCD, and LBL are developing a plasma deposition process that eliminates the problems with binders, carbonate reduction, peeling, and porosity. The emission layer is deposited using plasma deposition of metallic barium in vacuum with an oxygen background gas. An applied bias voltage drives the oxide plasma into the nickel surface. Since the oxide is deposited directly, it does not have problems with poisoning from a hydrocarbon binder. The density of the oxide layer is increased from the 40--50% for standard oxide cathodes to nearly 100% for plasma deposition

  7. Rapid biological oxidation of methanol in the tropical Atlantic: significance as a microbial carbon source

    Directory of Open Access Journals (Sweden)

    J. L. Dixon

    2011-09-01

    Full Text Available Methanol is the second most abundant organic gas in the atmosphere after methane, and is ubiquitous in the troposphere. It plays a significant role in atmospheric oxidant chemistry and is biogeochemically active. Large uncertainties exist about whether the oceans are a source or sink of methanol to the atmosphere. Even less is understood about what reactions in seawater determine its concentration, and hence flux across the sea surface interface. We report here concentrations of methanol between 151–296 nM in parts of the oligotrophic North Atlantic, with corresponding microbial uptake rates between 2–146 nM d−1, suggesting turnover times as low as 1 day (1–25 days in surface waters of the oligotrophic tropical North East Atlantic. Methanol is mainly (≥97% used by microbes for obtaining energy in oligotrophic regions, which contrasts with shelf and coastal areas where between 20–50% can be used for cell growth. Comparisons of microbial methanol oxidation rates with parallel determinations of bacterial leucine uptake suggest that methanol contributes on average 13% to bacterial carbon demand in the central northern Atlantic gyre (maximum of 54%. In addition, the contribution that methanol makes to bacterial carbon demand varies as a power function of chlorophyll a concentrations; suggesting for concentrations <0.2 μg l−1 that methanol can make a significant contribution to bacterial carbon demand. However, our low air to sea methanol flux estimates of 7.2–13 μmol m−2 d−1 suggest that the atmosphere is not a major methanol source. We conclude that there must be a major, as yet unidentified, in situ oceanic methanol source in these latitudes which we suggest is sunlight driven decomposition of organic matter.

  8. Analysis of the kinetics of methanol oxidation in a porous Pt-Ru anode

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Yan-Ping; Xing, Lei [Chemical Engineering Department, Taiyuan University of Technology, Shanxi 030024 (China); Scott, Keith [School of Chemical Engineering and Advanced Materials, Merz Court, University of Newcastle, Newcastle upon Tyne NE1 7RU (United Kingdom)

    2010-01-01

    A kinetic model of a porous Pt-Ru anode for methanol oxidation is presented. It was based on the dual-site mechanism for methanol oxidation and used to predict anode performance and the influence of species adsorption on the overall oxidation (macro-) kinetics. The performance of the porous Pt-Ru anode depended on the parameters of the intrinsic chemical kinetics of methanol oxidation and physical parameters such as electrode thickness, surface area, effective diffusion and charge transfer coefficients and concentration of methanol and temperature. The model was solved by using the finite difference method with a subroutine for solving a set of nonlinear algebraic equations in each step. Surface coverage ratio distributions of adsorbed species, effectiveness of the porous electrode and macro-polarisation curves were obtained. The simulated polarisation curves were compared to experimental polarisation data for methanol oxidation on Pt-Ru porous anodes at different temperatures and methanol concentrations. The intrinsic kinetic parameters were regressed from the corresponding experimental data. The predicted polarisation curves calculated by the model, were consistent with experimental polarisation data at lower current densities. The departure of experimental data from the predicted polarisation curves at high concentration and high apparent current densities was believed to be due to two-phase flow in the electrode. (author)

  9. Controllable deposition of platinum nanoparticles on single-wall carbon nanohorns as catalyst for direct methanol fuel cells.

    Science.gov (United States)

    Niu, Ben; Xu, Wei; Guo, Zhengduo; Zhou, Nengzhi; Liu, Yang; Shi, Zujin; Lian, Yongfu

    2012-09-01

    Uniform and well dispersed platinum nanoparticles were successfully deposited on single-walled carbon nanohorns with the assistance of 4,4-dipydine and ion liquids, respectively. In particular, the size of platinum nanoparticles could be controlled in a very narrow range (2.2 to 2.5 nm) when ion liquids were applied. The crystalline nature of these platinum nanoparticles was confirmed by high resolution transmission electron microscopy observation and X-ray power diffraction analysis, and two species of platinum Pt(0) and Pt(II) were detected by X-ray photoelectron spectroscopy. Electrochemical studies revealed that thus obtained nanocomposites had much better electrocatalytic activity for the methanol oxidation than those prepared with carbon nanotubes as supporter.

  10. Application of flexible micro temperature sensor in oxidative steam reforming by a methanol micro reformer.

    Science.gov (United States)

    Lee, Chi-Yuan; Lee, Shuo-Jen; Shen, Chia-Chieh; Yeh, Chuin-Tih; Chang, Chi-Chung; Lo, Yi-Man

    2011-01-01

    Advances in fuel cell applications reflect the ability of reformers to produce hydrogen. This work presents a flexible micro temperature sensor that is fabricated based on micro-electro-mechanical systems (MEMS) technology and integrated into a flat micro methanol reformer to observe the conditions inside that reformer. The micro temperature sensor has higher accuracy and sensitivity than a conventionally adopted thermocouple. Despite various micro temperature sensor applications, integrated micro reformers are still relatively new. This work proposes a novel method for integrating micro methanol reformers and micro temperature sensors, subsequently increasing the methanol conversion rate and the hydrogen production rate by varying the fuel supply rate and the water/methanol ratio. Importantly, the proposed micro temperature sensor adequately controls the interior temperature during oxidative steam reforming of methanol (OSRM), with the relevant parameters optimized as well.

  11. Application of Flexible Micro Temperature Sensor in Oxidative Steam Reforming by a Methanol Micro Reformer

    Directory of Open Access Journals (Sweden)

    Yi-Man Lo

    2011-02-01

    Full Text Available Advances in fuel cell applications reflect the ability of reformers to produce hydrogen. This work presents a flexible micro temperature sensor that is fabricated based on micro-electro-mechanical systems (MEMS technology and integrated into a flat micro methanol reformer to observe the conditions inside that reformer. The micro temperature sensor has higher accuracy and sensitivity than a conventionally adopted thermocouple. Despite various micro temperature sensor applications, integrated micro reformers are still relatively new. This work proposes a novel method for integrating micro methanol reformers and micro temperature sensors, subsequently increasing the methanol conversion rate and the hydrogen production rate by varying the fuel supply rate and the water/methanol ratio. Importantly, the proposed micro temperature sensor adequately controls the interior temperature during oxidative steam reforming of methanol (OSRM, with the relevant parameters optimized as well.

  12. Electrochemical Synthesis of Mesoporous CoPt Nanowires for Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Albert Serrà

    2014-03-01

    Full Text Available A new electrochemical method to synthesize mesoporous nanowires of alloys has been developed. Electrochemical deposition in ionic liquid-in-water (IL/W microemulsion has been successful to grow mesoporous CoPt nanowires in the interior of polycarbonate membranes. The viscosity of the medium was high, but it did not avoid the entrance of the microemulsion in the interior of the membrane’s channels. The structure of the IL/W microemulsions, with droplets of ionic liquid (4 nm average diameter dispersed in CoPt aqueous solution, defined the structure of the nanowires, with pores of a few nanometers, because CoPt alloy deposited only from the aqueous component of the microemulsion. The electrodeposition in IL/W microemulsion allows obtaining mesoporous structures in which the small pores must correspond to the size of the droplets of the electrolytic aqueous component of the microemulsion. The IL main phase is like a template for the confined electrodeposition. The comparison of the electrocatalytic behaviours towards methanol oxidation of mesoporous and compact CoPt nanowires of the same composition, demonstrated the porosity of the material. For the same material mass, the CoPt mesoporous nanowires present a surface area 16 times greater than compact ones, and comparable to that observed for commercial carbon-supported platinum nanoparticles.

  13. Pt-Si Bifunctional Surfaces for CO and Methanol Electro-Oxidation

    DEFF Research Database (Denmark)

    Permyakova, Anastasia A.; Han, Binghong; Jensen, Jens Oluf

    2015-01-01

    and storage. Here we report on Pt-Si bulk samples prepared by arc-melting, for the first time, with high activities toward the electro-oxidation of CO and methanol. Increasing the Si concentration on the surface was correlated with the shifts of onset oxidation potentials to lower values and higher activities...... for CO and methanol electro-oxidation. It is proposed that the reaction on the Pt-Si catalyst could follow a Langmuir-Hinshelwood type of mechanism, where substantially enhanced catalytic activity is attributed to the fine-tuning of the surface Pt-Si atomic structure....

  14. Oxidation of aromatic alcohols by purified methanol dehydrogenase from Methylosinus trichosporium.

    OpenAIRE

    Mountfort, D O

    1990-01-01

    Methanol dehydrogenase was found to be present in subcellular preparations of methanol-grown Methylosinus trichosporium and occurred almost wholly in the soluble fraction of the cell. The enzyme, purified by DEAE-Sephadex and Sephadex G-100 chromatography, showed broad specificity toward different substrates and oxidized the aromatic alcohols benzyl, vanillyl, and veratryl alcohols in addition to a range of aliphatic primary alcohols. No enzyme activity was found toward the corresponding alde...

  15. Sensitive methanol sensor based on PMMA-G-CNTs nanocomposites deposited onto glassy carbon electrodes.

    Science.gov (United States)

    Rahman, Mohammed M; Hussein, Mahmoud A; Alamry, Khalid A; Al Shehry, Faten M; Asiri, Abdullah M

    2016-04-01

    A new series of polymethyl methacrylate-graphene-carbon nanotubes crossbred nanocomposites in the form of PMMA-G-CNTs has been synthesized using simple dissolution procedure in organic media. The desired nanocomposites have been prepared using different loading (2 ∼ 30%) from consequently mixed GNPs/CNTs ratio and confirmed by various characterization techniques utilized to corroborate the assembly of these new hybrid series including X-ray diffraction analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. The PMMA-G-CNTs nanocomposites were deposited on flat glassy carbon electrodes (GCE) to result in a sensor that has a fast response toward methanol in the phosphate buffer phase. Features including high sensitivity, low-sample volume, reliability, reproducibility, ease of integration, long-term stability, and enhanced electrochemical responses are investigated. The calibration plot is linear (r(2)=0.9895) over the 1.0 nmol L(-1) to 10.0 mmol L(-1) methanol concentration ranges. The sensitivity and detection limit is 13.491 µA cm(-2) mmol L(-2) and 0.39 ± 0.1 nmol L(-1) (at a signal-to-noise-ratio, SNR of 3), respectively. With such excellent features of analytical parameters, the developed sensor provides a new strategy for determination of methanol in biomedical and environmental analytes with satisfactory results. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Controlled Synthesis of Pt Nanowires with Ordered Large Mesopores for Methanol Oxidation Reaction

    Science.gov (United States)

    Zhang, Chengwei; Xu, Lianbin; Yan, Yushan; Chen, Jianfeng

    2016-08-01

    Catalysts for methanol oxidation reaction (MOR) are at the heart of key green-energy fuel cell technology. Nanostructured Pt materials are the most popular and effective catalysts for MOR. Controlling the morphology and structure of Pt nanomaterials can provide opportunities to greatly increase their activity and stability. Ordered nanoporous Pt nanowires with controlled large mesopores (15, 30 and 45 nm) are facilely fabricated by chemical reduction deposition from dual templates using porous anodic aluminum oxide (AAO) membranes with silica nanospheres self-assembled in the channels. The prepared mesoporous Pt nanowires are highly active and stable electrocatalysts for MOR. The mesoporous Pt nanowires with 15 nm mesopores exhibit a large electrochemically active surface area (ECSA, 40.5 m2 g-1), a high mass activity (398 mA mg-1) and specific activity (0.98 mA cm-2), and a good If/Ib ratio (1.15), better than the other mesoporous Pt nanowires and the commercial Pt black catalyst.

  17. Characterization of Pt/Sn catalyst for the electrochemical oxidation of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Andrew, M.R.; Drury, J.S.; McNicol, B.D.; Pinnington, C.; Short, R.T.

    1976-03-01

    Pt/Sn electrodeposited catalysts have been prepared, characterized and tested for the electro-oxidation of methanol. Catalyst activities were measured in 3 M H/sub 2/SO/sub 4/ electrolyte between ambient temperature and 95/sup 0/C. Enhancement in specific activity by a factor of about 50 was found over electrodeposited platinum black. This behavior is in contrast to that of alloys of platinum and tin which were found to have very low activities compared with platinum catalysts and to be readily corroded in H/sub 2/SO/sub 4/ electrolyte. ESCA (electron spectroscopy for chemical analysis) studies and Moessbauer spectroscopy showed the majority of the tin in the deposit to be present in an oxidized form. A small amount (approximately 17%) was present as a dilute alloy of tin in platinum. Surface area measurements and X-ray powder diffraction indicated that the increase in activity over platinum black was not attributable to smaller platinum particle size. It seems that the combination of platinum and tin results in a decrease in the poisoning effect by strongly adsorbed organic residues. Whether this arises from the operation of a cyclic Sn(II)/Sn(IV) redox system or from modification of the platinum surface remains unresolved.

  18. Nitrogen doped graphene supported palladium-cobalt as a promising catalyst for methanol oxidation reaction: Synthesis, characterization and electrocatalytic performance

    International Nuclear Information System (INIS)

    Kiyani, Roya; Rowshanzamir, Soosan; Parnian, Mohammad Javad

    2016-01-01

    In this work, palladium and palladium-cobalt supported on nitrogen doped graphene as anode materials in direct methanol fuel cells is reported. A simple and low temperature solvothermal method is used to directly prepare nanoflower-like NG and then, Pd and Pd−Co nanoparticles are precipitated onto the surface of NG using a modified polyol reduction method. The synthesized electrocatalysts are characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) are used to measure electrocatalytic methanol oxidation activity and the durability of electrocatalysts. The results show that Pd−Co/NG has better electrocatalytic activity than Pd/NG toward methanol oxidation reaction (MOR) in alkaline media that is related at the presence of cobalt atoms. In addition, chronoamperometric results indicate that Pd−Co/NG is more stable than commercial Pt/C for MOR. - Highlights: • Nitrogen doped graphene (NG) was prepared by a simple solvothermal method. • Pd and Pd−Co nanoparticles were deposited on NG by polyol reduction method. • Promoting effects of cobalt over Pd/NG for MOR were investigated. • Higher activity and enhanced durability was observed for Pd−Co/NG catalyst.

  19. Steam reforming of methanol over oxide decorated nanoporous gold catalysts: a combined in situ FTIR and flow reactor study.

    Science.gov (United States)

    Shi, J; Mahr, C; Murshed, M M; Gesing, T M; Rosenauer, A; Bäumer, M; Wittstock, A

    2017-03-29

    Methanol as a green and renewable resource can be used to generate hydrogen by reforming, i.e., its catalytic oxidation with water. In combination with a fuel cell this hydrogen can be converted into electrical energy, a favorable concept, in particular for mobile applications. Its realization requires the development of novel types of structured catalysts, applicable in small scale reactor designs. Here, three different types of such catalysts were investigated for the steam reforming of methanol (SRM). Oxides such as TiO 2 and CeO 2 and mixtures thereof (Ce 1 Ti 2 O x ) were deposited inside a bulk nanoporous gold (npAu) material using wet chemical impregnation procedures. Transmission electron and scanning electron microscopy reveal oxide nanoparticles (1-2 nm in size) abundantly covering the strongly curved surface of the nanoporous gold host (ligaments and pores on the order of 40 nm in size). These catalysts were investigated in a laboratory scaled flow reactor. First conversion of methanol was detected at 200 °C. The measured turn over frequency at 300 °C of the CeO x /npAu catalyst was 0.06 s -1 . Parallel investigation by in situ infrared spectroscopy (DRIFTS) reveals that the activation of water and the formation of OH ads are the key to the activity/selectivity of the catalysts. While all catalysts generate sufficient OH ads to prevent complete dehydrogenation of methanol to CO, only the most active catalysts (e.g., CeO x /npAu) show direct reaction with formic acid and its decomposition to CO 2 and H 2 . The combination of flow reactor studies and in operando DRIFTS, thus, opens the door to further development of this type of catalyst.

  20. The enhancement of methanol oxidation electrocatalysis at low and high overpotentials

    International Nuclear Information System (INIS)

    Teliz, E.; Díaz, V.; Zinola, C.F.

    2014-01-01

    Highlights: • EIS results depicted two time constants. • Between 0.40 and 0.55 V methanol dehydrogenation was the rds. • Above 0.55 V CO-type and formiate adsorbed intermediates oxidation was the rds. • PtRuMo/C showed the highest tolerance to methanol intermediates. - Abstract: The preparation of new surfaces for anodic processes in methanol/air fuel cells has gained major attention due to the efficiency loss in the course of long-time operations. This paper proposes the use of electrochemical activated Pt/C, PtMo/C, PtRu/C, PtRuMo/C electrodes to study changes in the electrocatalytic behaviour of methanol oxidation under the potential ranges of interest for fuel cells. Electrochemical impedance spectroscopy together with polarization curves are applied to typify the interfacial behaviour of methanol electrooxidation on these activated electrodes. Impedance information discloses that these catalysts allow two distinct responses, i.e. methanol dehydrogenation as rate determining step in the low potential region (0.400-0.550 V), whereas a surface oxidation of adsorbed intermediates determining the process at high potentials (larger than 0.550 V). Moreover, we found new effects caused by molybdenum or ruthenium inclusions that are explained using the true Tafel slopes, that is, those corrected for mass transport. Thus, Tafel slopes of 0.060 V decade −1 are found for all carbon supported electrodes except for PtRu/C where the first electrochemical step as rate determining explained the experimental 0.120 V decade −1 value. The catalytic performance of carbon supported PtRuMo/C towards methanol electrooxidation showed the highest tolerance upon methanol intermediates formation

  1. Synthesis and Characterization of 1D Ceria Nanomaterials for CO Oxidation and Steam Reforming of Methanol

    Directory of Open Access Journals (Sweden)

    Sujan Chowdhury

    2011-01-01

    Full Text Available Novel one-dimensional (1D ceria nanostructure has been investigated as a promising and practical approach for the reforming of methanol reaction. Size and shape of the ceria nanomaterials are directly involved with the catalytic activities. Several general synthesis routes as including soft and hard template-assemble phenomenon for the preparation of 1D cerium oxide are discussed. This preparation phenomenon is consisting with low cost and ecofriendly. Nanometer-sized 1D structure provides a high-surface area that can interact with methanol and carbon-monoxide reaction. Overall, nanometer-sized structure provides desirable properties, such as easy recovery and regeneration. As a result, the use of 1D cerium has been suitable for catalytic application of reforming. In this paper, we describe the 1D cerium oxide syntheses route and then summarize their properties in the field of CO oxidation and steam reforming of methanol approach.

  2. Experimental and simulation analysis of hydrogen production by partial oxidation of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Sikander, U. [National Univ. of Science and Technology, Islamabad (Pakistan)

    2014-10-15

    Partial oxidation of methanol is the only self-sustaining process for onboard production of hydrogen. For this a fixed bed catalytic reactor is designed, based on heterogeneous catalytic reaction. To develop an optimized process, simulation is carried out using ASPEN HYSYS v 7.1. Reaction kinetics is developed on the basis of Langmuir Hinshel wood model. 45:55:5 of CuO: ZnO: Al/sub 2/O/sub 3/ is used as a catalyst. Simulation results are studied in detail to understand the phenomenon of partial oxidation of methanol inside the reactor. An experimental rig is developed for hydrogen production through partial oxidation of methanol. Results obtained from process simulation and experimental work; are compared with each other. (author)

  3. The Effect of PtRuIr Nanoparticle Crystallinity in Electrocatalytic Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Vladimir Linkov

    2013-04-01

    Full Text Available Two structural forms of a ternary alloy PtRuIr/C catalyst, one amorphous and one highly crystalline, were synthesized and compared to determine the effect of their respective structures on their activity and stability as anodic catalysts in methanol oxidation. Characterization techniques included TEM, XRD, and EDX. Electrochemical analysis using a glassy carbon disk electrode for cyclic voltammogram and chronoamperometry were tested in a solution of 0.5 mol L−1 CH3OH and 0.5 mol L−1 H2SO4. Amorphous PtRuIr/C catalyst was found to have a larger electrochemical surface area, while the crystalline PtRuIr/C catalyst had both a higher activity in methanol oxidation and increased CO poisoning rate. Crystallinity of the active alloy nanoparticles has a big impact on both methanol oxidation activity and in the CO poisoning rate.

  4. Methanol oxidation at platinum electrodes in acid solution: comparison between model and real catalysts

    Directory of Open Access Journals (Sweden)

    A. V. TRIPKOVIC

    2006-12-01

    Full Text Available Methanol oxidation in acid solution was studied at platinum single crystals, Pt(hkl, as the model catalyst, and at nanostructural platinum supported on high surface area carbon, Pt/C, as the real catalyst. The linear extrapolation method was used to determine the beginning of hydroxyl anion adsorption. Structural sensitivity of the adsorption was proved and a correlation with the onset of the methanol oxidation current was established at all catalysts. Bisulfate and chloride anions were found to decrease the methanol oxidation rate, but probably did not influence the reaction parth. The specific activity for the reaction increased in the sequence Pt(110 < Pt/C < Pt(111, suggesting that the activity of the supported Pt catalyst can be correlated with the activities of the dominating crystal planes on its surface.

  5. Advantages of electrodes with dendrimer-protected platinum nanoparticles and carbon nanotubes for electrochemical methanol oxidation.

    Science.gov (United States)

    Siriviriyanun, Ampornphan; Imae, Toyoko

    2013-04-14

    Electrochemical sensors consisting of electrodes loaded with carbon nanotubes and Pt nanoparticles (PtNPs) protected by dendrimers have been developed using a facile method to fabricate them on two types of disposable electrochemical printed chips with a screen-printed circular gold or a screen-printed circular glassy carbon working electrode. The electrochemical performance of these sensors in the oxidation of methanol was investigated by cyclic voltammetry. It was revealed that such sensors possess stable durability and high electrocatalytic activity: the potential and the current density of an anodic peak in the oxidation of methanol increased with increasing content of PtNPs on the electrodes, indicating the promotion of electrocatalytic activity in relation to the amount of catalyst. The low anodic potential suggests the easy electrochemical reaction, and the high catalyst tolerance supports the almost complete oxidation of methanol to carbon dioxide. The significant performance of these sensors in the detection of methanol oxidation comes from the high electrocatalytic ability of PtNPs, excellent energy transfer of carbon nanotubes and the remarkable ability of dendrimers to act as binders. Thus these systems are effective for a wide range of applications as chemical, biomedical, energy and environmental sensors and as units of direct methanol fuel cells.

  6. In Situ Raman Spectroscopy of Supported Chromium Oxide Catalysts: Reactivity Studies with Methanol and Butane

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Wachs, I.E.

    1996-01-01

    The interactions of methanol and butane with supported chromium oxide catalysts under oxidizing and reducing conditions were studied by in situ Raman spectroscopy as a function of the specific oxide support (Al2O3, ZrO2, TiO2, SiO2, Nb2O5, 3% SiO2/TiO2, 3% TiO2/SiO2, and a physical mixture of SiO2

  7. Enhancement of the catalytic activity of Pt nanoparticles toward methanol electro-oxidation using doped-SnO2 supporting materials

    Science.gov (United States)

    Merati, Zohreh; Basiri Parsa, Jalal

    2018-03-01

    Catalyst supports play important role in governing overall catalyst activity and durability. In this study metal oxides (SnO2, Sb and Nb doped SnO2) were electrochemically deposited on titanium substrate (Ti) as a new support material for Pt catalyst in order to electro-oxidation of methanol. Afterward platinum nanoparticles were deposited on metal oxide film via electro reduction of platinum salt in an acidic solution. The surface morphology of modified electrodes were evaluated by field-emission scanning electron microscopy (FESEM) and energy dispersive X-ray analysis (EDX) techniques. The electro-catalytic activities of prepared electrodes for methanol oxidation reaction (MOR) and oxidation of carbon monoxide (CO) absorbed on Pt was considered with cyclic voltammetry. The results showed high catalytic activity for Pt/Nb-SnO2/Ti electrode. The electrochemical surface area (ECSA) of a platinum electro-catalyst was determined by hydrogen adsorption. Pt/Nb-SnO2/Ti electrode has highest ECSA compared to other electrode resulting in high activity toward methanol electro-oxidation and CO stripping experiments. The doping of SnO2 with Sb and Nb improved ECSA and MOR activity, which act as electronic donors to increase electronic conductivity.

  8. Propionate oxidation by and methanol inhibition of anaerobic ammonium-oxidizing bacteria.

    Science.gov (United States)

    Güven, Didem; Dapena, Ana; Kartal, Boran; Schmid, Markus C; Maas, Bart; van de Pas-Schoonen, Katinka; Sozen, Seval; Mendez, Ramon; Op den Camp, Huub J M; Jetten, Mike S M; Strous, Marc; Schmidt, Ingo

    2005-02-01

    Anaerobic ammonium oxidation (anammox) is a recently discovered microbial pathway and a cost-effective way to remove ammonium from wastewater. Anammox bacteria have been described as obligate chemolithoautotrophs. However, many chemolithoautotrophs (i.e., nitrifiers) can use organic compounds as a supplementary carbon source. In this study, the effect of organic compounds on anammox bacteria was investigated. It was shown that alcohols inhibited anammox bacteria, while organic acids were converted by them. Methanol was the most potent inhibitor, leading to complete and irreversible loss of activity at concentrations as low as 0.5 mM. Of the organic acids acetate and propionate, propionate was consumed at a higher rate (0.8 nmol min(-1) mg of protein(-1)) by Percoll-purified anammox cells. Glucose, formate, and alanine had no effect on the anammox process. It was shown that propionate was oxidized mainly to CO(2), with nitrate and/or nitrite as the electron acceptor. The anammox bacteria carried out propionate oxidation simultaneously with anaerobic ammonium oxidation. In an anammox enrichment culture fed with propionate for 150 days, the relative amounts of anammox cells and denitrifiers did not change significantly over time, indicating that anammox bacteria could compete successfully with heterotrophic denitrifiers for propionate. In conclusion, this study shows that anammox bacteria have a more versatile metabolism than previously assumed.

  9. O2-enhanced methanol oxidation reaction at novel Pt-Ru-C co-sputtered electrodes

    International Nuclear Information System (INIS)

    Umeda, Minoru; Matsumoto, Yosuke; Inoue, Mitsuhiro; Shironita, Sayoko

    2013-01-01

    Highlights: ► Novel Pt-Ru-C electrodes were prepared by a co-sputtering technique. ► Co-sputtered electrodes with C result in highly efficient O 2 -enhanced methanol oxidation. ► Pt–Ru-alloy-based co-sputtered electrode induces a negative onset potential of methanol oxidation. ► The Pt-Ru-C electrodes allow a negative onset potential of O 2 -enhanced methanol oxidation. ► The optimum atomic ratios of Pt-Ru-C are Pt: 0.24–0.80, Ru: 0.14–0.61, C: 0.06–0.37. -- Abstract: A Pt-Ru-C electrode has been developed using a co-sputtering technique for use as the anode catalyst of a mixed-reactant fuel cell. The physical and electrochemical characteristics of the electrodes demonstrate that co-sputtered Pt and Ru form a Pt–Ru alloy. The crystallite sizes of the catalysts investigated in this study are reduced by the addition of C to the Pt–Ru alloy. Cu stripping voltammograms suggest that the sputtering of C and the formation of the Pt–Ru alloy synergically increase the electrochemical surface area of the electrodes. The methanol oxidation performances of the prepared electrodes were evaluated in N 2 and O 2 atmospheres; the Pt-Ru-C electrodes achieve an O 2 -induced negative shift in the onset potential of the methanol oxidation (E onset ) and enhance the methanol oxidation current density in the O 2 atmosphere. The mechanism of O 2 -enhanced methanol oxidation with a negative E onset at the Pt-Ru-C electrodes is attributed to a change in the electronic structure of Pt due to the formation of Pt–Ru alloy and the generation of O-based adsorption species by the reduction of O 2 . Finally, the composition of the Pt-Ru-C electrode for the O 2 -enhanced methanol oxidation with a negative E onset was found to be optimal at an atomic ratio of Pt: 0.24–0.80, Ru: 0.14–0.61, and C: 0.06–0.37

  10. Preparation of silver nanoparticles/graphene nanosheets as a catalyst for electrochemical oxidation of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Han, Kun; Miao, Peng; Tang, Yuguo, E-mail: tangyg@sibet.ac.cn [Suzhou Institute of Biomedical Engineering and Technology, Chinese Academy of Sciences, Suzhou 215163 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Tong, Hui; Zhu, Xiaoli [Laboratory of Biosensing Technology, School of Life Sciences, Shanghai University, Shanghai 200444 (China); Liu, Tao; Cheng, Wenbo [Suzhou Institute of Biomedical Engineering and Technology, Chinese Academy of Sciences, Suzhou 215163 (China)

    2014-02-03

    In this report, silver nanoparticles (AgNPs) decorated graphene nanosheets have been prepared based on the reduction of Ag ions by hydroquinone, and their catalytic performance towards the electrochemical oxidation of methanol is investigated. The synthesis of the nano-composite is confirmed by transmission electron microscope measurements and UV-vis absorption spectra. Excellent electrocatalytic performance of the material is demonstrated by cyclic voltammograms. This material also contributes to the low peak potential of methanol oxidation compared with most of the other materials.

  11. Excellent performance of Pt-C/TiO2 for methanol oxidation: Contribution of mesopores and partially coated carbon

    Science.gov (United States)

    Wu, Xinbing; Zhuang, Wei; Lu, Linghong; Li, Licheng; Zhu, Jiahua; Mu, Liwen; Li, Wei; Zhu, Yudan; Lu, Xiaohua

    2017-12-01

    Partial deposition of carbon onto mesoporous TiO2 (C/TiO2) were prepared as supporting substrate for Pt catalyst development. Carbon deposition is achieved by in-situ carbonization of furfuryl alcohol. The hybrid catalysts were characterized by XRD, Raman, SEM and TEM and exhibited outstanding catalytic activity and stability in methanol oxidation reaction. The heterogeneous carbon coated on mesoporous TiO2 fibers provided excellent electrical conductivity and strong interfacial interaction between TiO2 support and Pt metal nanoparticles. Methanol oxidation reaction results showed that the activity of Pt-C/TiO2 is 3.0 and 1.5 times higher than that of Pt-TiO2 and Pt-C, respectively. In addition, the Pt-C/TiO2 exhibited a 6.7 times enhanced stability compared with Pt-C after 2000 cycles. The synergistic effect of C/TiO2 is responsible for the enhanced activity of Pt-C/TiO2, and its excellent durability could be ascribed to the strong interfacial interaction between Pt nanoparticles and C/TiO2 support.

  12. Oxidation of methanol to formaldehyde over a series of Fe1-xAlx-V-oxide catalysts

    DEFF Research Database (Denmark)

    Häggblad, Robert; Wagner, Jakob Birkedal; Hansen, Staffan

    2008-01-01

    A series of triclinic Fe1−xAlxVO4 phases with 0x1 were prepared and used in the oxidation of methanol to formaldehyde. The activity measurements revealed that both the activity and especially the selectivity to formaldehyde increased with time of operation for at least 16 h, indicating...... restructuring of the catalysts. Characterisation of the catalysts with XRD, XANES, and electron microscopy after use in methanol oxidation showed that the stability of the bulk phases improved when Al was substituted for Fe in the structure. XRD and XANES of the used FeVO4 showed that it partly transformed...... in methanol oxidation revealed no significant change in the metal composition, in good agreement with the corresponding bulk values, except for a lower Fe value. Steady-state activity data showed a modest increase in specific activity with the Al content, whereas the selectivity to formaldehyde was about 90...

  13. Characterization of Pt-Pd/C Electrocatalyst for Methanol Oxidation in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    S. S. Mahapatra

    2011-01-01

    Full Text Available The Pt-Pd/C electrocatalyst was synthesized on graphite substrate by the electrochemical codeposition technique. The physicochemical characterization of the catalyst was done by SEM, XRD, and EDX. The electrochemical characterization of the Pt-Pd/C catalyst for methanol electro-oxidation was studied over a range of NaOH and methanol concentrations using cyclic voltammetry, quasisteady-state polarization, chronoamperometry, and electrochemical impedance spectroscopy. The activity of methanol oxidation increased with pH due to better OH species coverage on the electrode surface. At methanol concentration (>1.0 M, there is no change in the oxidation peak current density because of excess methanol at the electrode surface and/or depletion of OH− at the electrode surface. The Pt-Pd/C catalyst shows good stability and the low value of Tafel slope and charge transfer resistance. The enhanced electrocatalytic activity of the electrodes is ascribed to the synergistic effect of higher electrochemical surface area, preferred OH− adsorption, and ad-atom contribution on the alloyed surface.

  14. Effect of methanolic extract of Asparagus racemosus Willd. on lipopolysaccharide induced-oxidative stress in rats.

    Science.gov (United States)

    Ahmad, Mohammad Parwez; Hussain, Arshad; Siddiqui, Hefazat Hussain; Wahab, Shadma; Adak, Manoranjan

    2015-03-01

    Lipopolysaccharide (LPS) induced oxidative stress and impairment of normal physiological function generally categorized by increased anxiety and reduced mobility. Therefore, the present study was to find out the effect Methanolic extract of Asparagus racemosus (MEAR ) in lipopolysaccharide (LPS)-induced oxidative stress in rats . LPS-induced oxidative stress in rats was measured by locomotor activity by photoactometer test, anxiety with elevated plus maze test and also studied the oxidative stress markers, nitric oxide and cytokines. The obtained data shows that LPS markedly exhausted (pAsparagus racemosus Willd. is a functionally newer type of cerebroprotective agent.

  15. Synthesis of Pt-Ru PSB-Py catalysis by {gamma}-irradiation and their electrocatalytic efficiency for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Jung Ah; Sim, Kwang Sik; Choi, Seong Ho [Hannam University, Daejeon (Korea, Republic of); Jung, Sung Hee [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2009-09-15

    We report here that deposition of Pt-Ru catalysis on the surface of core-shell conductive balls by radiation-chemical reduction of Pt and Ru ions, in order to use as catalysis in a fuel cell. The poly(styrene-co-4-vinylphenylboronic acid)-pyrrole (PSB-Py) with core-shell structure was obtained by in situ polymerization of pyrrole in the presence of the poly(styrene-co-4-vinylphenylboronic acid) (PSB). Subsequently, Pt-Ru catalysis were deposited onto PSB-Py ball by {gamma}-irradiation, in the presence/absence of poly(vinypyrolidone) (PVP) to prepare electrocatalysis for a fuel cell. The catalytic efficiency of Pt-Ru PSB-Py catalyst was examined for carbon monoxide (CO) stripping and methanol oxidation.

  16. Synthesis of Pt-Ru PSB-Py catalysis by γ-irradiation and their electrocatalytic efficiency for methanol oxidation

    International Nuclear Information System (INIS)

    Yoon, Jung Ah; Sim, Kwang Sik; Choi, Seong Ho; Jung, Sung Hee

    2009-01-01

    We report here that deposition of Pt-Ru catalysis on the surface of core-shell conductive balls by radiation-chemical reduction of Pt and Ru ions, in order to use as catalysis in a fuel cell. The poly(styrene-co-4-vinylphenylboronic acid)-pyrrole (PSB-Py) with core-shell structure was obtained by in situ polymerization of pyrrole in the presence of the poly(styrene-co-4-vinylphenylboronic acid) (PSB). Subsequently, Pt-Ru catalysis were deposited onto PSB-Py ball by γ-irradiation, in the presence/absence of poly(vinypyrolidone) (PVP) to prepare electrocatalysis for a fuel cell. The catalytic efficiency of Pt-Ru PSB-Py catalyst was examined for carbon monoxide (CO) stripping and methanol oxidation

  17. Direct synthesis of few-layer graphene supported platinum nanocatalyst for methanol oxidation

    Science.gov (United States)

    Tan, Hong; Ma, Xiaohui; Sheng, Leimei; An, Kang; Yu, Liming; Zhao, Hongbin; Xu, Jiaqiang; Ren, Wei; Zhao, Xinluo

    2014-11-01

    High-crystalline few-layer graphene supported Pt nanoparticles have been synthesized by arc discharge evaporation of carbon electrodes containing Pt element. A high-temperature treatment under hydrogen atmosphere has been carried out to obtain a new type of Pt/graphene catalyst for methanol oxidation in direct methanol fuel cell. The morphology and structure characterizations of as-grown few-layer graphene supported Pt nanoparticles and Pt/graphene catalysts have been studied by Raman spectroscopy, scanning electron microscopy with energy-dispersive spectroscopy, and high-resolution transmission electron microscopy. Cyclic voltammograms and chronoamperometric curves show that our present Pt/graphene catalysts have larger current density for methanol oxidation, higher tolerance to carbon monoxide poisoning, and better stability during the operating procedure, compared to commercial Pt/C catalysts.

  18. Optimum Pt and Ru atomic composition of carbon-supported Pt-Ru alloy electrocatalyst for methanol oxidation studied by the polygonal barrel-sputtering method

    International Nuclear Information System (INIS)

    Hiromi, Chikako; Inoue, Mitsuhiro; Taguchi, Akira; Abe, Takayuki

    2011-01-01

    Highlights: → The sputtered Pt and Ru form the Pt-Ru alloy nanoparticles on the carbon support. → The deposited Pt-Ru alloy particles have uniform Pt:Ru atomic ratios. → The optimum Pt:Ru ratio of the Pt-Ru/C for methanol oxidation is 58:42 at.% at 25 deg. C. → The optimum Pt:Ru ratio of 58:42 shifts to 50:50 at.% at 40 and 60 deg. C. → The polygonal barrel-sputtering method is useful to prepare the DMFC anode catalyst. - Abstract: The optimum Pt and Ru atomic composition of a carbon-supported Pt-Ru alloy (Pt-Ru/C) used in a practical direct methanol fuel cell (DMFC) anode was investigated. The samples were prepared by the polygonal barrel-sputtering method. Based on the physical properties of the prepared Pt-Ru/C samples, the Pt-Ru alloy was found to be deposited on a carbon support. The microscopic characterization showed that the deposited alloy forms nanoparticles, of which the atomic ratios of Pt and Ru (Pt:Ru ratios) are uniform and are in accordance with the overall Pt:Ru ratios of the samples. The formation of the Pt-Ru alloy is also supported by the electrochemical characterization. Based on these results, methanol oxidation on the Pt-Ru/C samples was measured by cyclic voltammetry and chronoamperometry. The results indicated that the methanol oxidation activities of the prepared samples depended on the Pt:Ru ratios, of which the optimum Pt:Ru ratio is 58:42 at.% at 25 deg. C and 50:50 at.% at 40 and 60 deg. C. This temperature dependence of the optimum Pt:Ru ratio is well explained by the relationship between the methanol oxidation reaction process and the temperature, which is reflected in the rate-determining steps considered from the activation energies. It should be noted that at 25-60 deg. C, the Pt-Ru/C with Pt:Ru = 50:50 at.% prepared by our sputtering method has the higher methanol oxidation activity than that of a commercially available sample with the identical overall Pt:Ru ratio. Consequently, the polygonal barrel-sputtering method

  19. Selectivity and Activity of Iron Molybdate Catalysts in Oxidation of Methanol

    Directory of Open Access Journals (Sweden)

    Khalid Khazzal Hummadi

    2009-06-01

    Full Text Available The selectivity and activity of iron molybdate catalysts prepared by different methods are compared with those of a commercial catalyst in the oxidation of methanol to formaldehyde in a continuous tubular bed reactor at 200-350 oC (473-623 oK, 10 atm (1013 kPa, with a methanol-oxygen mixture fixed at 5.5% by volume methanol: air ratio. The iron(III molybdate catalyst prepared by co-precipitation and filtration had a selectivity towards formaldehyde in methanol oxidation comparable with a commercial catalyst; maximum selectivity (82.3% was obtained at 573oK when the conversion was 59.7%. Catalysts prepared by reacting iron (III and molybdate by kneading or precipitation followed by evaporation, omitting a filtration stage, were less active and less selective. The selectivity-activity relationships of these catalysts as a function of temperature were discussed in relation to the method of preparation, surface areas and composition. By combing this catalytic data with data from the patent literature we demonstrate a synergy between iron and molybdenum in regard to methanol oxidation to formaldehyde; the optimum composition corresponded to an iron mole fraction 0.2-0.3. The selectivity to formaldehyde was practically constant up to an iron mole fraction 0.3 and then decreased at higher iron concentrations. The iron component can be regarded as the activity promoter. The iron molybdate catalysts can thus be related to other two-component MoO3-based selective oxidation catalysts, e.g. bismuth and cobalt molybdates. The iron oxide functions as a relatively basic oxide abstracting, in the rate-controlling step, a proton from the methyl of a bound methoxy group of chemisorbed methanol. It was proposed that a crucial feature of the sought after iron(III molybdate catalyst is the presence of -O-Mo-O-Fe-O-Mo-O- groups as found in the compound Fe2(MoO43 and for Fe3+ well dispersed in MoO3 generally. At the higher iron(III concentrations the loss of

  20. Nitrogen Doped Ordered Mesoporous Carbon as Support of PtRu Nanoparticles for Methanol Electro-Oxidation

    Directory of Open Access Journals (Sweden)

    David Sebastián

    2018-04-01

    Full Text Available The low oxidation kinetics of alcohols and the need for expensive platinum group metals are still some of the main drawbacks for the commercialization of energy efficient direct alcohol fuel cells. In this work, we investigate the influence of nitrogen doping of ordered mesoporous carbon (CMK as support on the electrochemical activity of PtRu nanoparticles. Nitrogen doping procedures involve the utilization of pyrrole as both nitrogen and carbon precursor by means of a templating method using mesoporous silica. This method allows obtaining carbon supports with up to 14 wt. % nitrogen, with an effective introduction of pyridinic, pyrrolic and quaternary nitrogen. PtRu nanoparticles were deposited by sodium formate reduction method. The presence of nitrogen mainly influences the Pt:Ru atomic ratio at the near surface, passing from 50:50 on the bare (un-doped CMK to 70:30 for the N-doped CMK catalyst. The electroactivity towards the methanol oxidation reaction (MOR was evaluated in acid and alkaline electrolytes. The presence of nitrogen in the support favors a faster oxidation of methanol due to the enrichment of Pt at the near surface together with an increase of the intrinsic activity of PtRu nanoparticles.

  1. Synthesis, characterization and catalytic activity toward methanol oxidation of electrocatalyst Pt4+-NH2-MCM-41

    International Nuclear Information System (INIS)

    Zheng Huajun; Chen Zuo; Wang Limin; Ma Chun’an

    2012-01-01

    Highlights: ► It was first confirmed that the Pt 4+ exhibited a good electro-catalytic property for methanol oxidation. ► The Pt 4+ perfectly distributed on a mesoporous molecular sieve matrix synthesis by a facile method. ► The good performance of catalyst resistance to poisoning because of a homogeneous distribution of Pt 4+ and large specific surface area. - Abstract: Mesoporous material with functional group (Pt 4+ -NH 2 -MCM-41) was prepared by grafting aminopropyl group and adsorbing platinum ions on the surface of the commercial molecular sieve (MCM-41). The characterization carried out by X-ray photoelectron spectroscopy, X-ray diffraction, and N 2 adsorption–desorption measurement pointed out that Pt was adsorbed on the NH 2 -MCM-41 surface as the oxidation state (Pt 4+ ) and the surface area of Pt 4+ -NH 2 -MCM-41 was up to 564 m 2 /g. Transmission electron microscopy and elemental mapping indicated a homogeneous distribution of Pt 4+ throughout all surface of the mesoporous materials. Electro-catalytic properties of methanol oxidation on the Pt 4+ -NH 2 -MCM-41 electrode were investigated with electrochemical methods. The results showed that the Pt 4+ -NH 2 -MCM-41 electrode exhibited catalytic activity in the methanol electro-oxidation with the apparent activation energy being 49.29 kJ/mol, and the control step of methanol electro-oxidation was the mass transfer process. It is first proved that platinum ions had good electro-catalytic property for methanol oxidation and provided a new idea for developing electrode materials in future.

  2. Using Photocatalytic Oxidation and Analytic Techniques to Remediate Lab Wastewater Containing Methanol

    Science.gov (United States)

    Xiong, Qing; Luo, Mingliang; Bao, Xiaoming; Deng, Yurong; Qin, Song; Pu, Xuemei

    2018-01-01

    This experiment is dedicated to second-year and above undergraduates who are in their experimental session of the analytical chemistry course. Grouped students are required to use a TiO[subscript 2] photocatalytic oxidation process to treat the methanol-containing wastewater that resulted from their previous HPLC experiments. Students learn to…

  3. Inhibition of iNOS and DNA Oxidation by Methanol Extract of ...

    African Journals Online (AJOL)

    Purpose: To investigate the antioxidant properties of the methanol extract of S. tenuifolia as well as its effect on inducible nitric oxide synthase (iNOS) and cycleooxygenase-2 (COX-2) expression in lipopolysaccharides (LPS)-induced cell damage in macrophage cells. Methods: The antioxidant activities of the plant extract ...

  4. Atomic platinum layer coated titanium copper nitride supported on carbon nanotubes for the methanol oxidation reaction

    CSIR Research Space (South Africa)

    Zheng, Y

    2017-09-01

    Full Text Available measurements. The results confirm the core-shell structure of the prepared TiN@Pt/CNTs catalyst. More importantly, the catalyst exhibits superb mass activity and durability for the methanol oxidation reaction (MOR) than that of the commercial JM Pt/C catalyst...

  5. A Non-Heme Iron Photocatalyst for Light-Driven Aerobic Oxidation of Methanol

    NARCIS (Netherlands)

    Chen, Juan; Stepanovic, Stepan; Draksharapu, Apparao; Gruden, Maja; Browne, Wesley R

    2018-01-01

    Non-heme (L)FeIIIand (L)FeIII-O-FeIII(L) complexes (L=1,1-di(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)ethan-1-amine) underwent reduction under irradiation to the FeIIstate with concomitant oxidation of methanol to methanal, without the need for a secondary photosensitizer. Spectroscopic and DFT

  6. Mesoporous Pt and Pt/Ru alloy electrocatalysts for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Franceschini, Esteban A. [Grupo de Celdas de Combustible, Departamento de Fisica de la Materia Condensada, Centro Atomico Constituyentes, CNEA. Av. General Paz 1499 (1650), San Martin, Buenos Aires (Argentina); Planes, Gabriel A. [Departamento de Quimica, Facultad de Ciencias Exactas, Fisicoquimicas y Naturales, Universidad Nacional de Rio Cuarto, Agencia Postal No 3, 5800, Rio Cuarto (Argentina); Williams, Federico J. [Departamento de Quimica Inorganica, Analitica y Quimica-Fisica, INQUIMAE CONICET, Facultad Ciencias Exactas y Naturales, Pabellon 2, Ciudad Universitaria, Buenos Aires (Argentina); Soler-Illia, Galo J.A.A. [Gerencia de Quimica, Centro Atomico Constituyentes, CNEA. Av. General Paz 1499 (1650), San Martin, Buenos Aires (Argentina); Corti, Horacio R. [Grupo de Celdas de Combustible, Departamento de Fisica de la Materia Condensada, Centro Atomico Constituyentes, CNEA. Av. General Paz 1499 (1650), San Martin, Buenos Aires (Argentina); Departamento de Quimica Inorganica, Analitica y Quimica-Fisica, INQUIMAE CONICET, Facultad Ciencias Exactas y Naturales, Pabellon 2, Ciudad Universitaria, Buenos Aires (Argentina)

    2011-02-15

    Mesoporous Pt and Pt/Ru catalysts with 2D-hexagonal mesostructure were synthesized using a triblock poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) copolymer (Pluronic F127 {sup registered}) template, on a gold support. Large electrochemical surface areas were observed for the catalysts prepared at high overpotentials. Compared to the Pt catalyst, the Pt/Ru alloy containing 3 at% of Ru exhibited lower onset potential and more than three times the limit mass activity for methanol oxidation. This behavior is assigned to the larger pore size of the mesoporous Pt and Pt/Ru catalysts obtained with this template that seems to improve the methanol accessibility to the active sites compared to those obtained using lyotropic liquid crystals. (author)

  7. Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

    Science.gov (United States)

    Shan, Junjun; Li, Mengwei; Allard, Lawrence F.; Lee, Sungsik; Flytzani-Stephanopoulos, Maria

    2017-11-01

    An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid, which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. We find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolite-supported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. We anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful

  8. Kinetic study of methanol oxidation on carbon-supported PtRu electrocatalyst

    International Nuclear Information System (INIS)

    Gojkovic, S.Lj.; Vidakovic, T.R.; Durovic, D.R.

    2003-01-01

    Methanol electrooxidation was investigated on the carbon-supported PtRu electrocatalyst (1:1 atomic ratio) in acid media. X-ray diffraction measurement indicated alloying of Pt and Ru. Cyclic voltammetry of the sample reflects the amount of Ru in the catalyst and its ability to adsorb OH radicals. Tafel plots for the oxidation of 0.02-3 M methanol in the solutions containing 0.05-1 M HClO 4 and in the temperature range 27-40 deg. C showed reasonably well-defined linear region with the slope of about 115 mV dec -1 at the low currents, irrespective of the experimental conditions employed. Reaction order with respect to methanol was found to be 0.5. A correlation between methanol oxidation rate and pseudocapacitive current of OH adsorption on Ru sites was established. It was proposed that bifunctional mechanism is operative with the reaction between methanol residues adsorbed on Pt sites and OH radicals adsorbed on Ru sites as the rate-determining step

  9. Methanol electro-oxidation on Pt/C modified by polyaniline nanofibers for DMFC applications

    Energy Technology Data Exchange (ETDEWEB)

    Zhiani, Mohammad; Rezaei, Behzad; Jalili, Jalal [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran)

    2010-09-15

    In the present study, in order to achieve an inexpensive tolerable anode catalyst for direct methanol fuel cell applications, a composite of polyaniline nanofibers and Pt/C nano-particles, identified by PANI/Pt/C, was prepared by in-situ electropolymerization of aniline and trifluoromethane sulfonic acid on glassy carbon. The effect of synthesized PANI nanofibers in methanol electrooxidation reaction was compared by bare Pt/C by different electrochemical methods such as; cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and chronoamperometry. Scanning electron microscopy (SEM) was also employed to morphological study of the modified catalyst layer. The test results reveal that introduction of PANI nanofibers within catalyst layer improves the catalyst activity in methanol oxidation, hinders and prevents catalyst from more poisoning by intermediate products of methanol oxidation and improves the mechanical properties of the catalyst layer. SEM images also indicate that PANI nanofibers placed between platinum particles and anchor platinum particles and alleviate the Pt migration during methanol electrooxidation. (author)

  10. Promotion effect of manganese oxide on the electrocatalytic activity of Pt/C for methanol oxidation in acid medium

    International Nuclear Information System (INIS)

    Abdel Hameed, R.M.; Fetohi, Amani E.; Amin, R.S.; El-Khatib, K.M.

    2015-01-01

    Graphical abstract: Physical and electrochemical properties of Pt/C, Pt–MnO_2/C-1 and Pt–MnO_2/C-2 electrocatalysts. - Highlights: • Adding MnO_2 to Pt/C improved the dispersion of Pt nanoparticles. • The existence of MnO_2 improved the kinetics of methanol oxidation reaction. • R_c_t value of Pt–MnO_2/C was about 10 times as low as that at Pt/C. • The removal of CO_a_d_s poisoning species was facilitated at Pt–MnO_2/C. - Abstract: The modification of Pt/C by incorporating metal oxides for electrocatalytic oxidation of methanol has gained major attention because of the efficiency loss during the course of long-time operation. This work describes the preparation of Pt–MnO_2/C electrocatalysts through a chemical route using ethylene glycol or a mixture of ethylene glycol and sodium borohydride as a reducing agent. The crystallite structure and particle size of synthesized electrocatalysts are determined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The addition of MnO_2 improves the dispersion of Pt nanoparticles. The electrocatalytic activity of Pt–MnO_2/C towards methanol oxidation in H_2SO_4 solution is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The onset potential value of methanol oxidation peak is negatively shifted by 169 mV when MnO_2 is introduced to Pt/C. Moreover, the charge transfer resistance value at Pt–MnO_2/C is about 10 times as low as that at Pt/C. Chronoamperometry and chronopotentiometry show that CO tolerance is greatly improved at Pt–MnO_2/C. The increased electrocatalytic activity and enhanced ability to clean platinum surface elect manganese oxide as a suitable promoter for the anode performance in direct methanol fuel cells (DMFCs).

  11. Depolymerization of organosolv lignin using doped porous metal oxides in supercritical methanol

    DEFF Research Database (Denmark)

    Warner, Genoa; Hansen, Thomas Søndergaard; Riisager, Anders

    2014-01-01

    conversion to methanol-soluble products, without char formation, were based on copper in combination with other dopants based on relatively earth-abundant metals. Nearly complete conversion of lignin to bio-oil composed of monomers and low-mass oligomers with high aromatic content was obtained in 6. h at 310......An isolated, solvent-extracted lignin from candlenut (Aleurites moluccana) biomass was subjected to catalytic depolymerization in the presence of supercritical methanol, using a range of porous metal oxides derived from hydrotalcite-like precursors. The most effective catalysts in terms of lignin...

  12. Studies of catalyst material for the electro-oxidation of methanol, ethanol, formaldehyde and formic acid

    International Nuclear Information System (INIS)

    Bajwa, S.Z.; Ahmed, R.

    2007-01-01

    Fuel cell is an electrochemical device that converts the chemical energy of reaction directly into the electrical energy. It is highly efficient and environment friendly device. Normally used fuel in fuel cells is hydrogen, but due to the convenience in handling some other liquid fuels are also used and now direct methanol fuel cells are available in the market. Rapid electro-oxidation of the fuel at the fuel cell electrode is necessary for its optimum use. In addition to the methanol, other liquid fuels can also be used in the fuel cell. In this work, cyclic voltammetric studies have been done for the electro-oxidation of the methanol, ethanol, formic acid and formaldehyde on fuel cell catalyst. Platinum electrode is characterized by the measurement of active surface area and roughness factor. Classical electrochemical equations have been employed to find out rate constants for electro-oxidation of methanol fuel and calculations have been carried out to find out thermodynamic parameters. Exchange current density has been evaluated with reference to catalyst by drawing polarization curves. (author)

  13. Methanol Electro-Oxidation on Pt-Ru Alloy Nanoparticles Supported on Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Yangchuan Xing

    2009-09-01

    Full Text Available Carbon nanotubes (CNTs have been investigated in recent years as a catalyst support for proton exchange membrane fuel cells. Improved catalyst activities were observed and attributed to metal-support interactions. We report a study on the kinetics of methanol electro-oxidation on CNT supported Pt-Ru alloy nanoparticles. Alloy catalysts with different compositions, Pt53Ru47/CNT, Pt69Ru31/CNT and Pt77Ru23/CNT, were prepared and investigated in detail. Experiments were conducted at various temperatures, electrode potentials, and methanol concentrations. It was found that the reaction order of methanol electro-oxidation on the PtRu/CNT catalysts was consistent with what has been reported for PtRu alloys with a value of 0.5 in methanol concentrations. However, the electro-oxidation reaction on the PtRu/CNT catalysts displayed much lower activation energies than that on the Pt-Ru alloy catalysts unsupported or supported on carbon black (PtRu/CB. This study provides an overall kinetic evaluation of the PtRu/CNT catalysts and further demonstrates the beneficial role of CNTs.

  14. A p-n heterojunction of CuI/TiO2 with enhanced photoelectrocatalytic activity for methanol electro-oxidation

    International Nuclear Information System (INIS)

    Sun, Mingjuan; Hu, Jiayue; Zhai, Chunyang; Zhu, Mingshan; Pan, Jianguo

    2017-01-01

    Highlights: •A p-n heterojunction of CuI/TiO 2 is constructed. •CuI/TiO 2 is used as the support for depositing Pt nanoparticles. •Enhanced catalytic activity of MOR by using Pt-CuI/TiO 2 under light irradiation. •Improved charger separation contributes to enhanced photoelectrocatalytic activity. -- Abstract: In this paper, a p-n heterojunction including p-type CuI and n-type TiO 2 is first time constructed to be the support for the deposition of Pt. The as-prepared Pt-CuI/TiO 2 modified electrode is studied for the electrocatalytic oxidation of methanol both in dark and under light illumination. Compare to traditional electrocatalytic oxidation, the electrocatalytic activity of Pt-CuI/TiO 2 for methanol oxidation is improved with 4.0 times upon light illumination. Moreover, compare to bare CuI and TiO 2 upon light illumination, the heterostructure of CuI/TiO 2 displays 4.3 and 9.1 times enhanced electrocatalytic activity for methanol oxidation, respectively. The synergistic effects of photocatalysis and electrocatalysis as well as the effective charge transport in the p-n heterojunction of Pt-CuI/TiO 2 contribute such big enhancement. The present studies indicate that the constructing of p-n heterojunction provides more insights in the fields of photoelectrochemical and photo–assisted fuel cell system.

  15. Electrodeposition of Pt-Ru nanoparticles on fibrous carbon substrates in the presence of nonionic surfactant: Application for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Alex; Gyenge, Elod L.; Oloman, Colin W. [Department of Chemical and Biological Engineering, University of British Columbia, 2360 East Mall, Vancouver, BC (Canada)

    2006-07-28

    Liquid crystalline and micellar aqueous solutions of the nonionic surfactant Triton X-100 were used to direct the electrodeposition of Pt-Ru nanoparticles onto graphite felts, which were investigated as novel anodes for the direct methanol fuel cell. The effects of surfactant concentration, current density and deposition time in the preparation of these three-dimensional electrodes were studied in a factorial experiment and the electrodes were characterized by SEM and ICP-AES. Cyclic voltammetry, chronoamperometry and chronopotentiometry were carried out to assess the activity of the catalyzed felts for methanol oxidation. The presence of Triton X-100 (40-60wt.%) coupled with an acidic plating solution were essential for the efficient co-electrodeposition of Ru in the presence of Pt to yield approximately a 1:1 Pt:Ru atomic ratio in the deposit. The highest mass specific activity, 24Ag{sup -1} at 298K (determined by chronoamperometry after 180s at 0V versus Hg/Hg{sub 2}SO{sub 4}, K{sub 2}SO{sub 4std}), was obtained for the Pt-Ru electrodeposited in the presence of 40wt.% Triton X-100 at 60Am{sup -2}, 298K for 90min. Surfactant mediated electrodeposition is a promising method for meso-scale (ca. 10-60nm diameter) catalyst particle preparation on three-dimensional electrodes. (author)

  16. Electrodeposition of Pt-Ru nanoparticles on fibrous carbon substrates in the presence of nonionic surfactant: Application for methanol oxidation

    International Nuclear Information System (INIS)

    Bauer, Alex; Gyenge, Elod L.; Oloman, Colin W.

    2006-01-01

    Liquid crystalline and micellar aqueous solutions of the nonionic surfactant Triton X-100 were used to direct the electrodeposition of Pt-Ru nanoparticles onto graphite felts, which were investigated as novel anodes for the direct methanol fuel cell. The effects of surfactant concentration, current density and deposition time in the preparation of these three-dimensional electrodes were studied in a factorial experiment and the electrodes were characterized by SEM and ICP-AES. Cyclic voltammetry, chronoamperometry and chronopotentiometry were carried out to assess the activity of the catalyzed felts for methanol oxidation. The presence of Triton X-100 (40-60 wt.%) coupled with an acidic plating solution were essential for the efficient co-electrodeposition of Ru in the presence of Pt to yield approximately a 1:1 Pt:Ru atomic ratio in the deposit. The highest mass specific activity, 24 A g -1 at 298 K (determined by chronoamperometry after 180 s at 0 V versus Hg/Hg 2 SO 4 , K 2 SO 4std ), was obtained for the Pt-Ru electrodeposited in the presence of 40 wt.% Triton X-100 at 60 A m -2 , 298 K for 90 min. Surfactant mediated electrodeposition is a promising method for meso-scale (ca. 10-60 nm diameter) catalyst particle preparation on three-dimensional electrodes

  17. Temperature oscillations in methanol partial oxidation reactor for the production of hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jinsu; Byeon, Jeonguk; Seo, Il Gyu; Lee, Hyun Chan; Kim, Dong Hyun; Lee, Jietae [Kyungpook National University, Daegu (Korea, Republic of)

    2013-04-15

    Methanol partial oxidation (POX) is a well-known reforming reaction for the production of hydrogen from methanol. Since POX is relatively fast and highly exothermic, this reforming method will be efficient for the fast start-up and load-following operation. However, POX generates hot spots around catalyst and even oscillations in the reactor temperature. These should be relieved for longer operations of the reactor without catalyst degradations. For this, temperature oscillations in a POX reactor are investigated experimentally. Various patterns of temperature oscillations according to feed flow rates of reactants and reactor temperatures are obtained. The bifurcation phenomena from regular oscillations to chaotic oscillations are found as the methanol flow rate increases. These experimental results can be used for theoretical analyses of oscillations and for designing safe reforming reactors.

  18. Temperature oscillations in methanol partial oxidation reactor for the production of hydrogen

    International Nuclear Information System (INIS)

    Kim, Jinsu; Byeon, Jeonguk; Seo, Il Gyu; Lee, Hyun Chan; Kim, Dong Hyun; Lee, Jietae

    2013-01-01

    Methanol partial oxidation (POX) is a well-known reforming reaction for the production of hydrogen from methanol. Since POX is relatively fast and highly exothermic, this reforming method will be efficient for the fast start-up and load-following operation. However, POX generates hot spots around catalyst and even oscillations in the reactor temperature. These should be relieved for longer operations of the reactor without catalyst degradations. For this, temperature oscillations in a POX reactor are investigated experimentally. Various patterns of temperature oscillations according to feed flow rates of reactants and reactor temperatures are obtained. The bifurcation phenomena from regular oscillations to chaotic oscillations are found as the methanol flow rate increases. These experimental results can be used for theoretical analyses of oscillations and for designing safe reforming reactors

  19. In Situ Synthesis and Characterization of Polyethyleneimine-Modified Carbon Nanotubes Supported PtRu Electrocatalyst for Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Xi Geng

    2015-01-01

    Full Text Available PtRu bimetallic nanoparticles were successfully synthesized on polyethyleneimine- (PEI- functionalized multiwalled carbon nanotubes (MWCNTs via an effective and facile polyol reduction approach. Noncovalent surface modification of MWCNTs with PEI was confirmed by FTIR and zeta potential measurements. The morphology, crystalline structure, and composition of the hybrid material were characterized by transmission electron microscopy (TEM, scanning electron microscopy (SEM, X-ray powder diffraction (XRD, and energy dispersive X-ray spectroscopy (EDX, respectively. According to SEM and TEM observations, PtRu nanoparticles with narrow size distribution were homogeneously deposited on PEI-MWCNTs. Cyclic voltammetry tests demonstrated that the as-prepared PtRu/PEI-MWCNTs nanocomposite had a large electrochemical surface area and exhibited enhanced electrocatalytic activity towards methanol oxidation in comparison with oxidized MWCNTs as catalyst support. PEI-functionalized CNTs, as useful building blocks for the assembly of Pt-based electrocatalyst, may have great potential for applications such as direct methanol fuel cell (DMFC.

  20. Fluorescence-based detection of nitric oxide in aqueous and methanol media using a copper(II) complex.

    Science.gov (United States)

    Mondal, Biplab; Kumar, Pankaj; Ghosh, Pokhraj; Kalita, Apurba

    2011-03-14

    The quenched fluorescent intensity of a copper(II) complex, 1, of a fluorescent ligand, in degassed methanol or aqueous (buffered at pH 7.2) solution, was found to reappear on exposure to nitric oxide. Thus, it can function as a fluorescence based nitric oxide sensor. It has been found that the present complex can be used to sense nanomolar quantities of nitric oxide in both methanol and pH 7.2 buffered-water medium.

  1. Co-catalytic effect of Ni in the methanol electro-oxidation on Pt-Ru/C catalyst for direct methanol fuel cell

    International Nuclear Information System (INIS)

    Wang, Z.B.; Yin, G.P.; Zhang, J.; Sun, Y.C.; Shi, P.F.

    2006-01-01

    This research is aimed to improve the utilization and activity of anodic catalysts, thus to lower the contents of noble metals loading in anodes for methanol electro-oxidation. The direct methanol fuel cell anodic catalysts, Pt-Ru-Ni/C and Pt-Ru/C, were prepared by chemical reduction method. Their performances were tested by using a glassy carbon working electrode through cyclic voltammetric curves, chronoamperometric curves and half-cell measurement in a solution of 0.5 mol/L CH 3 OH and 0.5 mol/L H 2 SO 4 . The composition of the Pt-Ru-Ni and Pt-Ru surface particles were determined by EDAX analysis. The particle size and lattice parameter of the catalysts were determined by means of X-ray diffraction (XRD). XRD analysis showed that both of the catalysts exhibited face-centered cubic structures and had smaller lattice parameters than Pt-alone catalyst. Their sizes are small, about 4.5 nm. No significant differences in the methanol electro-oxidation on both electrodes were found by using cyclic voltammetry, especially regarding the onset potential for methanol electro-oxidation. The electrochemically active-specific areas of the Pt-Ru-Ni/C and Pt-Ru/C catalysts are almost the same. But, the catalytic activity of the Pt-Ru-Ni/C catalyst is higher for methanol electro-oxidation than that of the Pt-Ru/C catalyst. Its tolerance performance to CO formed as one of the intermediates of methanol electro-oxidation is better than that of the Pt-Ru/C catalyst

  2. Electrochemical oxidation of methanol and formic acid in fuel cell processes

    Energy Technology Data Exchange (ETDEWEB)

    Seland, Frode

    2005-07-01

    The main objectives of the thesis work were: (1), to study the oxidation of methanol and formic acid on platinum electrodes by employing conventional and advanced electrochemical methods, and (2), to develop membrane electrode assemblies based on polybenzimidazole membranes that can be used in fuel cells up to 200 C. D.c. voltammetry and a.c. voltammetry studies of methanol and formic acid on polycrystalline platinum in sulphuric acid electrolyte were performed to determine the mechanism and kinetics of the oxidation reactions. A combined potential step and fast cyclic voltammetry experiment was employed to investigate the time dependence primarily of methanol oxidation on platinum. Charge measurements clearly demonstrated the existence of a parallel path at low potentials and short times without formation of adsorbed CO. Furthermore, experimental results showed that only the serial path, via adsorbed CO, exists during continuous cycling, with the first step being diffusion controlled dissociative adsorption of methanol directly from the bulk electrolyte. The saturation charge of adsorbed CO derived from methanol was found to be significantly lower than CO derived from formic acid or dissolved CO. This was attributed to the site requirements of the dehydrogenation steps, and possibly different compositions of linear, bridged or multiply bonded CO. The coverage of adsorbed CO from formic acid decreased significantly at potentials just outside of the hydrogen region (0.35 V vs. RHE), while it did not start to decrease significantly until about 0.6 V vs. RHE for methanol. Adsorbed CO from dissolved CO rapidly oxidized at potentials above about 0.75 V due to formation of platinum oxide. Data from a.c. voltammograms from 0.5 Hz up to 30 kHz were assembled into electrochemical impedance spectra (EIS) and analyzed using equivalent circuits. The main advantages of collecting EIS spectra from a.c. voltammetry experiments are the ability to directly correlate the impedance

  3. Mixed ionic liquids/graphene-supported platinum nanoparticles as an electrocatalyst for methanol oxidation

    International Nuclear Information System (INIS)

    Shi, Guoyu; Wang, Zonghua; Xia, Jianfei; Bi, Sai; Li, Yue; Zhang, Feifei; Xia, Lin; Li, Yanhui; Xia, Yanzhi; Xia, Linhua

    2014-01-01

    Graphical abstract: A kind of mixed ionic liquids (ILs) of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4], IL1) and hexafluorophosphate ([bmim][PF6], IL2) was introduced to the functionalization of graphene (GN) nanosheets, which was used to the synthesis of platinum nanoparticles (Pt NPs) to obtain the Pt/IL1-IL2/GN nanocomposite. The as-prepared Pt/IL1-IL2/GN composites exhibited highly electrocatalytic activity (764.3 mA mg − 1Pt at 0.6 V vs. SCE) and stability toward methanol oxidation, demonstrating their promising potential as the anode catalyst for direct methanol fuel cells (DMFCs). - Highlights: • Pt/mixed ionic liquids/graphene composite catalyst was easily synthesized. • The special phase equilibrium characteristics exerted by the peculiar interactions between different ILs can promote the homogeneous growth of small Pt nanoparticles. • The as-made catalyst exhibited enhanced electro-catalytic performance for methanol oxidation. - Abstract: A kind of mixed ionic liquids (ILs) of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF 4 ], IL 1 ) and hexafluorophosphate ([bmim][PF 6 ], IL 2 ) was introduced to the functionalization of graphene (GN) nanosheets, which was used to the synthesis of platinum nanoparticles (Pt NPs) to obtain the Pt/IL 1 -IL 2 /GN nanocomposite. The interaction between mixed ILs and GN achieved a stable performance due to the excellent electronic and interfacial property of the fabricated nanocomposites, which was favorable for effective loading of Pt NPs on the IL 1 -IL 2 /GN support. The as-prepared Pt/IL 1 -IL 2 /GN composites exhibited highly electrocatalytic activity (764.3 mA mg −1 Pt at 0.6 V vs. SCE) and stability toward methanol oxidation, demonstrating their promising potential as the anode catalyst for direct methanol fuel cells (DMFCs)

  4. Enhanced methanol electro-oxidation reaction on Pt-CoOx/MWCNTs hybrid electro-catalyst

    International Nuclear Information System (INIS)

    Nouralishahi, Amideddin; Rashidi, Ali Morad; Mortazavi, Yadollah; Khodadadi, Abbas Ali; Choolaei, Mohammadmehdi

    2015-01-01

    Highlights: • Promoting effects of Cobalt oxide on methanol electro-oxidation over Pt/MWCNTs are investigated. • Higher activity, about 2.9 times, and enhanced stability are observed on Pt-CoO x /MWCNTs. • Electrochemical active surface area of Pt nanoparticles is significantly improved upon CoO x addition. • Bi-functional mechanism is facilitated in presence of CoO x . - Abstract: The electro-catalytic behavior of Pt-CoO x /MWCNTs in methanol electro-oxidation reaction (MOR) is investigated and compared to that of Pt/MWCNTs. The electro-catalysts were synthesized by an impregnation method using NaBH 4  as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoO x , Pt nanoparticles were highly distributed on the support with an average particle size of 2 nm, an obvious decrease from 5.1 nm for Pt/MWCNTs. Cyclic voltammetry, CO-stripping, Chronoamperometry, and electrochemical impedance spectroscopy (EIS) measurements are used to study the electrochemical behavior of the electro-catalysts. The results revealed a considerable enhancement in the oxidation kinetics of CO ads on Pt active sites by the participation of CoO x . Compared to Pt/MWCNTs, Pt-CoO x /MWCNTs sample has a larger electrochemical active surface area (ECSA) and higher electro-catalytic activity and stability toward methanol electro-oxidation. According to the results of cyclic voltammetry, the forward anodic peak current density enhances more than 89% at the optimum atomic ratio of Pt:Co = 2:1. Furthermore, inclusion of cobalt oxide species causes the onset potential of methanol electro-oxidation reaction to shift 84 mV to negative values compared to that on Pt/MWCNTs. Based on EIS data, dehydrogenation of methanol is the rate-determining step of MOR on both Pt/MWCNTs and Pt-CoO x /MWCNTs, at small overpotentials. However, at higher overpotentials, the oxidation of adsorbed oxygen-containing groups

  5. Development of a membrane-assisted fluidized bed reactor - 2 - Experimental demonstration and modeling for the partial oxidation of methanol

    NARCIS (Netherlands)

    Deshmukh, S.A.R.K.; Laverman, J.A.; van Sint Annaland, M.; Kuipers, J.A.M.

    2005-01-01

    A small laboratory-scale membrane-assisted fluidized bed reactor (MAFBR) was constructed in order to experimentally demonstrate the reactor concept for the partial oxidation of methanol to formaldehyde. Methanol conversion and product selectivities were measured at various overall fluidization

  6. Preparation and Characterization of Zirconia-Coated Nanodiamonds as a Pt Catalyst Support for Methanol Electro-Oxidation

    Directory of Open Access Journals (Sweden)

    Jing Lu

    2016-12-01

    Full Text Available Zirconia-coated nanodiamond (ZrO2/ND electrode material was successfully prepared by one-step isothermal hydrolyzing from ND-dispersed ZrOCl2·8H2O aqueous solution. High-resolution transmission electron microscopy reveals that a highly conformal and uniform ZrO2 shell was deposited on NDs by this simple method. The coating obtained at 90 °C without further calcination was mainly composed of monoclinic nanocrystalline ZrO2 rather than common amorphous Zr(OH4 clusters. The ZrO2/NDs and pristine ND powder were decorated with platinum (Pt nanoparticles by electrodeposition from 5 mM chloroplatinic acid solution. The electrochemical studies indicate that Pt/ZrO2/ND catalysts have higher electrocatalytic activity and better stability for methanol oxidation than Pt/ND catalysts in acid.

  7. Synthesis of Pt–Pd Bimetallic Porous Nanostructures as Electrocatalysts for the Methanol Oxidation Reaction

    Directory of Open Access Journals (Sweden)

    Yong Yang

    2018-03-01

    Full Text Available Pt-based bimetallic nanostructures have attracted a great deal of attention due to their unique nanostructures and excellent catalytic properties. In this study, we prepared porous Pt–Pd nanoparticles using an efficient, one-pot co-reduction process without using any templates or toxic reactants. In this process, Pt–Pd nanoparticles with different nanostructures were obtained by adjusting the temperature and ratio of the two precursors; and their catalytic properties for the oxidation of methanol were studied. The porous Pt–Pd nanostructures showed better electrocatalytic activity for the oxidation of methanol with a higher current density (0.67 mA/cm2, compared with the commercial Pt/C catalyst (0.31 mA/cm2. This method provides one easy pathway to economically prepare different alloy nanostructures for various applications.

  8. Electrochemical catalytic activities of nanoporous palladium rods for methanol electro-oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaoguang; Wang, Weimin; Qi, Zhen; Zhao, Changchun; Ji, Hong; Zhang, Zhonghua [Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials (MOE), School of Materials Science and Engineering, Shandong University, Jingshi Road 73, Jinan 250061 (China)

    2010-10-01

    A novel electrocatalyst, nanoporous palladium (npPd) rods can be facilely fabricated by dealloying a binary Al{sub 80}Pd{sub 20} alloy in a 5 wt.% HCl aqueous solution under free corrosion conditions. The microstructure of these nanoporous palladium rods has been characterized using scanning electron microscopy and transmission electron microscopy. The results show that each Pd rod is several microns in length and several hundred nanometers in diameter. Moreover, all the rods exhibit a typical three-dimensional bicontinuous interpenetrating ligament-channel structure with length scale of 15-20 nm. The electrochemical experiments demonstrate that these peculiar nanoporous palladium rods (mixed with Vulcan XC-72 carbon powders to form a npPd/C catalyst) reveal a superior electrocatalytic performance toward methanol oxidation in the alkaline media. In addition, the electrocatalytic activity obviously depends on the metal loading on the electrode and will reach to the highest level (223.52 mA mg{sup -1}) when applying 0.4 mg cm{sup -2} metal loading on the electrode. Moreover, a competing adsorption mechanism should exist when performing methanol oxidation on the surface of npPd rods, and the electro-oxidation reaction is a diffusion-controlled electrochemical process. Due to the advantages of simplicity and high efficiency in the mass production, the npPd rods can act as a promising candidate for the anode catalyst for direct methanol fuel cells (DMFCs). (author)

  9. Pt-Ru nanoparticles supported on functionalized carbon as electrocatalysts for the methanol oxidation

    International Nuclear Information System (INIS)

    Salgado, J.R.C.; Fernandes, J.C.S.; Botelho do Rego, A.M.; Ferraria, A.M.; Duarte, R.G.; Ferreira, M.G.S.

    2011-01-01

    Highlights: → The functionalized carbon using acid solutions contains surface oxygenated groups. → Uniform dispersion of PtRu nanoparticles on the carbon surface was achieved. → Physical analysis showed the formation of PtRu alloy catalysts on functionalized carbon. → PtRu alloy catalysts on functionalized carbon enhanced the methanol oxidation rate. - Abstract: Platinum-ruthenium alloy electrocatalysts, for methanol oxidation reaction, were prepared on carbons thermally treated in helium atmosphere or chemically functionalized in H 2 O 2 , or in HNO 3 + H 2 SO 4 or in HNO 3 solutions. The functionalized carbon that is produced using acid solutions contains more surface oxygenated functional groups than carbon treated with H 2 O 2 solution or HeTT. The XRD/HR-TEM analysis have showed the existence of a higher alloying degree for Pt-Ru electrocatalysts supported on functionalized carbon, which present superior electrocatalytic performance, assessed by cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy, as compared to electrocatalysts on unfunctionalized carbon. It also was found that Pt-Ru alloy electrocatalysts on functionalized carbon improve the reaction rate compared to Pt-Ru on carbons treated with H 2 O 2 solution and thermally. A mechanism is discussed, where oxygenated groups generated from acid functionalization of carbon and adsorbed on Pt-Ru electrocatalysts are considered to enhance the electrocatalytic activity of the methanol oxidation reaction.

  10. Uniform Pt Nanoparticles Incorporated into Reduced Graphene Oxides with MoO_3 as Advanced Anode Catalysts for Methanol Electro-oxidation

    International Nuclear Information System (INIS)

    Hao, Yanfei; Wang, Xudan; Zheng, Yuanyuan; Shen, Jianfeng; Yuan, Junhua; Wang, Ai-jun; Niu, Li; Huang, Shengtang

    2016-01-01

    Highlights: • Pt nanoparticles were uniformly deposited on graphene with MoO_3. Their size can be tuned by controlling MoO_3 loading. These Pt catalysts are high active on methanol oxidation. They also show high tolerance to CO poisoning. - Abstract: Pt nanoparticles (NPs) were uniformly deposited on the reduced graphene oxides (RGOs) by one-pot thermoreduction strategy with assist of MoO_3. MoO_3 can significantly reduce the size of Pt NPs on RGOs. These Pt NPs can be averaged to be 3.0 to 4.1 nm with MoO_3 loading from 27.4 to 8.8%. Without MoO_3, the size of Pt NPs can reach up to 15.2 nm. In addition, MoO_3 in Pt-MoO_3/RGO catalysts conducts a surface-confined reversible electron transfer. And the Pt-MoO_3/RGO catalysts show strong resistance to CO poisoning and high activity towards methanol oxidation reaction (MOR). Among these Pt-based catalysts, Pt-MoO_3/RGO catalysts with 16.5% MoO_3 loading possess a largest MOR current up to 610 mA mg"−"1 Pt with a smallest deteriorate rate of 0.000425 s"−"1 polarizing for 5000 s at 0.65 V. These results demonstrate commercial feasibility for Pt catalysts to reduce significantly the amount of precious metals Pt in parallel to maintain a high MOR activity and CO tolerance.

  11. Detection of Methanol with Fast Response by Monodispersed Indium Tungsten Oxide Ellipsoidal Nanospheres.

    Science.gov (United States)

    Wang, Chong; Kou, Xueying; Xie, Ning; Guo, Lanlan; Sun, Yanfeng; Chuai, Xiaohong; Ma, Jian; Sun, Peng; Wang, Yue; Lu, Geyu

    2017-05-26

    Indium tungsten oxide ellipsoidal nanospheres were prepared with different In/W ratios by using a simple hydrothermal method without any surfactant for the first time. Sensors based on different In/W ratios samples were fabricated, and one of the samples exhibited better response to methanol compared with others. High content of defective oxygen (Ov) and proper output proportion of In to W might be the main reasons for the better gas sensing properties. The length of the nanosphere was about 150-200 nm, and the width was about 100 nm. Various techniques were applied to investigate the nanospheres. Sensing characteristics toward methanol were investigated. Significantly, the sensor exhibited ultrafast response to methanol. The response time to 400 ppm methanol was no more than 2 s and the recovery time was 9 s at 312 °C. Most importantly, the humidity almost had no effect on the response of the sensor fabricated here, which is hard to achieve in gas-sensing applications.

  12. Experimental and Kinetic Modeling Study of Methanol Ignition and Oxidation at High Pressure

    DEFF Research Database (Denmark)

    Aranda, V.; Christensen, J. M.; Alzueta, Maria

    2013-01-01

    A detailed chemical kinetic model for oxidation of CH3OH at high pressure and intermediate temperatures has been developed and validated experimentally. Ab initio calculations and Rice–Ramsperger–Kassel–Marcus/transition state theory (RRKM/TST) analysis were used to obtain rate coefficients for CH...... the conditions studied, the onset temperature for methanol oxidation was not dependent on the stoichiometry, whereas increasing pressure shifted the ignition temperature toward lower values. Model predictions of the present experimental results, as well as rapid compression machine data from the literature, were...

  13. High methanol oxidation activity of electrocatalysts supported by directly grown nitrogen-containing carbon nanotubes on carbon cloth

    International Nuclear Information System (INIS)

    Wang, C.-H.; Shih, H.-C.; Tsai, Y.-T.; Du, H.-Y.; Chen, L.-C.; Chen, K.-H.

    2006-01-01

    The microstructure and electrochemical activity of the Pt-Ru supported by nitrogen-containing carbon nanotubes (CN x NTs) directly grown on the carbon cloth have been investigated. The CN x NTs directly grown on the carbon cloth (CN x NTs-carbon cloth composite electrode) were synthesized using microwave-plasma-enhanced chemical vapour deposition first and then use as the template to support the Pt-Ru nanoclusters subsequently sputtered on. The ferricyanide/ferrocyanide redox reaction in cyclic voltammetry (CV) measurements showed a faster electron transfer on the CN x NTs-carbon cloth composite electrode than the one with carbon cloth alone. Comparing their methanol oxidation abilities, it is found that the Pt-Ru nanoclusters supported by the CN x NTs-carbon cloth composite electrode have considerably higher electrocatalytic activity than the carbon cloth counterpart. This result suggests high performance of the CN x NTs-carbon cloth composite electrode, and demonstrates its suitability for direct methanol fuel cell applications

  14. High methanol oxidation activity of electrocatalysts supported by directly grown nitrogen-containing carbon nanotubes on carbon cloth

    Energy Technology Data Exchange (ETDEWEB)

    Wang, C.-H. [Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan (China); Shih, H.-C. [Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan (China); Institue of Materials Science and Nano Technology, Chinese Culture University, Taipei, Taiwan (China); Tsai, Y.-T. [Institue of Materials Science and Nano Technology, Chinese Culture University, Taipei, Taiwan (China); Du, H.-Y. [Institue of Materials Science and Nano Technology, Chinese Culture University, Taipei, Taiwan (China); Chen, L.-C. [Center for Condensed Matter Sciences, National Taiwan University, Taipei, Taiwan (China); Chen, K.-H. [Center for Condensed Matter Sciences, National Taiwan University, Taipei, Taiwan (China) and Institue of Atomic and Molecular Science, Academia Sinica, Taipei, Taiwan (China)]. E-mail: chenkh@pub.iams.sinica.edu.tw

    2006-12-01

    The microstructure and electrochemical activity of the Pt-Ru supported by nitrogen-containing carbon nanotubes (CN {sub x} NTs) directly grown on the carbon cloth have been investigated. The CN {sub x} NTs directly grown on the carbon cloth (CN {sub x} NTs-carbon cloth composite electrode) were synthesized using microwave-plasma-enhanced chemical vapour deposition first and then use as the template to support the Pt-Ru nanoclusters subsequently sputtered on. The ferricyanide/ferrocyanide redox reaction in cyclic voltammetry (CV) measurements showed a faster electron transfer on the CN {sub x} NTs-carbon cloth composite electrode than the one with carbon cloth alone. Comparing their methanol oxidation abilities, it is found that the Pt-Ru nanoclusters supported by the CN {sub x} NTs-carbon cloth composite electrode have considerably higher electrocatalytic activity than the carbon cloth counterpart. This result suggests high performance of the CN {sub x} NTs-carbon cloth composite electrode, and demonstrates its suitability for direct methanol fuel cell applications.

  15. Cyclic voltammetric study of electro-oxidation of methanol on platinum electrode in acidic and neutral media

    International Nuclear Information System (INIS)

    Khan, A.S.A.; Ahmed, R.; Mirza, M.L.

    2007-01-01

    The electro-oxidation of methanol on electrochemically treated platinum foil was investigated in acidic and neutral media for comparison of cyclic voltammetric characteristics and elucidation of mechanism of electro-oxidation of methanol. The surface area and roughness factor of platinum electrode was calculated. The electro-oxidation of mathanol is an irreversible process giving. anodic peaks in both anodic and cathodic sweep. The characteristic peaks of electrooxidation of methanol appeared at almost the same potential region in both acidic and neutral media. In neutral medium, certain additional cathodic/anodic peaks appeared which were confirmed to arise by the reduction/oxidation of hydrogen ions. The exchange current density and heterogeneous electron transfer rate constant was higher in neutral medium as. compared with acidic medium. The thermodynamic parameters delta H, delta S, and delta G/sub 298/ were calculated. The values of delta H and delta G/sub 298/were positive which indicated that the process of electro-oxidation of methanol is an endothermic and nonspontaneous. The mechanism of electro-oxidation of methanol was same in both acidic and neutral media involving the formation of various adsorbed intermediate species through dissociative adsorption steps leading to the formation of Co adsorbed radicals, which are removed. during interaction with adsorbed hydrous oxides provided by the oxidation of adsorbed water molecules. The higher rate of electro-oxidation of methanol in neutral medium was interpreted in the tight of electrochemical mechanism and was attributed to the presence of comparatively small amount of hydrogen ions only along the surface of working electrode, which are produced during electro-oxidation of methanol. (author)

  16. Microwave-Assisted Synthesis of Co3(PO42 Nanospheres for Electrocatalytic Oxidation of Methanol in Alkaline Media

    Directory of Open Access Journals (Sweden)

    Prabhakarn Arunachalam

    2017-04-01

    Full Text Available Low-cost and high-performance advanced electrocatalysts for direct methanol fuel cells are of key significance for the improvement of environmentally-pleasant energy technologies. Herein, we report the facile synthesis of cobalt phosphate (Co3(PO42 nanospheres by a microwave-assisted process and utilized as an electrocatalyst for methanol oxidation. The phase formation, morphological surface structure, elemental composition, and textural properties of the synthesized (Co3(PO42 nanospheres have been examined by powder X-ray diffraction (XRD, Fourier transform-infrared spectroscopy (FT-IR, field emission-scanning electron microscopy (FE-SEM, high-resolution transmission electron microscopy (HRTEM, X-ray photoelectron spectroscopy (XPS, and nitrogen adsorption-desorption isotherm investigations. The performance of an electrocatalytic oxidation of methanol over a Co3(PO42 nanosphere-modified electrode was evaluated in an alkaline solution using cyclic voltammetry (CV and chronopotentiometry (CP techniques. Detailed studies were made for the methanol oxidation by varying the experimental parameters, such as catalyst loading, methanol concentration, and long-term stability for the electro-oxidation of methanol. The good electrocatalytic performances of Co3(PO42 should be related to its good surface morphological structure and high number of active surface sites. The present investigation illustrates the promising application of Co3(PO42 nanospheres as a low-cost and more abundant electrocatalyst for direct methanol fuel cells.

  17. Promotion effect of manganese oxide on the electrocatalytic activity of Pt/C for methanol oxidation in acid medium

    Energy Technology Data Exchange (ETDEWEB)

    Abdel Hameed, R.M., E-mail: randa311eg@yahoo.com [Chemistry Department, Faculty of Science, Cairo University, Giza (Egypt); Fetohi, Amani E.; Amin, R.S.; El-Khatib, K.M. [Chemical Engineering Department, National Research Center, Dokki, Giza (Egypt)

    2015-12-30

    Graphical abstract: Physical and electrochemical properties of Pt/C, Pt–MnO{sub 2}/C-1 and Pt–MnO{sub 2}/C-2 electrocatalysts. - Highlights: • Adding MnO{sub 2} to Pt/C improved the dispersion of Pt nanoparticles. • The existence of MnO{sub 2} improved the kinetics of methanol oxidation reaction. • R{sub ct} value of Pt–MnO{sub 2}/C was about 10 times as low as that at Pt/C. • The removal of CO{sub ads} poisoning species was facilitated at Pt–MnO{sub 2}/C. - Abstract: The modification of Pt/C by incorporating metal oxides for electrocatalytic oxidation of methanol has gained major attention because of the efficiency loss during the course of long-time operation. This work describes the preparation of Pt–MnO{sub 2}/C electrocatalysts through a chemical route using ethylene glycol or a mixture of ethylene glycol and sodium borohydride as a reducing agent. The crystallite structure and particle size of synthesized electrocatalysts are determined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The addition of MnO{sub 2} improves the dispersion of Pt nanoparticles. The electrocatalytic activity of Pt–MnO{sub 2}/C towards methanol oxidation in H{sub 2}SO{sub 4} solution is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The onset potential value of methanol oxidation peak is negatively shifted by 169 mV when MnO{sub 2} is introduced to Pt/C. Moreover, the charge transfer resistance value at Pt–MnO{sub 2}/C is about 10 times as low as that at Pt/C. Chronoamperometry and chronopotentiometry show that CO tolerance is greatly improved at Pt–MnO{sub 2}/C. The increased electrocatalytic activity and enhanced ability to clean platinum surface elect manganese oxide as a suitable promoter for the anode performance in direct methanol fuel cells (DMFCs).

  18. Ru-decorated Pt nanoparticles on N-doped multi-walled carbon nanotubes by atomic layer deposition for direct methanol fuel cells

    DEFF Research Database (Denmark)

    Johansson, Anne-Charlotte Elisabeth Birgitta; Yang, R.B.; Haugshøj, K.B.

    2013-01-01

    We present atomic layer deposition (ALD) as a new method for the preparation of highly dispersed Ru-decorated Pt nanoparticles for use as catalyst in direct methanol fuel cells (DMFCs). The nanoparticles were deposited onto N-doped multi-walled carbon nanotubes (MWCNTs) at 250 °C using trimethyl......(methylcyclopentadienyl)platinum MeCpPtMe3, bis(ethylcyclopentadienyl)ruthenium Ru(EtCp)2 and O2 as the precursors. Catalysts with 5, 10 and 20 ALD Ru cycles grown onto the CNT-supported ALD Pt nanoparticles (150 cycles) were prepared and tested towards the electro-oxidation of CO and methanol, using cyclic voltammetry...... and chronoamperometry in a three-electrode electrochemical set-up. The catalyst decorated with 5 ALD Ru cycles was of highest activity in both reactions, followed by the ones with 10 and 20 ALD Ru cycles. It is demonstrated that ALD is a promising technique in the field of catalysis as highly dispersed nanoparticles...

  19. IDENTITY OF THE PINK-PIGMENTED METHANOL-OXIDIZING BACTERIA AS VIBRIO EXTORQUENS.

    Science.gov (United States)

    STOCKS, P K; MCCLESKEY, C S

    1964-10-01

    Stocks, Peter K. (Louisiana State University, Baton Rouge), and C. S. McCleskey. Identity of the pink-pigmented methanol-oxidizing bacteria as Vibrio extorquens. J. Bacteriol. 88:1065-1070. 1964.-Pink-pigmented bacteria isolated from enrichment cultures of methane oxidizers were found to possess similar morphological, cultural, and physiological characteristics. All the strains utilized methanol, formate, oxalate, succinate, glycerol, and benzene as sole carbon sources; methanol, formate, and glycerol afforded best growth. Most strains utilized fructose and ribose; other carbohydrates tested were not available as carbon and energy sources. There was strain variation in the use of hexane, heptane, n-propanol, n-butanol, acetate, and propionate. Methane, ethane, n-propane, and n-butane were not utilized. Our isolates, and Pseudomonas methanica of Harrington and Kallio (not the methane-dependent P. methanica of Dworkin and Foster), Pseudomonas AM1 of Peele and Quayle, Pseudomonas PRL-W4 of Kaneda and Roxburgh, and Protaminobacter ruber den Dooren de Jong are nearly identical with Vibrio extorquens (Bassalik) Bhat and Barker, and should be considered the same species.

  20. Effect of Ni Core Structure on the Electrocatalytic Activity of Pt-Ni/C in Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Vladimir Linkov

    2013-07-01

    Full Text Available Methanol oxidation catalysts comprising an outer Pt-shell with an inner Ni-core supported on carbon, (Pt-Ni/C, were prepared with either crystalline or amorphous Ni core structures. Structural comparisons of the two forms of catalyst were made using transmission electron microscopy (TEM, X-ray diffraction (XRD and X-ray photoelectron spectroscopy (XPS, and methanol oxidation activity compared using CV and chronoamperometry (CA. While both the amorphous Ni core and crystalline Ni core structures were covered by similar Pt shell thickness and structure, the Pt-Ni(amorphous/C catalyst had higher methanol oxidation activity. The amorphous Ni core thus offers improved Pt usage efficiency in direct methanol fuel cells.

  1. Development of vanadium-phosphate catalysts for methanol production by selective oxidation of methane

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, R.L. [Colorado School of Mines, Golden, CO (United States)

    1995-12-31

    The United States has vast natural gas reserves which could contribute significantly to our energy security if economical technologies for conversion to liquid fuels and chemicals were developed. Many of these reserves are small scale or in remote locations and of little value unless they can be transported to consumers. Transportation is economically performed via pipeline, but this route is usually unavailable in remote locations. Another option is to convert the methane in the gas to liquid hydrocarbons, such as methanol, which can easily and economically be transported by truck. Therefore, the conversion of methane to liquid hydrocarbons has the potential to decrease our dependence upon oil imports by opening new markets for natural gas and increasing its use in the transportation and chemical sectors of the economy. In this project, we are attempting to develop, and explore new catalysts capable of direct oxidation of methane to methanol. The specific objectives of this work are discussed.

  2. Oxidation of CO and Methanol on Pd-Ni Catalysts Supported on Different Chemically-Treated Carbon Nanofibers

    Directory of Open Access Journals (Sweden)

    Juan Carlos Calderón

    2016-10-01

    Full Text Available In this work, palladium-nickel nanoparticles supported on carbon nanofibers were synthesized, with metal contents close to 25 wt % and Pd:Ni atomic ratios near to 1:2. These catalysts were previously studied in order to determine their activity toward the oxygen reduction reaction. Before the deposition of metals, the carbon nanofibers were chemically treated in order to generate oxygen and nitrogen groups on their surface. Transmission electron microscopy analysis (TEM images revealed particle diameters between 3 and 4 nm, overcoming the sizes observed for the nanoparticles supported on carbon black (catalyst Pd-Ni CB 1:2. From the CO oxidation at different temperatures, the activation energy Eact for this reaction was determined. These values indicated a high tolerance of the catalysts toward the CO poisoning, especially in the case of the catalysts supported on the non-chemically treated carbon nanofibers. On the other hand, apparent activation energy Eap for the methanol oxidation was also determined finding—as a rate determining step—the COads diffusion to the OHads for the catalysts supported on carbon nanofibers. The results here presented showed that the surface functional groups only play a role in the obtaining of lower particle sizes, which is an important factor in the obtaining of low CO oxidation activation energies.

  3. Methanol oxidation reaction on core-shell structured Ruthenium-Palladium nanoparticles: Relationship between structure and electrochemical behavior

    Science.gov (United States)

    Kübler, Markus; Jurzinsky, Tilman; Ziegenbalg, Dirk; Cremers, Carsten

    2018-01-01

    In this work the relationship between structural composition and electrochemical characteristics of Palladium(Pd)-Ruthenium(Ru) nanoparticles during alkaline methanol oxidation reaction is investigated. The comparative study of a standard alloyed and a precisely Ru-core-Pd-shell structured catalyst allows for a distinct investigation of the electronic effect and the bifunctional mechanism. Core-shell catalysts benefit from a strong electronic effect and an efficient Pd utilization. It is found that core-shell nanoparticles are highly active towards methanol oxidation reaction for potentials ≥0.6 V, whereas alloyed catalysts show higher current outputs in the lower potential range. However, differential electrochemical mass spectrometry (DEMS) experiments reveal that the methanol oxidation reaction on core-shell structured catalysts proceeds via the incomplete oxidation pathway yielding formaldehyde, formic acid or methyl formate. Contrary, the alloyed catalyst benefits from the Ru atoms at its surface. Those are found to be responsible for high methanol oxidation activity at lower potentials as well as for complete oxidation of CH3OH to CO2 via the bifunctional mechanism. Based on these findings a new Ru-core-Pd-shell-Ru-terrace catalyst was synthesized, which combines the advantages of the core-shell structure and the alloy. This novel catalyst shows high methanol electrooxidation activity as well as excellent selectivity for the complete oxidation pathway.

  4. Facile preparation of a Pt/Prussian blue/graphene composite and its application as an enhanced catalyst for methanol oxidation

    International Nuclear Information System (INIS)

    Wang, Zonghua; Shi, Guoyu; Xia, Jianfei; Xia, Yanzhi; Zhang, Feifei; Xia, Lin; Song, Daimin; Liu, Jingquan; Li, Yanhui; Xia, Linhua; Brito, Manuel E.

    2014-01-01

    Graphical abstract: - Highlights: • Pt/Prussian blue/graphene catalyst was easily synthesized by the sequential electrodeposition method. • Prussian blue can promote the homogeneous growth of small Pt nanoparticles. • The as-made catalyst exhibited enhanced electro-catalytic performance for methanol oxidation. • The interplay of Prussian blue and Pt plays a significant role in reducing CO poisoning of the catalyst. - Abstract: Graphene nanosheets (GN) are modified by electrodeposition of Prussian blue (PB) followed by shape-regulated depositing of small Pt nanoparticles via the interaction between PB and PtCl 6 2− to form a novel catalyst Pt/PB/GN. The Pt/PB/GN composite exhibits significantly enhanced electrocatalytic activity with a mass activity of 445 mA mg −1 Pt (at 0.68 V vs. SCE) and high stability towards methanol oxidation. The high catalytic activity can be attributed to the unique porous architecture and peculiar electrical property of Prussian blue integrated with graphene layers which can not only well accommodate Pt nanoparticles but also provide multidimensional pathways to facilitate the mass and electron transport for methanol oxidation. This strategy can be readily extended to fabrication of other graphene-based hybrid supports for precious metal catalysts in fuel cell applications

  5. Microwave Plasma Enhanced Chemical Vapor Deposition of Diamond in Vapor of Methanol-Based Liquid Solutions

    National Research Council Canada - National Science Library

    Tzeng, Yonhua

    2000-01-01

    .... Liquid solutions are prepared by mixing methanol with other carbon containing liquid compounds which contain a greater than one ratio of carbon to oxygen such as acetone, ethanol, and iso-propanol...

  6. Preparation of PtRu/C anode electrocatalysts using gamma radiation for methanol electro-oxidation

    International Nuclear Information System (INIS)

    Silva, Dionisio Fortunato da

    2006-01-01

    Pt Ru/C (carbon-supported Pt Ru nanoparticles) anode electrocatalysts were prepared using radiolytic process (gamma radiation) and tested for methanol electro-oxidation. In this process, water/2-propanol and water/ethylene glycol solutions containing the metallic ions and the carbon support were submitted to gamma radiation under stirring. The water/alcohol ratio (v/v) and the total dose (kGy) were studied. A nominal Pt Ru atomic ratio of 50:50 were used in all experiments. The electrocatalysts were characterized by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and cyclic voltammetry (CV). The electro-oxidation of methanol was studied by cyclic voltammetry using the thin porous coating technique. The electrocatalysts prepared in water/2-propanol showed crystallite size in the range of 3-5 nm and Pt Ru atomic ratio of 50:50. The electrocatalysts prepared in water/ethylene glycol showed crystallite size (2-3 nm) smaller than the ones obtained in water/2-propanol, however, the Pt Ru atomic ratios obtained were approximately 80:20, showing that only part of ruthenium ions were reduced. For methanol oxidation the electrocatalytic activity depends on the water/2-propanol and water/ethylene glycol ratio used in the reaction medium. The electrocatalysts prepared in water/2-propanol showed inferior performance to the ones prepared in water/ethylene glycol, which showed similar or superior performances (amperes per gram of platinum) to the commercial electrocatalyst from E-TEK. (author)

  7. The effect of titanium nickel nitride decorated carbon nanotubes-reduced graphene oxide hybrid support for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Gen [School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, Guangdong 510006 (China); Pan, Zhanchang, E-mail: panzhanchang@163.com [School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, Guangdong 510006 (China); Li, Wuyi; Yu, Ke [School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, Guangdong 510006 (China); Xia, Guowei; Zhao, Qixiang; Shi, Shikun [Victory Giant Technology (Hui Zhou) Co., Ltd., Huizhou 516083 (China); Hu, Guanghui; Xiao, Chumin; Wei, Zhigang [School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, Guangdong 510006 (China)

    2017-07-15

    Highlights: • TiNiN/CNT-rGO support with an interactive three-dimensional structure and high surface area was synthesized. • Pt nanoparticles with small size were well dispersed on TiNiN/CNT-rGO support. • Pt/TiNiN/CNT-rGO shows remarkably enhanced methanol oxidation activity and durability. - Abstract: Titanium nickel nitride (TiNiN) decorated three-dimensional (3D) carbon nanotubes-reduced graphene oxide (CNT-rGO), a fancy 3D platinum (Pt)-based catalyst hybrid support, is prepared by a solvothermal process followed by a nitriding process, which is tested as anodic catalyst support for the methanol oxidation reaction (MOR). The structure, morphology and composition of the synthesized TiNiN/CNT-rGO exhibits a uniform particle dispersion with high purity and interpenetrating 3D network structure. Notably, Pt/TiNiN/CNT-rGO catalyst exhibits significantly improved catalytic activity and durability for methanol oxidation in comparison with Pt/CNT-rGO and conventional Pt/C (JM). The outstanding electrochemical performance was attributed to structure and properties. That is, the 3D CNT-rGO provided a fast transport network for charge-transfer and mass-transfer as well as TiNiN NPs with good synergistic effect and the strong electronic coupling between different domains in TiNiN/CNT-rGO, thus the catalytic activity of the novel catalyst is greatly improved. These results evidences 3D TiNiN/CNT-rGO as a promising catalyst support for a wide range of applications in fuel cells.

  8. The effect of titanium nickel nitride decorated carbon nanotubes-reduced graphene oxide hybrid support for methanol oxidation

    International Nuclear Information System (INIS)

    Liu, Gen; Pan, Zhanchang; Li, Wuyi; Yu, Ke; Xia, Guowei; Zhao, Qixiang; Shi, Shikun; Hu, Guanghui; Xiao, Chumin; Wei, Zhigang

    2017-01-01

    Highlights: • TiNiN/CNT-rGO support with an interactive three-dimensional structure and high surface area was synthesized. • Pt nanoparticles with small size were well dispersed on TiNiN/CNT-rGO support. • Pt/TiNiN/CNT-rGO shows remarkably enhanced methanol oxidation activity and durability. - Abstract: Titanium nickel nitride (TiNiN) decorated three-dimensional (3D) carbon nanotubes-reduced graphene oxide (CNT-rGO), a fancy 3D platinum (Pt)-based catalyst hybrid support, is prepared by a solvothermal process followed by a nitriding process, which is tested as anodic catalyst support for the methanol oxidation reaction (MOR). The structure, morphology and composition of the synthesized TiNiN/CNT-rGO exhibits a uniform particle dispersion with high purity and interpenetrating 3D network structure. Notably, Pt/TiNiN/CNT-rGO catalyst exhibits significantly improved catalytic activity and durability for methanol oxidation in comparison with Pt/CNT-rGO and conventional Pt/C (JM). The outstanding electrochemical performance was attributed to structure and properties. That is, the 3D CNT-rGO provided a fast transport network for charge-transfer and mass-transfer as well as TiNiN NPs with good synergistic effect and the strong electronic coupling between different domains in TiNiN/CNT-rGO, thus the catalytic activity of the novel catalyst is greatly improved. These results evidences 3D TiNiN/CNT-rGO as a promising catalyst support for a wide range of applications in fuel cells.

  9. Titanium Oxide/Platinum Catalysis: Charge Transfer from a Titanium Oxide Support Controls Activity and Selectivity in Methanol Oxidation on Platinum

    KAUST Repository

    Hervier, Antoine; Baker, L. Robert; Komvopoulos, Kyriakos; Somorjai, Gabor A.

    2011-01-01

    formaldehyde, methyl formate, and carbon dioxide. F-doped samples demonstrated significantly higher activity for methanol oxidation when the TiOx was stoichiometric (TiO 2), but lower activity when it was nonstoichiometric (TiO 1.7 and TiO1.9). These results

  10. The effect of titanium nickel nitride decorated carbon nanotubes-reduced graphene oxide hybrid support for methanol oxidation

    Science.gov (United States)

    Liu, Gen; Pan, Zhanchang; Li, Wuyi; Yu, Ke; Xia, Guowei; Zhao, Qixiang; Shi, Shikun; Hu, Guanghui; Xiao, Chumin; Wei, Zhigang

    2017-07-01

    Titanium nickel nitride (TiNiN) decorated three-dimensional (3D) carbon nanotubes-reduced graphene oxide (CNT-rGO), a fancy 3D platinum (Pt)-based catalyst hybrid support, is prepared by a solvothermal process followed by a nitriding process, which is tested as anodic catalyst support for the methanol oxidation reaction (MOR). The structure, morphology and composition of the synthesized TiNiN/CNT-rGO exhibits a uniform particle dispersion with high purity and interpenetrating 3D network structure. Notably, Pt/TiNiN/CNT-rGO catalyst exhibits significantly improved catalytic activity and durability for methanol oxidation in comparison with Pt/CNT-rGO and conventional Pt/C (JM). The outstanding electrochemical performance was attributed to structure and properties. That is, the 3D CNT-rGO provided a fast transport network for charge-transfer and mass-transfer as well as TiNiN NPs with good synergistic effect and the strong electronic coupling between different domains in TiNiN/CNT-rGO, thus the catalytic activity of the novel catalyst is greatly improved. These results evidences 3D TiNiN/CNT-rGO as a promising catalyst support for a wide range of applications in fuel cells.

  11. Preparation of NO-doped β-MoO{sub 3} and its methanol oxidation property

    Energy Technology Data Exchange (ETDEWEB)

    Pham, Thi Thuy Phuong, E-mail: pttphuong@ict.vast.vn; Nguyen, Phuc Hoang Duy; Vo, Tan Tai; Luu, Cam Loc; Nguyen, Huu Huy Phuc

    2016-12-01

    The major drawback of the industrial iron molybdate catalysts which is their deactivation problem has driven the study of alternative catalysts for formaldehyde production from methanol. In this paper, NO-doped β-MoO{sub 3} was successfully synthesized from the commercial molybdic acid powder (H{sub 2}MoO{sub 4}) and characterized by differential thermal analysis (DTA), X-ray Diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Results obtained from XRD and Raman spectroscopy indicated that the synthesized sample has all features of the well-known β-MoO{sub 3} except for the presence of a new small peak. The curve-fitting of XPS spectra revealed that nitrogen-containing species may be present in the form of negatively charged nitrogen oxide in the prepared sample. Due to its metastable nature, NO-doped β-MoO{sub 3} may be transformed into the thermally stable α-MoO{sub 3} at temperature higher than 400 °C as pointed out by DTA study. However, when the reaction temperature was as low as 300 °C, the catalyst was stable for partial methanol oxidation with no significant change in activity during 30 h of catalytic study. Methanol conversion and formaldehyde selectivity were maintained at about 98% and 99%, respectively. - Highlights: • NO-doped β-MoO{sub 3} was synthesized by a facile and effective method. • Its structure was confirmed by XRD, Raman and XPS analysis. • X{sub MeOH} and S{sub HCHO} were stabilized at 98% and 99%, respectively, for the first 30 h.

  12. Catalyst development and systems analysis of methanol partial oxidation for the fuel processor - fuel cell integration

    Energy Technology Data Exchange (ETDEWEB)

    Newson, E; Mizsey, P; Hottinger, P; Truong, T B; Roth, F von; Schucan, Th H [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    Methanol partial oxidation (pox) to produce hydrogen for mobile fuel cell applications has proved initially more successful than hydrocarbon pox. Recent results of catalyst screening and kinetic studies with methanol show that hydrogen production rates have reached 7000 litres/hour/(litre reactor volume) for the dry pox route and 12,000 litres/hour/(litre reactor volume) for wet pox. These rates are equivalent to 21 and 35 kW{sub th}/(litre reactor volume) respectively. The reaction engineering problems remain to be solved for dry pox due to the significant exotherm of the reaction (hot spots of 100-200{sup o}C), but wet pox is essentially isothermal in operation. Analyses of the integrated fuel processor - fuel cell systems show that two routes are available to satisfy the sensitivity of the fuel cell catalysts to carbon monoxide, i.e. a preferential oxidation reactor or a membrane separator. Targets for individual system components are evaluated for the base and best case systems for both routes to reach the combined 40% efficiency required for the integrated fuel processor - fuel cell system. (author) 2 figs., 1 tab., 3 refs.

  13. Synthesis and Characterization of Electrodeposited C-PANI-Pd-Ni Composite Electrocatalyst for Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    S. S. Mahapatra

    2014-01-01

    Full Text Available Electropolymerization of aniline at the graphite electrodes was achieved by potentiodynamic method. Electrodeposition of Pd (C-PANI-Pd and Ni (C-PANI-Ni and codeposition of Pd-Ni (C-PANI-Pd-Ni microparticles into the polyaniline (PANI film coated graphite (C-PANI were carried out under galvanostatic control. The morphology and composition of the composite electrodes were obtained using scanning electron microscopy (SEM and energy dispersive X-ray analysis (EDX techniques. The electrochemical behavior and electrocatalytic activity of the electrode were characterized using cyclic voltammetry (CV, electrochemical impedance spectroscopy (EIS, and chronoamperometric (CA methods in acidic medium. The C-PANI-Pd-Ni electrode showed an improved catalytic performance towards methanol oxidation in terms of lower onset potential, higher anodic oxidation current, greater stability, lower activation energy, and lower charge transfer resistance. The enhanced electrocatalytic activity might be due to the greater permeability of C-PANI films for methanol molecules, better dispersion of Pd-Ni microparticles into the polymer matrixes, and the synergistic effects between the dispersed metal particles and their matrixes.

  14. Nanocomposite for methanol oxidation: synthesis and characterization of cubic Pt nanoparticles on graphene sheets

    Directory of Open Access Journals (Sweden)

    Tung-Yuan Yung, Jer-Yeu Lee and Ling-Kang Liu

    2013-01-01

    Full Text Available We present our recent results on Pt nanoparticles on graphene sheets (Pt-NPs/G, a nanocomposite prepared with microwave assistance in ionic liquid 2-hydroxyethanaminiumformate. Preparation of Pt-NPs/G was achieved without the addition of extra reductant such as hydrazine or ethylene glycol. The Pt nanoparticles on graphene have a cubic-like shape (about 60 wt% Pt loading, Pt-NPs/G and the particle size is 6 ± 3 nm from transmission electron microscopy results. Electrochemical cyclic voltammetry studies in 0.5 M aqueous H2SO4 were performed using Pt-NPs/G and separately, for comparison, using a commercially available electrocatalyst (60 wt% Pt loading, Pt/C. The electrochemical surface ratio of Pt-NPs/G to Pt/C is 0.745. The results of a methanol oxidation reaction (MOR in 0.5 M aqueous H2SO4 + 1.0 M methanol for the two samples are presented. The MOR results show that the ratios of the current density of oxidation (If to the current density of reduction (Ib are 3.49 (Pt-NPs/G and 1.37 (Pt/C, respectively, with a preference by 2.55 times favoring Pt-NPs/G. That is, the tolerance CO poisoning of Pt-NPs/G is better than that of commercial Pt/C.

  15. A Graphite Oxide Paper Polymer Electrolyte for Direct Methanol Fuel Cells

    Directory of Open Access Journals (Sweden)

    Ravi Kumar

    2011-01-01

    Full Text Available A flow directed assembly of graphite oxide solution was used in the formation of free-standing graphene oxide paper of approximate thickness of 100 μm. The GO papers were characterised by XRD and SEM. Electrochemical characterization of the GO paper membrane electrode assembly revealed proton conductivities of 4.1 × 10−2 S cm−1 to 8.2 × 10−2 S cm−1 at temperatures of 25–90°C. A direct methanol fuel cell, at 60°C, gave a peak power density of 8 mW cm−2 at a current density of 35 mA cm−2.

  16. Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

    International Nuclear Information System (INIS)

    Nagaraju, D.H.; Devaraj, S.; Balaya, P.

    2014-01-01

    Highlights: • Palladium nanoparticles decorated graphene is synthesized in a single step. • Electro-catalytic activity of Gra/Pd toward alcohol oxidation is evaluated. • 1:1 Gra/Pd exhibits good electro-catalytic activity and efficient electron transfer. - Abstract: Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd 2+ ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl 2 . X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells

  17. Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

    Energy Technology Data Exchange (ETDEWEB)

    Nagaraju, D.H., E-mail: dhnagu@gmail.com [Department of Mechanical Engineering, 117 576 (Singapore); Materials Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900 (Saudi Arabia); Devaraj, S. [Department of Mechanical Engineering, 117 576 (Singapore); School of Chemical and Biotechnology, SASTRA University, Thanjavur, 613 401 (India); Balaya, P., E-mail: mpepb@nus.edu.sg [Department of Mechanical Engineering, 117 576 (Singapore); Engineering Science Program, National University of Singapore, 117 576 (Singapore)

    2014-12-15

    Highlights: • Palladium nanoparticles decorated graphene is synthesized in a single step. • Electro-catalytic activity of Gra/Pd toward alcohol oxidation is evaluated. • 1:1 Gra/Pd exhibits good electro-catalytic activity and efficient electron transfer. - Abstract: Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd{sup 2+} ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl{sub 2}. X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells.

  18. Oxygen reduction and methanol oxidation behaviour of SiC based Pt nanocatalysts for proton exchange membrane fuel cells

    DEFF Research Database (Denmark)

    Dhiman, Rajnish; Stamatin, Serban Nicolae; Andersen, Shuang Ma

    2013-01-01

    for carbon based commercial catalyst, when HClO4 is used as electrolyte. The Pt (110) & Pt (111) facets are shown to have higher electrochemical activities than Pt (100) facets. To the best of our knowledge, methanol oxidation studies and the comparison of peak deconvolutions of the H desorption region in CV...... and methanol oxidation reactions of SiC supported catalysts and measured them against commercially available carbon based catalysts. The deconvolution of the hydrogen desorption signals in CV cycles shows a higher contribution of Pt (110) & Pt (111) peaks compared to Pt (100) for SiC based supports than...... cyclic studies are here reported for the first time for SiC based catalysts. The reaction kinetics for the oxygen reduction and for methanol oxidation with Pt/SiC are observed to be similar to the carbon based catalysts. The SiC based catalyst shows a higher specific surface activity than BASF (Pt...

  19. The kinetics and mechanism of methanol oxidation on Pt and PtRu catalysts in alkaline and acid media

    Directory of Open Access Journals (Sweden)

    JELENA LOVIC

    2007-07-01

    Full Text Available The kinetic of methanol electrochemical oxidation for a series of platinum and platinum–ruthenium catalysts was investigated. A correlation between the beginning of OHad adsorption and methanol oxidation was demonstarated on Pt single crystals and Pt nanocatalyst. The activity of the nano-structured Pt catalyst was compared with single crystal platinum electrodes assuming the Kinoshita model of nanoparticles. The ruthenium-containing catalysts shifted the onset of methanol oxidation to more negative potentials. The effect was more pronounced in acid than in alkaline media. Based on the established diagnostic criteria, the reaction between COad and OHad species according to the Langmuir–Hinshelwood mechanism was proposed as the rate determining step in alkaline and acid media on Pt and PtRu catalysts.

  20. Electrochemical oxidation of methanol on Pt/(RuxSn1-xO2 nanocatalyst

    Directory of Open Access Journals (Sweden)

    Krstajić Mila N.

    2013-01-01

    Full Text Available The Ru-doped SnO2 powder, (RuxSn1-xO2, with the Sn:Ru atomic ratio of 9:1 was synthesized and used as a support for Pt nanoparticles (30 mass% loading. The (RuxSn1-xO2 support and Pt/(RuxSn1-xO2 catalyst were characterized by X-ray diffraction, energy dispersive X-ray spectroscopy and transmission electron microscopy (TEM. (RuxSn1-xO2 was found to be two-phase material consisting of probably solid solution of RuO2 in SnO2 and pure RuO2. The average Pt particle size determined by TEM was 5.3 nm. Cyclic voltammetry of Pt/(RuxSn1-xO2 indicated good conductivity of the sup-port and displayed usual features of Pt. The results of the electrochemical oxidation of COads and methanol on Pt/(RuxSn1-xO2 were compared with those on commercial Pt/C and PtRu/C catalysts. Oxidation of COads on Pt/(RuxSn1-xO2 starts at less positive potentials than on PtRu/C and Pt/C. Potentiodynamic polarization curves and chronoamperometric curves of methanol oxidation indicated higher initial activity of Pt/(RuxSn1-xO2 catalyst compared to PtRu/C, but also a greater loss in the current density over time. Potentiodynamic stability test of the catalysts revealed that deactivation of the Pt/(RuxSn1-xO2 and Pt/C was primarily caused by the poisoning of Pt surface by the methanol oxidation residues, which mostly occurred during the first potential cycle. In the case of PtRu/C the poisoning of the surface was minor and deactivation was caused by the PtRu surface area loss. [Projekat Ministarstva nauke Republike Srbije, br. ON-172054

  1. Mesoporous NiCo2O4 nanoneedles grown on 3D graphene-nickel foam for supercapacitor and methanol electro-oxidation

    International Nuclear Information System (INIS)

    Yu, Mei; Chen, Jianpeng; Liu, Jianhua; Li, Songmei; Ma, Yuxiao; Zhang, Jingdan; An, Junwei

    2015-01-01

    Mesoporous NiCo 2 O 4 nanoneedles were directly grown on three dimensional (3D) graphene-nickel foam which was prepared by chemical vapor deposition, labeled as NCO/GNF. The structure and morphology of NCO/GNF were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, element mapping and Raman spectroscopy. The NCO/GNF was employed as electrodes for supercapacitor and methanol electro-oxidation. When used for supercapacitor, the NiCo 2 O 4 nanoneedles exhibit hi exhibit high specific capacitance (1588 F g −1 at 1 A g −1 ), high power density and energy density (33.88 Wh kg −1 at 5 kW kg −1 ) as well as long cycling stability. In methanol electro-oxidation, the NiCo 2 O 4 nanoneedles deliver high electro-oxidation activity (93.3 A g −1 at 0.65 V) and electro-oxidation stability. The good electrochemical performance of NiCo 2 O 4 nanoneedles is attributed to the 3D structure with large specific area, high conductivity and fast ions/electrons transport

  2. Study by electron paramagnetic resonance of the radiolysis of pyridine N-oxide in a vitreous methanol matrix

    International Nuclear Information System (INIS)

    Quaegebeur, J.P.; Perly, B.

    1977-01-01

    The analysis of esr spectra derived from γ irradiated pyridine N-oxide in a methanolic vitreous matrix at 77 K shows the presence of a mixture of 2- and 4-azacyclohexadienyl N-oxide radicals formed by the addition of the hydroxymethyl primary species to the pyridine ring. The structure of the different radicals was determined by comparison with spectra derived from several substituted pyridine N-oxides

  3. Catalysts with Cu base supported in mixed oxides to generate H2: reformed of methanol in oxidant atmosphere

    International Nuclear Information System (INIS)

    Aguila M, M.M.; Perez H, R.; Rodriguez L, V.

    2006-01-01

    In this work, the characterization of Cu supported in CeO 2 -ZrO 2 , for to generate H 2 starting from the one reformed of methanol with water vapor and oxygen is presented. The sol-gel technique and classic impregnation for the obtaining of the supports and catalysts respectively were used. The materials were characterized by XRD, SEM, adsorption- desorption of N 2 and TPR. The catalytic materials presented crystalline phases associated with the zircon (tetragonal and monoclinic phase) and the ceria (cubic phase) depending on the CeO 2 /ZrO 2 relationship. The morphology of the catalysts was analyzed by SEM being observed semispheric particles for the rich materials in ZrO 2 and added planars in the rich materials in CeO 2 . The ceria addition to the zircon favors the specific area of the mixed oxides CeO 2 -ZrO 2 and it promotes the reducibility of the copper oxide at low temperatures. The rich catalysts in ceria also showed high activity in the methanol transformation and bigger selectivity toward the production of H 2 . This result is associated with the presence of copper species that decrease to low temperature present in the rich catalysts in ceria and that they are not present in the rich catalysts in zircon. (Author)

  4. Supported 3-D Pt nanostructures: the straightforward synthesis and enhanced electrochemical performance for methanol oxidation in an acidic medium

    International Nuclear Information System (INIS)

    Li, Zesheng; Ji, Shan; Pollet, Bruno G.; Shen, Pei Kang

    2013-01-01

    Noble metal nanostructures with branched morphologies [i.e., 3-D Pt nanoflowers (NFs)] by tri-dimensionally integrating onto conductive carbon materials are proved to be an efficient and durable electrocatalysts for methanol oxidation. The well-supported 3-D Pt NFs are readily achieved by an efficient cobalt-induced/carbon-mediated galvanic reaction approach. Due to the favorable nanostructures (3-D Pt configuration allowing a facile mass transfer) and supporting effects (including framework stabilization, spatially separate feature, and improved charge transport effects), these 3-D Pt NFs manifest much higher electrocatalytic activity and stability toward methanol oxidation than that of the commercial Pt/C and Pt-based electrocatalysts

  5. Supported 3-D Pt nanostructures: the straightforward synthesis and enhanced electrochemical performance for methanol oxidation in an acidic medium

    Energy Technology Data Exchange (ETDEWEB)

    Li, Zesheng [Sun Yat-sen University, The State Key Laboratory of Optoelectronic Materials and Technologies, and Guangdong Province Key Laboratory of Low-carbon Chemistry and Energy Conservation, School of Physics and Engineering (China); Ji, Shan; Pollet, Bruno G. [University of the Western Cape, South African Institute for Advanced Materials Chemistry (SAIAMC) (South Africa); Shen, Pei Kang, E-mail: stsspk@mail.sysu.edu.cn [Sun Yat-sen University, The State Key Laboratory of Optoelectronic Materials and Technologies, and Guangdong Province Key Laboratory of Low-carbon Chemistry and Energy Conservation, School of Physics and Engineering (China)

    2013-10-15

    Noble metal nanostructures with branched morphologies [i.e., 3-D Pt nanoflowers (NFs)] by tri-dimensionally integrating onto conductive carbon materials are proved to be an efficient and durable electrocatalysts for methanol oxidation. The well-supported 3-D Pt NFs are readily achieved by an efficient cobalt-induced/carbon-mediated galvanic reaction approach. Due to the favorable nanostructures (3-D Pt configuration allowing a facile mass transfer) and supporting effects (including framework stabilization, spatially separate feature, and improved charge transport effects), these 3-D Pt NFs manifest much higher electrocatalytic activity and stability toward methanol oxidation than that of the commercial Pt/C and Pt-based electrocatalysts.

  6. Oxidation of hydrogen terminated Ge(1 0 0) surface in the presence of iodine in methanol

    International Nuclear Information System (INIS)

    Lee, Younghwan; Park, Kibyung; Lim, Sangwoo

    2008-01-01

    Surface reaction on Ge(1 0 0) in liquid methanol (MeOH) was systematically studied. In particular, the characteristics of the Ge surface in the presence of iodine (I 2 ) in MeOH were investigated. MeOH treatment of the Ge surface in the presence of 0.05 or 0.005 mM of I 2 exhibited a similar result to that without I 2 , which produces a GeO x -dominant oxide structure. However, when the concentration of I 2 in MeOH increased to 0.5 mM, Ge surface revealed a GeO 2 -dominant oxide structure. Therefore, it is believed that the addition of enough I 2 in MeOH modifies the Ge oxidation mechanism. Hydroxide produced by the reaction between MeOH and the iodine radical may oxidize the Ge surface to form a Ge-O layer. Because MeOH is greatly consumed by chain and series reactions when I 2 concentration is high, a GeO 2 structure is not etched and a GeO 2 -dominant oxide structure is obtained with the addition of 0.5 mM I 2 in MeOH. The modified oxide layer prepared in MeOH with 0.5 mM I 2 exhibited an atomically smoother surface compared to a pure MeOH- or H 2 O 2 -treated Ge surface and a much thinner oxide layer than H 2 O 2 treatment.

  7. Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

    KAUST Repository

    Nagaraju, Doddahalli H.

    2014-12-01

    Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd2+ ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl2. X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells. © 2014 Elsevier Ltd.

  8. Electrolytes for methanol-air fuel cells. I. The performance of methanol electro-oxidation catalysts in sulphuric acid and phosphoric acid electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Andrew, M.R.; McNicol, B.D.; Short, R.T.; Drury, J.S.

    1977-03-01

    Phosphoric acid and sulphuric acid have been compared as potential electrolytes for methanol-air fuel cells. The performances of typical electro-oxidation catalysts were measured in both electrolytes over a range of concentrations. With all catalysts the activity falls with increasing acid concentration. While this is to some extent due to the decrease in water activity at higher concentrations it seems that with both acids there is significant poisoning of the catalyst. The results can be explained for both electrolytes by assuming that adsorption of undissociated acid poisons the catalyst surfaces and that the reaction rate on the poisoned surfaces is proportional to the water activity.

  9. Functional multi-walled carbon nanotube/polysiloxane composite films as supports of PtNi alloy nanoparticles for methanol electro-oxidation

    International Nuclear Information System (INIS)

    Wang Zhicai; Ma Zhengming; Li Hulin

    2008-01-01

    We demonstrate the use of molecular monolayers to enhance the nucleation of electrocatalytically active PtNi alloy nanoparticles onto the multi-walled carbon nanotubes (MWCNTs). After the siloxane was polymerized on the nanotube surfaces, the carbon nanotubes were embedded within the polysiloxane shell with a hydrophilic amino group situated outside. Subsequent deposition of PtNi nanoparticles led to high density of 3-10 nm diameter PtNi alloy nanoparticles uniformly deposited along the length of the carbon nanotubes. The presence of MWCNTs and PtNi in the composite films was confirmed by transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersion X-ray spectra analysis (EDS). The electrocatalytic activity of the PtNi-modified MWCNT/polysiloxane (PtNi/Si-MWCNT) composite electrode for electro-oxidation of methanol was investigated by cyclic voltammetry (CV), and excellent electrocatalytic activity can be observed

  10. Pt-Fe catalyst nanoparticles supported on single-wall carbon nanotubes: Direct synthesis and electrochemical performance for methanol oxidation

    Science.gov (United States)

    Ma, Xiaohui; Luo, Liqiang; Zhu, Limei; Yu, Liming; Sheng, Leimei; An, Kang; Ando, Yoshinori; Zhao, Xinluo

    2013-11-01

    Single-wall carbon nanotubes (SWCNTs) supported Pt-Fe nanoparticles have been prepared by one-step hydrogen arc discharge evaporation of carbon electrode containing both Pt and Fe metal elements. The formation of SWCNTs and Pt-Fe nanoparticles occur simultaneously during the evaporation process. High-temperature hydrogen treatment and hydrochloric acid soaking have been carried out to purify and activate those materials in order to obtain a new type of Pt-Fe/SWCNTs catalyst for methanol oxidation. The Pt-Fe/SWCNTs catalyst performs much higher electrocatalytic activity for methanol oxidation, better stability and better durability than a commercial Pt/C catalyst according to the electrochemical measurements, indicating that it has a great potential for applications in direct methanol fuel cells.

  11. High Methanol Oxidation Activity of Well-Dispersed Pt Nanoparticles on Carbon Nanotubes Using Nitrogen Doping

    Directory of Open Access Journals (Sweden)

    Fang Wei-Chuan

    2009-01-01

    Full Text Available Abstract Pt nanoparticles (NPs with the average size of 3.14 nm well dispersed on N-doped carbon nanotubes (CNTs without any pretreatment have been demonstrated. Structural properties show the characteristic N bonding within CNTs, which provide the good support for uniform distribution of Pt NPs. In electrochemical characteristics, N-doped CNTs covered with Pt NPs show superior current density due to the fact that the so-called N incorporation could give rise to the formation of preferential sites within CNTs accompanied by the low interfacial energy for immobilizing Pt NPs. Therefore, the substantially enhanced methanol oxidation activity performed by N-incorporation technique is highly promising in energy-generation applications.

  12. Kinetic study of methanol oxidation on Pt2Ru3/C catalyst in the alkaline media

    Directory of Open Access Journals (Sweden)

    A. V. TRIPKOVIC

    2007-11-01

    Full Text Available The interaction of acridine orange (AO with double-stranded (ds The electrochemical oxidation of methanol in NaOH solution was examined on a thin film Pt2Ru3/C electrode. The XRD pattern revealed that the Pt2Ru3 alloy consisted of a solid solution of Ru in Pt and a small amount of Ru or a solid solution of Pt in Ru. It was shown that in alkaline solution, the difference in activity between Pt/C and Pt2Ru3/C is significantly smaller than in acid solution. It is proposed that the reaction follows a quasi bifunctional mechanism. The kinetic parameters indicated that the chemical reaction between adsorbed COad and OHad species could be the rate limiting step.

  13. High electrocatalytic performance of nitrogen-doped carbon nanofiber-supported nickel oxide nanocomposite for methanol oxidation in alkaline medium

    Energy Technology Data Exchange (ETDEWEB)

    Al-Enizi, Abdullah M. [Department of Chemistry, King Saud University, PO Box: 2455, Riyadh 11451 (Saudi Arabia); Elzatahry, Ahmed A., E-mail: aelzatahry@ksu.edu.sa [Materials Science and Technology Program, College of Arts and Science, Qatar University, Doha 2713 (Qatar); Advanced Technology and New Materials Research Institute, City of Scientific Research and Technology Applications, New Borg El-Arab City, Alexandria 21934 (Egypt); Abdullah, Aboubakr M., E-mail: bakr@qu.edu.qa [Center for Advanced Materials, Qatar University, Doha 2713 (Qatar); Vinu, Ajayan [Future Industries Institute, University of South Australia, Building X-X2-09, Mawson Lakes Campus, Mawson Lakes 5095 SA (Australia); Iwai, Hideo [Materials Analysis Station, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki, 305-0047 (Japan); Al-Deyab, Salem S. [Petrochemical Research Chair, Department of Chemistry, King Saud University, PO Box: 2455, Riyadh 11451 (Saudi Arabia)

    2017-04-15

    Highlights: • A mixture of Polyvinylpyrrolidone (PVP), graphene and emeraldine base polyaniline (PANi) was electrospun and used as starting materials to prepare a nitrogen-doped carbon nanofiber (N-CNF). • Nickel oxide was loaded on the N-CNF to form a nanocomposite which was calcined later at different temperatures. • The effect of calcination temperature on the electrocatalytic behavior of the nanocomposite was studied which shows that the nanocomposite calcined at 500 °C was proved to be very high compared to the other calcination temperatures. • The stability of catalyst was excellent and its resistance to the adsorption of the intermediates generated from the methanol oxidation was very high. - Abstract: Nitrogen-Doped Carbon Nanofiber (N-CNF)–supported NiO composite was prepared by electrospinning a sol-gel mixture of graphene and polyaniline (PANi) with aqueous solutions of Polyvinylpyrrolidone (PVP) followed by a high-temperature annealing process. The electrospun was stabilized for 2 h at 280 °C, carbonized for 5 h at 1200 °C then loaded by 10% NiO. The electrocatalytic activities of the produced nanocomposite have been studied using cyclic voltammetry, and chronoamperometry. Also, N-CNF was characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area (BET), X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), and scanning-electron microscopy (SEM). The obtained N-doped carbon nanofiber was found to have a nitrogen content of 2.6 atomic% with a diameter range of (140–160) nm, and a surface area (393.3 m{sup 2} g{sup −1}). In addition, it showed a high electrocatalytic behavior towards methanol oxidation reaction in alkaline medium and high stability and resistivity to the adsorption of intermediates.

  14. Synthesis of highly active and dual-functional electrocatalysts for methanol oxidation and oxygen reduction reactions

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Qi; Zhang, Geng; Xu, Guangran; Li, Yingjun [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Liu, Baocang [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Gong, Xia [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Zheng, Dafang [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China); Zhang, Jun [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Wang, Qin, E-mail: qinwang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China)

    2016-12-15

    Graphical abstract: Ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities (NDs) catalysts, are successfully synthesized by using a facile method. The as-obtained ternary catalysts manifest superior catalytic activity and stability both in terms of surface and mass specific activities toward the methanol oxidation and oxygen reduction reactions, as compared to the binary catalysts and the commercial Pt/C catalysts. - Highlights: • Ternary RuMPt catalysts are synthesized by using a facile method. • The catalysts manifest superior catalytic activity towards the MOR and ORR. • High activities are attributed to enhanced electron density and synergistic effects. - Abstract: The promising Pt-based ternary catalyst is crucial for polymer electrolyte membrane fuel cells (PEMFCs) due to improving catalytic activity and durability for both methanol oxidation reaction and oxygen reduction reaction. In this work, a facile strategy is used for the synthesis ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities catalysts. The ternary RuMPt alloys exhibit enhanced specific and mass activity, positive half-wave potential, and long-term stability, compared with binary Pt-based alloy and the commercial Pt/C catalyst, which is attributed to the high electron density and upshifting of the d-band center for Pt atoms, and synergistic catalytic effects among Pt, M, and Ru atoms by introducing a transition metal. Impressively, the ternary RuCoPt catalyst exhibits superior mass activity (801.59 mA mg{sup −1}) and positive half-wave potential (0.857 V vs. RHE) towards MOR and ORR, respectively. Thus, the RuMPt nanocomposite is a very promising material to be used as dual electrocatalyst in the application of PEMFCs.

  15. Improving the Durability of Methanol Oxidation Reaction Electro-Catalysts Through the Modification of Carbon Architectures

    Science.gov (United States)

    2014-01-01

    PEMFC Direct Methanol Fuel Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . DMFC Colorado School of Mines...Thus, a methanol-fed proton exchange membrane fuel cell ( PEMFC ) utilizing this potentially inexpensive fuel, would provide a sustainable and renewable

  16. Cuprous oxide thin films grown by hydrothermal electrochemical deposition technique

    International Nuclear Information System (INIS)

    Majumder, M.; Biswas, I.; Pujaru, S.; Chakraborty, A.K.

    2015-01-01

    Semiconducting cuprous oxide films were grown by a hydrothermal electro-deposition technique on metal (Cu) and glass (ITO) substrates between 60 °C and 100 °C. X-ray diffraction studies reveal the formation of cubic cuprous oxide films in different preferred orientations depending upon the deposition technique used. Film growth, uniformity, grain size, optical band gap and photoelectrochemical response were found to improve in the hydrothermal electrochemical deposition technique. - Highlights: • Cu 2 O thin films were grown on Cu and glass substrates. • Conventional and hydrothermal electrochemical deposition techniques were used. • Hydrothermal electrochemical growth showed improved morphology, thickness and optical band gap

  17. Microwave-irradiation polyol synthesis of PVP-protected Pt–Ni electrocatalysts for methanol oxidation reaction

    CSIR Research Space (South Africa)

    Mathe, Ntombizodwa R

    2017-01-01

    Full Text Available ://doi.org/10.1007/s12678-017-0441-3 Microwave-Irradiation Polyol Synthesis of PVP-Protected Pt–Ni Electrocatalysts for Methanol Oxidation Reaction Ntombizodwa R. Mathe Manfred R. Scriba Rirhandzu S. Rikhotso Neil J. Coville ABSTRACT: Bimetallic Pt...

  18. Methanol electro-oxidation on Pt-Ru-P/C and Pt-Ru-P/MWCNT in acidic medium

    CSIR Research Space (South Africa)

    Modibedi, M

    2009-06-01

    Full Text Available . The electro-catalytic activity towards methanol oxidation in acidic medium was studied by cyclic voltammetry and linear sweep voltammetry. Pt-Ru-P/MWCNT showed excellent activity compared to that of Pt-Ru-P/C. This may be attributed to the effectiveness...

  19. How bimetallic electrocatalysts does work for reactions involved in fuel cells? Example of ethanol oxidation and comparison to methanol

    Energy Technology Data Exchange (ETDEWEB)

    Leger, J.-M.; Rousseau, S.; Coutanceau, C.; Hahn, F.; Lamy, C. [UMR 6503, Electrocatalysis Group, CNRS - University of Poitiers, 40 Avenue du Recteur Pineau, 86022 Poitiers Cedex (France)

    2005-09-05

    Carbon-supported Pt-based nanosized electrocatalysts can be synthesized for methanol and ethanol electrooxidation. The electrocatalytic activity of Pt can be greatly enhanced by using Pt-Ru/C for methanol oxidation or Pt-Sn/C for ethanol oxidation. In situ IR reflectance spectroscopy is a convenient tool to better understand the importance of the different adsorption steps involved in the mechanisms of electrooxidation. With Pt/C, it appears clearly that linearly adsorbed CO is the poisoning species formed during methanol and ethanol oxidation. In the case of methanol, even with Pt-Ru/C (the most active catalyst), adsorbed CO is also a reactive intermediate. The enhancement of activity observed in such a case is due to the possibility to activate water at lower potentials in the presence of Ru. With Pt-Sn/C, the mechanism of the electrooxidation of ethanol is strongly modified. If at low potentials, poisoning with adsorbed CO still exists (as with Pt/C), the oxidation of ethanol at potentials greater than 0.4 V versus RHE occurs through an adsorbed acetyl species which can lead to the formation of acetaldehyde and acetic acid as final products in addition to carbon dioxide. (author)

  20. The influence of water on the oxygen-silver interaction and on the oxidative dehydrogenation of methanol

    NARCIS (Netherlands)

    Lefferts, Leon; Van Ommen, Jan G.; Ross, Julian R H

    1988-01-01

    Experiments carried out using temperature-programmed desorption and reduction could detect no interaction between water and silver at 200 °C. However, separate experiments on the effect of water on the oxidative dehydrogenation of methanol over a silver catalyst showed that water affected the

  1. The oxidative dehydrogenation of methanol to formaldehyde over silver catalysts in relation to the oxygen-silver interaction

    NARCIS (Netherlands)

    Lefferts, Leonardus; van Ommen, J.G.; Ross, J.R.H.

    1986-01-01

    The properties of silver in the oxidative dehydrogenation of methanol were studied in a flow reactor under near industrial conditions. The influences of temperature, concentration of both reactants, gas velocity, space velocity, the form of the silver catalyst and surface composition of the catalyst

  2. Biogenesis and Turnover of Peroxisomes Involved in the Concurrent Oxidation of Methanol and Methylamine in Hansenula polymorpha

    NARCIS (Netherlands)

    Veenhuis, M.; Zwart, K.B.; Harder, W.

    1981-01-01

    Growth of Hansenula polymorpha in shake flasks and chemostat cultures in the presence of methanol as the sole source of carbon and methylamine as the sole source of nitrogen was associated with the development of peroxisomes in the cells. The organelles were involved in the concurrent oxidation of

  3. Platinized titanium dioxide electrodes for methanol oxidation and photo-oxidation

    OpenAIRE

    IOANNIS POULIOS; GEORGIOS KOKKINIDIS; EUGENIA VALOVA; STEPHAN ARMYANOV; JENIA GEORGIEVA; IOANNA MINTSOULI; SVETLOZAR IVANOV; SOTIRIS SOTIROPOULOS

    2012-01-01

    Platinized deposits have been formed on TiO2 particulate films supported on Ti substrates, by means of galvanic replacement of pre-deposited metallic Cu and subsequent immersion of the Cu/TiO2 coatings into a chloroplatinic acid solution. The spontaneous replacement of Cu by Pt results in Pt(Cu)/TiO2/Ti electrodes. Both the platinized and the precursor TiO2/Ti electrodes have been characterized by SEM micro­scopy/EDS spectroscopy, their surface electrochemistry has been assessed by cyclic vol...

  4. Self-assembled platinum nanoparticles on sulfonic acid-grafted graphene as effective electrocatalysts for methanol oxidation in direct methanol fuel cells.

    Science.gov (United States)

    Lu, Jinlin; Li, Yanhong; Li, Shengli; Jiang, San Ping

    2016-02-15

    In this article, sulfonic acid-grafted reduced graphene oxide (S-rGO) were synthesized using a one-pot method under mild conditions, and used as Pt catalyst supports to prepare Pt/S-rGO electrocatalysts through a self-assembly route. The structure, morphologies and physicochemical properties of S-rGO were examined in detail by techniques such as atomic force microscope (AFM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The S-rGO nanosheets show excellent solubility and stability in water and the average particle size of Pt nanoparticles supported on S-rGO is ~3.8 nm with symmetrical and uniform distribution. The electrocatalytic properties of Pt/S-rGO were investigated for methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). In comparison to Pt supported on high surface area Vulcan XC-72 carbon (Pt/VC) and Pt/rGO, the Pt/S-rGO electrocatalyst exhibits a much higher electrocatalytic activity, faster reaction kinetics and a better stability. The results indicate that Pt/S-rGO is a promising and effective electrocatalyst for MOR of DMFCs.

  5. Self-assembled platinum nanoparticles on sulfonic acid-grafted graphene as effective electrocatalysts for methanol oxidation in direct methanol fuel cells

    Science.gov (United States)

    Lu, Jinlin; Li, Yanhong; Li, Shengli; Jiang, San Ping

    2016-02-01

    In this article, sulfonic acid-grafted reduced graphene oxide (S-rGO) were synthesized using a one-pot method under mild conditions, and used as Pt catalyst supports to prepare Pt/S-rGO electrocatalysts through a self-assembly route. The structure, morphologies and physicochemical properties of S-rGO were examined in detail by techniques such as atomic force microscope (AFM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The S-rGO nanosheets show excellent solubility and stability in water and the average particle size of Pt nanoparticles supported on S-rGO is ~3.8 nm with symmetrical and uniform distribution. The electrocatalytic properties of Pt/S-rGO were investigated for methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). In comparison to Pt supported on high surface area Vulcan XC-72 carbon (Pt/VC) and Pt/rGO, the Pt/S-rGO electrocatalyst exhibits a much higher electrocatalytic activity, faster reaction kinetics and a better stability. The results indicate that Pt/S-rGO is a promising and effective electrocatalyst for MOR of DMFCs.

  6. Influence of Catalyst Acid/Base Properties in Acrolein Production by Oxidative Coupling of Ethanol and Methanol.

    Science.gov (United States)

    Lilić, Aleksandra; Bennici, Simona; Devaux, Jean-François; Dubois, Jean-Luc; Auroux, Aline

    2017-05-09

    Oxidative coupling of methanol and ethanol represents a new route to produce acrolein. In this work, the overall reaction was decoupled in two steps, the oxidation and the aldolization, by using two consecutive reactors to investigate the role of the acid/base properties of silica-supported oxide catalysts. The oxidation of a mixture of methanol and ethanol to formaldehyde and acetaldehyde was performed over a FeMoO x catalyst, and then the product mixture was transferred without intermediate separation to a second reactor, in which the aldol condensation and dehydration to acrolein were performed over the supported oxides. The impact of the acid/base properties on the selectivity towards acrolein was investigated under oxidizing conditions for the first time. The acid/base properties of the catalysts were investigated by NH 3 -, SO 2 -, and methanol-adsorption microcalorimetry. A MgO/SiO 2 catalyst was the most active in acrolein production owing to an appropriate ratio of basic to acidic sites. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Chemical solution deposition of functional oxide thin films

    CERN Document Server

    Schneller, Theodor; Kosec, Marija

    2014-01-01

    Chemical Solution Deposition (CSD) is a highly-flexible and inexpensive technique for the fabrication of functional oxide thin films. Featuring nearly 400 illustrations, this text covers all aspects of the technique.

  8. A role for glutathione, independent of oxidative stress, in the developmental toxicity of methanol

    International Nuclear Information System (INIS)

    Siu, Michelle T.; Shapiro, Aaron M.; Wiley, Michael J.; Wells, Peter G.

    2013-01-01

    Oxidative stress and reactive oxygen species (ROS) have been implicated in the teratogenicity of methanol (MeOH) in rodents, both in vivo and in embryo culture. We explored the ROS hypothesis further in vivo in pregnant C57BL/6J mice. Following maternal treatment with a teratogenic dose of MeOH, 4 g/kg via intraperitoneal (ip) injection on gestational day (GD) 12, there was no increase 6 h later in embryonic ROS formation, measured by 2′,7′-dichlorodihydrofluorescin diacetate (DCFH-DA) fluorescence, despite an increase observed with the positive control ethanol (EtOH), nor was there an increase in embryonic oxidatively damaged DNA, quantified as 8-oxo-2′-deoxyguanosine (8-oxodG) formation. MeOH teratogenicity (primarily ophthalmic anomalies, cleft palate) also was not altered by pre- and post-treatment with varying doses of the free radical spin trapping agent alpha-phenyl-N-tert-butylnitrone (PBN). In contrast, pretreatment with L-buthionine-(S,R)-sulfoximine (BSO), an inhibitor of glutathione (GSH) synthesis, depleted maternal hepatic and embryonic GSH, and enhanced some new anomalies (micrognathia, agnathia, short snout, fused digits, cleft lip, low set ears), but not the most common teratogenic effects of MeOH (ophthalmic anomalies, cleft palate) in this strain. These results suggest that ROS did not contribute to the teratogenic effects of MeOH in this in vivo mouse model, in contrast to results in embryo culture from our laboratory, and that the protective effect of GSH in this model may arise from its role as a cofactor for formaldehyde dehydrogenase in the detoxification of formaldehyde. - Highlights: • In vivo, a free radical scavenger did not block methanol (MeOH) teratogenesis. • MeOH did not increase embryonic reactive oxygen species formation or DNA oxidation. • MeOH teratogenesis was enhanced by glutathione (GSH) depletion. • GSH may protect as the cofactor for formaldehyde dehydrogenase (ADH3). • Formaldehyde may be a ROS

  9. A role for glutathione, independent of oxidative stress, in the developmental toxicity of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Siu, Michelle T.; Shapiro, Aaron M. [Division of Biomolecular Sciences, Faculty of Pharmacy, University of Toronto, Toronto, Ontario (Canada); Wiley, Michael J. [Division of Anatomy, Faculty of Medicine, University of Toronto, Toronto, Ontario (Canada); Wells, Peter G., E-mail: pg.wells@utoronto.ca [Division of Biomolecular Sciences, Faculty of Pharmacy, University of Toronto, Toronto, Ontario (Canada); Department of Pharmacology and Toxicology, Faculty of Medicine, University of Toronto, Toronto, Ontario (Canada)

    2013-12-15

    Oxidative stress and reactive oxygen species (ROS) have been implicated in the teratogenicity of methanol (MeOH) in rodents, both in vivo and in embryo culture. We explored the ROS hypothesis further in vivo in pregnant C57BL/6J mice. Following maternal treatment with a teratogenic dose of MeOH, 4 g/kg via intraperitoneal (ip) injection on gestational day (GD) 12, there was no increase 6 h later in embryonic ROS formation, measured by 2′,7′-dichlorodihydrofluorescin diacetate (DCFH-DA) fluorescence, despite an increase observed with the positive control ethanol (EtOH), nor was there an increase in embryonic oxidatively damaged DNA, quantified as 8-oxo-2′-deoxyguanosine (8-oxodG) formation. MeOH teratogenicity (primarily ophthalmic anomalies, cleft palate) also was not altered by pre- and post-treatment with varying doses of the free radical spin trapping agent alpha-phenyl-N-tert-butylnitrone (PBN). In contrast, pretreatment with L-buthionine-(S,R)-sulfoximine (BSO), an inhibitor of glutathione (GSH) synthesis, depleted maternal hepatic and embryonic GSH, and enhanced some new anomalies (micrognathia, agnathia, short snout, fused digits, cleft lip, low set ears), but not the most common teratogenic effects of MeOH (ophthalmic anomalies, cleft palate) in this strain. These results suggest that ROS did not contribute to the teratogenic effects of MeOH in this in vivo mouse model, in contrast to results in embryo culture from our laboratory, and that the protective effect of GSH in this model may arise from its role as a cofactor for formaldehyde dehydrogenase in the detoxification of formaldehyde. - Highlights: • In vivo, a free radical scavenger did not block methanol (MeOH) teratogenesis. • MeOH did not increase embryonic reactive oxygen species formation or DNA oxidation. • MeOH teratogenesis was enhanced by glutathione (GSH) depletion. • GSH may protect as the cofactor for formaldehyde dehydrogenase (ADH3). • Formaldehyde may be a ROS

  10. Enhanced photocatalytic reduction of CO2 to methanol by ZnO nanoparticles deposited on ZnSe nanosheet

    Science.gov (United States)

    Zhang, Shuangfang; Yin, Xiaohong; Zheng, Yinan

    2018-02-01

    In this work ZnO/ZnSe composites were successfully synthesized via solvothermal method and characterized by a series of experiments for investigating into their compositions, morphologies, microstructures and the activities of photocatalytic reduction of CO2. The methanol rates of bare ZnO and ZnSe respectively were 763.9 μmol/gcat/h and 503.88 μmol/gcat/h. However, the sample of 3 wt% ZnO/ZnSe performed better photocatalytic activity up 1581.82 μmol/gcat/h compared to bare ZnO and ZnSe. In the as-prepared photocatalyst the nanosheet of ZnSe benefited the light harvest; suitable deposition of ZnO on the ZnSe nanosheet constructed a type II heterojunction for transferring the photo-generated electron to reduce CO2.

  11. Platinum assisted by carbon quantum dots for methanol electro-oxidation

    Science.gov (United States)

    Pan, Dan; Li, Xingwei; Zhang, Aofeng

    2018-01-01

    Various types of fuel cells as clean and portable power sources show a great attraction, especially direct methanol fuel cell (DMFC) having high energy density, low operating temperature and convenient fuel storage. However, the preparation of low-cost Pt-based catalysts with satisfactory catalytic performance still faces many challenges for its commercialization on large scale. Here, Pt catalysts assisted by carbon quantum dots (CQDs) are reported. The synergistic effect of carbon quantum dots and Pt metals is similar to a bi-component catalyst, such as PtRu. First, carbon quantum dots derived from Vulcan XC-72 carbon black are synthesized by mixed acid etching. Then, carbon black (Vulcan XC-72) is soaked in carbon quantum dots solution for several days to obtain carbon black modified by carbon quantum dots (XC-72-CQDs). Finally, Pt catalysts are supported on XC-72-CQDs (Pt/XC-72-CQDs) through a simple chemical reduction method. For methanol electro-oxidation reaction, the catalytic performance of Pt/XC-72-CQDs is compared with commercial PtRu/C (30% Pt + 15% Ru). Results show that a typical product (Pt/XC-72-CQDs5) exhibits a better catalytic activity than PtRu/C. In cyclic voltammetry test, the specific activity of Pt/XC-72-CQDs5 is 1.06 mA cm-2 Pt and 477.6 mA mg-1 Pt, while that of PtRu/C is 0.77 mA cm-2 Pt and 280.6 mA mg-1 Pt.

  12. Platinum nano-cluster thin film formed on glassy carbon and the application for methanol oxidation

    International Nuclear Information System (INIS)

    Chang, Gang; Oyama, Munetaka; Hirao, Kazuyuki

    2007-01-01

    As an interesting platinum nanostructured material, a Pt nano-cluster film (PtNCF) attached on glassy carbon (GC) is reported. Through the reduction of PtCl 4 2- by ascorbic acid in the presence of GC substrate, a Pt thin continuous film composed of small nano-clusters which had a further agglomerated nanostructure of small grains could be attached on the GC surface. It was found that the electrocatalytic ability of PtNCF for the methanol oxidation was apparently higher than those of the Pt nano-clusters dispersedly attached on GC or indium in oxides. In addition, the electrocatalytic performance of PtNCF per Pt amount was superior to that of Pt black on GC. These results indicate that, in spite of the continuous nanostructures, nano-grains of PtNCF worked effectively for the catalytic electrolysis. The present PtNCF can be regarded as an interesting thin film material, which can be easily prepared by one-step chemical reduction

  13. Method of plasma enhanced chemical vapor deposition of diamond using methanol-based solutions

    Science.gov (United States)

    Tzeng, Yonhua (Inventor)

    2009-01-01

    Briefly described, methods of forming diamond are described. A representative method, among others, includes: providing a substrate in a reaction chamber in a non-magnetic-field microwave plasma system; introducing, in the absence of a gas stream, a liquid precursor substantially free of water and containing methanol and at least one carbon and oxygen containing compound having a carbon to oxygen ratio greater than one, into an inlet of the reaction chamber; vaporizing the liquid precursor; and subjecting the vaporized precursor, in the absence of a carrier gas and in the absence in a reactive gas, to a plasma under conditions effective to disassociate the vaporized precursor and promote diamond growth on the substrate in a pressure range from about 70 to 130 Torr.

  14. Deposition of heated whey proteins on a chromium oxide surface.

    NARCIS (Netherlands)

    Jeurnink, Th.; Verheul, M.; Cohen Stuart, M.A.; Kruif, de C.G.

    1996-01-01

    Whey protein solutions were given different heat treatments after which their deposition on a chromium oxide surface (the outer layer of stainless steel) was measured by reflectometry. The deposition was studied under controlled flow conditions by using a stagnation point flow configuration. The

  15. High catalytic activity of ultrafine nanoporous palladium for electro-oxidation of methanol, ethanol, and formic acid

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaoguang; Wang, Weimin; Qi, Zhen; Zhao, Changchun; Ji, Hong; Zhang, Zhonghua [Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials (MOE), School of Materials Science and Engineering, Shandong University, Jingshi Road 73, Jinan 250061 (China)

    2009-10-15

    Nanoporous palladium (NPPd) with ultrafine ligament size of 3-6 nm was fabricated by dealloying of an Al-Pd alloy in an alkaline solution. Electrochemical measurements indicate that NPPd exhibits significantly high electrochemical active specific surface area (23 m{sup 2} g{sup -1}), and high catalytic activity for electro-oxidation of methanol, ethanol, and formic acid. Mass activities can reach 149, 148, 262 mA mg{sup -1} for the oxidation of methanol, ethanol and formic acid, respectively. Moreover, superior steady-state activities can be observed for all the electro-oxidation processes. NPPd will be a promising candidate for the anode catalyst for direct alcohol or formic acid fuel cells. (author)

  16. Catalytic oxidation of methanol on Pt/X (X = CaTP, NaTP electrodes in sulfuric acid solution

    Directory of Open Access Journals (Sweden)

    Said Benmokhtar

    2013-10-01

    Full Text Available In this paper, we report the synthesis and characterization of electrodes based on NASICON type phosphates. The study of the electrochemical oxidation of methanol at ambient temperature on electrodes based on NASICON type Ca0,5Ti2(PO43 (CaTP and Na5Ti(PO43 (NaTP compared to that of the platinum electrode model has been conducted by cyclic voltammetry in acidic medium. The results showed a significant increase of current density on the electro oxidation of methanol on the material developed based NASICON structure CaTP, cons deactivation of the electro oxidation is observed the closed structure type NaTP.

  17. Methanol oxidation by temperate soils and environmental determinants of associated methylotrophs

    Science.gov (United States)

    Stacheter, Astrid; Noll, Matthias; Lee, Charles K; Selzer, Mirjam; Glowik, Beate; Ebertsch, Linda; Mertel, Ralf; Schulz, Daria; Lampert, Niclas; Drake, Harold L; Kolb, Steffen

    2013-01-01

    The role of soil methylotrophs in methanol exchange with the atmosphere has been widely overlooked. Methanol can be derived from plant polymers and be consumed by soil microbial communities. In the current study, methanol-utilizing methylotrophs of 14 aerated soils were examined to resolve their comparative diversities and capacities to utilize ambient concentrations of methanol. Abundances of cultivable methylotrophs ranged from 106–108 gsoilDW−1. Methanol dissimilation was measured based on conversion of supplemented 14C-methanol, and occurred at concentrations down to 0.002 μmol methanol gsoilDW−1. Tested soils exhibited specific affinities to methanol (a0s=0.01 d−1) that were similar to those of other environments suggesting that methylotrophs with similar affinities were present. Two deep-branching alphaproteobacterial genotypes of mch responded to the addition of ambient concentrations of methanol (⩽0.6 μmol methanol gsoilDW−1) in one of these soils. Methylotroph community structures were assessed by amplicon pyrosequencing of genes of mono carbon metabolism (mxaF, mch and fae). Alphaproteobacteria-affiliated genotypes were predominant in all investigated soils, and the occurrence of novel genotypes indicated a hitherto unveiled diversity of methylotrophs. Correlations between vegetation type, soil pH and methylotroph community structure suggested that plant–methylotroph interactions were determinative for soil methylotrophs. PMID:23254514

  18. Electrical and optical performance of transparent conducting oxide films deposited by electrostatic spray assisted vapour deposition.

    Science.gov (United States)

    Hou, Xianghui; Choy, Kwang-Leong; Liu, Jun-Peng

    2011-09-01

    Transparent conducting oxide (TCO) films have the remarkable combination of high electrical conductivity and optical transparency. There is always a strong motivation to produce TCO films with good performance at low cost. Electrostatic Spray Assisted Vapor Deposition (ESAVD), as a variant of chemical vapour deposition (CVD), is a non-vacuum and low-cost deposition method. Several types of TCO films have been deposited using ESAVD process, including indium tin oxide (ITO), antimony-doped tin oxide (ATO), and fluorine doped tin oxide (FTO). This paper reports the electrical and optical properties of TCO films produced by ESAVD methods, as well as the effects of post treatment by plasma hydrogenation on these TCO films. The possible mechanisms involved during plasma hydrogenation of TCO films are also discussed. Reduction and etching effect during plasma hydrogenation are the most important factors which determine the optical and electrical performance of TCO films.

  19. Enhanced Proton Conductivity and Methanol Permeability Reduction via Sodium Alginate Electrolyte-Sulfonated Graphene Oxide Bio-membrane

    Science.gov (United States)

    Shaari, N.; Kamarudin, S. K.; Basri, S.; Shyuan, L. K.; Masdar, M. S.; Nordin, D.

    2018-03-01

    The high methanol crossover and high cost of Nafion® membrane are the major challenges for direct methanol fuel cell application. With the aim of solving these problems, a non-Nafion polymer electrolyte membrane with low methanol permeability and high proton conductivity based on the sodium alginate (SA) polymer as the matrix and sulfonated graphene oxide (SGO) as an inorganic filler (0.02-0.2 wt%) was prepared by a simple solution casting technique. The strong electrostatic attraction between -SO3H of SGO and the sodium alginate polymer increased the mechanical stability, optimized the water absorption and thus inhibited the methanol crossover in the membrane. The optimum properties and performances were presented by the SA/SGO membrane with a loading of 0.2 wt% SGO, which gave a proton conductivity of 13.2 × 10-3 Scm-1, and the methanol permeability was 1.535 × 10-7 cm2 s-1 at 25 °C, far below that of Nafion (25.1 × 10-7 cm2 s-1) at 25 °C. The mechanical properties of the sodium alginate polymer in terms of tensile strength and elongation at break were improved by the addition of SGO.

  20. Electrodeposition of mesoscopic Pt-Ru on reticulated vitreous carbon from reverse emulsions and microemulsions: Application to methanol electro-oxidation

    International Nuclear Information System (INIS)

    Cheng, Tommy T.; Gyenge, Elod L.

    2006-01-01

    High surface area Pt-Ru (between 120 and 400 cm 2 mg -1 ) meso-sized particles and mesoporous coatings were electrodeposited on reticulated vitreous carbon (RVC) three-dimensional electrodes using reverse emulsions and microemulsions. The organic phase of the colloidal media was composed of cyclohexane, Triton X-100 non-ionic surfactant and tetrabutylammonium perchlorate (for ionic conductivity) while the aqueous phase contained H 2 PtCl 6 and RuCl 3 (or (NH 4 ) 2 RuCl 6 ). For microemulsification to occur isopropanol was also added as co-surfactant. The catalytic activity for the electro-oxidation of methanol was assessed by cyclic voltammetry and chronopotentiometry in conjunction with surface area measurement by Cu underpotential deposition. The composition and morphology of the Pt-Ru deposit was analyzed by inductively coupled plasma atomic emission spectroscopy and scanning electron microscopy, respectively. The effects on the catalytic activity of the deposition current density, temperature, RVC pretreatment and plating bath composition are presented. It was found that the electrodeposition of Pt-Ru in reverse microemulsion yielded the highest specific surface area (400 cm 2 mg -1 ) and catalytic activity toward CH 3 OH electro-oxidation as shown, for example, by a 50-200 mV more negative anode potential determined by chronopotentiometry compared to a catalyst obtained by pure aqueous and emulsion electroplating

  1. Electrodeposition of mesoscopic Pt-Ru on reticulated vitreous carbon from reverse emulsions and microemulsions: Application to methanol electro-oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Tommy T. [2360 East Mall, Department of Chemical and Biological Engineering, University of British Columbia, Vancouver, BC, V6T 1Z3 (Canada); Gyenge, Elod L. [2360 East Mall, Department of Chemical and Biological Engineering, University of British Columbia, Vancouver, BC, V6T 1Z3 (Canada)]. E-mail: egyenge@chml.ubc.ca

    2006-05-20

    High surface area Pt-Ru (between 120 and 400 cm{sup 2} mg{sup -1}) meso-sized particles and mesoporous coatings were electrodeposited on reticulated vitreous carbon (RVC) three-dimensional electrodes using reverse emulsions and microemulsions. The organic phase of the colloidal media was composed of cyclohexane, Triton X-100 non-ionic surfactant and tetrabutylammonium perchlorate (for ionic conductivity) while the aqueous phase contained H{sub 2}PtCl{sub 6} and RuCl{sub 3} (or (NH{sub 4}){sub 2}RuCl{sub 6}). For microemulsification to occur isopropanol was also added as co-surfactant. The catalytic activity for the electro-oxidation of methanol was assessed by cyclic voltammetry and chronopotentiometry in conjunction with surface area measurement by Cu underpotential deposition. The composition and morphology of the Pt-Ru deposit was analyzed by inductively coupled plasma atomic emission spectroscopy and scanning electron microscopy, respectively. The effects on the catalytic activity of the deposition current density, temperature, RVC pretreatment and plating bath composition are presented. It was found that the electrodeposition of Pt-Ru in reverse microemulsion yielded the highest specific surface area (400 cm{sup 2} mg{sup -1}) and catalytic activity toward CH{sub 3}OH electro-oxidation as shown, for example, by a 50-200 mV more negative anode potential determined by chronopotentiometry compared to a catalyst obtained by pure aqueous and emulsion electroplating.

  2. Exploring the deposition of oxides on silicon for photovoltaic cells by pulsed laser deposition

    NARCIS (Netherlands)

    Doeswijk, L.M.; de Moor, Hugo H.C.; Rogalla, Horst; Blank, David H.A.

    2002-01-01

    Since most commercially available solar cells are still made from silicon, we are exploring the introduction of passivating qualities in oxides, with the potential to serve as an antireflection coating. Pulsed laser deposition (PLD) was used to deposit TiO2 and SrTiO3 coatings on silicon substrates.

  3. Organization of Genes Required for the Oxidation of Methanol to Formaldehyde in Three Type II Methylotrophs

    Science.gov (United States)

    Bastien, C.; Machlin, S.; Zhang, Y.; Donaldson, K.; Hanson, R. S.

    1989-01-01

    Restriction maps of genes required for the synthesis of active methanol dehydrogenase in Methylobacterium organophilum XX and Methylobacterium sp. strain AM1 have been completed and compared. In these two species of pink-pigmented, type II methylotrophs, 15 genes were identified that were required for the expression of methanol dehydrogenase activity. None of these genes were required for the synthesis of the prosthetic group of methanol dehydrogenase, pyrroloquinoline quinone. The structural gene required for the synthesis of cytochrome cL, an electron acceptor uniquely required for methanol dehydrogenase, and the genes encoding small basic peptides that copurified with methanol dehydrogenases were closely linked to the methanol dehydrogenase structural genes. A cloned 22-kilobase DNA insert from Methylsporovibrio methanica 81Z, an obligate type II methanotroph, complemented mutants that contained lesions in four genes closely linked to the methanol dehydrogenase structural genes. The methanol dehydrogenase and cytochrome cL structural genes were found to be transcribed independently in M. organophilum XX. Only two of the genes required for methanol dehydrogenase synthesis in this bacterium were found to be cotranscribed. PMID:16348074

  4. On the deposition parameters of indium oxide (IO) and tin oxide (TO) by reactive evaporation technique

    International Nuclear Information System (INIS)

    Hassan, F.; Abdullah, A.H.; Salam, R.

    1990-01-01

    Thin films of tin oxide (TO) and indium oxide (IO) are prepared by the reactive evaporation technique, where indium or tin sources are evaporated and made to react with oxygen gas injected close to the substrate. In both depositions a substrate temperature of 380 0 C and a chamber pressure of 2x10 -5 mbar are utilized, but however different oxygen flow rates has been maintained. For TO, the deposition rate is found to be constant up to about 55 minutes of deposition time with a deposition rate of about 0.10 A/s, but for longer deposition time the deposition rate increases rapidly up to about 0.30 A/s. The IO displays a higher deposition rate of about 0.80 A/s over a deposition time 30 minutes, beyond which the deposition rate increases gradually

  5. Novel precursors for the deposition of rare earth oxides

    International Nuclear Information System (INIS)

    Ahlers, Mareike

    2010-01-01

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

  6. Formaldehyde formation in coupled oxidation of methane and methanol over V2O5 and MoO3 silica supported catalysts

    International Nuclear Information System (INIS)

    Lojewska, J.; Makowski, W.; Fajardo Farre, A.; Dziembaj, R.

    2003-01-01

    The effect of methanol on partial oxidation of methane has been studied on standard molybdena and vanadia catalysts supported on silica. Prior to catalytic tests the catalysts were characterized by BET, SEM/EDAX and TPR/O methods. Three types of catalytic tests were performed giving temperature and contact time dependence on the catalyst activity and selectivity: partial oxidations of methane, methanol and methane/methanol mixtures. The methanol showed an activating impact on the partial oxidation of methane over all used catalysts samples, but the strongest one over Mo 3 /SiO 2 . In the absence of CH 3 OH the only catalyst, which exhibited HCHO selectivity, was low loaded vanadia catalyst. It has been put forward that methanol may enhance formation of oxygen active species, prerequisites for activating methane molecules, through reducing vanadia cations and causing breakage of vanadium oxygen bonds. (author)

  7. Improved Catalysis of Green-Synthesized Pd-Ag Alloy-Nanoparticles for Anodic Oxidation of Methanol in Alkali

    International Nuclear Information System (INIS)

    Roy Chowdhury, Sreya; Ghosh, Srabanti; Bhattachrya, Swapan Kumar

    2017-01-01

    Highlights: • Pd and Pd x Ag y nanoalloys are synthesised by simple green synthetic method without using any capping agent. • Increased electrochemical surface area and roughness factor in case of Pd x Ag y alloy generates enhanced catalytically active sites which help methanol oxidation reaction. • By analysing the products of MOR reaction by CV, FTIR and HPLC plausible mechanism of the reaction is proposed. • Among different compositions Pd 4 Ag and Pd are the best electrodes for oxidation of methanol and formate respectively in alkali. - Abstract: Monometallic Pd, Ag and bimetallic Pd x Ag y alloy nanoparticles were synthesized in a single pot using a green synthetic protocol in absence of any capping agent. X-ray, electron diffraction, microscopic and spectroscopic studies of synthesized material demonstrate the formation of nanoballs with radius of 10–20 nm of face centred cubic metals and alloys. The electrochemical studies of as-synthesized materials loaded on carbon support reveal that the Pd 4 Ag nanoparticles exhibit the best and synergistic electro-catalytic activity in reference to oxidation of methanol in alkali. The most active Pd 4 Ag nanoparticles show higher peak current (201 mA mg −1 ) in comparison to that (133 mA mg −1 ) of Pd in cyclic voltammetric study. The electrode shows the highest exchange current density (1.95 × 10 −2 mA mg −1 of Pd) for methanol oxidation reaction (MOR) and higher catalytic activity for oxidation of possible intermediates like formaldehyde and sodium formate of MOR. Ex-situ infrared spectrometry and chromatographic studies of reaction products reveal that Ag accelerates the formation of formate rather than carbonate elucidating the plausible mechanism of the reaction. These findings have important implications for further fine-tuning of the Pd nano alloys toward highly active and selective catalysts for alcohol fuel cells.

  8. Enhanced methanol electro-oxidation reaction on Pt-CoO{sub x}/MWCNTs hybrid electro-catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Nouralishahi, Amideddin, E-mail: Nouralishahi@ut.ac.ir [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, P.O. Box 11155/4563, Tehran (Iran, Islamic Republic of); Caspian Faculty of Engineering, University of Tehran, P.O. Box 43841-119, Rezvanshahr (Iran, Islamic Republic of); Catalysis and Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of); Rashidi, Ali Morad, E-mail: Rashidiam@ripi.ir [Catalysis and Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of); Mortazavi, Yadollah, E-mail: Mortazav@ut.ac.ir [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, P.O. Box 11155/4563, Tehran (Iran, Islamic Republic of); Khodadadi, Abbas Ali, E-mail: Khodadad@ut.ac.ir [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, P.O. Box 11155/4563, Tehran (Iran, Islamic Republic of); Choolaei, Mohammadmehdi, E-mail: Choolaeimm@ripi.ir [Catalysis and Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of)

    2015-04-30

    Highlights: • Promoting effects of Cobalt oxide on methanol electro-oxidation over Pt/MWCNTs are investigated. • Higher activity, about 2.9 times, and enhanced stability are observed on Pt-CoO{sub x}/MWCNTs. • Electrochemical active surface area of Pt nanoparticles is significantly improved upon CoO{sub x} addition. • Bi-functional mechanism is facilitated in presence of CoO{sub x}. - Abstract: The electro-catalytic behavior of Pt-CoO{sub x}/MWCNTs in methanol electro-oxidation reaction (MOR) is investigated and compared to that of Pt/MWCNTs. The electro-catalysts were synthesized by an impregnation method using NaBH{sub 4} as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoO{sub x}, Pt nanoparticles were highly distributed on the support with an average particle size of 2 nm, an obvious decrease from 5.1 nm for Pt/MWCNTs. Cyclic voltammetry, CO-stripping, Chronoamperometry, and electrochemical impedance spectroscopy (EIS) measurements are used to study the electrochemical behavior of the electro-catalysts. The results revealed a considerable enhancement in the oxidation kinetics of CO{sub ads} on Pt active sites by the participation of CoO{sub x}. Compared to Pt/MWCNTs, Pt-CoO{sub x}/MWCNTs sample has a larger electrochemical active surface area (ECSA) and higher electro-catalytic activity and stability toward methanol electro-oxidation. According to the results of cyclic voltammetry, the forward anodic peak current density enhances more than 89% at the optimum atomic ratio of Pt:Co = 2:1. Furthermore, inclusion of cobalt oxide species causes the onset potential of methanol electro-oxidation reaction to shift 84 mV to negative values compared to that on Pt/MWCNTs. Based on EIS data, dehydrogenation of methanol is the rate-determining step of MOR on both Pt/MWCNTs and Pt-CoO{sub x}/MWCNTs, at small overpotentials. However, at higher overpotentials, the

  9. Plasma Deposition of Oxide-Coated Cathodes

    National Research Council Canada - National Science Library

    Umstattd, Ryan

    1998-01-01

    ...; such cathodes may also have applicability for lower current density continuous wave devices. This novel approach to manufacturing an oxide cathode eliminates the binders that may subsequently (and unpredictably...

  10. Facile synthesis of hollow dendritic Ag/Pt alloy nanoparticles for enhanced methanol oxidation efficiency.

    Science.gov (United States)

    Sui, Ning; Wang, Ke; Shan, Xinyao; Bai, Qiang; Wang, Lina; Xiao, Hailian; Liu, Manhong; Colvin, Vicki L; Yu, William W

    2017-11-14

    Hollow dendritic Ag/Pt alloy nanoparticles were synthesized by a double template method: Ag nanoparticles as the hard template to obtain hollow spheres by a galvanic replacement reaction between PtCl 6 2- and metallic Ag and surfactant micelles (Brij58) as the soft template to generate porous dendrites. The formation of a Ag/Pt alloy phase was confirmed by XRD and HRTEM. Elemental mapping and line scanning revealed the formation of the hollow architecture. We studied the effects of the Ag/Pt ratio, surfactant and reaction temperature on the morphology. In addition, we explored the formation process of hollow dendritic Ag/Pt nanoparticles by tracking the morphologies of the nanostructures formed at different stages. In order to improve the electrocatalytic property, we controlled the size of the nanoparticles and the thickness of the shell by adjusting the amount of the precursor. We found that these Ag/Pt alloy nanoparticles exhibited high activity (440 mA mg -1 ) and stability as an electrocatalyst for catalyzing methanol oxidation.

  11. Seed-mediated synthesis of cross-linked Pt-NiO nanochains for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Gu, Zhulan; Bin, Duan; Feng, Yue; Zhang, Ke; Wang, Jin; Yan, Bo; Li, Shumin; Xiong, Zhiping; Wang, Caiqin; Shiraishi, Yukihide; Du, Yukou, E-mail: duyk@suda.edu.cn

    2017-07-31

    Highlights: • Cross-linked Pt-NiO nanochains using seed-mediated growth method are synthesized. • The as-prepared catalysts exhibit higher electrocatalytic activity than Pt/C for MOR. • The Pt-NiO(1:1 by molar) catalyst shows the best electrocatalytic property towards MOR. - Abstract: A simple method was reported for employing NiO nanoparticles act as seeds and then different amounts of Pt{sup 2+} were reduced on the NiO nanoparticles, forming a cross-linked Pt-NiO nanocatalysts. These as-prepared catalysts were characterized using different physical-chemical techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results indicate that the morphology of the cross-linked Pt-NiO nanochain was successfully produced regardless of the molar ratio of Pt{sup 2+} to NiO precursors. The electrochemical characteristics of Pt-NiO nanochain catalysts were evaluated for the oxidation of methanol as a model reaction, which verify that the Pt-NiO catalysts show enhanced activity and high stability in comparison with the commercial Pt/C catalyst. The optimized ratio of Pt to NiO is 1:1, then tuned by simple adjusting the feed ratio of the precursors as well. The synthesized nanocatalysts will be found the great potential applications as electrocatalysts for fuel cells owe to their enhanced catalytic performance and long-term stability.

  12. Seed-mediated synthesis of cross-linked Pt-NiO nanochains for methanol oxidation

    Science.gov (United States)

    Gu, Zhulan; Bin, Duan; Feng, Yue; Zhang, Ke; Wang, Jin; Yan, Bo; Li, Shumin; Xiong, Zhiping; Wang, Caiqin; Shiraishi, Yukihide; Du, Yukou

    2017-07-01

    A simple method was reported for employing NiO nanoparticles act as seeds and then different amounts of Pt2+ were reduced on the NiO nanoparticles, forming a cross-linked Pt-NiO nanocatalysts. These as-prepared catalysts were characterized using different physical-chemical techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results indicate that the morphology of the cross-linked Pt-NiO nanochain was successfully produced regardless of the molar ratio of Pt2+ to NiO precursors. The electrochemical characteristics of Pt-NiO nanochain catalysts were evaluated for the oxidation of methanol as a model reaction, which verify that the Pt-NiO catalysts show enhanced activity and high stability in comparison with the commercial Pt/C catalyst. The optimized ratio of Pt to NiO is 1:1, then tuned by simple adjusting the feed ratio of the precursors as well. The synthesized nanocatalysts will be found the great potential applications as electrocatalysts for fuel cells owe to their enhanced catalytic performance and long-term stability.

  13. Seed-mediated synthesis of cross-linked Pt-NiO nanochains for methanol oxidation

    International Nuclear Information System (INIS)

    Gu, Zhulan; Bin, Duan; Feng, Yue; Zhang, Ke; Wang, Jin; Yan, Bo; Li, Shumin; Xiong, Zhiping; Wang, Caiqin; Shiraishi, Yukihide; Du, Yukou

    2017-01-01

    Highlights: • Cross-linked Pt-NiO nanochains using seed-mediated growth method are synthesized. • The as-prepared catalysts exhibit higher electrocatalytic activity than Pt/C for MOR. • The Pt-NiO(1:1 by molar) catalyst shows the best electrocatalytic property towards MOR. - Abstract: A simple method was reported for employing NiO nanoparticles act as seeds and then different amounts of Pt 2+ were reduced on the NiO nanoparticles, forming a cross-linked Pt-NiO nanocatalysts. These as-prepared catalysts were characterized using different physical-chemical techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results indicate that the morphology of the cross-linked Pt-NiO nanochain was successfully produced regardless of the molar ratio of Pt 2+ to NiO precursors. The electrochemical characteristics of Pt-NiO nanochain catalysts were evaluated for the oxidation of methanol as a model reaction, which verify that the Pt-NiO catalysts show enhanced activity and high stability in comparison with the commercial Pt/C catalyst. The optimized ratio of Pt to NiO is 1:1, then tuned by simple adjusting the feed ratio of the precursors as well. The synthesized nanocatalysts will be found the great potential applications as electrocatalysts for fuel cells owe to their enhanced catalytic performance and long-term stability.

  14. Influence of the nature of conductive support on the electrocatalytic activity of electrodeposited Ni films towards methanol oxidation in 1 M KOH

    Energy Technology Data Exchange (ETDEWEB)

    Singh, R.N.; Singh, A.; Anindita; Mishra, D. [Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi 221005 (India)

    2008-12-15

    The study of electrochemical behaviour of dispersed Ni on graphite, glassy carbon, and Ti electrodes, obtained by an electro-deposition method, is carried out in 1 M KOH + 1 M CH{sub 3}OH at 25 C. Results show that the nature of substrate influences the apparent electrocatalytic activities of the Ni over layer greatly. It is observed that at E = 0.50 V vs. Hg/HgO (25 C), the dispersed Ni on graphite is approx. 300 times more active than that dispersed on Ti and is approx. 260 times more active than that dispersed on glassy carbon. Further, these electrodes show quite good resistance against electrode poisoning by the methanol oxidation intermediates/products. (author)

  15. Remote plasma-enhanced metalorganic chemical vapor deposition of aluminum oxide thin films

    NARCIS (Netherlands)

    Volintiru, I.; Creatore, M.; Hemmen, van J.L.; Sanden, van de M.C.M.

    2008-01-01

    Aluminum oxide films were deposited using remote plasma-enhanced metalorganic chemical vapor deposition from oxygen/trimethylaluminum mixtures. Initial studies by in situ spectroscopic ellipsometry demonstrated that the aluminum oxide films deposited at temperatures

  16. Methanol-Sensing Property Improvement of Meso structured Zinc Oxide Prepared by the Nano casting Strategy

    International Nuclear Information System (INIS)

    Gao, Q.; Zheng, W.T.; Wei, C.D.; Lin, H.M.

    2013-01-01

    The specific structure and morphology often play a critical role in governing the excellent intrinsic properties of the compound semiconductor. Herein, meso structured ZnO with excellent methanol-sensing properties was prepared by a structure replication procedure through the incipient wetness technique. The investigation on the crystal structure and morphology of the resultant material shows that the product consists of hexagonally arranged meso pores and crystalline walls, and its structure is an ideal replication of CMK-3 template. Consequently, meso structured ZnO was fabricated as a gas sensor for methanol. The excellent methanol-sensing performance was achieved at a relatively low operating temperature of 120°C. In comparison with the non porous ZnO prepared through conventional coprecipitation approach, meso structured ZnO material shows the higher sensitivity and stability. Furthermore, it shows the discrimination between methanol and ethanol sensitivity, which makes it a good candidate in fabricating selective methanol sensor in practice

  17. Methanol-Sensing Property Improvement of Mesostructured Zinc Oxide Prepared by the Nanocasting Strategy

    Directory of Open Access Journals (Sweden)

    Qian Gao

    2013-01-01

    Full Text Available The specific structure and morphology often play a critical role in governing the excellent intrinsic properties of the compound semiconductor. Herein, mesostructured ZnO with excellent methanol-sensing properties was prepared by a structure replication procedure through the incipient wetness technique. The investigation on the crystal structure and morphology of the resultant material shows that the product consists of hexagonally arranged mesopores and crystalline walls, and its structure is an ideal replication of CMK-3 template. Consequently, mesostructured ZnO was fabricated as a gas sensor for methanol. The excellent methanol-sensing performance was achieved at a relatively low operating temperature of 120°C. In comparison with the nonporous ZnO prepared through conventional coprecipitation approach, mesostructured ZnO material shows the higher sensitivity and stability. Furthermore, it shows the discrimination between methanol and ethanol sensitivity, which makes it a good candidate in fabricating selective methanol sensor in practice.

  18. Pt and PtRu nanoparticles supported on N-doped carbons as electrocatalysts for methanol electro oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Pereira, Viviane Santos; Silva, Julio Cesar Martins; Oliveira Neto, Almir; Spinace, Estevam Vitorio, E-mail: viviane_sp_saopaulo@yahoo.com.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2016-07-01

    Full text: Methanol is a liquid transportation fuel that can be produced from fossil or renewable resources. Fuel cells employing methanol directly as fuel (Direct Methanol Fuel Cell - DMFC) are very attractive as power source for portable, mobile and stationary applications [1]. PtRu/C electrocatalyst has been considered the best electrocatalyst for methanol electro-oxidation, however, its performance is strongly dependent on the method of preparation and on the characteristics of the carbon support. N-doped carbons with different N contents (1, 2 and 5 wt%) were prepared by thermal treatment of carbon with urea at 800 deg C. Pt and PtRu nanoparticles were supported on N-doped carbons by coreduction of Pt(IV) and Ru(III) ions using an alcohol-reduction process [2]. The obtained materials were characterized by Energy Dispersive X-ray spectroscopy, X-ray diffraction, Transmission electron microscopy and Cyclic Voltammetry. Pt and PtRu nanoparticles supported on N-doped carbons showed superior performance for methanol electro-oxidation when compared to the materials supported on non-modified carbon and to Pt/C and PtRu/C commercial electrocatalysts. Pt/C and PtRu/C prepared with the carbon modified with 2.5 wt% of N content showed the best activities. (author) [1] Y. Zhou, K. Neyerlin, T.S. Olson, S. Pylypenko, J. Bult, H.N. Dinh, T. Gennett, Z. Shao and R. O'Hayre, Energy Environ. Sci. 3, 1437 (2010); [2] E.V. Spinace, A.Oliveira Neto, T.R.R. Vasconcellos, M. Linardi, J. Power Sources 137, 17 (2004)

  19. Plasma-induced synthesis of Pt nanoparticles supported on TiO2 nanotubes for enhanced methanol electro-oxidation

    Science.gov (United States)

    Su, Nan; Hu, Xiulan; Zhang, Jianbo; Huang, Huihong; Cheng, Jiexu; Yu, Jinchen; Ge, Chao

    2017-03-01

    A Pt/C/TiO2 nanotube composite catalyst was successfully prepared for enhanced methanol electro-oxidation. Pt nanoparticles with a particle size of 2 nm were synthesized by plasma sputtering in water, and anatase TiO2 nanotubes with an inner diameter of approximately 100 nm were prepared by a simple two-step anodization method and annealing process. Field-emission scanning electron microscopy images indicated that the different morphologies of TiO2 synthesized on the surface of Ti foils were dependent on the different anodization parameters. The electrochemical performance of Pt/C/TiO2 catalysts for methanol oxidation showed that TiO2 nanotubes were more suitable for use as Pt nanoparticle support materials than irregular TiO2 short nanorods due to their tubular morphology and better electronic conductivity. X-ray photoelectron spectroscopy characterization showed that the binding energies of the Pt 4f of the Pt/C/TiO2 nanotubes exhibited a slightly positive shift caused by the relatively strong interaction between Pt and the TiO2 nanotubes, which could mitigate the poisoning of the Pt catalyst by COads, and further enhance the electrocatalytic performance. Thus, the as-obtained Pt/C/TiO2 nanotubes composites may become a promising catalyst for methanol electro-oxidation.

  20. Direct Synthesis of Methanol by Partial Oxidation of Methane with Oxygen over Cobalt Modified Mesoporous H-ZSM-5 Catalyst

    Directory of Open Access Journals (Sweden)

    Yuni Krisyuningsih Krisnandi

    2015-11-01

    Full Text Available Partial oxidation of methane over mesoporous catalyst cobalt modified H-ZSM-5 has been carried out. Mesoporous Na-ZSM-5 (Si/Al = 35.4 was successfully synthesized using double template method which has high surface area (450 m2/g and average pore diameter distribution of 1.9 nm. The as-synthesized Na-ZSM-5 was converted to H-ZSM-5 through multi-exchange treatment with ammonium ion solution, causing decreased crystallinity and surface area, but increased porous diameter, due to dealumination during treatment process. Moreover, H-ZSM-5 was loaded with cobalt (Co = 2.5% w by the incipient impregnation method and calcined at 550 °C. Partial oxidation of methane was performed in the batch reactor with 0.75 bar methane and 2 bar of nitrogen (with impurities of 0.5% oxygen as the input at various reaction time (30, 60 and 120 min. The reaction results show that cobalt species in catalyst has an important role, because H-ZSM-5 cannot produce methanol in partial oxidation of methane. The presence of molecular oxygen increased the percentage of methanol yield. The reaction is time-dependent with the highest methanol yield (79% was acquired using Co/H-ZSM-5 catalyst for 60 min.

  1. CeO2/rGO/Pt sandwich nanostructure: rGO-enhanced electron transmission between metal oxide and metal nanoparticles for anodic methanol oxidation of direct methanol fuel cells.

    Science.gov (United States)

    Yu, Xue; Kuai, Long; Geng, Baoyou

    2012-09-21

    Pt-based nanocomposites have been of great research interest. In this paper, we design an efficient MO/rGO/Pt sandwich nanostructure as an anodic electrocatalyst for DMFCs with combination of the merits of rigid structure of metallic oxides (MOs) and excellent electronic conductivity of reduced oxidized graphene (rGO) as well as overcoming their shortcomings. In this case, the CeO(2)/rGO/Pt sandwich nanostructure is successfully fabricated through a facile hydrothermal approach in the presence of graphene oxide and CeO(2) nanoparticles. This structure has a unique building architecture where rGO wraps up the CeO(2) nanoparticles and Pt nanoparticles are homogeneously dispersed on the surface of rGO. This novel structure endows this material with great electrocatalytic performance in methanol oxidation: it reduces the overpotential of methanol oxidation significantly and its electrocatalytic activity and stability are much enhanced compared with Pt/rGO, CeO(2)/Pt and Pt/C catalysts. This work supplies a unique MO/rGO/Pt sandwich nanostructure as an efficient way to improve the electrocatalytic performance, which will surely shed some light on the exploration of some novel structures of electrocatalyst for DMFCs.

  2. Electrochemical Deposition of Platinum and Palladium on Gold Nanoparticles Loaded Carbon Nanotube Support for Oxidation Reactions in Fuel Cell

    Directory of Open Access Journals (Sweden)

    Surin Saipanya

    2014-01-01

    Full Text Available Pt and Pd sequentially electrodeposited Au nanoparticles loaded carbon nanotube (Au-CNT was prepared for the electrocatalytic study of methanol, ethanol, and formic acid oxidations. All electrochemical measurements were carried out in a three-electrode cell. A platinum wire and Ag/AgCl were used as auxiliary and reference electrodes, respectively. Suspension of the Au-CNT, phosphate buffer, isopropanol, and Nafion was mixed and dropped on glassy carbon as a working electrode. By sequential deposition method, PdPtPt/Au-CNT, PtPdPd/Au-CNT, and PtPdPt/Au-CNT catalysts were prepared. Cyclic voltammograms (CVs of those catalysts in 1 M H2SO4 solution showed hydrogen adsorption and hydrogen desorption reactions. CV responses for those three catalysts in methanol, ethanol, and formic acid electrooxidations studied in 2 M CH3OH, CH3CH2OH, and HCOOH in 1 M H2SO4 show characteristic oxidation peaks. The oxidation peaks at anodic scan contribute to those organic substance oxidations while the peaks at cathodic scan are related with the reoxidation of the adsorbed carbonaceous species. Comparing all those three catalysts, it can be found that the PdPtPt/Au-CNT catalyst is good at methanol oxidation; the PtPdPt/Au-CNT effectively enhances ethanol oxidation while the PtPdPd/Au-CNT exceptionally catalyzes formic acid oxidation. Therefore, a different stoichiometry affects the electrochemical active surface area of the catalysts to achieve the catalytic oxidation reactions.

  3. Dry deposition of gaseous oxidized mercury in Western Maryland.

    Science.gov (United States)

    Castro, Mark S; Moore, Chris; Sherwell, John; Brooks, Steve B

    2012-02-15

    The purpose of this study was to directly measure the dry deposition of gaseous oxidized mercury (GOM) in western Maryland. Annual estimates were made using passive ion-exchange surrogate surfaces and a resistance model. Surrogate surfaces were deployed for seventeen weekly sampling periods between September 2009 and October 2010. Dry deposition rates from surrogate surfaces ranged from 80 to 1512 pgm(-2)h(-1). GOM dry deposition rates were strongly correlated (r(2)=0.75) with the weekly average atmospheric GOM concentrations, which ranged from 2.3 to 34.1 pgm(-3). Dry deposition of GOM could be predicted from the ambient air concentrations of GOM using this equation: GOM dry deposition (pgm(-2)h(-1))=43.2 × GOM concentration-80.3. Dry deposition velocities computed using GOM concentrations and surrogate surface GOM dry deposition rates, ranged from 0.2 to 1.7 cms(-1). Modeled dry deposition rates were highly correlated (r(2)=0.80) with surrogate surface dry deposition rates. Using the overall weekly average surrogate surface dry deposition rate (369 ± 340 pg m(-2)h(-1)), we estimated an annual GOM dry deposition rate of 3.2 μg m(-2)year(-1). Using the resistance model, we estimated an annual GOM dry deposition rate of 3.5 μg m(-2)year(-1). Our annual GOM dry deposition rates were similar to the dry deposition (3.3 μg m(-2)h(-1)) of gaseous elemental mercury (GEM) at our site. In addition, annual GOM dry deposition was approximately 1/2 of the average annual wet deposition of total mercury (7.7 ± 1.9 μg m(-2)year(-1)) at our site. Total annual mercury deposition from dry deposition of GOM and GEM and wet deposition was approximately 14.4 μg m(-2)year(-1), which was similar to the average annual litterfall deposition (15 ± 2.1 μg m(-2)year(-1)) of mercury, which was also measured at our site. Copyright © 2012 Elsevier B.V. All rights reserved.

  4. Dynamics of electrocatalytic oxidation of ethylene glycol, methanol and formic acid at MWCNT platform electrochemically modified with Pt/Ru nanoparticles

    CSIR Research Space (South Africa)

    Maxakato, NW

    2010-03-01

    Full Text Available Comparative electrocatalytic behavior of functionalized multiwalled carbon nanotubes (fMWCNTs) electrodecorated with Pt/Ru nanoparticles towards the oxidation of methanol (MeOH), ethylene glycol (EG) and formic acid (FA) has been investigated...

  5. Nanocomposite oxide thin films grown by pulsed energy beam deposition

    International Nuclear Information System (INIS)

    Nistor, M.; Petitmangin, A.; Hebert, C.; Seiler, W.

    2011-01-01

    Highly non-stoichiometric indium tin oxide (ITO) thin films were grown by pulsed energy beam deposition (pulsed laser deposition-PLD and pulsed electron beam deposition-PED) under low oxygen pressure. The analysis of the structure and electrical transport properties showed that ITO films with a large oxygen deficiency (more than 20%) are nanocomposite films with metallic (In, Sn) clusters embedded in a stoichiometric and crystalline oxide matrix. The presence of the metallic clusters induces specific transport properties, i.e. a metallic conductivity via percolation with a superconducting transition at low temperature (about 6 K) and the melting and freezing of the In-Sn clusters in the room temperature to 450 K range evidenced by large changes in resistivity and a hysteresis cycle. By controlling the oxygen deficiency and temperature during the growth, the transport and optical properties of the nanocomposite oxide films could be tuned from metallic-like to insulating and from transparent to absorbing films.

  6. Facile synthesis of porous Pt-Pd nanospheres supported on reduced graphene oxide nanosheets for enhanced methanol electrooxidation

    Science.gov (United States)

    Li, Shan-Shan; Lv, Jing-Jing; Hu, Yuan-Yuan; Zheng, Jie-Ning; Chen, Jian-Rong; Wang, Ai-Jun; Feng, Jiu-Ju

    2014-02-01

    In this study, a simple, facile, and effective wet-chemical strategy was developed in the synthesis of uniform porous Pt-Pd nanospheres (Pt-Pd NSs) supported on reduced graphene oxide nanosheets (RGOs) under ambient temperature, where octylphenoxypolye thoxyethanol (NP-40) is used as a soft template, without any seed, organic solvent or special instruments. The as-prepared nanocomposites display enhanced electrocatalytic activity and good stability toward methanol oxidation, compared with commercial Pd/C and Pt/C catalysts. This strategy may open a new route to design and prepare advanced electrocatalysts for fuel cells.

  7. Methanol-dispersed of ternary Fe3O4@γ-APS/graphene oxide-based nanohybrid for novel removal of benzotriazole from aqueous solution.

    Science.gov (United States)

    Minh, Tran Dinh; Lee, Byeong-Kyu; Nguyen-Le, Minh-Tri

    2018-03-01

    A novel nanohybrid: Fe 3 O 4 coated with γ-APS polymer deposited on graphene oxide (F@γ-A/G), to remove an emergent heterocyclic contaminant benzotriazole (BTA) from solution. F@γ-A/G was synthesized in methanol-dispersion via aminosilanization under ultra-sonication. We newly found that F@γ-A/G crystallite lattice has a 2D triangular-network intersection with angle of 60° in three types of d 311 , d 220 and d 111 planes with different interplanar spacings. Textural characteristics did not affect BTA adsorption, which was desired at high temperature (40 °C), neutral solution (pH = 6) and controlled by endothermic process. Considering the maximum BTA adsorption capacity of 312.5 mg/g, which was much higher than previously reported adsorbents, the plausible mechanism was attributed to hydrophobic, electrostatic and π-π interaction. Effects of pH and temperature are significant on BTA adsorption to F@γ-A/G. Methanol was the best solvent for multiple cycle regeneration with only 2% loss of BTA removal efficiency even after five cycles of F@γ-A/G. Copyright © 2018 Elsevier Ltd. All rights reserved.

  8. Phosphate-Doped Carbon Black as Pt Catalyst Support: Co-catalytic Functionality for Dimethyl Ether and Methanol Electro-oxidation

    DEFF Research Database (Denmark)

    Yin, Min; Huang, Yunjie; Li, Qingfeng

    2014-01-01

    ). The supported Pt catalysts show significant improvement in catalytic activity towards the direct oxidation of methanol and DME, attributable to the enhanced adsorption and dehydrogenation of methanol and DME, as well as the presence of activated OH species in the catalysts. The latter is demonstrated......Niobium-phosphate-doped (NbP-doped) carbon blacks were prepared as the composite catalyst support for Pt nanoparticles. Functionalities of the composite include intrinsic proton conductivity, surface acidity, and interfacial synergistic interactions with methanol and dimethyl ether (DME...... to facilitate the removal of CO intermediates formed during the oxidation reactions....

  9. Microwave irradiated Ni–MnO{sub x}/C as an electrocatalyst for methanol oxidation in KOH solution for fuel cell application

    Energy Technology Data Exchange (ETDEWEB)

    Hameed, R.M. Abdel, E-mail: randa311eg@yahoo.com

    2015-12-01

    Graphical abstract: - Highlights: • Ni–MnO{sub x}/C had nickel nanoparticles with an average diameter of 4.5 nm. • Oxidation current density increased by 1.43 times at Ni–MnO{sub x}/C. • Ni–MnO{sub x}/C showed k{sub s} value of 3.26 × 103 cm{sup 3} mol{sup −1} s{sup −1}. • Adding MnO{sub x} to Ni/C lowered its phase angle and impedance values. - Abstract: Ni–MnO{sub x}/C electrocatalyst was synthesized by the reduction of nickel precursor salt on MnO{sub x}/C powder using NaBH{sub 4} and the deposition process was motivated with the aid of microwave irradiation. Finer nickel nanoparticles were detected in Ni–MnO{sub x}/C using transmission electron microscopy with a lower particle size of 4.5 nm compared to 6 nm in Ni/C. Cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy (EIS) were applied to study the electrocatalytic activity of Ni–MnO{sub x}/C for methanol oxidation in 0.5 M KOH solution. The presence of 7.5 wt.% MnO{sub x} in Ni–MnO{sub x}/C enhanced the oxidation current density by 1.43 times. The catalytic rate constant of methanol oxidation at Ni–MnO{sub x}/C was calculated as 3.26 × 10{sup 3} cm{sup 3} mol{sup −1} s{sup −1}. An appreciable shift in the maximum frequency at the transition from the resistive to capacitive regions to a higher value in Bode plots of Ni–MnO{sub x}/C was shown when compared to Ni/C. It was accompanied by lowered phase angle values. The lowered Warburg impedance value (W) of Ni–MnO{sub x}/C at 400 mV confirmed the faster methanol diffusion rate at its surface.

  10. Enhanced photo-catalytic activity of ordered mesoporous indium oxide nanocrystals in the conversion of CO2 into methanol.

    Science.gov (United States)

    Gondal, M A; Dastageer, M A; Oloore, L E; Baig, U; Rashid, S G

    2017-07-03

    Ordered mesoporous indium oxide nanocrystal (m-In 2 O 3 ) was synthesized by nanocasting technique, in which highly ordered mesoporous silca (SBA-15) was used as structural matrix. X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM) Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halanda (BJH) studies were carried out on m-In 2 O 3 and the results revealed that this material has a highly ordered mesoporous surface with reduced grain size, increased surface area and surface volume compared to the non porous indium oxide. The diffuse reluctance spectrum exhibited substantially improved light absorption efficiency in m-In 2 O 3 compared to normal indium oxide, however, no considerable change in the band gap energies of these materials was observed. When m-In 2 O 3 was used as a photo-catalyst in the photo-catalytic process of converting carbon dioxide (CO 2 ) into methanol under the pulsed laser radiation of 266-nm wavelengths, an enhanced photo-catalytic activity with the quantum efficiency of 4.5% and conversion efficiency of 46.3% were observed. It was found that the methanol production yield in this chemical process is as high as 485 µlg -1 h -1 after 150 min of irradiation, which is substantially higher than the yields reported in the literature. It is quite clear from the results that the introduction of mesoporosity in indium oxide, and the consequent enhancement of positive attributes required for a photo-catalyst, transformed photo-catalytically weak indium oxide into an effective photo-catalyst for the conversion of CO 2 into methanol.

  11. Rapid Deposition of Oxidized Biogenic Compounds to a Temperate Forest

    Science.gov (United States)

    Nguyen, Tran B.; Crounse, John D.; Teng, Alex P.; St. Clair, Jason M.; Paulot, Fabien; Wolfe, Glenn M.; Wennberg, Paul O.

    2015-01-01

    We report fluxes and dry deposition velocities for 16 atmospheric compounds above a southeastern United States forest, including: hydrogen peroxide (H2O2), nitric acid (HNO3), hydrogen cyanide (HCN), hydroxymethyl hydroperoxide, peroxyacetic acid, organic hydroxy nitrates, and other multifunctional species derived from the oxidation of isoprene and monoterpenes. The data suggest that dry deposition is the dominant daytime sink for small, saturated oxygenates. Greater than 6 wt %C emitted as isoprene by the forest was returned by dry deposition of its oxidized products. Peroxides account for a large fraction of the oxidant flux, possibly eclipsing ozone in more pristine regions. The measured organic nitrates comprise a sizable portion (15%) of the oxidized nitrogen input into the canopy, with HNO3 making up the balance. We observe that water-soluble compounds (e.g., strong acids and hydroperoxides) deposit with low surface resistance whereas compounds with moderate solubility (e.g., organic nitrates and hydroxycarbonyls) or poor solubility (e.g., HCN) exhibited reduced uptake at the surface of plants. To first order, the relative deposition velocities of water-soluble compounds are constrained by their molecular diffusivity. From resistance modeling, we infer a substantial emission flux of formic acid at the canopy level (approx. 1 nmol m(exp.-2)·s(exp.-1)). GEOS-Chem, awidely used atmospheric chemical transport model, currently underestimates dry deposition for most molecules studied in this work. Reconciling GEOS-Chem deposition velocities with observations resulted in up to a 45% decrease in the simulated surface concentration of trace gases.

  12. Improvement of oxidation resistance of copper by atomic layer deposition

    Energy Technology Data Exchange (ETDEWEB)

    Chang, M.L.; Cheng, T.C. [Department of Materials Science and Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 106, Taiwan (China); Lin, M.C. [Research Center for Biomedical Devices and Prototyping Production, Taipei Medical University, No. 250, Wu-Hsing Street, Taipei 110, Taiwan (China); Lin, H.C., E-mail: hclinntu@ntu.edu.tw [Department of Materials Science and Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 106, Taiwan (China); Chen, M.J., E-mail: mjchen@ntu.edu.tw [Department of Materials Science and Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 106, Taiwan (China)

    2012-10-01

    Graphical abstract: Results of glancing incident angle diffraction (GIXD) show the bare-Cu specimen was attacked by oxidation, whereas the coated-Cu specimens prevented from this problem. Highlights: Black-Right-Pointing-Pointer Deposition of Al{sub 2}O{sub 3} films on pure copper by an atomic layer deposition (ALD) technique. Black-Right-Pointing-Pointer Analysis of properties of the films coated at various substrate temperatures using the ALD technique. Black-Right-Pointing-Pointer Identification of the improvement of oxidation resistance of pure copper by the ALD-Al{sub 2}O{sub 3} films. Black-Right-Pointing-Pointer Assessment of the durability of the ALD-Al{sub 2}O{sub 3} films by adhesion strength. - Abstract: Al{sub 2}O{sub 3} films were deposited by the atomic layer deposition (ALD) technique onto pure copper at temperatures in the range 100-200 Degree-Sign C. The chemical composition, microstructure, and mechanic properties of the ALD-deposited Al{sub 2}O{sub 3} films were systematically analyzed. The variations in the film characteristics with substrate temperature were observed. Oxidation trials revealed that 20-nm-thick Al{sub 2}O{sub 3} films deposited at a substrate temperature as low as 100 Degree-Sign C suppress oxidative attack on pure copper. The Al{sub 2}O{sub 3} films also showed excellent durability of adhesion strength, according to predictions using the Coffin-Manson model based on the results of accelerated temperature cycling tests. These features indicate that ALD-deposited Al{sub 2}O{sub 3} film is a very promising candidate to be a protective coating for pure copper.

  13. Cold sprayed WO3 and TiO2 electrodes for photoelectrochemical water and methanol oxidation in renewable energy applications.

    Science.gov (United States)

    Haisch, Christoph; Schneider, Jenny; Fleisch, Manuel; Gutzmann, Henning; Klassen, Thomas; Bahnemann, Detlef W

    2017-10-03

    Films prepared by cold spray have potential applications as photoanodes in electrochemical water splitting and waste water purification. In the present study cold sprayed photoelectrodes produced with WO 3 (active under visible light illumination) and TiO 2 (active under UV illumination) on titanium metal substrates were investigated as photoanodes for the oxidation of water and methanol, respectively. Methanol was chosen as organic model pollutant in acidic electrolytes. Main advantages of the cold sprayed photoelectrodes are the improved metal-semiconductor junctions and the superior mechanical stability. Additionally, the cold spray method can be utilized as a large-scale electrode fabrication technique for photoelectrochemical applications. Incident photon to current efficiencies reveal that cold sprayed TiO 2 /WO 3 photoanodes exhibit the best photoelectrochemical properties with regard to the water and methanol oxidation reactions in comparison with the benchmark photocatalyst Aeroxide TiO 2 P25 due to more efficient harvesting of the total solar light irradiation related to their smaller band gap energies.

  14. Synthesis of PtNi Alloy Nanoparticles on Graphene-Based Polymer Nanohybrids for Electrocatalytic Oxidation of Methanol

    Directory of Open Access Journals (Sweden)

    Tung-Yuan Yung

    2016-12-01

    Full Text Available We have successfully produced bimetallic PtNi alloy nanoparticles on poly(diallyldimethylammonium chloride (PDDA-modified graphene nanosheets (PtNi/PDDA-G by the “one-pot” hydrothermal method. The size of PtNi alloy nanoparticles is approximately 2–5 nm. The PDDA-modified graphene nanosheets (PDDA-G provides an anchored site for metal precursors; hence, the PtNi nanoparticles could be easily bond on the PDDA-G substrate. PtNi alloy nanoparticles (2–5 nm display a homogenous alloy phase embedded on the PDDA-G substrate, evaluated by Raman, X-ray diffractometer (XRD, thermal gravity analysis (TGA, electron surface chemical analysis (ESCA, and electron energy loss spectroscopy (EELS. The Pt/Ni ratio of PtNi alloy nanoparticles is ~1.7, examined by the energy dispersive spectroscopy (EDS spectra of transmitting electron microscopy (EDS/TEM spectra and mapping technique. The methanol electro-oxidation of PtNi/PDDA-G was evaluated by cyclic voltammetry (CV in 0.5 M of H2SO4 and 0.5 M of CH3OH. Compared to Pt on carbon nanoparticles (Pt/C and Pt on Graphene (Pt/G, the PtNi/PDDA-G exhibits the optimal electrochemical surface area (ECSA, methanol oxidation reaction (MOR activity, and durability by chrono amperometry (CA test, which can be a candidate for MOR in the electro-catalysis of direct methanol fuel cells (DMFC.

  15. Partial oxidation of methane to methanol over catalyst ZSM-5 from coal fly ash and rice husk ash

    Directory of Open Access Journals (Sweden)

    Mirda Yanti Fusia

    2017-01-01

    Full Text Available Methane is one of the greenhouse gases that can be converted into liquid fuels such as methanol to retain most of the energy of methane and produce a cleaner environment. The conversion of methane to methanol using ZMS-5 represents a breakthrough in the utilization of methane. However, material sources for zeolite synthesis as catalyst usually are pro-analysis grade materials, which are expensive. Therefore, in this research, coal fly ash and rice husk ash were used as raw materials for mesoporous ZSM-5 zeolite synthesis. First, coal fly ash and rice husk were subjected to pre-treatment to extract silicate (SiO44− and aluminate (AlO45− and impurities separation. The ZSM-5 zeolite was synthesized through hydrothermal treatment using two types of templates. After ZSM-5 was synthesized, it was modified with Cobalt through impregnation method. The catalytic activity of both ZSM-5 and Co/ZSM-5 zeolites as heterogeneous catalysts in partial oxidation of methane were preliminary tested and compared with that commercial one. The result showed that the zeolite catalyst ZSM-5 from fly ash coal and rice husk ash has the potential to be used as catalysts in the partial oxidation of methane to methanol.

  16. Steam reforming and oxidative steam reforming of methanol over CuO-CeO{sub 2} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Udani, P.P.C.; Gunawardana, P.V.D.S.; Lee, Hyun Chan; Kim, Dong Hyun [Department of Chemical Engineering, Kyungpook National University, Daegu 702-701 (Korea)

    2009-09-15

    Steam reforming (SRM) and oxidative steam reforming of methanol (OSRM) were carried out over a series of coprecipitated CuO-CeO{sub 2} catalysts with varying copper content in the range of 30-80 at.% Cu (= 100 x Cu/(Cu + Ce)). The effects of copper content, reaction temperature and O{sub 2} concentration on catalytic activity were investigated. The activity of CuO-CeO{sub 2} catalysts for SRM and OSRM increased with the copper content and 70 at.% CuO-CeO{sub 2} catalyst showed the highest activity in the temperature range of 160-300 C for both SRM and OSRM. After SRM or OSRM, the copper species in the catalysts observed by XRD were mainly metallic copper with small amount of CuO and Cu{sub 2}O, an indication that metallic copper is an active species in the catalysis of both SRM and OSRM. It was observed that the methanol conversion increased considerably with the addition of O{sub 2} into the feed stream, indicating that the partial oxidation of methanol (POM) is much faster than SRM. The optimum 70 at.% CuO-CeO{sub 2} catalyst showed stable activities for both SRM and OSRM reactions at 300 C. (author)

  17. Developments in hot-filament metal oxide deposition (HFMOD)

    International Nuclear Information System (INIS)

    Durrant, Steven F.; Trasferetti, Benedito C.; Scarminio, Jair; Davanzo, Celso U.; Rouxinol, Francisco P.M.; Gelamo, Rogerio V.; Bica de Moraes, Mario A.

    2008-01-01

    Hot-filament metal oxide deposition (HFMOD) is a variant of conventional hot-filament chemical vapor deposition (HFCVD) recently developed in our laboratory and successfully used to obtain high-quality, uniform films of MO x , WO x and VO x . The method employs the controlled oxidation of a filament of a transition metal heated to 1000 deg. C or more in a rarefied oxygen atmosphere (typically, of about 1 Pa). Metal oxide vapor formed on the surface of the filament is transported a few centimetres to deposit on a suitable substrate. Key system parameters include the choice of filament material and diameter, the applied current and the partial pressures of oxygen in the chamber. Relatively high film deposition rates, such as 31 nm min -1 for MoO x , are obtained. The film stoichiometry depends on the exact deposition conditions. MoO x films, for example, present a mixture of MoO 2 and MoO 3 phases, as revealed by XPS. As determined by Li + intercalation using an electrochemical cell, these films also show a colouration efficiency of 19.5 cm 2 C -1 at a wavelength of 700 nm. MO x and WO x films are promising in applications involving electrochromism and characteristics of their colouring/bleaching cycles are presented. The chemical composition and structure of VO x films examined using IRRAS (infrared reflection-absorption spectroscopy), RBS (Rutherford backscattering spectrometry) and XPS (X-ray photoelectron spectrometry) are also presented

  18. Structural and Optical Properties of Chemical Bath Deposited Silver Oxide Thin Films: Role of Deposition Time

    Directory of Open Access Journals (Sweden)

    A. C. Nwanya

    2013-01-01

    Full Text Available Silver oxide thin films were deposited on glass substrates at a temperature of 50°C by chemical bath deposition technique under different deposition times using pure AgNO3 precursor and triethanolamine as the complexing agent. The chemical analysis based on EDX technique shows the presence of Ag and O at the appropriate energy levels. The morphological features obtained from SEM showed that the AgxO structures varied as the deposition time changes. The X-ray diffraction showed the peaks of Ag2O and AgO in the structure. The direct band gap and the refractive index increased as the deposition time increased and was in the range of 1.64–1.95 eV and 1.02–2.07, respectively. The values of the band gap and refractive index obtained indicate possible applications in photovoltaic and photothermal systems.

  19. Hydrothermal deposition and characterization of silicon oxide nanospheres

    International Nuclear Information System (INIS)

    Pei, L.Z.

    2008-01-01

    Silicon oxide nanospheres with the average diameter of about 100 nm have been synthesized by hydrothermal deposition process using silicon and silica as the starting materials. The silicon oxide nanospheres were characterized by field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectrum (EDS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and photoluminescence (PL) spectrum, respectively. The results show that large scale silicon oxide nanospheres with the uniform size are composed of Si and O showing the amorphous structure. Strong PL peak at 435 nm is observed demonstrating the good blue light emission property

  20. Controls of nitrous oxide emission after simulated cattle urine deposition

    DEFF Research Database (Denmark)

    Baral, Khagendra Raj; Thomsen, Anton Gårde; Olesen, Jørgen E

    2014-01-01

    Urine deposited during grazing is a significant source of atmospheric nitrous oxide (N2O). The potential for N2O emissions from urine patches is high, and a better understanding of controls is needed. This study investigated soil nitrogen (N) dynamics and N2O emissions from cattle urine...

  1. Direct Patterning of Oxides by Pulsed Laser Stencil Deposition

    NARCIS (Netherlands)

    te Riele, P.M.

    2008-01-01

    This thesis describes a detailed study of the application of stencil technology in the patterning of epitaxial oxide thin films by pulsed laser deposition (PLD). Stencil patterning has been applied in thin film sub-micron patterning of metals successfully for decades since it has several advantages

  2. Chemical solution deposition techniques for epitaxial growth of complex oxides

    NARCIS (Netherlands)

    ten Elshof, Johan E.; Koster, G.; Huijben, Mark; Rijnders, G.

    2015-01-01

    The chemical solution deposition (CSD) process is a wet-chemical process that is employed to fabricate a wide variety of amorphous and crystalline oxide thin films. This chapter describes the typical steps in a CSD process and their influence on the final microstructure and properties of films, and

  3. Minerals of oxidation zone of the Chokadambulaq iron deposit

    International Nuclear Information System (INIS)

    Safaraliev, N.S.

    2008-01-01

    The zone of oxidation of Chokadambulaq iron deposit has original mineral composition, which characterized specificity of their formation. Here is formed a secondary zone of enrichment marit ores, having practical meaning. In last is concentrated from 0.5 up to 1.0% from total quantities of reserves

  4. RF Reactive Magnetron Sputter Deposition of Silicon Sub-Oxides

    NARCIS (Netherlands)

    Hattum, E.D. van

    2007-01-01

    RF reactive magnetron plasma sputter deposition of silicon sub oxide E.D. van Hattum Department of Physics and Astronomy, Faculty of Sciences, Utrecht University The work described in the thesis has been inspired and stimulated by the use of SiOx layers in the direct inductive printing technology,

  5. Ellipsometric investigations of pyrolytically deposited thin indium oxide films

    International Nuclear Information System (INIS)

    Winkler, U.

    1980-01-01

    Ellipsometric measurements have been carried out of thin indium oxide films deposited pyrolytically on glass substrates. It was found that the roughness of the films affected the measuring results. Therefore, only after applying a two-layer model a reasonable interpretation of the measuring results became possible

  6. High utilization platinum deposition on single-walled carbon nanotubes as catalysts for direct methanol fuel cell

    International Nuclear Information System (INIS)

    Wang, J.J.; Yin, G.P.; Zhang, J.; Wang, Z.B.; Gao, Y.Z.

    2007-01-01

    This research aims to enhance the activity of Pt catalysts, thus to lower the loading of Pt metal in fuel cell. Highly dispersed platinum supported on single-walled carbon nanotubes (SWNTs) as catalyst was prepared by ion exchange method. The homemade Pt/SWNTs underwent a repetition of ion exchange and reduction process in order to achieve an increase of the metal loading. For comparison, the similar loading of Pt catalyst supported on carbon nanotubes was prepared by borohydride reduction method. The catalysts were characterized by using energy dispersive analysis of X-ray (EDAX), transmission electron micrograph (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectrum (XPS). Compared with the Pt/SWNTs catalyst prepared by borohydride method, higher Pt utilization was achieved on the SWNTs by ion exchange method. Furthermore, in comparison to the E-TEK 20 wt.% Pt/C catalyst with the support of carbon black, the results from electrochemical measurement indicated that the Pt/SWNTs prepared by ion exchange method displayed a higher catalytic activity for methanol oxidation and higher Pt utilization, while no significant increasing in the catalytic activity of the Pt/SWNTs catalyst obtained by borohydride method

  7. Oxidation of hazardous waste in supercritical water: A comparison of modeling and experimental results for methanol destruction

    International Nuclear Information System (INIS)

    Butler, P.B.; Bergan, N.E.; Bramlette, T.T.; Pitz, W.J.; Westbrook, C.K.

    1991-01-01

    Recent experiments at Sandia National Laboratories conducted in conjunction with MODEC Corporation have demonstrated successful clean- up of contaminated water in a supercritical water reactor. These experiments targeted wastes of interest to Department of Energy production facilities. In this paper we present modeling and experimental results for a surrogate waste containing 98% water, 2% methanol, and parts per million of chlorinated hydrocarbons and laser dyes. Our initial modeling results consider only methanol and water. Experimental data are available for inlet and outlet conditions and axial temperature profiles along the outside reactor wall. The purpose of our model is to study the chemical and physical processes inside the reactor. We are particularly interested in the parameters that control the location of the reaction zone. The laboratory-scale reactor operates at 25 MPa., between 300 K and 900 K; it is modeled as a plug-flow reactor with a specified temperature profile. We use Chemkin Real-Gas to calculate mixture density, with the Peng-Robinson equation of state. The elementary reaction set for methanol oxidation and reactions of other C 1 and C 2 hydrocarbons is based on previous models for gas-phase kinetics. Results from our calculations show that the methanol is 99.9% destroyed at 1/3 the total reactor length. Although we were not able to measure composition of the fluid inside the experimental reactor, this prediction occurs near the location of the highest reactor temperature. This indicates that the chemical reaction is triggered by thermal effects, not kinetic rates. Results from ideal-gas calculations show nearly identical chemical profiles inside the reactor in dimensionless distance. However, reactor residence times are overpredicted by nearly 150% using an ideal-gas assumption. Our results indicate that this oxidation process can be successfully modeled using gas-phase chemical mechanisms. 23 refs., 8 figs

  8. Electrocatalytic properties of monometallic and bimetallic nanoparticles-incorporated polypyrrole films for electro-oxidation of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Selvaraj, V.; Alagar, M. [Department of Chemical Engineering, Alagappa College of Technology, Anna University, Chennai 600025 (India); Hamerton, I. [Chemistry Division, School of Biomedical and Molecular Sciences, University of Surrey, Guildford, Surrey GU2 7XH (United Kingdom)

    2006-10-06

    Oxidative electrochemical polymerization of pyrrole at indium-doped tin oxide (ITO) is accomplished from a neat monomer solution with a supporting electrolyte (0.3M n-tetrabutyl ammonium tetrafluoroborate) by multiple-scan cyclic voltammetry. Polypyrrole (Ppy) films containing nanometer-sized platinum and Pt/Pd bimetallic particles are electro-synthesized on ITO glass plates by voltammetric cycling between -0.1 and +1V (versus Ag/AgCl/3M NaCl). The electrocatalytic oxidation of methanol on the nanoparticle-modified polypyrrole films is studied by means of electrochemical techniques. The modified electrode exhibits significant eletrocatalytic activity for methanol oxidation. The enhanced electrocatalytic activities may be due to the uniform dispersion of nanoparticles in the polypyrrole film and a synergistic effect of the highly-dispersed metal particles so that the polypyrrole film reduces electrode poisoning by adsorbed CO species. The monometallic (Pt) and bimetallic (Pt/Pd) nanoparticles are uniformly dispersed in polypyrrole matrixes, as confirmed by scanning electron microscopic and atomic force microscopic analysis. Energy dispersive X-ray analysis is used to characterize the composition of metal present in the nanoparticle-modified electrodes. (author)

  9. Therapeutic effect of methanolic extract of Laportea aestuans (L.) Chew, on oxidative stress in the brain of male Wistar rats

    Science.gov (United States)

    Elizabeth, Omotosho Omolola; Olawumi, Ogunlade Oladipupo

    2018-04-01

    The aim of this study was to assess the effect of diclofenac-induced oxidative stress in the brain of Wistar rats. The experiment was carried out using thirty-six rats. Six groups contained six rats in each. The first group being the control group received 1ml of gum acacia which is the vehicle. Groups 2 to 6 were induced with oxidative stress by oral administration of 40 mg/kg body weight of diclofenac and pretreated as follows: group 2 received only diclofenac, group 3 with 200 mg/kg body weight of methanolic extract of Laportea aestuans (L.) Chew, group 4 with 400 mg/kg body weight of Laportea aestuans extract, group 5 with 800 mg/kg body weight of Laportea aestuans and group 6 with 50 mg/kg body weight of cimetidine. The pretreatment was carried out for a period of seven days after which oxidative stress was induced. The animals were thereafter sacrificed and brain was excised. Antioxidant enzymes and molecules such as superoxide dismutase, catalase, glutathione, levels of malondialdehyde and protein carbonyl were assayed by standard methods. The results showed significant increases in glutathione level and activities of catalase, superoxide dismutase and significant decrease in lipid peroxidation and protein carbonyl in groups 3 to 5 when compared to group 2. This shows that the methanolic extract of Laportea aestuans has a protective effect on the brain against oxidative stress.

  10. PtRu catalysts supported on heteropolyacid and chitosan functionalized carbon nanotubes for methanol oxidation reaction of fuel cells.

    Science.gov (United States)

    Cui, Zhiming; Li, Chang Ming; Jiang, San Ping

    2011-09-28

    A simple self-assembly approach has been developed to functionalize carbon nanotubes (CNTs) with chitosan (CS) and heteropolyacids (HPAs) of phosphomolybdic acid (H(3)PMo(12)O(40), HPMo) and phosphotungstic acid (H(3)PW(12)O(40), HPW). The non-covalent functionalization method, which introduces homogenous surface functional groups with no detrimental effect on graphene structures of CNTs, can be carried out at room temperature without the use of corrosive acids. The PtRu nanoparticles supported on HPAs-CS-CNTs have a uniform distribution and much smaller size as compared to those of the PtRu nanoparticles supported on conventional acid treated CNTs (PtRu/AO-CNTs). The onset and peak potentials for CO(ad) oxidation on PtRu/HPAs-CS-CNTs catalysts are more negative than those on PtRu/AO-CNTs, indicating that HPAs facilitate the electro-oxidation of CO. The PtRu/HPMo-CS-CNTs catalyst has a higher electrocatalytic activity for methanol oxidation and higher tolerance toward CO poisoning than PtRu/HPW-CS-CNTs. The better electrocatalytic enhancement of HPMo on the PtRu/HPAs-CS-CNTs catalyst is most likely related to the fact that molybdenum-containing HPAs such as HPMo have more labile terminal oxygen to provide additional active oxygen sites while accelerating the CO and methanol oxidation in a similar way to that of Ru in the PtRu binary alloy system.

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

    Directory of Open Access Journals (Sweden)

    N.V. Nikolenko

    2018-03-01

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

  12. Conversion of Methane into Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Okolie, Chukwuemeka [School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA; Belhseine, Yasmeen F. [School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA; Lyu, Yimeng [School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA; Yung, Matthew M. [National Renewable Energy Laboratory, Golden CO 80401 USA; Engelhard, Mark H. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Lab, Richland WA 99354 USA; Kovarik, Libor [Environmental Molecular Sciences Laboratory, Pacific Northwest National Lab, Richland WA 99354 USA; Stavitski, Eli [National Synchrotron Light Source II, Brookhaven National Laboratory, Upton NY 11973 USA; Sievers, Carsten [School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA

    2017-09-26

    Direct conversion of methane into alcohols is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can selectively oxidize methane to methanol and ethanol in a single, steady-state process at 723 K using O2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to the synergy between the small Lewis acidic NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.

  13. Methanol oxidation at carbon paste electrodes modified with (Pt–Ru)/carbon aerogels nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Fort, Carmen I., E-mail: iladiu@chem.ubbcluj.ro [Laboratory of Electrochemical Research and Nonconventional Materials, Babes-Bolyai University, Arany Janos 11, RO-400028, Cluj-Napoca (Romania); Cotet, Liviu C. [Laboratory of Electrochemical Research and Nonconventional Materials, Babes-Bolyai University, Arany Janos 11, RO-400028, Cluj-Napoca (Romania); Vasiliu, Florin [The National Institute of Materials Physics, Atomistilor str. 105 bis, PO Box MG. 7, Magurele, RO 077125, Bucharest (Romania); Marginean, Petre [National Institute for Research and Development of Isotopic and Molecular Technologies, RO 400293, Cluj-Napoca (Romania); Danciu, Virginia; Popescu, Ionel C. [Laboratory of Electrochemical Research and Nonconventional Materials, Babes-Bolyai University, Arany Janos 11, RO-400028, Cluj-Napoca (Romania)

    2016-04-01

    Mesoporous carbon aerogels (CAs) impregnated with (Pt–Ru) nanoparticles were prepared, incorporated into carbon paste electrodes (CPEs) and investigated as electrocatalysts for CH{sub 3}OH electro-oxidation. The sol–gel method, followed by supercritical drying with liquid CO{sub 2} and thermal pyrolysis in an inert atmosphere, was used to obtain high mesoporous CAs. (Pt–Ru)/CAs nanocomposites with various (Pt–Ru) loading were prepared by using Ru(AcAc){sub 3} and H{sub 2}PtCl{sub 6} as metal precursors and the impregnation method. The morpho-structural peculiarities of the so prepared (Pt–Ru)/CAs electrocatalysts were examined by using elemental analysis, N{sub 2} adsorption-desorption isotherms, transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), energy dispersive X-ray (EDX) and selected area electron diffraction (SAED). Cyclic voltammetry measurements, carried out at (Pt–Ru)/CA-CPEs incorporating nanocomposites with various Pt–Ru loading and different specific surface areas, showed that CA with the highest specific surface area (843 m{sup 2}/g) and impregnated with 6% (w/w) (Pt–Ru) nanoparticles exhibit the best CH{sub 3}OH electro-oxidation efficiency. The Michaelis–Menten formalism was used to describe the dependence of the oxidation peak current on the CH{sub 3}OH concentration, allowing the estimation of the modified electrodes sensitivities. Thus, for (Pt–Ru, 10%)/CA{sub 535}-CPE was observed the highest sensitivity (12.5 ± 0.8 mA/M) and, at the same time, the highest maximum current density ever reported (153.1 mA/cm{sup 2} for 2 M CH{sub 3}OH and an applied potential of 600 mV vs. SHE). - Highlights: • (Pt–Ru) nanoparticles were deposited on high mesoporous carbon aerogels (CAs). • (Pt–Ru)/CAs were characterized by TEM, EDX, SAED and N{sub 2} adsorption-desorption. • Carbon paste electrodes modified with (Pt–Ru)/CA were used for CH{sub 3}OH oxidation. • (Pt–Ru, 10

  14. Facile synthesis of palladium–graphene nanocomposites and their catalysis for electro-oxidation of methanol and ethanol

    International Nuclear Information System (INIS)

    Zhang, Yuting; Shu, Honghui; Chang, Gang; Ji, Kai; Oyama, Munetaka; Liu, Xiong; He, Yunbin

    2013-01-01

    Highlights: • Pd nanoparticles/graphene (PdNPs/graphene) was synthesized within one-step process. • Environment friendly ascorbic acid was chosen as the reductant. • The synthesized PdNPs/graphene shows superior electrocatalytic activity to both methanol and ethanol. • PdNPs/graphene shows superior electrocatalytic stability in methanol and ethanol electro-oxidation. -- Abstract: Well-dispersed Pd nanoparticles (PdNPs) supported on graphene sheets were successfully prepared by a simple one-pot process, in which the reduction of Poly Vingl Pyrrolidone-functionalized graphite oxide and Pd precursor was carried out simultaneously using ascorbic acid as a soft reductant. The Pd nanoparticles decorated graphene composite (PdNPs/PVP-graphene) was characterized by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. Morphology and structure characterizations directly showed that Pd nanoparticles with crystallite size of about 8.5 nm were evenly formed on graphene. Catalysis activity as in fuel cells was investigated by further electrochemical experiments including cyclic voltammograms and chronoamperometric measurements. Compared to the commercial Vulcan XC-72 supported Pd nanoparticles, PdNPs/PVP-graphene exhibits superior electrocatalytic activity and stability toward electro-oxidation of alcohols, showing its potential use as new electrode material for direct alcohol fuel cells (DAFCs)

  15. Catalytic properties of nickel ferrites for oxidation of glucose, β-nicotiamide adenine dinucleotide (NADH) and methanol

    Energy Technology Data Exchange (ETDEWEB)

    Galindo, R. [Departamento de Química, Universidad de Guanajuato, Cerro de la Venada s/n, Pueblito de Rocha, C.P. 36040 Guanajuato, Gto (Mexico); Departamento de Química Física Aplicada, Universidad Autónoma de Madrid, Cantoblanco s/n, C.P. 28049 Madrid (Spain); Gutiérrez, S. [Departamento de Química, Universidad de Guanajuato, Cerro de la Venada s/n, Pueblito de Rocha, C.P. 36040 Guanajuato, Gto (Mexico); Menéndez, N. [Departamento de Química Física Aplicada, Universidad Autónoma de Madrid, Cantoblanco s/n, C.P. 28049 Madrid (Spain); Herrasti, P., E-mail: pilar.herrasti@uam.es [Departamento de Química Física Aplicada, Universidad Autónoma de Madrid, Cantoblanco s/n, C.P. 28049 Madrid (Spain)

    2014-02-15

    Highlights: ► NiFe{sub 2}O{sub 4} nanoparticles obtained by electrochemical method are effective catalyst. ► A partially inverse spinel was obtained with 57% Fe{sup 3+} in tetrahedral position. ► A non-enzymatic electrode using NiFe{sub 2}O{sub 4} nanoparticles has been manufactured. -- Abstract: Nickel ferrite nanoparticles (NiFe{sub 2}O{sub 4}) were synthesized by electrochemical method and used as catalyst for direct oxidation of glucose, NADH and methanol. Characterization of these nanoparticles was carried out by X-ray diffraction, Mössbauer spectroscopy, and colloidal properties such as hydrodynamic radius and Zeta potential. To evaluate the catalytic properties of these nanoparticles against the oxidation process, paste graphite electrodes mixing nickel ferrites and different conductive materials (graphite, carbon nanotubes) and binders agents (mineral oil, 1-octylpyridinium hexafluorophosphate (nOPPF6)) were used. The results prove good catalytic properties of these materials, with an oxidation potential around 0.75, 0.5 and 0.8 V for glucose, NADH, and methanol, respectively.

  16. Tungsten carbide/porous carbon composite as superior support for platinum catalyst toward methanol electro-oxidation

    International Nuclear Information System (INIS)

    Jiang, Liming; Fu, Honggang; Wang, Lei; Mu, Guang; Jiang, Baojiang; Zhou, Wei; Wang, Ruihong

    2014-01-01

    Graphical abstract: The WC nanoparticles are well dispersed in the carbon matrix. The size of WC nanoparticles is about 30 nm. It can be concluded that tungsten carbide and carbon composite was successfully prepared by the present synthesis conditions. - Highlights: • The WC/PC composite with high specific surface area was prepared by a simple way. • The Pt/WC/PC catalyst has superior performance toward methanol electro-oxidation. • The current density for methanol electro-oxidation is as high as 595.93 A g −1 Pt. • The Pt/WC/PC catalyst shows better durability and stronger CO electro-oxidation. • The performance of Pt/WC/PC is superior to the commercial Pt/C (JM) catalyst. - Abstract: Tungsten carbide/porous carbon (WC/PC) composites have been successfully synthesized through a surfactant assisted evaporation-induced-assembly method, followed by a thermal treatment process. In particular, WC/PC-35-1000 composite with tungsten content of 35% synthesized at the carbonized temperature of 1000 °C, exhibited a specific surface area (S BET ) of 457.92 m 2 g −1 . After loading Pt nanoparticles (NPs), the obtained Pt/WC/PC-35-1000 catalyst exhibits the highest unit mass electroactivity (595.93 A g −1 Pt) toward methanol electro-oxidation, which is about 2.6 times as that of the commercial Pt/C (JM) catalyst. Furthermore, the Pt/WC/PC-35-1000 catalyst displays much stronger resistance to CO poisoning and better durability toward methanol electrooxidation compared with the commercial Pt/C (JM) catalyst. The high electrocatalytic activity, strong poison-resistivity and good stability of Pt/WC/PC-35-1000 catalyst are attributed to the porous structures and high specific surface area of WC/PC support could facilitate the rapid mass transportation. Moreover, synergistic effect between WC and Pt NPs is favorable to the higher catalytic performance

  17. N, P-codoped Mesoporous Carbon Supported PtCox Nanoparticles and Their Superior Electrochemical toward Methanol Oxidation

    Science.gov (United States)

    Cui, Hangjun; Li, Yueming; Liu, Shimin

    2018-03-01

    In this report, a novel strategy by using the N, P co-doped mesoporous carbon structure as catalyst support to enhance the electrochemical catalytic activity of Pt-based catalysts is proposed. The as-synthesized PtCox@N, P-doped mesoporous carbon nanocomposties have been studied as an anode catalyst toward methanol oxidation, exhibiting greatly improved electrochemical activity and stability compared with Pt@mesoporous carbon. The synergistic effects of N, P dual-doping and porous carbon structure help to achieve better electron transport at the electrode surface, which eventually leads to greatly enhanced catalytic activity compared to the pristine Pt/mesoporous carbon.…

  18. Tungsten carbide/porous carbon composite as superior support for platinum catalyst toward methanol electro-oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Liming [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Fu, Honggang, E-mail: fuhg@vip.sina.com [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Key Laboratory of Functional Inorganic Material Chemistry, Heilongjiang University, Harbin 150080 (China); Wang, Lei; Mu, Guang; Jiang, Baojiang; Zhou, Wei; Wang, Ruihong [Key Laboratory of Functional Inorganic Material Chemistry, Heilongjiang University, Harbin 150080 (China)

    2014-01-01

    Graphical abstract: The WC nanoparticles are well dispersed in the carbon matrix. The size of WC nanoparticles is about 30 nm. It can be concluded that tungsten carbide and carbon composite was successfully prepared by the present synthesis conditions. - Highlights: • The WC/PC composite with high specific surface area was prepared by a simple way. • The Pt/WC/PC catalyst has superior performance toward methanol electro-oxidation. • The current density for methanol electro-oxidation is as high as 595.93 A g{sup −1} Pt. • The Pt/WC/PC catalyst shows better durability and stronger CO electro-oxidation. • The performance of Pt/WC/PC is superior to the commercial Pt/C (JM) catalyst. - Abstract: Tungsten carbide/porous carbon (WC/PC) composites have been successfully synthesized through a surfactant assisted evaporation-induced-assembly method, followed by a thermal treatment process. In particular, WC/PC-35-1000 composite with tungsten content of 35% synthesized at the carbonized temperature of 1000 °C, exhibited a specific surface area (S{sub BET}) of 457.92 m{sup 2} g{sup −1}. After loading Pt nanoparticles (NPs), the obtained Pt/WC/PC-35-1000 catalyst exhibits the highest unit mass electroactivity (595.93 A g{sup −1} Pt) toward methanol electro-oxidation, which is about 2.6 times as that of the commercial Pt/C (JM) catalyst. Furthermore, the Pt/WC/PC-35-1000 catalyst displays much stronger resistance to CO poisoning and better durability toward methanol electrooxidation compared with the commercial Pt/C (JM) catalyst. The high electrocatalytic activity, strong poison-resistivity and good stability of Pt/WC/PC-35-1000 catalyst are attributed to the porous structures and high specific surface area of WC/PC support could facilitate the rapid mass transportation. Moreover, synergistic effect between WC and Pt NPs is favorable to the higher catalytic performance.

  19. Evaluation of the Optimum Composition of Low-Temperature Fuel Cell Electrocatalysts for Methanol Oxidation by Combinatorial Screening.

    Science.gov (United States)

    Antolini, Ermete

    2017-02-13

    Combinatorial chemistry and high-throughput screening represent an innovative and rapid tool to prepare and evaluate a large number of new materials, saving time and expense for research and development. Considering that the activity and selectivity of catalysts depend on complex kinetic phenomena, making their development largely empirical in practice, they are prime candidates for combinatorial discovery and optimization. This review presents an overview of recent results of combinatorial screening of low-temperature fuel cell electrocatalysts for methanol oxidation. Optimum catalyst compositions obtained by combinatorial screening were compared with those of bulk catalysts, and the effect of the library geometry on the screening of catalyst composition is highlighted.

  20. Gas phase deposition of oxide and metal-oxide coatings on fuel particles

    International Nuclear Information System (INIS)

    Patokin, A.P.; Khrebtov, V.L.; Shirokov, B.M.

    2008-01-01

    Production processes and properties of oxide (Al 2 O 3 , ZrO 2 ) and metal-oxide (Mo-Al 2 O 3 , Mo-ZrO 2 , W-Al 2 O 3 , W-ZrO 2 ) coatings on molybdenum substrates and uranium dioxide fuel particles were investigated. It is shown that the main factors that have an effect on the deposition rate, density, microstructure and other properties of coatings are the deposition temperature, the ratio of H 2 and CO 2 flow rates, the total reactor pressure and the ratio of partial pressures of corresponding metal chlorides during formation of metal-oxide coatings

  1. Two component system that regulates methanol and formaldehyde oxidation in Paracoccus denitrificans.

    NARCIS (Netherlands)

    Harms, N.; Reijnders, W.N.M.; Koning, S.; van Spanning, R.J.M.

    2001-01-01

    A chromosomal region encoding a two-component regulatory system, FlhRS, has been isolated from Paracoccus denitrificans. FlhRS-deficient mutants were unable to grow on methanol, methylamine, or choline as the carbon and energy source. Expression of the gene encoding glutathione-dependent

  2. Two-component system that regulates methanol and formaldehyde oxidation in Paracoccus denitrificans.

    NARCIS (Netherlands)

    Harms, N.; Reijnders, W.N.M.; Koning, S.; van Spanning, R.J.M.

    2001-01-01

    A chromosomal region encoding a two-component regulatory system, FlhRS, has been isolated from Paracoccus denitrificans. FlhRS-deficient mutants were unable to grow on methanol, methylamine, or choline as the carbon and energy source. Expression of the gene encoding glutathione-dependent

  3. Preparation and characterization of stable copper/zinc oxide/alumina catalysts for methanol synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Hoeppener, R H; Doesburg, E B; Scholten, J J

    1986-08-15

    A series of Cu/ZnO/Al/sub 2/O/sub 3/ catalysts for the low pressure methanol synthesis has been prepared by coprecipitation with a sodium carbonate solution from solutions of a mixture of the corresponding metal nitrates, followed by drying, calcination and reduction. The catalysts and their precursors were analyzed by techniques like X-ray diffraction, X-ray line broadening, differential thermal analysis, chemical analysis, adsorptive decomposition of N/sub 2/O and B.E.T.-measurements. The catalytic activity for the methanol synthesis was determined in a flow reactor under industrial conditions. Depending on the metal ion ratio in the initial metal nitrate solutions different compounds were formed during coprecipitation, like rosasite, malachite, Cu, Zn-hydrotalcite and a ternary compound which was called roderite. Its structure is unknown and it contains, besides Zn/sup 2+/, up to 28 at% Cu/sup 2+/ and up to 17 at% Al/sup 3+/. Addition of 7 at% Mg/sup 2+/ stabilizes the Cu, Zn-hydrotalcite structure but leads to a drastic decrease in catalytic activity. The rate of methanol production depends on the phase composition of the precursors. Rosasite containing precursors give the highest activity; hydrotalcite proves to be an excellent catalyst stabilizer which evokes the formation of small Cu and ZnO particles. Mg/sup 2+/ inhibits methanol production. 6 figs., 1 tab., 18 refs.

  4. N-formylation of amines via the aerobic oxidation of methanol over supported gold nanoparticles.

    Science.gov (United States)

    Ishida, Tamao; Haruta, Masatake

    2009-01-01

    Dress code: formyl. Gold nanoparticles supported on NiO catalyze the one-pot N-formylation of amines with methanol and molecular oxygen to produce formamide at a selectivity of 90 %. This process generates methyl formate in situ, followed by reaction with amines.

  5. Effect of nitrogen source on methanol oxidation and genetic diversity of methylotrophic mixed cultures enriched from pulp and paper mill biofilms.

    Science.gov (United States)

    Babbitt, Callie W; Lindner, Angela S

    2011-04-01

    Methanol-oxidizing bacteria may play an important role in the development and use of biological treatment systems for the removal of methanol from industrial effluents. Optimization of methanol degradation potential in such systems is contingent on availability of nutrients, such as nitrogen, in the most favorable form and concentration. To that end, this study examined the variation in growth, methanol degradation, and bacterial diversity of two mixed methylotrophic cultures that were provided nitrogen either as ammonium or nitrate and in three different concentrations. Methanol-degrading cultures were enriched from biofilms sampled at a pulp and paper mill and grown in liquid batch culture with methanol as the only carbon source and either ammonium or nitrate as the only added nitrogen source. Results indicate that growth and methanol removal of the mixed cultures increase directly with increased nitrogen, added in either form. However, methanol removal and bacterial diversity, as observed by polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) methods, were higher when using nitrate as the nitrogen source for enrichment and growth, rather than ammonium. Based on results described here, nitrate may potentially be a better nitrogen source when enriching or working with mixed methylotrophic cultures, and possibly more effective when used as a nutrient addition to biofilters.

  6. CuOX thin films by direct oxidation of Cu films deposited by physical vapor deposition

    Directory of Open Access Journals (Sweden)

    D. Santos-Cruz

    Full Text Available Thin films of Cu2O and CuO oxides were developed by direct oxidation of physical vapor deposited copper films in an open atmosphere by varying the temperature in the range between 250 and 400 °C. In this work, the influence of oxidation temperature on structural, optical and electrical properties of copper oxide films has been discussed. The characterization results revealed that at lower temperatures (<300 °C, it is feasible to obtained coper (I oxide whereas at temperatures higher than 300 °C, the copper (II oxide is formed. The band gap is found to vary in between 1.54 and 2.21 eV depending on the oxidation temperature. Both oxides present p-type electrical conductivity. The carrier concentration has been increased as a function of the oxidation temperature from 1.61 × 1012 at 250 °C to 6.8 × 1012 cm−3 at 400 °C. The mobility has attained its maximum of 34.5 cm2 V−1 s−1 at a temperature of 300 °C, and a minimum of 13.8 cm2 V−1 s−1 for 400 °C. Finally, the resistivity of copper oxide films decreases as a function of oxidation temperature from 5.4 × 106 to 2.4 × 105 Ω-cm at 250 and 400 °C, respectively. Keywords: PVD, Oxidizing annealed treatment, Non-toxic material

  7. Fabrication of graphene-fullerene hybrid by self-assembly and its application as support material for methanol electrocatalytic oxidation reaction

    Science.gov (United States)

    Zhang, Xuan; Zhang, Jia-Wei; Xiang, Ping-Hua; Qiao, Jinli

    2018-05-01

    Graphene-fullerene hybrids were facilely fabricated by self-assembly of graphene oxide (GO) and multi-substituted fulleropyrrolidines (PyrC60). The hybrids (GO-PyrC60) were applied as support materials to deposit Pd nanoparticle catalyst by a simple hydrothermal co-reduction approach. The as-prepared electrocatalysts (Pd/RGO-PyrC60) were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), respectively. The RGO-PyrC60 hybrid supported Pd catalyst with the optimal ratio of RGO to PyrC60, exhibited much enhanced electrocatalytic activity and stability toward methanol oxidation reaction (MOR) compared to the RGO alone supported Pd as well as commercial Pd/C. The introduction of fulleropyrrolidine as spacer between graphene layers could increase the electrocatalytic activity and improve the long-term stability. This strategy may contribute to developing graphene-fullerene hydrids as effective support materials for advanced electrocatalysts.

  8. One Pot Synthesis of Pt/Graphene Composite Using Polyamidoamine/Chitosan as a Template and Its Electrocatalysis for Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Yanli Wang

    2016-10-01

    Full Text Available A one-pot hydrothermal strategy was used to synthesize Pt/GNs (PAMAM & Pt/GNs (CS composites. Pt nanoparticles are deposited onto graphene sheets (GNs via synchronous reduction of K2PtCl4 and graphene oxide (GO under hydrothermal conditons without additional reducing agent. During the synthesis process, polyamidoamine (PAMAM or chitosan (CS was used as a template respectively to obtain shape controlled Pt particles on the surface of GNs, leading to the formation of flower-like Pt nanoclusters for Pt/GNs (PAMAM and uniform spherical Pt nanoparticles for Pt/GNs (CS. PAMAM and CS are simultaneously served as intrinsic reducing agents to accelerate reduction process; ensuring excellent electrical conductivity of the composites. Electrochemical tests show that Pt/GNs (PAMAM and Pt/GNs (CS have much higher electrocatalytic activity and better stability toward methanol oxidation reaction (MOR in comparison with counterpart Pt/GNs and the commercially available 20% Pt/C catalyst (Pt/C due to their better dispersion of Pt particles, stronger interaction between Pt and substrate materials, and better electron transfer capability.

  9. Statistical analysis of the electrocatalytic activity of Pt nanoparticles supported on novel functionalized reduced graphene oxide-chitosan for methanol electrooxidation

    Science.gov (United States)

    Ekrami-Kakhki, Mehri-Saddat; Abbasi, Sedigheh; Farzaneh, Nahid

    2018-01-01

    The purpose of this study is to statistically analyze the anodic current density and peak potential of methanol oxidation at Pt nanoparticles supported on functionalized reduced graphene oxide (RGO), using design of experiments methodology. RGO is functionalized with methyl viologen (MV) and chitosan (CH). The novel Pt/MV-RGO-CH catalyst is successfully prepared and characterized with transmission electron microscopy (TEM) image. The electrocatalytic activity of Pt/MV-RGOCH catalyst is experimentally evaluated for methanol oxidation. The effects of methanol concentration and scan rate factors are also investigated experimentally and statistically. The effects of these two main factors and their interactions are investigated, using analysis of variance test, Duncan's multiple range test and response surface method. The results of the analysis of variance show that all the main factors and their interactions have a significant effect on anodic current density and peak potential of methanol oxidation at α = 0.05. The suggested models which encompass significant factors can predict the variation of the anodic current density and peak potential of methanol oxidation. The results of Duncan's multiple range test confirmed that there is a significant difference between the studied levels of the main factors. [Figure not available: see fulltext.

  10. Electro-oxidation of methanol on gold in alkaline media: Adsorption characteristics of reaction intermediates studied using time resolved electro-chemical impedance and surface plasmon resonance techniques

    Science.gov (United States)

    Assiongbon, K. A.; Roy, D.

    2005-12-01

    Electro-catalytic oxidation of methanol is the anode reaction in direct methanol fuel cells. We have studied the adsorption characteristics of the intermediate reactants of this multistep reaction on a gold film electrode in alkaline solutions by combining surface plasmon resonance (SPR) measurements with Fourier transform electro-chemical impedance spectroscopy (FT-EIS). Methanol oxidation in this system shows no significant effects of "site poisoning" by chemisorbed CO. Our results suggest that OH - chemisorbed onto Au acts as a stabilizing agent for the surface species of electro-active methanol. Double layer charging/discharging and adsorption/desorption of OH - show more pronounced effects than adsorption/oxidation of methanol in controlling the surface charge density of the Au substrate. These effects are manifested in both the EIS and the SPR data, and serve as key indicators of the surface reaction kinetics. The data presented here describe the important role of adsorbed OH - in electro-catalysis of methanol on Au, and demonstrate how SPR and FT-EIS can be combined for quantitative probing of catalytically active metal-solution interfaces.

  11. Developments in hot-filament metal oxide deposition (HFMOD)

    Energy Technology Data Exchange (ETDEWEB)

    Durrant, Steven F. [Laboratorio de Plasmas Tecnologicos, Campus Experimental de Sorocaba, Universidade Estadual Paulista (UNESP), Avenida Tres de Marco, 511, Alto de Boa Vista, 18087-180 Sorocaba, SP (Brazil)], E-mail: steve@sorocaba.unesp.br; Trasferetti, Benedito C. [Departamento de Policia Federal, Superintendencia Regional no Piaui, Setor Tecnico-Cientifico, Avenida Maranhao, 1022/N, 64.000-010, Teresina, PI (Brazil); Scarminio, Jair [Departamento de Fisica, Universidade Estadual de Londrina (UEL), 86051-990, Londrina, PR (Brazil); Davanzo, Celso U. [Instituto de Quimica, Universidade Estadual de Campinas (UNICAMP), 13083-970, Campinas, SP (Brazil); Rouxinol, Francisco P.M.; Gelamo, Rogerio V.; Bica de Moraes, Mario A. [Laboratorio de Processos de Plasma, Departamento de Fisica Aplicada, Instituto de Fisica Gleb Wataghin, Universidade Estadual de Campinas (UNICAMP), 13083-970, Campinas, SP (Brazil)

    2008-01-15

    Hot-filament metal oxide deposition (HFMOD) is a variant of conventional hot-filament chemical vapor deposition (HFCVD) recently developed in our laboratory and successfully used to obtain high-quality, uniform films of MO{sub x}, WO{sub x} and VO{sub x}. The method employs the controlled oxidation of a filament of a transition metal heated to 1000 deg. C or more in a rarefied oxygen atmosphere (typically, of about 1 Pa). Metal oxide vapor formed on the surface of the filament is transported a few centimetres to deposit on a suitable substrate. Key system parameters include the choice of filament material and diameter, the applied current and the partial pressures of oxygen in the chamber. Relatively high film deposition rates, such as 31 nm min{sup -1} for MoO{sub x}, are obtained. The film stoichiometry depends on the exact deposition conditions. MoO{sub x} films, for example, present a mixture of MoO{sub 2} and MoO{sub 3} phases, as revealed by XPS. As determined by Li{sup +} intercalation using an electrochemical cell, these films also show a colouration efficiency of 19.5 cm{sup 2} C{sup -1} at a wavelength of 700 nm. MO{sub x} and WO{sub x} films are promising in applications involving electrochromism and characteristics of their colouring/bleaching cycles are presented. The chemical composition and structure of VO{sub x} films examined using IRRAS (infrared reflection-absorption spectroscopy), RBS (Rutherford backscattering spectrometry) and XPS (X-ray photoelectron spectrometry) are also presented.

  12. Methods of preparing deposits containing iron oxides for recycling

    Directory of Open Access Journals (Sweden)

    T. Lis

    2013-04-01

    Full Text Available The metallurgical industry is one of the largest sources of wastes. Some of them, however, owing to their content of metals such as zinc or iron, may become valuable secondary raw materials. In order to achieve that purpose, they require appropriate preparation. This article provides a discussion on the methods of preparation of scrap from steelworks, namely deposits containing iron oxides, enabling their recycling.

  13. Preparation of Pt-mesoporous tungsten carbide/carbon composites via a soft-template method for electrochemical methanol oxidation

    International Nuclear Information System (INIS)

    Ma, Chun’an; Kang, Lingzhi; Shi, Meiqin; Lang, Xiaoling; Jiang, Yekun

    2014-01-01

    Highlights: • Mesoporous composite Pt-m(WC/C) is prepared by a soft template method. • The structure of phenolic gives a space limitation effect on the growth of WC. • Analysis of the effect of F127 on controlling the structure of composites. • Pt-m(WC/C) exhibits more than three times higher than Pt/C in catalytic activity. -- Abstract: This paper introduces a simple and reproducible chemical process for synthesis of Pt-mesoporous tungsten carbide/carbon composites composites Pt-m(WC/C) by means of a soft-template method. In this process, low-molecular-weight phenolic resol acted as the precursor both for carbon support and also the carbon resource of tungsten carbide. Tungsten hexachloride was used as a tungsten precursor along with different amount of triblock copolymer Pluronic F127 as pore-forming component. The best performance of Pt-m(WC/C) towards methanol oxidation is found when the mass ratios of WCl 6 :F127 is 1:0.6. The composite presents an improved methanol oxidation performance evidenced by a negative shift in onset potential, and increase of peak current density, compared with commercial Pt/C. The difference is explained by the adding of appropriate amount of F127 which facilitates the construction of mesoporous matrix structure of WC/C

  14. N-Doped Carbon Nanofibrous Network Derived from Bacterial Cellulose for the Loading of Pt Nanoparticles for Methanol Oxidation Reaction.

    Science.gov (United States)

    Yuan, Fanshu; Huang, Yang; Fan, Mengmeng; Chen, Chuntao; Qian, Jieshu; Hao, Qingli; Yang, Jiazhi; Sun, Dongping

    2018-02-06

    The large-scale, low-cost preparation of Pt-based catalysts with high activity and durability for the methanol oxidation reaction is still challenging. The key to achieving this aim is finding suitable supporting materials. In this paper, N-doped carbon nanofibrous networks are prepared by annealing a gel containing two inexpensive and ecofriendly precursors, that is, bacterial cellulose and urea, for the loading of Pt nanoparticles. An undoped analogue is also prepared for comparison. Meanwhile, the effect of the annealing temperature on the performance of the catalysts is evaluated. The results show that the N doping and higher annealing temperature can improve the electron conductivity of the catalyst and provide more active sites for the loading of ultrafine Pt nanoparticles with a narrow size distribution. The best catalyst exhibits a remarkably high electrocatalytic activity (627 mA mg -1 ), excellent poison tolerance, and high durability. This work demonstrates an ideal Pt supporting material for the methanol oxidation reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Characteristics of hydrogen produced by partial oxidation and auto-thermal reforming in a small methanol reformer

    Science.gov (United States)

    Horng, Rong-Fang; Chou, Huann-Ming; Lee, Chiou-Hwang; Tsai, Hsien-Te

    This paper investigates experimentally, the transient characteristics of a small methanol reformer using partial oxidation (POX) and auto-thermal reforming (ATR) for fuel cell applications. The parameters varied were heating temperature, methanol supply rate, steady mode shifting temperature, O 2/C (O 2/CH 3OH) and S/C (H 2O/CH 3OH) molar ratios with the main aim of promoting a rapid response and a high flow rate of hydrogen. The experiments showed that a high steady mode shifting temperature resulted in a faster temperature rise at the catalyst outlet and vice versa and that a low steady mode shifting temperature resulted in a lower final hydrogen concentration. However, when the mode shifting temperature was too high, the hydrogen production response was not necessarily improved. It was subsequently shown that the optimum steady mode shifting temperature for this experimental set-up was approximately 75 °C. Further, the hydrogen concentration produced by the auto-thermal process was as high as 49.12% and the volume flow rate up to 23.0 L min -1 compared to 40.0% and 20.5 L min -1 produced by partial oxidation.

  16. Preparation of Pt-mesoporous tungsten carbide/carbon composites via a soft-template method for electrochemical methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Chun’an, E-mail: science@zjut.edu.cn; Kang, Lingzhi; Shi, Meiqin; Lang, Xiaoling; Jiang, Yekun

    2014-03-05

    Highlights: • Mesoporous composite Pt-m(WC/C) is prepared by a soft template method. • The structure of phenolic gives a space limitation effect on the growth of WC. • Analysis of the effect of F127 on controlling the structure of composites. • Pt-m(WC/C) exhibits more than three times higher than Pt/C in catalytic activity. -- Abstract: This paper introduces a simple and reproducible chemical process for synthesis of Pt-mesoporous tungsten carbide/carbon composites composites Pt-m(WC/C) by means of a soft-template method. In this process, low-molecular-weight phenolic resol acted as the precursor both for carbon support and also the carbon resource of tungsten carbide. Tungsten hexachloride was used as a tungsten precursor along with different amount of triblock copolymer Pluronic F127 as pore-forming component. The best performance of Pt-m(WC/C) towards methanol oxidation is found when the mass ratios of WCl{sub 6}:F127 is 1:0.6. The composite presents an improved methanol oxidation performance evidenced by a negative shift in onset potential, and increase of peak current density, compared with commercial Pt/C. The difference is explained by the adding of appropriate amount of F127 which facilitates the construction of mesoporous matrix structure of WC/C.

  17. Pulse electrodeposition of Pt and Pt–Ru methanol-oxidation nanocatalysts onto carbon nanotubes in citric acid aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Chou, Huei-Yu [Department of Engineering and System Science, National Tsing Hua University, Hsinchu 30013, Taiwan, ROC (China); Hsieh, Chien-Kuo [Department of Materials Engineering, Ming Chi University of Technology, New Taipei City 24301, Taiwan, ROC (China); Tsai, Ming-Chi; Wei, Yu-Hsuan; Yeh, Tsung-Kuang [Department of Engineering and System Science, National Tsing Hua University, Hsinchu 30013, Taiwan, ROC (China); Tsai, Chuen-Horng, E-mail: tsai@aec.gov.tw [Department of Engineering and System Science, National Tsing Hua University, Hsinchu 30013, Taiwan, ROC (China)

    2015-06-01

    In this study, platinum nanoparticle/carbon nanotube (Pt NP/CNT) and platinum–ruthenium nanoparticle (Pt–Ru NP/CNT) hybrid nanocatalysts were prepared by the pulse-electrodeposition method in different aqueous solutions containing citric acid (CA) or sulfuric acid (SA). The electrocatalytic properties of the Pt NP/CNT and Pt–Ru NP/CNT electrodes prepared using different aqueous solutions were investigated for methanol oxidation. The results show that the electrochemical mass activities of these hybrid nanocatalysts prepared in the CA aqueous solution were increased by factors of 1.46 and 2.77 for Pt NPs and Pt–Ru NPs, respectively, compared with those prepared in SA aqueous solutions using the same procedure. These increased mass activities are attributed to the CA playing dual roles as both a stabilizing agent and a particle size reducing agent in the aqueous solutions. The approach developed in this work enables further reductions in the particle sizes of noble-metal nanocatalysts. - Highlights: • Pulse-electrodeposition of Pt or Pt–Ru nanoparticles on carbon nanotubes • Carbon nanotubes used as a catalyst-supporting material • Citric acid used as reducing agent in the aqueous electrodeposition solutions • Electrochemical activity for methanol oxidation improved by a factor of 1.46 to 2.77.

  18. A facile preparation of Pt–Ru nanoparticles supported on polyaniline modified fullerene [60] for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Bai, Zhengyu, E-mail: baizhengyu2000@163.com; Shi, Min; Niu, Lu; Li, Zhichao; Jiang, Libin; Yang, Lin, E-mail: yanglin1819@163.com [School of Chemistry and Chemical Engineering, Henan Normal University, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education (China)

    2013-11-15

    The use of fullerene [60] (C{sub 60}) as carbon support material for the dispersion of catalysts, which provides new ways to develop the advanced electrocatalyst materials for its distorted structure. In this article, polyaniline (PANI)-modified C{sub 60} (abbreviated as PANI-C{sub 60}) is introduced, and the platinum–ruthenium alloy nanoparticles are successfully supported on PANI-C{sub 60.} According to the transmission electron microscopy measurements, the average particle size of the as-prepared nanoparticles dispersed on PANI-C{sub 60} is 2.4 nm. Electrochemical studies reveal that the Pt-Ru/PANI-C{sub 60} nanocomposites show excellent electrocatalytic activity toward methanol oxidation, showing that the PANI-C{sub 60} may be a better potential candidate to be used as the supports of catalyst for electrochemical oxidation.

  19. Deposition and characterisation of epitaxial oxide thin films for SOFCs

    KAUST Repository

    Santiso, José

    2010-10-24

    This paper reviews the recent advances in the use of thin films, mostly epitaxial, for fundamental studies of materials for solid oxide fuel cell (SOFC) applications. These studies include the influence of film microstructure, crystal orientation and strain in oxide ionic conducting materials used as electrolytes, such as fluorites, and in mixed ionic and electronic conducting materials used as electrodes, typically oxides with perovskite or perovskite-related layered structures. The recent effort towards the enhancement of the electrochemical performance of SOFC materials through the deposition of artificial film heterostructures is also presented. These thin films have been engineered at a nanoscale level, such as the case of epitaxial multilayers or nanocomposite cermet materials. The recent progress in the implementation of thin films in SOFC devices is also reported. © 2010 Springer-Verlag.

  20. Electrochromism of the electroless deposited cuprous oxide films

    International Nuclear Information System (INIS)

    Neskovska, R.; Ristova, M.; Velevska, J.; Ristov, M.

    2007-01-01

    Thin cuprous oxide films were prepared by a low cost, chemical deposition (electroless) method onto glass substrates pre-coated with fluorine doped tin oxide. The X-ray diffraction pattern confirmed the Cu 2 O composition of the films. Visible transmittance spectra of the cuprous oxide films were studied for the as-prepared, colored and bleached films. The cyclic voltammetry study showed that those films exhibited cathode coloring electrochromism, i.e. the films showed change of color from yellowish to black upon application of an electric field. The transmittance across the films for laser light of 670 nm was found to change due to the voltage change for about 50%. The coloration memory of those films was also studied during 6 h, ex-situ. The coloration efficiency at 670 nm was calculated to be 37 cm 2 /C

  1. Methanol oxidation in a flow reactor: Implications for the branching ratio of the CH3OH+OH reaction

    DEFF Research Database (Denmark)

    Rasmussen, Christian Lund; Wassard, K.H.; Dam-Johansen, Kim

    2008-01-01

    The oxidation of methanol in a flow reactor has been studied experimentally under diluted, fuel-lean conditions at 650-1350 K, over a wide range of O-2 concentrations (1%-16%), and with and without the presence of nitric oxide. The reaction is initiated above 900 K, with the oxidation rate...... decreasing slightly with the increasing O-2 concentration. Addition of NO results in a mutually promoted oxidation of CH3OH and NO in the 750-1100 K range. The experimental results are interpreted in terms of a revised chemical kinetic model. Owing to the high sensitivity of the mutual sensitization of CH3OH...... and NO oxidation to the partitioning of CH3O and CH2OH, the CH3OH + OH branching fraction could be estimated as alpha = 0.10 +/- 0.05 at 990 K. Combined with low-temperature measurements, this value implies a branching fraction that is largely independent of temperature. It is in good agreement with recent...

  2. The use of a hierarchically platinum-free electrode composed of tin oxide decorated polypyrrole on nanoporous copper in catalysis of methanol electrooxidation

    Energy Technology Data Exchange (ETDEWEB)

    Asghari, Elnaz, E-mail: elnazasghari@yahoo.com; Ashassi-Sorkhabi, Habib; Vahed, Akram; Rezaei-Moghadam, Babak; Charmi, Gholam Reza

    2016-01-01

    Tin oxide nanoparticles were synthesized through a galvanostatic pathway on polypyrrole, PPy, coated nanoporous copper. The morphology and surface analysis of the assemblies were evaluated by field emission scanning electron microscopy, FESEM, and energy dispersive X-ray, EDX, analysis, respectively. The electrocatalytic behavior of electrodes was studied by cyclic voltammetry and chronoamperometry tests in methanol solution. FESEM results showed that uniformly distributed nanoparticles with diameters of about 20–30 nm have been dispersed on PPy matrix. Cyclic voltammetry and chronoamperometry tests in methanol solution showed a significant enhancement in the catalytic action of PPy after decoration of tin oxide nanoparticles. Porous Cu/PPy/SnO{sub x} electrodes showed enhanced anodic peak current density for methanol oxidation compared to smooth Cu/PPy/SnO{sub x} and porous Cu/PPy. The effects of synthesis current density and time on the electrocatalytic behavior of the electrodes were evaluated. The significant enhancement of electrocatalytic behavior of the Cu/PPy electrode after decoration of SnO{sub x} overlayer was attributed to the effect of tin oxide on the adsorption of intermediates of methanol oxidation as well as oxidation of bi-products such as CO; huge tendency of tin oxides for dehydrogenation of the alcohols and the increase in microscopic surface area of the electrodes were introduced as other affecting factors. - Highlights: • Nanoporous copper–zinc substrates were formed by chemical leaching of zinc. • Polypyrrole thin film was electrodeposited on nanoporous copper. • Thin oxide nanoparticles were synthesized electrochemically on polypyrrole layer. • The catalytic performance of the electrodes was evaluated for methanol oxidation.

  3. Nanostructured high valence silver oxide produced by pulsed laser deposition

    International Nuclear Information System (INIS)

    Dellasega, D.; Facibeni, A.; Di Fonzo, F.; Russo, V.; Conti, C.; Ducati, C.; Casari, C.S.; Li Bassi, A.; Bottani, C.E.

    2009-01-01

    Among silver oxides, Ag 4 O 4 , i.e. high valence Ag(I)Ag(III) oxide, is interesting for applications in high energy batteries and for the development of antimicrobial coatings. We here show that ns UV pulsed laser deposition (PLD) in an oxygen containing atmosphere allows the synthesis of pure Ag 4 O 4 nanocrystalline thin films, permitting at the same time to control the morphology of the material at the sub-micrometer scale. Ag 4 O 4 films with a crystalline domain size of the order of tens of nm can be deposited provided the deposition pressure is above a threshold (roughly 4 Pa pure O 2 or 20 Pa synthetic air). The formation of this particular high valence silver oxide is explained in terms of the reactions occurring during the expansion of the ablated species in the reactive atmosphere. In particular, expansion of the PLD plasma plume is accompanied by formation of low stability Ag-O dimers and atomic oxygen, providing reactive species at the substrate where the film grows. Evidence of reactive collisions in the expanding ablation plume is obtained by analysis of the plume visible shape in inert and reactive atmospheres. In addition, we show how the dimensionless deposition parameter L, relating the target-to-substrate distance to the ablation plume maximum expansion length, can be used to classify different growth regimes. It is thus possible to vary the stoichiometry and the morphology of the films, from compact and columnar to foam-like, by controlling both the gas pressure and the target-to-substrate distance

  4. Partially and fully de-alloyed glassy ribbons based on Au: Application in methanol electro-oxidation studies

    Energy Technology Data Exchange (ETDEWEB)

    Paschalidou, Eirini Maria, E-mail: epaschal@unito.it [Dipartimento di Chimica e Centro Interdipartimentale NIS (Nanostructured Surfaces and Interfaces), Università di Torino, Via Pietro Giuria 7, 10125, Torino (Italy); Scaglione, Federico [Dipartimento di Chimica e Centro Interdipartimentale NIS (Nanostructured Surfaces and Interfaces), Università di Torino, Via Pietro Giuria 7, 10125, Torino (Italy); Gebert, Annett; Oswald, Steffen [Leibniz Institut für Festkörper- und Werkstoffforschung IFW, Helmholtzstraße 20, 01069, Dresden (Germany); Rizzi, Paola; Battezzati, Livio [Dipartimento di Chimica e Centro Interdipartimentale NIS (Nanostructured Surfaces and Interfaces), Università di Torino, Via Pietro Giuria 7, 10125, Torino (Italy)

    2016-05-15

    In this work, electrochemical de-alloying of an amorphous alloy, Au{sub 40}Cu{sub 28}Ag{sub 7}Pd{sub 5}Si{sub 20}, cast in ribbon form by melt spinning, has been performed, obtaining self standing nanoporous materials suitable for use as electrodes for electrocatalytic applications. The de-alloying encompasses removal of less noble elements and the crystallization of Au, resulting in interconnected ligaments whose size and morphology are described as a function of time. Depending on de-alloying time, the crystals may contain residual amounts of Cu, Ag and Pd, as shown by Auger Electron Spectroscopy (AES), Energy Dispersive Spectroscopy (EDS) and Cyclic Voltammetry (CV) in a basic solution. Current density peaks in the 0.16–0.28 V range (vs Ag/AgCl) indicate that the porous ribbons are active for the electro-oxidation of methanol. The partially de-alloyed samples, which still partially contain the amorphous phase because of the shorter etching times, have finer ligaments and display peaks at lower potential. However, the current density decreases rapidly during repeated potential scans. This is attributed to the obstruction of Au sites, mainly by the Cu oxides formed during the scans. The fully de-alloyed ribbons display current peaks at about 0.20 V and remain active for hundreds of scans at more than 60% of the initial current density. They can be fully re-activated to achieve the same performance levels after a brief immersion in nitric acid. The good activity is due to trapped Ag and Pd atoms in combination with ligament morphology. - Graphical abstract: Fine ligaments and pores made by de-alloying a glassy ribbon of a Au-based alloy, homogeneously produced across the thickness (25 μm) for studying methanol's electro-oxidation behavior. - Highlights: • Size and composition of nanoporous layers tailored in de-alloying Au-based glassy ribbons. • From amorphous precursor fine crystals occur in ligaments with residual Pd and Ag. • Fully de

  5. A novel differential electrochemical mass spectrometry method to determine the product distribution from parasitic Methanol oxidation reaction on oxygen reduction reaction catalysts

    Science.gov (United States)

    Jurzinsky, Tilman; Kurzhals, Philipp; Cremers, Carsten

    2018-06-01

    The oxygen reduction reaction is in research focus since several decades due to its importance for the overall fuel cell performance. In direct methanol fuel cells, the crossover of methanol and its subsequent parasitic oxidation are main issues when it comes to preventing fuel cell performance losses. In this work, we present a novel differential electrochemical mass spectrometry method to evaluate oxygen reduction reaction catalysts on their tolerance to methanol being present at the cathode. Besides this, the setup allows to measure under more realistic fuel cell conditions than typical rotating disc electrode measurements, because the oxygen reduction reaction is evaluated in gaseous phase and a gas diffusion electrode is used as working electrode. Due to the new method, it was possible to investigate the oxygen reduction reaction on two commonly used catalysts (Pt/C and Pt3Co/C) in absence and presence of methanol. It was found, that Pt3Co/C is less prone to parasitic current losses due to methanol oxidation reaction. By connecting a mass spectrometer to the electrochemical cell, the new method allows to determine the products formed on the catalysts due to parasitic methanol electrooxidation.

  6. Optimisation of polypyrrole/Nafion composite membranes for direct methanol fuel cells

    International Nuclear Information System (INIS)

    Zhu Jun; Sattler, Rita R.; Garsuch, Arnd; Yepez, Omar; Pickup, Peter G.

    2006-01-01

    Acidic and neutral Nafion[reg] 115 perfluorosulphonate membranes have been modified by in situ polymerization of pyrrole using Fe(III) and H 2 O 2 as oxidizing agents, in order to decrease methanol crossover in direct methanol fuel cells. Improved selectivities for proton over methanol transport and improved fuel cell performances were only obtained with membranes that were modified while in the acid form. Use of Fe(III) as the oxidizing agent can produce a large decrease in methanol crossover, but causes polypyrrole deposition on the surface of the membrane. This increases the resistance of the membrane, and leads to poor fuel cell performances due to poor bonding with the electrodes. Surface polypyrrole deposition can be minimized, and surface polypyrrole can be removed, by using H 2 O 2 . The use of Nafion in its tetrabutylammonium form leads to very low methanol permeabilities, and appears to offer potential for manipulating the location of polypyrrole within the Nafion structure

  7. Properties of indium tin oxide films deposited on unheated polymer substrates by ion beam assisted deposition

    International Nuclear Information System (INIS)

    Yu Zhinong; Li Yuqiong; Xia Fan; Zhao Zhiwei; Xue Wei

    2009-01-01

    The optical, electrical and mechanical properties of indium tin oxide (ITO) films prepared on polyethylene terephthalate (PET) substrates by ion beam assisted deposition at room temperature were investigated. The properties of ITO films can be improved by introducing a buffer layer of silicon dioxide (SiO 2 ) between the ITO film and the PET substrate. ITO films deposited on SiO 2 -coated PET have better crystallinity, lower electrical resistivity, and improved resistance stability under bending than those deposited on bare PET. The average transmittance and the resistivity of ITO films deposited on SiO 2 -coated PET are 85% and 0.90 x 10 -3 Ω cm, respectively, and when the films are bent, the resistance remains almost constant until a bending radius of 1 cm and it increases slowly under a given bending radius with an increase of the bending cycles. The improved resistance stability of ITO films deposited on SiO 2 -coated PET is mainly attributed to the perfect adhesion of ITO films induced by the SiO 2 buffer layer.

  8. The substrate oxidation mechanism of pyranose 2-oxidase and other related enzymes in the glucose-methanol-choline superfamily.

    Science.gov (United States)

    Wongnate, Thanyaporn; Chaiyen, Pimchai

    2013-07-01

    Enzymes in the glucose-methanol-choline (GMC) oxidoreductase superfamily catalyze the oxidation of an alcohol moiety to the corresponding aldehyde. In this review, the current understanding of the sugar oxidation mechanism in the reaction of pyranose 2-oxidase (P2O) is highlighted and compared with that of other enzymes in the GMC family for which structural and mechanistic information is available, including glucose oxidase, choline oxidase, cholesterol oxidase, cellobiose dehydrogenase, aryl-alcohol oxidase, and pyridoxine 4-oxidase. Other enzymes in the family that have been newly discovered or for which less information is available are also discussed. A large primary kinetic isotope effect was observed for the flavin reduction when 2-d-D-glucose was used as a substrate, but no solvent kinetic isotope effect was detected for the flavin reduction step. The reaction of P2O is consistent with a hydride transfer mechanism in which there is stepwise formation of d-glucose alkoxide prior to the hydride transfer. Site-directed mutagenesis of P2O and pH-dependence studies indicated that His548 is a catalytic base that facilitates the deprotonation of C2-OH in D-glucose. This finding agrees with the current mechanistic model for aryl-alcohol oxidase, glucose oxidase, cellobiose dehydrogenase, methanol oxidase, and pyridoxine 4-oxidase, but is different from that of cholesterol oxidase and choline oxidase. Although all of the GMC enzymes share similar structural folding and use the hydride transfer mechanism for flavin reduction, they appear to have subtle differences in the fine-tuned details of how they catalyze substrate oxidation. © 2013 The Authors Journal compilation © 2013 FEBS.

  9. Synthesis of dimethyl carbonate (DMC) by oxidative carbonylation of methanol using polymer-supported CuCl{sub 2} catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Sato, Y. [Daicel Chemical Industries, Ltd., Hyogo (Japan). Research Center; Kobe University, Kobe (Japan); Kagotani, M. [Daicel Chemical Industries, Ltd., Hyogo (Japan). Research Center; Soma, Y. [Osaka National Research Institute, Osaka (Japan)

    2000-01-01

    Polymer, including 2,2'-bipyridine, poly(4-methyl-4'-vinyl-2,2'-bipyridine)(Pvbpy), was investigated for the synthesis of dimethyl carbonate (DMC) as a support for CuCl{sub 2}, by oxidative carbonylation of methanol in the liquid-phase. The CuCl{sub 2} complex (Pvbpy-CuCl{sub 2}) was insoluble in methanol, and the reaction system was heterogeneous. The Pvbpy-CuCl{sub 2} catalyst showed considerable catalytic activity (DMC yield: 44.4 % and DMC selectivity: 9206 %, at methanol conversion: 1.79 %), which is comparable to the previously reported data of poly (vinylpyridine) (PVP)-CuCl{sub 2} catalyst; the Pvbpy-CuCl{sub 2} catalyst could be recycled after filtration and washing thrice, provided, not having lost activity. The corrosion originating from Cl{sup -} was greatly improved by immobilizing the CuCl{sub 2} by Pvbpy. Elimination of CuCl{sub 2} from the Pvbpy support was observed during the reaction. In the first reaction, about 38 % of the initially supported Cl was released, and in the second and the third reactions, most of the Cl was retained. The rate of corrosion of stainless steels in the first use of the catalyst (0.6 mg h{sup -1} for HC276) was greater than that in the rate of the second and the third uses (<0.1 mg h{sup -1}). These results are closely related to the amount of Cl{sup -} released from the Pvbpy support, which demonstrates that the main cause of corrosion in the catalytic system is Cl{sup -} released from the Pvbpy-CuCl{sub 2} catalyst. From XPS study of the catalyst, it became obvious that Cu(2) was gradually reduced to Cu(1) during the reaction. (author)

  10. Electrochemically reduced graphene-oxide supported bimetallic nanoparticles highly efficient for oxygen reduction reaction with excellent methanol tolerance

    Science.gov (United States)

    Yasmin, Sabina; Cho, Sung; Jeon, Seungwon

    2018-03-01

    We report a simple and facile method for the fabrication of bimetallic nanoparticles on electrochemically reduced graphene oxide (ErGO) for electrocatalytic oxygen reduction reaction (ORR) in alkaline media. First, reduced graphene oxide supported palladium and manganese oxide nanoparticle (rGO/Pd-Mn2O3) catalyst was synthesized via a simple chemical method at room temperature; then, it was electrochemically reduced for oxidation reduction reaction (ORR) in alkaline media. The chemical composition and morphological properties of ErGO/Pd-Mn2O3 was characterized by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). The TEM images reveals that, nano-sized Pd and Mn2O3 particles were disperse on the ErGO sheet without aggregation. The as-prepared ErGO/Pd-Mn2O3 was employed for ORR in alkaline media which shows higher ORR activity with more positive onset and half-wave potential, respectively. Remarkably, ErGO/Pd-Mn2O3 reduced oxygen via four-electron transfer pathway with negligible amount of intermediate peroxide species (HO2-). Furthermore, the higher stability and excellent methanol tolerance of the ErGO/Pd-Mn2O3 compared to commercial Pt/C (20 wt%) catalyst, indicating its suitability for fuel cells.

  11. Model surface studies of metal oxides: Adsorption of water and methanol on ultrathin MgO films on Mo(100)

    International Nuclear Information System (INIS)

    Wu, M.; Estrada, C.A.; Corneille, J.S.; Goodman, D.W.

    1992-01-01

    Model surface studies of magnesium oxide have been carried out using surface sensitive techniques. Ultrathin MgO films have been synthesized under ultrahigh vacuum (UHV) conditions by thermally evaporating Mg onto Mo(100) in the presence of oxygen. Low-energy electron diffraction (LEED) studies indicate that the MgO films grow epitaxially with the (100) face of MgO oriented parallel to Mo(100). The MgO films, prepared under optimum synthesis conditions, have essentially one-to-one stoichiometry, are nearly free from pointlike surface defects, and have properties essentially identical to those of bulk, single-crystal MgO. Adsorption of water and methanol onto the MgO films has been studied using high-resolution electron energy-loss spectroscopy (HREELS) and temperature programmed desorption (TPD). In order to circumvent the difficulty associated with intense multiple surface optical phonon (Fuchs--Kliewer modes) losses, a new approach to acquisition of HREELS data has been demonstrated. This new approach enables the direct observation of weak loss features due to excitation of the adsorbates without serious interference from multiple phonon losses. Our HREELS studies show that water and methanol undergo heterolytic dissociation, leading to the formation of hydroxyl and methoxy species, respectively

  12. Pt supported self-assembled nest-like-porous WO3 hierarchical microspheres as electrocatalyst for methanol oxidation

    International Nuclear Information System (INIS)

    Zhang, Jun; Tu, Jiang-ping; Du, Gao-hui; Dong, Zi-min; Su, Qing-mei; Xie, Dong; Wang, Xiu-li

    2013-01-01

    Highlights: ► Nest-like-porous (NLP) WO 3 microspheres are assembled by a hydrothermal method. ► The NLP-WO 3 microspheres have a hexagonal structure and high porous surface. ► Great enhancement of electrochemical property is achieved for Pt/NLP-WO 3 microspheres. -- Abstract: Hexagonal tungsten trioxide (hex-WO 3 ) hierarchical microspheres with nest-like pores are synthesized by a facile hydrothermal method. The nest-like-porous (NLP) WO 3 hierarchical microspheres with 5–6 μm in diameters are self-assembled of single-crystal nanowires. The nanowires have lengths of several hundred nanometers and diameters of 5–30 nm; the long axis of nanowire is oriented toward 〈0 0 1〉 direction. The specific surface area of hex-WO 3 microspheres is 62 m 2 g −1 . 20 wt.% Pt nanoparticles with ∼7 nm are loaded onto the WO 3 microspheres using a conventional microwave-assisted ethylene glycol (EG) method. The electrocatalytic activity for methanol oxidation of Pt/NLP-WO 3 microspheres is investigated by cyclic voltammetry and chronoamperometry. Due to the large tunnels of hexagonal structure and high porous surface morphology, great enhancement of electrochemical performance is achieved. The Pt/NLP-WO 3 microspheres are demonstrated to be a promising anode material for direct methanol fuel cells (DMFC)

  13. Methanol from biomass and hydrogen

    International Nuclear Information System (INIS)

    Anon.

    1989-01-01

    For Hawaii in the near term, the only liquid fuels indigenous sources will be those that can be made from biomass, and of these, methanol is the most promising. In addition, hydrogen produced by electrolysis can be used to markedly increase the yield of biomass methanol. This paper calculates cost of producing methanol by an integrated system including a geothermal electricity facility plus a plant producing methanol by gasifying biomass and adding hydrogen produced by electrolysis. Other studies cover methanol from biomass without added hydrogen and methanol from biomass by steam and carbon dioxide reforming. Methanol is made in a two-step process: the first is the gasification of biomass by partial oxidation with pure oxygen to produce carbon oxides and hydrogen, and the second is the reaction of gases to form methanol. Geothermal steam is used to generate the electricity used for the electrolysis to produce the added hydrogen

  14. A low-temperature partial-oxidation-methanol micro reformer with high fuel conversion rate and hydrogen production yield

    International Nuclear Information System (INIS)

    Wang, Hsueh-Sheng; Huang, Kuo-Yang; Huang, Yuh-Jeen; Su, Yu-Chuan; Tseng, Fan-Gang

    2015-01-01

    Highlights: • A low-operating temperature of the POM-mode micro methanol reformer is obtained. • The effect of channel design on the performance is studied. • The effect of solid content and binder’ ratio on the performance is studied. • The centrifugal process is benefit for the modification of performance. • 98% of methanol conversion rate of the micro reformer can be obtained at 180 °C. - Abstract: A partial oxidation methanol micro reformer (POM-μReformer) with finger-shaped channels for low operating temperature and high conversing efficiency is proposed in this study. The micro reformer employs POM reaction for low temperature operation (less than 200 °C), exothermic reaction, and quick start-up, as well as air feeding capability; and the finger type reaction chambers for increasing catalyst loading as well as reaction area for performance enhancement. In this study, centrifugal technique was introduced to assist on the catalyst loading with high amount and uniform distribution. The solid content (S), binder’s ratio (B), and channel design (the ratio between channel’s length and width, R) were investigated in detail to optimize the design parameters. Scanning electron microscopy (SEM), gas chromatography (GC), and inductively coupled plasma-mass spectrometer (ICP-MS) were employed to analyze the performance of the POM-μReformer. The result depicted that the catalyst content and reactive area could be much improved at the optimized condition, and the conversion rate and hydrogen selectivity approached 97.9% and 97.4%, respectively, at a very low operating temperature of 180 °C with scarce or no binder in catalyst. The POM-μReformer can supply hydrogen to fuel cells by generating 2.23 J/min for 80% H 2 utilization and 60% fuel cell efficiency at 2 ml/min of supplied reactant gas, including methanol, oxygen and argon at a mixing ratio of 12.2%, 6.1% and 81.7%, respectively

  15. Investigation of methanol oxidation on a highly active and stable Pt–Sn electrocatalyst supported on carbon–polyaniline composite for application in a passive direct methanol fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Amani, Mitra [Department of Chemical Engineering, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Kazemeini, Mohammad [Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran (Iran, Islamic Republic of); Hamedanian, Mahboobeh [Department of Chemistry, Faculty of Science, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Pahlavanzadeh, Hassan [Department of Chemical Engineering, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Gharibi, Hussein, E-mail: h.gharibi@utah.edu [Department of Chemistry, Faculty of Science, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Department of Material Science & Engineering, 122 S Campus Drive, University of Utah, Salt Lake City, UT 84112 (United States)

    2015-08-15

    Highlights: • PtSn/C-PANI performed superior in the MOR compared with a commercial PtRu/C. • Catalytic activity of PtRu/C was highly reduced during the accelerated durability test. • Anode of the PtSn/C-PANI in a passive DMFC lowered methanol crossover by 30%. - Abstract: Polyaniline fiber (PANI) was synthesized and utilized to fabricate a vulcan–polyaniline (C-PANI) composite. Pt/C-PANI and PtSn/C-PANI electro-catalysts with different Pt:Sn atomic ratios were prepared by the impregnation method. These electro-catalysts, along with commercial PtRu/C (Electrochem), were characterized with respect to their structural and electrochemical properties in methanol oxidation reaction (MOR). PtSn(70:30)/C-PANI showed excellent performance in MOR, the obtained maximum current density being about 40% and 50% higher than that for PtRu/C and Pt/C-PANI, respectively. It was also found that the CO tolerance and stability of PtSn(70:30)/C-PANI was considerably higher than that of PtRu/C. Finally, the performance of these two materials was compared in a passive direct methanol fuel cell (DMFC). The DMFC test results demonstrated that the membrane electrode assembly (MEA) prepared using PtSn(70:30)/C-PANI anode catalyst performed more satisfactorily in terms of maximum power density and lower methanol crossover.

  16. Preparation and characterization of mesoporous VO(x)-TiO2 complex oxides for the selective oxidation of methanol to dimethoxymethane.

    Science.gov (United States)

    Liu, Jingwei; Sun, Qing; Fu, Yuchuan; Shen, Jianyi

    2009-07-15

    Mesoporous VO(x)-TiO(2) with high surface areas were prepared using the procedure of evaporation-induced self-assembly combined with ammonia posttreatment. The samples were characterized by X-ray diffraction (XRD), laser Raman spectroscopy (LRS), transmission electron microscopy (TEM), N(2) adsorption, temperature-programmed reduction (H(2)-TPR), microcalorimetry for the adsorption of NH(3), and isopropanol probe reaction. Their catalytic activities were evaluated for the reaction of selective oxidation of methanol to dimethoxymethane (DMM). It was found that the VO(x)-TiO(2) materials exhibited high surface areas with pore diameters of 4 nm. The vanadia species were highly dispersed in the VO(x)-TiO(2) within 30 wt% VO(x) content, evidenced by the results of XRD and LRS. The VO(x)-TiO(2) samples exhibited both surface acidic and redox properties. The surface acidity was further enhanced on the addition of SO(4)2-. The catalyst SO(4)2-/30VO(x)-TiO(2) exhibited good performance for the selective oxidation of methanol (57% conversion) to DMM (83% selectivity) at 423 K.

  17. Optimizing the deposition of hydrogen evolution sites on suspended semiconductor particles using on-line photocatalytic reforming of aqueous methanol solutions.

    Science.gov (United States)

    Busser, G Wilma; Mei, Bastian; Muhler, Martin

    2012-11-01

    The deposition of hydrogen evolution sites on photocatalysts is a crucial step in the multistep process of synthesizing a catalyst that is active for overall photocatalytic water splitting. An alternative approach to conventional photodeposition was developed, applying the photocatalytic reforming of aqueous methanol solutions to deposit metal particles on semiconductor materials such as Ga₂O₃ and (Ga₀.₆ Zn₀.₄)(N₀.₆O₀.₄). The method allows optimizing the loading of the co-catalysts based on the stepwise addition of their precursors and the continuous online monitoring of the evolved hydrogen. Moreover, a synergetic effect between different co-catalysts can be directly established. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. In vitro thrombolytic, anthelmintic, anti-oxidant and cytotoxic activity with phytochemical screening of methanolic extract of Xanthium indicum leaves

    Directory of Open Access Journals (Sweden)

    Antara Ghosh

    2015-12-01

    Full Text Available Xanthium indicum is an important medicinal plant traditionally used in Bangladesh as a folkloric treatment. The current study was undertaken to evaluate thrombolytic, anthelmintic, anti-oxidant, cytotoxic properties with phytochemical screening of methanolic extract of X. indicum leaves. The analysis of phytochemical screening confirmed the existence of phytosetrols and diterpenes. In thrombolytic assay, a significant clot lysis was observed at four concentrations of plant extract compare to the positive control streptokinase (30,000 IU, 15,000 IU and negative control normal saline. The extract revealed potent anthelmintic activity at different concentrations. In anti-oxidant activity evaluation by two potential experiments namely total phenolic content determination and free radical scavenging assay by 2, 2-diphenylpicrylhydrazyl (DPPH, the leaves extract possess good anti-oxidant property. In the brine shrimp lethality bioassay, the crude extract showed potent (LC50 1.3 μg/mL cytotoxic activity compare to the vincristine sulfate as a positive control (LC50 0.8 μg/mL.

  19. High activity PtRu/C catalysts synthesized by a modified impregnation method for methanol electro-oxidation

    International Nuclear Information System (INIS)

    Ma Liang; Liu Changpeng; Liao Jianhui; Lu Tianhong; Xing Wei; Zhang Jiujun

    2009-01-01

    A modified impregnation method was used to prepare highly dispersive carbon-supported PtRu catalyst (PtRu/C). Two modifications to the conventional impregnation method were performed: one was to precipitate the precursors ((NH 4 ) 2 PtCl 6 and Ru(OH) 3 ) on the carbon support before metal reduction; the other was to add a buffer into the synthetic solution to stabilize the pH. The prepared catalyst showed a much higher activity for methanol electro-oxidation than a catalyst prepared by the conventional impregnation method, even higher than that of current commercially available, state-of-the-art catalysts. The morphology of the prepared catalyst was characterized using TEM and XRD measurements to determine particle sizes, alloying degree, and lattice parameters. Electrochemical methods were also used to ascertain the electrochemical active surface area and the specific activity of the catalyst. Based on XPS measurements, the high activity of this catalyst was found to originate from both metallic Ru (Ru 0 ) and hydrous ruthenium oxides (RuO x H y ) species on the catalyst surface. However, RuO x H y was found to be more active than metallic Ru. In addition, the anhydrous ruthenium oxide (RuO 2 ) species on the catalyst surface was found to be less active.

  20. A Comparative Study of Basic, Amphoteric, and Acidic Catalysts in the Oxidative Coupling of Methanol and Ethanol for Acrolein Production.

    Science.gov (United States)

    Lilić, Aleksandra; Wei, Tiantian; Bennici, Simona; Devaux, Jean-François; Dubois, Jean-Luc; Auroux, Aline

    2017-09-11

    The impact of acid/base properties (determined by adsorption microcalorimetry) of various catalysts on the cross-aldolization of acetaldehyde and formaldehyde leading to acrolein was methodically studied in oxidizing conditions starting from a mixture of methanol and ethanol. The aldol condensation and further dehydration to acrolein were carried out on catalysts presenting various acid/base properties (MgO, Mg-Al oxides, Mg/SiO 2 , NbP, and heteropolyanions on silica, HPA/SiO 2 ). Thermodynamic calculations revealed that cross-aldolization is always favored compared with self-aldolization of acetaldehyde, which leads to crotonaldehyde formation. The presence of strong basic sites is shown to be necessary, but a too high amount drastically increases CO x production. On strong acid sites, production of acrolein and carbon oxides (CO x ) does not increase with temperature. The optimal catalyst for this process should be amphoteric with a balanced acid/base cooperation of medium strength sites and a small amount (150 kJ mol -1 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Methanol oxidation catalysis and substructure of PtRu bimetallic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Nitani, Hiroaki; Nakagawa, Takashi; Ono, Takahiro; Honda, Yusuke; Koizumi, Akiko; Seino, Satoshi; Yamamoto, Takao A. [Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871 (Japan); Daimon, Hideo; Kurobe, Yukiko [Development and Technology Division, Hitachi Maxell Ltd., 6-20-1 Kinunodai, Tsukubamirai, Ibaraki 300-2496 (Japan)

    2007-07-15

    Catalytic material of PtRu nanoparticles supported on carbon (PtRu/C) for direct methanol fuel cells was synthesized by a polyol reduction method. Addition of phosphorus was effective for downsizing PtRu particles and improving their catalytic activity. The activity obtained was six times of that of a commercial catalysis. The samples were analyzed by techniques of X-ray absorption fine structure (XAFS) at Pt L{sub III}-edge and Ru K-edge, transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray fluorescence (XRF). These results indicated a core-shell structure consisting of a Pt-rich core and Ru-rich shell. By examining coordination numbers determined by XAFS analysis, we found a clear correlation between the catalytic activity and the Pt-Ru atomic pair frequency occurring on the particle surface, which supports the 'bi-functional mechanism'. (author)

  2. Incorporation effect of nanosized perovskite LaFe₀.₇Co₀.₃O₃ on the electrochemical activity of Pt nanoparticles-multi walled carbon nanotube composite toward methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Noroozifar, Meissam, E-mail: mnoroozifar@chem.usb.ac.ir [Department of Chemistry, University of Sistan and Baluchestan, PO Box 98155-147, Zahedan (Iran, Islamic Republic of); Khorasani-Motlagh, Mozhgan; Khaleghian-Moghadam, Roghayeh; Ekrami-Kakhki, Mehri-Saddat; Shahraki, Mohammad [Department of Chemistry, University of Sistan and Baluchestan, PO Box 98155-147, Zahedan (Iran, Islamic Republic of)

    2013-05-01

    Nanosized perovskite LaFe₀.₇Co₀.₃O₃ (LFCO) is synthesized through conventional co-precipitation method and characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) techniques. The incorporation effect of the mentioned perovskite to catalytic activity of the PtNPs-MWCNTs-nafion (or -chitosan) catalyst toward methanol oxidation has been studied by cyclic voltammetry. Based on the electrochemical studies, all MWCNTs-PtNPs-nafion (or chitosan) and MWCNTs-PtNPs-LFCO-nafion (or chitosan) catalysts show a considerable activity for methanol oxidation. However, a synergistic effect is observed when LFCO is added to the catalyst by decreasing the poisoning rate of the Pt catalyst. - Graphical abstract: Nanosized perovskite LaFe₀.₇Co₀.₃O₃ is synthesized and characterized. The incorporation effect of the mentioned perovskite to catalytic activity of the PtNPS-MWCNTs-nafion (or -chitosan) catalyst toward methanol oxidation is studied. Highlights: • Nanocrystalline LaFe₀.₇Co₀.₃O₃ (LFCO) is prepared by a new simple co-precipitation method. • Effect of LFCO to catalytic activity of PtNPS for methanol oxidation is studied. • A synergistic effect is observed when LFCO is added to the Pt catalyst. • Oxygen of LFCO could be considered as active oxygen to remove CO intermediates.

  3. Role of atomic layer deposited aluminum oxide as oxidation barrier for silicon based materials

    Energy Technology Data Exchange (ETDEWEB)

    Fiorentino, Giuseppe, E-mail: g.fiorentino@tudelft.nl; Morana, Bruno [Department of Microelectronic, Delft University of Technology, Feldmannweg 17, 2628 CT Delft (Netherlands); Forte, Salvatore [Department of Electronic, University of Naples Federico II, Piazzale Tecchio, 80125 Napoli (Italy); Sarro, Pasqualina Maria [Department of Microelectronic, Delft University of Technology, Feldmannweg 17, 2628 CT, Delft (Netherlands)

    2015-01-15

    In this paper, the authors study the protective effect against oxidation of a thin layer of atomic layer deposited (ALD) aluminum oxide (Al{sub 2}O{sub 3}). Nitrogen doped silicon carbide (poly-SiC:N) based microheaters coated with ALD Al{sub 2}O{sub 3} are used as test structure to investigate the barrier effect of the alumina layers to oxygen and water vapor at very high temperature (up to 1000 °C). Different device sets have been fabricated changing the doping levels, to evaluate possible interaction between the dopants and the alumina layer. The as-deposited alumina layer morphology has been evaluated by means of AFM analysis and compared to an annealed sample (8 h at 1000 °C) to estimate the change in the grain structure and the film density. The coated microheaters are subjected to very long oxidation time in dry and wet environment (up to 8 h at 900 and 1000 °C). By evaluating the electrical resistance variation between uncoated reference devices and the ALD coated devices, the oxide growth on the SiC is estimated. The results show that the ALD alumina coating completely prevents the oxidation of the SiC up to 900 °C in wet environment, while an oxide thickness reduction of 50% is observed at 1000 °C compared to uncoated devices.

  4. Effect of preparation procedure on the formation of nanosized mesoporous TiO2-CeO2 catalysts for ethyl acetate total oxidation and methanol decomposition

    Czech Academy of Sciences Publication Activity Database

    Mileva, A.; Issa, G.; Henych, Jiří; Štengl, Václav; Kovacheva, D.; Tsoncheva, T.

    2016-01-01

    Roč. 48, G (2016), s. 115-119 ISSN 0324-1130. [Scientific Session on Advanced Materials and Technologies. Sofia, 10.10.2016-11.10.2016] R&D Projects: GA MŠk(CZ) LM2015073 Institutional support: RVO:61388980 Keywords : Ti-Ce oxides * ethyl acetate total oxidation * methanol decomposition Subject RIV: CA - Inorganic Chemistry Impact factor: 0.238, year: 2016 http://www.bcc.bas.bg/BCC_Volumes/Volume_48_Special_G_2016

  5. Thermodynamic and Kinetic Requirements in Anaerobic Methane Oxidizing Consortia Exclude Hydrogen, Acetate, and Methanol as Possible Electron Shuttles.

    Science.gov (United States)

    Sørensen, K.B.; Finster, K.; Ramsing, N.B.

    2001-07-01

    Anaerobic methane oxidation (AMO) has long remained an enigma in microbial ecology. In the process the net reaction appears to be an oxidation of methane with sulfate as electron acceptor. In order to explain experimental data such as effects of inhibitors and isotopic signals in biomarkers it has been suggested that the process is carried out by a consortium of bacteria using an unknown compound to shuttle electrons between the participants. The overall change in free energy during AMO with sulfate is very small (?22 kJ mol-1) at in situ concentrations of methane and sulfate. In order to share the available free energy between the members of the consortium, the concentration of the intermediate electron shuttle compound becomes crucial. Diffusive flux of a substrate (i.e, the electron shuttle) between bacteria requires a stable concentration gradient where the concentration is higher in the producing organism than in the consuming organism. Since changes in concentrations cause changes in reaction free energies, the diffusive flux of a catabolic product/substrate between bacteria is associated with a net loss of available energy. This restricts maximal inter-bacterial distances in consortia composed of stationary bacteria. A simple theoretical model was used to describe the relationship between inter-bacterial distances and the energy lost due to concentration differences in consortia. Key parameters turned out to be the permissible concentration range of the electron shuttle in the consortium (i.e., the concentration range that allows both participants to gain sufficient energy) and the stoichiometry of the partial reactions. The model was applied to two known consortia degrading ethanol and butyrate and to four hypothetical methane-oxidizing consortia (MOC) based on interspecies transfer of hydrogen, methanol, acetate, or formate, respectively. In the first three MOCs the permissible distances between producers and consumers of the transferred compounds were

  6. Experimental investigation on regulated and unregulated emissions of a diesel/methanol compound combustion engine with and without diesel oxidation catalyst.

    Science.gov (United States)

    Zhang, Z H; Cheung, C S; Chan, T L; Yao, C D

    2010-01-15

    The use of methanol in combination with diesel fuel is an effective measure to reduce particulate matter (PM) and nitrogen oxides (NOx) emissions from in-use diesel vehicles. In this study, a diesel/methanol compound combustion (DMCC) scheme was proposed and a 4-cylinder naturally-aspirated direct-injection diesel engine modified to operate on the proposed combustion scheme. The effect of DMCC and diesel oxidation catalyst (DOC) on the regulated emissions of total hydrocarbons (THC), carbon monoxide (CO), NOx and PM was investigated based on the Japanese 13 Mode test cycle. Certain unregulated emissions, including methane, ethyne, ethene, 1,3-butadiene, BTX (benzene, toluene, xylene), unburned methanol and formaldehyde were also evaluated based on the same test cycle. In addition, the soluble organic fraction (SOF) in the particulate and the particulate number concentration and size distribution were investigated at certain selected modes of operation. The results show that the DMCC scheme can effectively reduce NOx, particulate mass and number concentrations, ethyne, ethene and 1,3-butadiene emissions but significantly increase the emissions of THC, CO, NO(2), BTX, unburned methanol, formaldehyde, and the proportion of SOF in the particles. After the DOC, the emission of THC, CO, NO(2), as well as the unregulated gaseous emissions, can be significantly reduced when the exhaust gas temperature is sufficiently high while the particulate mass concentration is further reduced due to oxidation of the SOF. Copyright 2009 Elsevier B.V. All rights reserved.

  7. Well-dispersed NiO nanoparticles supported on nitrogen-doped carbon nanotube for methanol electrocatalytic oxidation in alkaline media

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Pengcheng; Zhou, Yingke, E-mail: zhouyk888@hotmail.com; Hu, Min; Chen, Jian

    2017-01-15

    Highlights: • Nitrogen-doped carbon nanotube supporting ultrafine NiO nanoparticles with high dispersity are facile synthesized. • The nitrogen doping, calcination temperature and NiO loading present great effects on the catalyst morphology, structure and electrochemical performance. • NiO-NCNT-3x-400 demonstrates remarkable catalytic activity and stability for the methanol electrolytic oxidation reaction. - Abstract: Nitrogen-doped carbon nanotube supporting NiO nanoparticles were synthesized by a chemical precipitation process coupled with subsequent calcination. The morphology and structure of the composites were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), and the electrochemical performance was evaluated using cyclic voltammetry and chronoamperometric technique. The effects of nitrogen doping, calcination temperature and content of NiO nanoparticles on the electrocatalytic activity toward methanol oxidation were systematically studied. The results show that the uniformly dispersed ultrafine NiO nanoparticles supported on nitrogen-doped carbon nanotube are obtained after calcination at 400 °C. The optimized composite catalysts present high electrocatalytic activity, fast charge-transfer process, excellent accessibility and stability for methanol oxidation reaction, which are promising for application in the alkaline direct methanol fuel cells.

  8. Bismuth iron oxide thin films using atomic layer deposition of alternating bismuth oxide and iron oxide layers

    Energy Technology Data Exchange (ETDEWEB)

    Puttaswamy, Manjunath; Vehkamäki, Marko [University of Helsinki, Department of Chemistry, P.O. Box 55, FI-00014 Helsinki (Finland); Kukli, Kaupo, E-mail: kaupo.kukli@helsinki.fi [University of Helsinki, Department of Chemistry, P.O. Box 55, FI-00014 Helsinki (Finland); University of Tartu, Institute of Physics, W. Ostwald 1, EE-50411 Tartu (Estonia); Dimri, Mukesh Chandra [National Institute of Chemical Physics and Biophysics, Akadeemia tee 23, EE-12618 Tallinn (Estonia); Kemell, Marianna; Hatanpää, Timo; Heikkilä, Mikko J. [University of Helsinki, Department of Chemistry, P.O. Box 55, FI-00014 Helsinki (Finland); Mizohata, Kenichiro [University of Helsinki, Department of Physics, P.O. Box 64, FI-00014 Helsinki (Finland); Stern, Raivo [National Institute of Chemical Physics and Biophysics, Akadeemia tee 23, EE-12618 Tallinn (Estonia); Ritala, Mikko; Leskelä, Markku [University of Helsinki, Department of Chemistry, P.O. Box 55, FI-00014 Helsinki (Finland)

    2016-07-29

    Bismuth iron oxide films with varying contributions from Fe{sub 2}O{sub 3} or Bi{sub 2}O{sub 3} were prepared using atomic layer deposition. Bismuth (III) 2,3-dimethyl-2-butoxide, was used as the bismuth source, iron(III) tert-butoxide as the iron source and water vapor as the oxygen source. The films were deposited as stacks of alternate Bi{sub 2}O{sub 3} and Fe{sub 2}O{sub 3} layers. Films grown at 140 °C to the thickness of 200–220 nm were amorphous, but crystallized upon post-deposition annealing at 500 °C in nitrogen. Annealing of films with intermittent bismuth and iron oxide layers grown to different thicknesses influenced their surface morphology, crystal structure, composition, electrical and magnetic properties. Implications of multiferroic performance were recognized in the films with the remanent charge polarization varying from 1 to 5 μC/cm{sup 2} and magnetic coercivity varying from a few up to 8000 A/m. - Highlights: • Bismuth iron oxide thin films were grown by atomic layer deposition at 140 °C. • The major phase formed in the films upon annealing at 500 °C was BiFeO{sub 3}. • BiFeO{sub 3} films and films containing excess Bi favored electrical charge polarization. • Slight excess of iron oxide enhanced saturative magnetization behavior.

  9. Syntheses of carbon porous materials with varied pore sizes and their performances as catalyst supports during methanol oxidation reaction

    International Nuclear Information System (INIS)

    Lo, An-Ya; Hung, Chin-Te; Yu, Ningya; Kuo, Cheng-Tzu; Liu, Shang-Bin

    2012-01-01

    Highlights: ► CPMs with varied pore sizes (1–400 nm) were replicated from various porous silicas by CVI method. ► MOR activities of Pt/CPM electrocatalysts increase with increasing pore size of CPM support. ► Microporous CPMs are favorable supports for Pt in terms of catalytic performance and CO-tolerance. -- Abstract: Carbon porous materials (CPMs) with extended ranges of pore size and morphology were replicated using various porous silicas, such as zeolites, mesoporous silicas, and photonic crystals, as templates by means of chemical vapor infiltration (CVI) method. The micro-, meso-, and macro-porous carbons so fabricated were adopted as supports for the metal (Pt) catalyst for direct methanol fuel cells (DMFCs), and the supported Pt/CPM electrocatalysts were characterized by a variety of different spectroscopic/analytical techniques, viz. transmission electron microscopy (TEM), Raman, X-ray photoelectron spectroscopy (XPS), gas physisorption/chemisorption analyses, and cyclic voltammetry (CV). That these Pt/CPMs were found to exhibit superior electrocatalytic activities compared to the commercial Pt/XC-72 with a comparable Pt loading during methanol oxidation reaction (MOR) is attributed to the presence of Pt nanoparticles (NPs; typically 1–3 nm in size) that are highly dispersed in the CPMs, facilitating an improved tolerance for CO poisoning. While the MOR activity observed for various Pt/CPMs tend to increase with increasing pore size of the carbon supports, Pt catalyst supported on carbon substrates possessing microporosities was found to have superior stability in terms of tolerance for CO poisoning than those with greater pore size or having meso- and macroporosities.

  10. Facile Synthesis of Bimetallic Pt-Ag/Graphene Composite and Its Electro-Photo-Synergistic Catalytic Properties for Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Shuhong Xu

    2016-09-01

    Full Text Available A Pt-Ag/graphene composite (Pt-Ag/GNs was synthesized by the facile aqueous solution method, in which Ag+ was first transformed into Ag2O under UV light irradiation, and then Ag2O, Pt2+, and graphene oxide (GO were simultaneously reduced by formic acid. It was found that Pt-Ag bimetallic nanoparticles were highly dispersed on the surface of graphene, and their size distribution was narrow with an average diameter of 3.3 nm. Electrocatalytic properties of the Pt-Ag/GNs composite were investigated by cyclic voltammograms (CVs, chronoamperometry (CA, CO-stripping voltammograms, and electrochemical impedance spectrum (EIS techniques. It was shown that the Pt-Ag/GNs composite has much higher catalytic activity and stability for the methanol oxidation reaction (MOR and better tolerance toward CO poisoning when compared with Pt/GNs and the commercially available Johnson Matthey 20% Pt/C catalyst (Pt/C-JM. Furthermore, the Pt-Ag/GNs composite showed efficient electro-photo-synergistic catalysis for MOR under UV or visible light irradiation. Particularly in the presence of UV irradiation, the Pt-Ag/GNs composite exhibited an ultrahigh mass activity of 1842.4 mA·mg−1, nearly 2.0 times higher than that without light irradiation (838.3 mA·mg−1.

  11. Study on The Potency of Methanol Extracts From Xanthosoma nigrum Stellfeld As Natural Anti Oxidant by Thiobarbituric Acid Method

    Directory of Open Access Journals (Sweden)

    Devi Ratnawati

    2013-12-01

    Full Text Available In this research Xanthosoma nigrum Stellfeld (the Purple yam was selected as experimental material. This plant was collected from Rejang Lebong region, Bengkulu Province. Methanol extract 96% from stem of purple yam was studied its anti-oxidant activity in various concentrations with α-tocopherol (200 ppm as standard of antioxidant. Antioxidant activity was determined using Thiobarbituric Acid (TBA method. Linoleic acid was oxidized at 40 ºC for seven days with or without extract and the final product malondialdehyde (MDA was reacted with thiostembituric acid to be of red colored complex (MDA-TBA and was then measured by UV-VIS spectrophotometer at λ 532 nm. Stem extract of purple yam with concentration of 100 ppm, 150 ppm, 200 ppm and 300 ppm respectively had the inhibition of 19.32%, 21.85%, 29.47%, and 31.05%. α-Tocopherol as positive control which showed inhibition ability of 85.14% at 200 ppm. Based on the result obtained in this study, the stem’s extract of Purpel yam plant showed that antioxidant activity was lower than α-tocopherol.

  12. Development of Vanadium Phosphaate Catalysts for Methanol Production by Selective Oxidation of Methane.

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, R.L.

    1997-10-01

    This DOE sponsored study of methane partial oxidation was initiated at Amax Research and Development in Golden, CO in October of 1993. Shortly thereafter the management of Amax closed this R&D facility and the PI moved to the Colorado School of Mines. The project was begun again after contract transfer via a novation agreement. Experimental work began with testing of vandyl pyrophosphate (VPO), a well known alkane selective oxidation catalyst. It was found that VPO was not a selective catalyst for methane conversion yielding primarily CO. However, promotion of VPO with Fe, Cr, and other first row transition metals led to measurable yields for formaldehyde, as noted in the summary table. Catalyst characterization studies indicated that the role of promoters was to stabilize some of the vanadium in the V{sup 5+} oxidation state rather than the V{sup 4+} state formally expected for (VO){sub 2}P{sub 2}O{sub 7}.

  13. PtNi alloy nanoparticles supported on carbon-doped TiO2 nanotube arrays for photo-assisted methanol oxidation

    International Nuclear Information System (INIS)

    He, Huichao; Xiao, Peng; Zhou, Ming; Liu, Feila; Yu, Shujuan; Qiao, Lei; Zhang, Yunhuai

    2013-01-01

    To develop anode catalysts for photo-assisted direct methanol fuel cell (PDMFC), carbon-doped TiO 2 nanotube arrays-supported PtNi alloy nanoparticles with different Pt/Ni atomic ratio (PtNi/C-TiO 2 NTs) prepared by pulsed electrodeposition method are evaluated as catalysts for photo-assisted methanol oxidation. The cyclic voltammetry (CV) and chronoamperometry results show that the PtNi/C-TiO 2 NTs prepared at t onPt :t onNi : = 10:7 (t on is the current-on time) with a Pt:Ni atomic ratio of 6.1:5.7 presents the highest catalytic activity for methanol oxidation both in the dark and under illumination. In addition, according to the results obtained from the CO stripping voltammetry and electrochemical impedance spectroscopy (EIS) tests, it was found that the light play an accelerative role in the oxidation of methanol on PtNi/C-TiO 2 NTs under illumination. The effect of illumination which enhancing the catalytic activity of PtNi/C-TiO 2 NTs are attributed to (1) methanol and the intermediates be oxidized directly on C-TiO 2 NTs for the light-induced catalytic effect; (2) more abundant oxygen-donating species be produced on C-TiO 2 NTs in the presence of light; (3) less CO ads adsorbing on catalysts due to the presence of stronger metal–support interactions between PtNi alloy nanoparticles and C-TiO 2 NTs under illumination

  14. A potentiometric study of (acid+base) equilibria in substituted 4-nitropyridine N-oxide systems in methanol and dimethyl sulfoxide

    International Nuclear Information System (INIS)

    Gurzynski, Lukasz; Puszko, Aniela; Makowski, Mariusz; Chmurzynski, Lech

    2007-01-01

    The acid dissociation constants for cationic acids conjugated with 4-nitropyridine N-oxides have been determined using potentiometric titration method. The measurements in the systems of thirteen 4-nitropyridine N-oxide derivatives were carried out in the polar amphiprotic methanol (MeOH) and in the aprotic protophilic dimethyl sulfoxide (DMSO). Likewise as in the polar aprotic protophobic solvents (acetonitrile, acetone) it was found that in MeOH for all N-oxides studied the pK a values were readily determinable, whereas in DMSO the pK a values were hardly determinable or indeterminable by using the potentiometric method. In addition, just like in our previous investigations it was revealed that the sequence of the pK a values of the cationic acids in methanol is the same as in the water and the values are lower than those determined in acetonitrile and acetone. Also, it was found that the phenomenon of cationic homoconjugation equilibria was not present in the systems involving 4-nitropyridine N-oxide derivatives in both solvents used. Furthermore, protonation energies, ΔE prot , and Gibbs free enthalpies, ΔG prot , in vacuo have been compared with acid dissociation constants (expressed as pK a MeOH values) of the protonated N-oxides determined by potentiometric titration in methanol to establish a correlation between these magnitudes

  15. A potentiometric study of (acid+base) equilibria in substituted 4-nitropyridine N-oxide systems in methanol and dimethyl sulfoxide

    Energy Technology Data Exchange (ETDEWEB)

    Gurzynski, Lukasz [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Puszko, Aniela [Department of Organic Chemistry, School of Economics, Wroclaw (Poland); Makowski, Mariusz [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Chmurzynski, Lech [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland)]. E-mail: lech@chemik.chem.univ.gda.pl

    2007-02-15

    The acid dissociation constants for cationic acids conjugated with 4-nitropyridine N-oxides have been determined using potentiometric titration method. The measurements in the systems of thirteen 4-nitropyridine N-oxide derivatives were carried out in the polar amphiprotic methanol (MeOH) and in the aprotic protophilic dimethyl sulfoxide (DMSO). Likewise as in the polar aprotic protophobic solvents (acetonitrile, acetone) it was found that in MeOH for all N-oxides studied the pK{sub a} values were readily determinable, whereas in DMSO the pK{sub a} values were hardly determinable or indeterminable by using the potentiometric method. In addition, just like in our previous investigations it was revealed that the sequence of the pK{sub a} values of the cationic acids in methanol is the same as in the water and the values are lower than those determined in acetonitrile and acetone. Also, it was found that the phenomenon of cationic homoconjugation equilibria was not present in the systems involving 4-nitropyridine N-oxide derivatives in both solvents used. Furthermore, protonation energies, {delta}E{sub prot}, and Gibbs free enthalpies, {delta}G{sub prot}, in vacuo have been compared with acid dissociation constants (expressed as pK{sub a}{sup MeOH} values) of the protonated N-oxides determined by potentiometric titration in methanol to establish a correlation between these magnitudes.

  16. Application of the GRI 1.2 Methane Oxidation Model to Methane and Methanol Oxidation in Supercritical Water

    National Research Council Canada - National Science Library

    Rice, Steven

    1997-01-01

    The Gas Research Institute (GRI) has been leading an effort over the past few years to consolidate recent developments in the elementary reaction modeling of the oxidation of methane for combustion applications into a single...

  17. Chemical vapour deposition of vanadium oxide thermochromic thin films

    Science.gov (United States)

    Piccirillo, Clara

    Thermochromic materials change optical properties, such as transmittance or reflectance, with a variation in temperature. An ideal intelligent (smart) material will allow solar radiation in through a window in cold conditions, but reflect that radiation in warmer conditions. The variation in the properties is often associated with a phase change, which takes place at a definite temperature, and is normally reversible. Such materials are usually applied to window glass as thin films. This thesis presents the work on the development of thermochromic vanadium (IV) oxide (VO2) thin films - both undoped and doped with tungsten, niobium and gold nanoparticles - which could be employed as solar control coatings. The films were deposited using Chemical Vapour Deposition (CVD), using improved Atmospheric Pressure (APCVD), novel Aerosol Assisted (AACVD) and novel hybrid AP/AACVD techniques. The effects of dopants on the metalto- semiconductor transition temperature and transmittance/reflectance characteristics were also investigated. This work significantly increased the understanding of the mechanisms behind thermochromic behaviour, and resulted in thermochromic materials based on VO2 with greatly improved properties.

  18. Depth Profiling Analysis of Aluminum Oxidation During Film Deposition in a Conventional High Vacuum System

    Science.gov (United States)

    Kim, Jongmin; Weimer, Jeffrey J.; Zukic, Muamer; Torr, Douglas G.

    1994-01-01

    The oxidation of aluminum thin films deposited in a conventional high vacuum chamber has been investigated using x-ray photoelectron spectroscopy (XPS) and depth profiling. The state of the Al layer was preserved by coating it with a protective MgF2 layer in the deposition chamber. Oxygen concentrations in the film layers were determined as a function of sputter time (depth into the film). The results show that an oxidized layer is formed at the start of Al deposition and that a less extensively oxidized Al layer is deposited if the deposition rate is fast. The top surface of the Al layer oxidizes very quickly. This top oxidized layer may be thicker than has been previously reported by optical methods. Maximum oxygen concentrations measured by XPS at each Al interface are related to pressure to rate ratios determined during the Al layer deposition.

  19. Copolymers Based on Indole-6-Carboxylic Acid and 3,4-Ethylenedioxythiophene as Platinum Catalyst Support for Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Tzi-Yi Wu

    2015-10-01

    Full Text Available Indole-6-carboxylic acid (ICA and 3,4-ethylenedioxythiophene (EDOT are copolymerized electrochemically on a stainless steel (SS electrode to obtain poly(indole-6-carboxylic acid-co-3,4-ethylenedioxythiophenes (P(ICA-co-EDOTs. The morphology of P(ICA-co-EDOTs is checked using scanning electron microscopy (SEM, and the SEM images reveal that these films are composed of highly porous fibers when the feed molar ratio of ICA/EDOT is greater than 3/2. Platinum particles can be electrochemically deposited into the P(ICA-co-EDOTs and PICA films to obtain P(ICA-co-EDOTs-Pt and PICA-Pt composite electrodes, respectively. These composite electrodes are further characterized using X-ray photoelectron spectroscopy (XPS, SEM, X-ray diffraction analysis (XRD, and cyclic voltammetry (CV. The SEM result indicates that Pt particles disperse more uniformly into the highly porous P(ICA3-co-EDOT2 fibers (feed molar ratio of ICA/EDOT = 3/2. The P(ICA3-co-EDOT2-Pt nanocomposite electrode exhibited excellent catalytic activity for the electrooxidation of methanol in these electrodes, which reveals that P(ICA3-co-EDOT2-Pt nanocomposite electrodes are more promising for application in an electrocatalyst as a support material.

  20. Atomic layer deposition of perovskite oxides and their epitaxial integration with Si, Ge, and other semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    McDaniel, Martin D.; Ngo, Thong Q.; Hu, Shen; Ekerdt, John G., E-mail: ekerdt@utexas.edu [Department of Chemical Engineering, The University of Texas at Austin, Austin, Texas 78712 (United States); Posadas, Agham; Demkov, Alexander A. [Department of Physics, The University of Texas at Austin, Austin, Texas 78712 (United States)

    2015-12-15

    Atomic layer deposition (ALD) is a proven technique for the conformal deposition of oxide thin films with nanoscale thickness control. Most successful industrial applications have been with binary oxides, such as Al{sub 2}O{sub 3} and HfO{sub 2}. However, there has been much effort to deposit ternary oxides, such as perovskites (ABO{sub 3}), with desirable properties for advanced thin film applications. Distinct challenges are presented by the deposition of multi-component oxides using ALD. This review is intended to highlight the research of the many groups that have deposited perovskite oxides by ALD methods. Several commonalities between the studies are discussed. Special emphasis is put on precursor selection, deposition temperatures, and specific property performance (high-k, ferroelectric, ferromagnetic, etc.). Finally, the monolithic integration of perovskite oxides with semiconductors by ALD is reviewed. High-quality epitaxial growth of oxide thin films has traditionally been limited to physical vapor deposition techniques (e.g., molecular beam epitaxy). However, recent studies have demonstrated that epitaxial oxide thin films may be deposited on semiconductor substrates using ALD. This presents an exciting opportunity to integrate functional perovskite oxides for advanced semiconductor applications in a process that is economical and scalable.

  1. Atomic layer deposition of perovskite oxides and their epitaxial integration with Si, Ge, and other semiconductors

    International Nuclear Information System (INIS)

    McDaniel, Martin D.; Ngo, Thong Q.; Hu, Shen; Ekerdt, John G.; Posadas, Agham; Demkov, Alexander A.

    2015-01-01

    Atomic layer deposition (ALD) is a proven technique for the conformal deposition of oxide thin films with nanoscale thickness control. Most successful industrial applications have been with binary oxides, such as Al 2 O 3 and HfO 2 . However, there has been much effort to deposit ternary oxides, such as perovskites (ABO 3 ), with desirable properties for advanced thin film applications. Distinct challenges are presented by the deposition of multi-component oxides using ALD. This review is intended to highlight the research of the many groups that have deposited perovskite oxides by ALD methods. Several commonalities between the studies are discussed. Special emphasis is put on precursor selection, deposition temperatures, and specific property performance (high-k, ferroelectric, ferromagnetic, etc.). Finally, the monolithic integration of perovskite oxides with semiconductors by ALD is reviewed. High-quality epitaxial growth of oxide thin films has traditionally been limited to physical vapor deposition techniques (e.g., molecular beam epitaxy). However, recent studies have demonstrated that epitaxial oxide thin films may be deposited on semiconductor substrates using ALD. This presents an exciting opportunity to integrate functional perovskite oxides for advanced semiconductor applications in a process that is economical and scalable

  2. A green method to prepare Pd-Ag nanoparticles supported on reduced graphene oxide and their electrochemical catalysis of methanol and ethanol oxidation

    Science.gov (United States)

    Li, Lingzhi; Chen, Mingxi; Huang, Guanbo; Yang, Nian; Zhang, Li; Wang, Huan; Liu, Yu; Wang, Wei; Gao, Jianping

    2014-10-01

    Bimetallic palladium-silver nanoparticles (NPs) supported on reduced oxide graphene (RGO) with different Pd/Ag ratios (Pd-Ag/RGO) were prepared by an easy green method which did not use any additional reducing agents or a dispersing agent. During the process, simultaneous redox reactions between AgNO3, K2PdCl4 and graphene oxide (GO) led to bimetallic Pd-Ag NPs. The morphology and composition of the Pd-Ag/RGO were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis and Raman spectroscopy. Cyclic voltammetry and chronoamperometry were used to investigate the electrochemical activities and stabilities of these Pd-Ag/RGO catalysts for the electro-oxidation of methanol and ethanol in alkaline media. Among the different Pd/Ag ratios, the Pd-Ag (1:1)/RGO had the best catalytic activities and stability. So it is a promising catalyst for direct alcohol fuel cell applications.

  3. One-pot synthesis of reduced graphene oxide supported PtCuy catalysts with enhanced electro-catalytic activity for the methanol oxidation reaction

    International Nuclear Information System (INIS)

    Peng, Xinglan; Zhao, Yanchun; Chen, Duhong; Fan, Yanfang; Wang, Xiao; Wang, Weili; Tian, Jianniao

    2014-01-01

    The outstanding performance PtCu y (y = 1,2,3) alloy nanoparticles supported on reduced graphene oxide (rGO) have been synthesized by a facile, efficient, one-pot hydrothermal synthesis approach. The as-prepared PtCu y /rGO catalysts are comprehensively characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy. Cyclic voltammetry, CO-stripping voltammetry and chronoamperometry results reveal that the PtCu y /rGO catalysts have higher electro-catalytic activity, more negative onset oxidative potential, more excellent tolerance ability for CO poisoning and enhanced stability for the electro-oxidation of methanol compared to pure Pt/rGO. As far as the as-made PtCu y /rGO catalysts are concerned, the PtCu 2 /rGO exhibits the highest electro-catalytic activity. The mechanism of the promoting effect of Cu on Pt is explained based on the electronic modification effect. The nature of interfacial interactions between the Pt-Cu active metal phase and the rGO supporting materials is crucial to achieving high performance

  4. Optimum deposition, structure, and properties of tantalum oxide films

    International Nuclear Information System (INIS)

    Lin, Y.C.

    1985-01-01

    Amorphous, ductile, and uniform Ta 2 O 5 films that acted as diffusion barriers were developed by sputter depositing Ta metal on Al single crystals (99.99%) and subsequently anodizing these thin films. The morphology, microstructure, composition and properties were characterized by scanning and transmission electron microscopy, surface and Fourier transform infrared spectroscopy, X-ray diffraction, and fluorescence. Superior corrosion resistance in a water saturated Cl 2 atmosphere was provided by Ta 2 O 5 coating on Al single crystal substrates but not on Al alloys. The strong Ta-O bond, the non-porous nature of the film and good adhesion to the substrate are attributed to the outstanding corrosion resistance of these oxide coatings. Al alloy surfaces are not protected, since the anodic film formed over grain boundaries, processing lines and emergent precipitates is poorly adherent, thus providing loci for corrosion. These problems were eliminated by casting a 400 A layer of tantalum oxyhydroxide polymer from ethanol solution onto Al substrate and curing to a Ta 2 O 5 layer that effectively resisted attack by wet Cl 2 . The mechanical properties of Ta 2 O 5 films on Al alloys were studied at various pH's by in-situ fatigue loading coupled with electrochemical measurements of corrosion potential and corrosion current. These results indicate the fatigue resistance of this oxide film effectively protects the underlying metal from strong HCl solution attack. The very unusual ductility and high corrosion resistance of Ta 2 O 5 films could be related to the graphite-like structure that exists in the amorphous state of this oxide

  5. Amorphous carbon nanofibres inducing high specific capacitance of deposited hydrous ruthenium oxide

    International Nuclear Information System (INIS)

    Barranco, V.; Pico, F.; Ibanez, J.; Lillo-Rodenas, M.A.; Linares-Solano, A.; Kimura, M.; Oya, A.; Rojas, R.M.; Amarilla, J.M.; Rojo, J.M.

    2009-01-01

    Composites consisting of ruthenium oxide particles deposited on amorphous carbon nanofibres are prepared by a repetitive impregnation procedure. The choice of amorphous carbon nanofibres as support of amorphous ruthenium oxide leads to composites in which the deposited oxide consists of aggregates of extremely small primary particles (1-1.5 nm-size) and showing high porosity (specific surface area of 450 m 2 g -1 ). This special deposition of the oxide seems to favour: (i) high oxide capacitance (1000 Fg -1 ) at high oxide loadings (up to 20 wt%) and (ii) high capacitance retention (ca. 80% from the initial oxide capacitance) at high current densities (200 mA cm -2 ). Amorphous carbon nanofibres are suitable supports for amorphous ruthenium oxide and perhaps for other amorphous oxides acting as active electrode materials.

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

    International Nuclear Information System (INIS)

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

    2006-01-01

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

  7. Application of Mössbauer spectroscopy in industrial heterogeneous catalysis: effect of oxidant on FePO{sub 4} material phase transformations in direct methanol synthesis from methane

    Energy Technology Data Exchange (ETDEWEB)

    Dasireddy, Venkata D. B. C., E-mail: dasireddy@ki.si [National Institute of Chemistry, Department of Catalysis and Chemical Reaction Engineering (Slovenia); Khan, Faiza B. [Energy Technology (South Africa); Hanzel, Darko [Jozef Stefan Institute (Slovenia); Bharuth-Ram, Krish [Durban University of Technology, Physics Department (South Africa); Likozar, Blaž [National Institute of Chemistry, Department of Catalysis and Chemical Reaction Engineering (Slovenia)

    2017-11-15

    The effect of the FePO{sub 4} material phase transformation in the direct selective oxidation of methane to methanol was studied using various oxidants, i.e. O{sub 2}, H{sub 2}O and N{sub 2}O. The phases of the heterogeneous catalyst applied, before and after the reactions, were characterized by M¨ossbauer spectroscopy. The main reaction products were methanol, carbon monoxide and carbon dioxide, whereas formaldehyde was produced in rather minute amounts. The Mössbauer spectra showed the change of the initial catalyst material, FePO{sub 4} (tridymite-like phase (tdm)), to the reduced metal form, iron(II) pyrophosphate, Fe{sub 2}P{sub 2}O{sub 7}, and thereafter, the material phase change was governed by the oxidation with individual oxidizing species.Mössbauer spectroscopy measurements applied along with X-ray diffraction (XRD) studies on fresh, reduced and spent catalytic materials demonstrated a transformation of the catalyst to a mixture of phases which depended on operating process conditions. Generally, activity was low and should be a subject of further material optimization and engineering, while the selectivity towards methanol at low temperatures applied was adequate. The proceeding redox mechanism should thus play a key role in catalytic material design, while the advantage of iron-based heterogeneous catalysts primarily lies in them being comparably inexpensive and comprising non-critical raw materials only.

  8. Development of a selective oxidation CO removal reactor for methanol reformate gas

    Energy Technology Data Exchange (ETDEWEB)

    Okada, Shunji; Takatani, Yoshiaki; Terada, Seijo; Ohtani, Shinichi [Kawasaki Heavy Industry, Ltd., Hyogo-ken (Japan)] [and others

    1996-12-31

    This report forms part of a joint study on a PEFC propulsion system for surface ships, summarized in a presentation to this Seminar, entitled {open_quotes}Study on a Polymer Electrolyte Fuel Cell (PEFC) Propulsion System for Surface Ships{close_quotes}, and which envisages application to a 1,500 DWT cargo vessel. The aspect treated here concerns laboratory-scale tests aimed at reducing by selective oxidation to a level below 10 ppm the carbon monoxide (CO) contained to a concentration of around 1% in reformate gas.

  9. Electrocatalytic oxidation of methanol by the [Ru3O(OAc6(py2(CH3OH]3+cluster: improving the metal-ligand electron transfer by accessing the higher oxidation states of a multicentered system

    Directory of Open Access Journals (Sweden)

    Henrique E. Toma

    2010-01-01

    Full Text Available The [Ru3O(Ac6(py2(CH3OH]+ cluster provides an effective electrocatalytic species for the oxidation of methanol under mild conditions. This complex exhibits characteristic electrochemical waves at -1.02, 0.15 and 1.18 V, associated with the Ru3III,II,II/Ru3III,III,II/Ru 3III,III,III /Ru3IV,III,III successive redox couples, respectively. Above 1.7 V, formation of two RuIV centers enhances the 2-electron oxidation of the methanol ligand yielding formaldehyde, in agreement with the theoretical evolution of the HOMO levels as a function of the oxidation states. This work illustrates an important strategy to improve the efficiency of the oxidation catalysis, by using a multicentered redox catalyst and accessing its multiple higher oxidation states.

  10. Robust non-carbon titanium nitride nanotubes supported Pt catalyst with enhanced catalytic activity and durability for methanol oxidation reaction

    International Nuclear Information System (INIS)

    Xiao, Yonghao; Zhan, Guohe; Fu, Zhenggao; Pan, Zhanchang; Xiao, Chumin; Wu, Shoukun; Chen, Chun; Hu, Guanghui; Wei, Zhigang

    2014-01-01

    By the combination of solvothermal alcoholysis and post-nitriding method, titanium nitride nanotubes (TiN NTs), with high surface area, hollow and interior porous structure are prepared successfully and used at a support for Pt nanoparticles. The TiN NTs supported Pt (Pt/TiN NTs) catalyst displays enhanced activity and durability towards methanol oxidation reaction (MOR) compared with the commercial Pt/C (E-TEK) catalyst. X ray diffraction (XRD), nitrogen adsorption/desorption, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) measurements are performed to investigate the physicochemical properties of the synthesized catalyst. SEM and TEM images reveal that the wall of the TiN NTs is porous and Pt nanoparticles supported on the dendritic TiN nanocrystals exhibit small size and good dispersion. Effects of inherent corrosion-resistant, tubular and porous nanostructures and electron transfer due to the strong metal–support interactions of TiN NTs contribute to the enhanced catalytic activity and stability of Pt/TiN NTs towards the MOR

  11. Fabrication of Nitrogen-Doped Mesoporous-Carbon-Coated Palladium Nanoparticles: An Intriguing Electrocatalyst for Methanol and Formic Acid Oxidation.

    Science.gov (United States)

    Ray, Chaiti; Dutta, Soumen; Sahoo, Ramkrishna; Roy, Anindita; Negishi, Yuichi; Pal, Tarasankar

    2016-05-20

    Inspired by the attractive catalytic properties of palladium and the inert nature of carbon supports in catalysis, a concise and simple methodology for in situ nitrogen-doped mesoporous-carbon-supported palladium nanoparticles (Pd/N-C) has been developed by carbonizing a palladium dimethylglyoximate complex. The as-synthesized Pd/N-C has been exfoliated as a fuel cell catalyst by studying the electro-oxidation of methanol and formic acid. The material synthesized at 400 °C,namely, Pd/N-C-400,exhibitssuperior mass activity and stability among catalysts synthesized under different carbonization temperaturesbetween300 and 500 °C. The unique 1D porous structure in Pd/N-C-400 helps better electron transport at the electrode surface, which eventually leads to about five times better catalytic activity and about two times higher stability than that of commercial Pd/C. Thus, our designed sacrificial metal-organic templatedirected pathway becomes a promising technique for Pd/N-C synthesis with superior catalytic performances. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Acetonic and Methanolic Extracts of Heterotheca inuloides, and Quercetin, Decrease CCl4-Oxidative Stress in Several Rat Tissues

    Science.gov (United States)

    Coballase-Urrutia, Elvia; Pedraza-Chaverri, José; Cárdenas-Rodríguez, Noemí; Huerta-Gertrudis, Bernardino; García-Cruz, Mercedes Edna; Montesinos-Correa, Hortencia; Sánchez-González, Dolores Javier; Camacho-Carranza, Rafael; Espinosa-Aguirre, Jesús Javier

    2013-01-01

    The present study was designed to test the hypothesis that the acetonic and methanolic extracts of H. inuloides prevent carbon tetrachloride-(CCl4) induced oxidative stress in vital tissues. Pretreatment with both H. inuloides extracts or quercetin attenuated the increase in serum activity of alkaline phosphatase (ALP), total bilirubin (BB), creatinine (CRE), and creatine kinase (CK), and impeded the decrease of γ-globulin (γ-GLOB) and albumin (ALB) observed in CCl4-induced tissue injury. The protective effect was confirmed by histological analysis with hematoxylin-eosin and periodic acid/Schiff's reagent. Level of lipid peroxidation was higher in the organs of rats exposed to CCl4 than in those of the animals treated with Heterohteca extracts or quercetin, and these showed levels similar to the untreated group. Pretreatment of animals with either of the extracts or quercetin also prevented the increase of 4-hydroxynonenal and 3-nitrotyrosine. Pretreatment with the plant extracts or quercetin attenuated CCl4 toxic effects on the activity of several antioxidant enzymes. The present results strongly suggest that the chemopreventive effect of the extracts used and quercetin, against CCl4 toxicity, is associated with their antioxidant properties and corroborated previous results obtained in liver tissue. PMID:23365610

  13. PtRu nanoparticles dispersed on nitrogen-doped carbon nanohorns as an efficient electrocatalyst for methanol oxidation reaction

    International Nuclear Information System (INIS)

    Zhang, Linwei; Gao, Ang; Liu, Yan; Wang, Yuan; Ma, Jiantai

    2014-01-01

    Highlights: • A novel anode catalyst is synthesized using N-doped carbon nanohorns as support. • PtRu/NCNHs exhibits an excellent activity for MOR relative to PtRu/C catalysts. • The enhancement is due to the electronic interaction between NCNHs and PtRu NPs. - Abstract: A novel anode catalyst (PtRu/NCNHs) assembled with nitrogen-doped carbon nanohorns (NCNHs) and PtRu nanoparticles (1.9 nm) exhibits an obvious enhancement in the tolerance to carbonaceous intermediates and the electocatalytic activity for methanol oxidation reaction (MOR) in comparison to a commercial PtRu/C-JM catalyst and a home-made PtRu/Vulcan catalyst. The MOR mass activity of PtRu/NCNHs (850 mA mg −1 PtRu ) is 2.5 times as high as that of PtRu/C-JM (341 mA mg −1 PtRu ). The MOR specific activity of PtRu/NCNHs is 1.8 times as high as that of PtRu/Vulcan having similar Pt/Ru atomic ratios, specific electrochemical surface areas and particle sizes of PtRu NPs. The electronic interaction between PtRu NPs and NCNHs is responsible for the enhancement in the MOR activity of PtRu/NCNHs

  14. Mechanism of potentiostatic deposition of MnO2 and electrochemical characteristics of the deposit in relation to carbohydrate oxidation

    International Nuclear Information System (INIS)

    Das, Debasmita; Sen, Pratik Kumar; Das, Kaushik

    2008-01-01

    Cyclic voltammetric (CV) and chronoamperometric (CA) studies on potentiostatic deposition of MnO 2 on Pt from Mn(II) solution in very weakly alkaline media show the process to be controlled by a one-electron transfer step, which means that the deposition proceeds through the generation of Mn(III). The electrocatalytic activity of the deposited electrode towards carbohydrate oxidation is found to be maximum at an optimum amount of deposition. Chronopotentiometric (CP) and CV measurements show that the oxidation of carbohydrates on the deposited electrodes follows a catalytic EC (electrochemical-chemical) mechanism via electrolytic formation of Mn(V) and its subsequent consumption either by disproportionation or by chemical reaction in the presence of carbohydrates. The rate constants of the reaction of Mn(V) with dextrose and fructose have been obtained from CA results. The relative order of the oxidation currents for dextrose and fructose as well as their dependence on carbohydrate concentration has been discussed. Replacement of Pt by carbon as the electrode support material does not affect the electrocatalytic activity of the MnO 2 deposit. The observed linear variation of the steady state oxidation currents with carbohydrate concentration can be exploited for analytical application

  15. Diffusion of Oxygen in Alginate Gels Related to the Kinetics of Methanol Oxidation by Immobilized Hansenula polymorpha Cells

    NARCIS (Netherlands)

    Hiemstra, Harry; Dijkhuizen, Lubbert; Harder, Willem

    1983-01-01

    In the yeast Hansenula polymorpha an oxygen-requiring enzyme, alcohol oxidase, catalyzes the conversion of methanol into formaldehyde. After growth on methanol cells of the organism were harvested and entrapped in barium-alginate gels. The diffusion of oxygen towards these cells is seriously

  16. Regulation of methanol oxidation and carbon dioxide fixation in Xanthobacter strain 25a grown in continuous culture

    NARCIS (Netherlands)

    Croes, L.M.; Meijer, Wilhelmus; Dijkhuizen, L.

    The regulation of C1-metabolism in Xanthobacter strain 25a was studied during growth of the organism on acetate, formate and methanol in chemostat cultures. No activity of methanol dehydrogenase (MDH), formate dehydrogenase (FDS) or ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisC/O) could be

  17. Characterization of hafnium oxide resistive memory layers deposited on copper by atomic layer deposition

    Energy Technology Data Exchange (ETDEWEB)

    Briggs, B.D.; Bishop, S.M. [SUNY College of Nanoscale Science and Engineering, 255 Fuller Road, Albany, NY 12203 (United States); Leedy, K.D. [Air Force Research Laboratory, 2241 Avionics Circle, Wright Patterson Air Force Base, Dayton, OH 45433 (United States); Cady, N.C., E-mail: ncady@albany.edu [SUNY College of Nanoscale Science and Engineering, 255 Fuller Road, Albany, NY 12203 (United States)

    2014-07-01

    Hafnium oxide-based resistive memory devices have been fabricated on copper bottom electrodes. The HfO{sub x} active layers in these devices were deposited by atomic layer deposition (ALD) at 250 °C with tetrakis(dimethylamido)hafnium(IV) as the metal precursor and an O{sub 2} plasma as the reactant. Depth profiles of the HfO{sub x} by X-ray photoelectron spectroscopy and secondary ion mass spectroscopy revealed a copper concentration on the order of five atomic percent throughout the HfO{sub x} film. In addition to the Cu doped HfO{sub x}, a thin layer (20 nm) of Cu{sub x}O is present at the surface. This surface layer is believed to have formed during the ALD process, and greatly complicates the analysis of the switching mechanism. The resistive memory structures fabricated from the ALD HfO{sub x} exhibited non-polar resistive switching, independent of the top metal electrode (Ni, Pt, Al, Au). Resistive switching current voltage (I–V) curves were analyzed using Schottky emission and ionic hopping models to gain insight into the physical mechanisms underpinning the device behavior. During the forming process it was determined that, at voltages in excess of 2.5 V, an ionic hopping model is in good agreement with the I–V data. The extracted ion hopping distance ∼ 4 Å was within the range of interatomic spacing of HfO{sub 2} during the forming process consistent with ionic motion of Cu{sup 2+} ions. Lastly the on state I–V data was dominated at larger voltages by Schottky emission with an estimated barrier height of ∼ 0.5 eV and a refractive index of 2.59. The consequence of the Schottky emission analysis indicates the on state resistance to be a product of a Pt/Cu{sub 2}O/Cu filament(s)/Cu{sub 2}O/Cu structure. - Highlights: • HfO{sub 2} was grown via atomic layer deposition at 250 and 100 °C on Cu substrates. • A Cu{sub 2}O surface layer and Cu doping were observed in post-deposition of HfO{sub 2}. • Resistive memory devices were fabricated and

  18. A two step method to synthesize palladium-copper nanoparticles on reduced graphene oxide and their extremely high electrocatalytic activity for the electrooxidation of methanol and ethanol

    Science.gov (United States)

    Na, HeYa; Zhang, Lei; Qiu, HaiXia; Wu, Tao; Chen, MingXi; Yang, Nian; Li, LingZhi; Xing, FuBao; Gao, JianPing

    2015-08-01

    Palladium-copper nanoparticles (Pd-Cu NPs) supported on reduced graphene oxide (RGO) with different Pd/Cu ratios (Pd-Cu/RGO) were prepared by a two step method. The Pd-Cu/RGO hybrids were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction and thermogravimetric analyses. Cyclic voltammetry and chronoamperometry were used to investigate the electrochemical activities and stabilities of the Pd-Cu/RGO catalysts for the electro-oxidation of methanol and ethanol in alkaline media. The Pd-Cu/RGO catalysts exhibited high catalytic activities and good stabilities. This is because the catalysts have a bimetallic structure consisting of a small Pd-Cu core surrounded by a thin Pd-rich shell which improves the catalytic activities of the Pd-Cu/RGO hybrids. Thus they should be useful in direct methanol and ethanol fuel cells.

  19. Probing electronic and vibrational properties at the electrochemical interface using SFG spectroscopy: Methanol electro-oxidation on Pt(1 1 0)

    Science.gov (United States)

    Vidal, F.; Busson, B.; Tadjeddine, A.

    2005-02-01

    We report the study of methanol electro-oxidation on Pt(1 1 0) using infrared-visible sum-frequency generation (SFG) vibrational spectroscopy. The use of this technique enables to probe the vibrational and electronic properties of the interface simultaneously in situ. We have investigated the vibrational properties of the interface in the CO ads internal stretch spectral region (1700-2150 cm -1) over a wide range of potentials. The analysis of the evolution of the C-O stretch line shape, which is related to the interference between the vibrational and electronic parts of the non-linear response, with the potential allows us to show that the onset of bulk methanol oxidation corresponds to the transition from a negatively to a positively charged surface.

  20. Direct synthesis of bimetallic PtCo mesoporous nanospheres as efficient bifunctional electrocatalysts for both oxygen reduction reaction and methanol oxidation reaction

    Science.gov (United States)

    Wang, Hongjing; Yu, Hongjie; Li, Yinghao; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

    2018-04-01

    The engineering of electrocatalysts with high performance for cathodic and/or anodic catalytic reactions is of great urgency for the development of direct methanol fuel cells. Pt-based bimetallic alloys have recently received considerable attention in the field of fuel cells because of their superior catalytic performance towards both fuel molecule electro-oxidation and oxygen reduction. In this work, bimetallic PtCo mesoporous nanospheres (PtCo MNs) with uniform size and morphology have been prepared by a one-step method with a high yield. The as-made PtCo MNs show superior catalytic activities for both oxygen reduction reaction and methanol oxidation reaction relative to Pt MNs and commercial Pt/C catalyst, attributed to their mesoporous structure and bimetallic composition.

  1. Transesterification of jatropha oil with methanol over Mg–Zn mixed metal oxide catalysts

    International Nuclear Information System (INIS)

    Lee, H.V.; Taufiq-Yap, Y.H.; Hussein, M.Z.; Yunus, R.

    2013-01-01

    A design was developed for the transesterification reaction of non-edible Jatropha Curcas oil using a heterogeneous catalysis system to replace the use of a homogeneous catalytic reaction. Investigations were conducted on solid MgO–ZnO mixed metal oxide catalyst bases with different atomic ratios of magnesium to zinc (Mg/Zn). These catalysts were characterized by BET (Brunauer–Emmer–Teller) surface area analysis, X-ray Diffraction (XRD), and Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray Spectroscopy (EDS), and the alkalinity of the catalysts was studied by Temperature Programmed Desorption of carbon dioxide (TPD-CO 2 ). The physicochemical properties of the MgO–ZnO binary system were superior to those of the individual bulk oxides of MgO and ZnO. In addition, the formation of a binary system between MgO and ZnO established an effective method for transesterification processes. In this study, the effects of stoichiometric composition and surface characteristics on the transesterification activity of MgO–ZnO were investigated. The catalysts exhibited high catalytic activity (∼80%) with reliable reusability for biodiesel production. -- Highlights: ► Transesterification reaction of non-edible jatropha oil using solid base catalyst. ► MgO–ZnO binary system showed superior effect than the individual MgO and ZnO. ► More than 80% of FAME yield was achieved under mild condition. ► MgO–ZnO catalyst showed reliable reusability throughout 5 runs. ► Fuel properties of prepared biodiesel were complying with the biodiesel standards.

  2. Surface Preparation and Deposited Gate Oxides for Gallium Nitride Based Metal Oxide Semiconductor Devices

    Directory of Open Access Journals (Sweden)

    Paul C. McIntyre

    2012-07-01

    Full Text Available The literature on polar Gallium Nitride (GaN surfaces, surface treatments and gate dielectrics relevant to metal oxide semiconductor devices is reviewed. The significance of the GaN growth technique and growth parameters on the properties of GaN epilayers, the ability to modify GaN surface properties using in situ and ex situ processes and progress on the understanding and performance of GaN metal oxide semiconductor (MOS devices are presented and discussed. Although a reasonably consistent picture is emerging from focused studies on issues covered in each of these topics, future research can achieve a better understanding of the critical oxide-semiconductor interface by probing the connections between these topics. The challenges in analyzing defect concentrations and energies in GaN MOS gate stacks are discussed. Promising gate dielectric deposition techniques such as atomic layer deposition, which is already accepted by the semiconductor industry for silicon CMOS device fabrication, coupled with more advanced physical and electrical characterization methods will likely accelerate the pace of learning required to develop future GaN-based MOS technology.

  3. Atmospheric pressure plasma enhanced chemical vapor deposition of zinc oxide and aluminum zinc oxide

    International Nuclear Information System (INIS)

    Johnson, Kyle W.; Guruvenket, Srinivasan; Sailer, Robert A.; Ahrenkiel, S. Phillip; Schulz, Douglas L.

    2013-01-01

    Zinc oxide (ZnO) and aluminum-doped zinc oxide (AZO) thin films were deposited via atmospheric pressure plasma enhanced chemical vapor deposition. A second-generation precursor, bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)(N,N′-diethylethylenediamine) zinc, exhibited significant vapor pressure and good stability at one atmosphere where a vaporization temperature of 110 °C gave flux ∼ 7 μmol/min. Auger electron spectroscopy confirmed that addition of H 2 O to the carrier gas stream mitigated F contamination giving nearly 1:1 metal:oxide stoichiometries for both ZnO and AZO with little precursor-derived C contamination. ZnO and AZO thin film resistivities ranged from 14 to 28 Ω·cm for the former and 1.1 to 2.7 Ω·cm for the latter. - Highlights: • A second generation precursor was utilized for atmospheric pressure film growth. • Addition of water vapor to the carrier gas stream led to a marked reduction of ZnF 2 . • Carbonaceous contamination from the precursor was minimal

  4. Stoichiometry control of complex oxides by sequential pulsed-laser deposition from binary-oxide targets

    Energy Technology Data Exchange (ETDEWEB)

    Herklotz, A. [ORNL, Materials Science and Technology Division, Bethel Valley Road, Oak Ridge, Tennessee 37831-6056 (United States); Martin Luther University Halle-Wittenberg, Institute for Physics, Von-Danckelmann-Platz 3, 06120 Halle (Germany); Dörr, K. [Martin Luther University Halle-Wittenberg, Institute for Physics, Von-Danckelmann-Platz 3, 06120 Halle (Germany); Ward, T. Z.; Eres, G. [ORNL, Materials Science and Technology Division, Bethel Valley Road, Oak Ridge, Tennessee 37831-6056 (United States); Christen, H. M.; Biegalski, M. D. [ORNL, Center for Nanophase Materials Sciences, Bethel Valley Road, Oak Ridge, Tennessee 37831-6496 (United States)

    2015-03-30

    To have precise atomic layer control over interfaces, we examine the growth of complex oxides through the sequential deposition from binary targets by pulsed laser deposition. In situ reflection high-energy electron diffraction (RHEED) is used to control the growth and achieve films with excellent structural quality. The growth from binary oxide targets is fundamentally different from single target growth modes and shows more similarities to shuttered growth by molecular beam epitaxy. The RHEED intensity oscillations of non-stoichiometric growth are consistent with a model of island growth and accumulation of excess material on the surface that can be utilized to determine the correct stoichiometry for growth. Correct monolayer doses can be determined through an envelope frequency in the RHEED intensity oscillations. In order to demonstrate the ability of this growth technique to create complex heterostructures, the artificial n = 2 and 3 Sr{sub n+1}Ti{sub n}O{sub 3n+1} Ruddlesden-Popper phases are grown with good long-range order. This method enables the precise unit-cell level control over the structure of perovskite-type oxides, and thus the growth of complex materials with improved structural quality and electronic functionality.

  5. A deposit model for magmatic iron-titanium-oxide deposits related to Proterozoic massif anorthosite plutonic suites: Chapter K in Mineral Deposit Models for Resource Assessment

    Science.gov (United States)

    Woodruff, Laurel G.; Nicholson, Suzanne W.; Fey, David L.

    2013-01-01

    This descriptive model for magmatic iron-titanium-oxide (Fe-Ti-oxide) deposits hosted by Proterozoic age massif-type anorthosite and related rock types presents their geological, mineralogical, geochemical, and geoenvironmental attributes. Although these Proterozoic rocks are found worldwide, the majority of known deposits are found within exposed rocks of the Grenville Province, stretching from southwestern United States through eastern Canada; its extension into Norway is termed the Rogaland Anorthosite Province. This type of Fe-Ti-oxide deposit dominated by ilmenite rarely contains more than 300 million tons of ore, with between 10- to 45-percent titanium dioxide (TiO2), 32- to 45-percent iron oxide (FeO), and less than 0.2-percent vanadium (V).

  6. The Role of Catalyst Properties on Methanol Oxidation over V{sub 2}O{sub 5}-TiO{sub 2} Using Ozone

    Energy Technology Data Exchange (ETDEWEB)

    Sahle-Demessie, Endalkachew [US EPA, Office of Research and Development, NRML (United States)], E-mail: sahle-demessie.endalkachew@epa.gov; Almquist, Catherine B. [Miami University, Paper Science and Chemical Engineering Department (United States); Sehker, Sridara Chandra [US EPA, Office of Research and Development, NRML (United States)

    2008-08-15

    Oxidation of methanol over V{sub 2}O{sub 5} catalysts supported on anatase TiO{sub 2} that were prepared using sol-gel formation and impregnation procedures were investigated. The effects of incorporating Mg in sol-gel to influence the properties of the catalyst were also studied. The process provides an alternative low temperature reaction pathway for reducing emissions of hazardous air pollutant (HAPs) such as methanol and total reduced sulfur compounds (TRS) from pulp and paper mills. The bulk and surface composition of the catalysts were determined by XRD and SEM-EDAX, respectively. The X-ray diffraction patterns of the vanadia-titania catalysts showed mainly the anatase phase of TiO{sub 2}. Temperature programmed desorption of methanol from the different catalyst showed that the {alpha} and {beta} peaks differ significantly with V content and addition of Mg. The combination of gas phase and surface reactions on the V/TiO{sub 2} catalysts reduced the amount of ozone required for high degradation of methanol to mainly CO{sub x} with small quantities of methyl formate. In the absence of ozone the catalysts showed very low activity. It is hypothesized that the ozone is directly influencing the V{sup 4+} and V{sup 5+} redox cycle of the catalyst. Oxidation of methanol is influenced by the operation variables and catalyst properties. The results of this study revealed that the V content has significant influence on the catalyst activity, and the optimum vanadia loading of about 6 wt%. Higher turnover frequencies were observed over sol-gel catalysts than with catalysts prepared by the impregnation method.

  7. Photocatalysis of zinc oxide nanotip array/titanium oxide film heterojunction prepared by aqueous solution deposition

    Science.gov (United States)

    Lee, Ming-Kwei; Lee, Bo-Wei; Kao, Chen-Yu

    2017-05-01

    A TiO2 film was prepared on indium tin oxide (ITO)/glass by aqueous solution deposition (ASD) with precursors of ammonium hexafluoro-titanate and boric acid at 40 °C. The photocatalysis of annealed TiO2 film increases with increasing growth time and decreases with increasing growth times longer than 60 min. A ZnO nanotip array was prepared on ZnO seed layer/TiO2 film/glass by aqueous solution deposition with precursors of zinc nitrate and ammonium hydroxide at 70 °C. The photocatalysis of ASD-ZnO/ASD-TiO2 film/ITO glass can be better than that of P25.

  8. Synthesis of honeycomb-like mesoporous nitrogen-doped carbon nanospheres as Pt catalyst supports for methanol oxidation in alkaline media

    Science.gov (United States)

    Zhang, Yunmao; Liu, Yong; Liu, Weihua; Li, Xiying; Mao, Liqun

    2017-06-01

    This paper reports the convenient synthesis of honeycomb-like mesoporous nitrogen-doped carbon spheres (MNCS) using a self-assembly strategy that employs dopamine (DA) as a carbon and nitrogen precursor and a polystyrene-b-poly(ethylene oxide) (PS173-b-PEO170) diblock copolymer as a soft template. The MNCS have large BET surface areas of up to 554 m2 g-1 and high nitrogen contents of up to 6.9 wt%. The obtained MNCS are used as a support for Pt catalysts, which promote methanol oxidation in alkaline media. The MNCS-supported Pt (Pt/MNCS) catalyst has a larger electrochemically active surface area (ESA) (89.2 m2 g-1) than does a commercially available Vulcan XC-72R supported Pt/C catalyst. Compared to the Pt/C catalyst, Pt/MNCS displays a higher peak current density (1007 mA mg-1) and is more stable during methanol oxidation. These improvements are attributed to the honeycomb-like porous structure of the MNCS and the introduction of nitrogen to the carbon support. The MNCS effectively stabilize Pt nanoparticles and assuage the agglomeration of the nanoparticles, suggesting that MNCS are potential and promising application as electrocatalyst supports in alkaline direct methanol fuel cells.

  9. Green synthesis of Pt-on-Pd bimetallic nanodendrites on graphene via in situ reduction, and their enhanced electrocatalytic activity for methanol oxidation

    International Nuclear Information System (INIS)

    Cai, Zhi-xiong; Liu, Cong-cong; Wu, Geng-huang; Chen, Xiao-mei; Chen, Xi

    2014-01-01

    Graphical abstract: - Highlights: • Porous 3D dendrite-like structure of Pt-on-Pd bimetallic nanostructures supported on graphene were prepared. • The surface of nanostructures was very “clean” because of the surfactant-free formation process and the use of green reagent. • The hetero-nanostructures showed excellent electrocatalytic performance in methanol oxidation. - Abstract: A green synthesis of Pt-on-Pd bimetallic nanodendrites supported on graphene (GPtPdNDs) with a Pd interior and a dendrite-like Pt exterior was achieved using a two-step preparation, mixing graphene and PdCl 4 2− first, then adding PtCl 4 2− and ethanol without any other solvent. The morphology, structure and composition of the thus-prepared GPtPdNDs were characterized by transmission electron microscopy (TEM), high resolution TEM, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. Because no halide ions (refer in particular to Br - , I − ) or surfactant was involved in the synthesis, the prepared GPtPdNDs were directly modified onto a glassy carbon electrode and showed excellent electrocatalytic performance in methanol oxidation without any pretreatments. Moreover, with the special structure of PtPdNDs and the synergetic effects of Pt and Pd and the enhanced electron transfer by graphene, the GPtPdNDs composites exhibited higher electrocatalytic activity and better tolerance to Pt nanoparticles supported on graphene (GPtNPs) and Pt/C for methanol oxidation

  10. Preparation of Pt Ag alloy nanoisland/graphene hybrid composites and its high stability and catalytic activity in methanol electro-oxidation

    Directory of Open Access Journals (Sweden)

    Feng Lili

    2011-01-01

    Full Text Available Abstract In this article, PtAg alloy nanoislands/graphene hybrid composites were prepared based on the self-organization of Au@PtAg nanorods on graphene sheets. Graphite oxides (GO were prepared and separated to individual sheets using Hummer's method. Graphene nano-sheets were prepared by chemical reduction with hydrazine. The prepared PtAg alloy nanomaterial and the hybrid composites with graphene were characterized by SEM, TEM, and zeta potential measurements. It is confirmed that the prepared Au@PtAg alloy nanorods/graphene hybrid composites own good catalytic function for methanol electro-oxidation by cyclic voltammograms measurements, and exhibited higher catalytic activity and more stability than pure Au@Pt nanorods and Au@AgPt alloy nanorods. In conclusion, the prepared PtAg alloy nanoislands/graphene hybrid composites own high stability and catalytic activity in methanol electro-oxidation, so that it is one kind of high-performance catalyst, and has great potential in applications such as methanol fuel cells in near future.

  11. TiO2/C composite as a support for Pd-nanoparticles toward the electrocatalytic oxidation of methanol in alkaline media

    International Nuclear Information System (INIS)

    Estudillo-Wong, L.A.; Vargas-Gómez, A.M.; Arce-Estrada, E.M.; Manzo-Robledo, A.

    2013-01-01

    The electro-oxidation of methanol was studied in alkaline solution on Pd nanoparticles supported on carbon black (XC-72R, C) and TiO 2 /C composite. The materials were prepared via organic colloid route at 170 °C with 5 wt% of Pd. X-ray diffraction (XRD), PdO monolayer reduction (PdO red ) and CO-stripping was employed to characterize both structure and electrochemical properties. According to this, the lattice parameter decreases from 0.3991 to 0.3905 nm due to a possible formation of Pd–Ti alloy. This modification is linked with the electrochemical active surface area (ECSA) decreasing from 22 to 18 m 2 g −1 . On the other hand, studies as a function of temperature and alcohol concentration indicated that the current for methanol electro-oxidation is higher and more stable at Pd/TiO 2 –C, with E a = 44.042 kJ mol −1 . Then, it is highly possible that at Pd/TiO 2 –C, the OH − /OH ads couple is adsorbed at the TiO 2 sites, increasing the kinetic of methanol oxidation reaction at the catalyst surface

  12. Novel synthesis of core-shell Au-Pt dendritic nanoparticles supported on carbon black for enhanced methanol electro-oxidation

    Science.gov (United States)

    Cao, Ribing; Xia, Tiantian; Zhu, Ruizhi; Liu, Zhihua; Guo, Jinming; Chang, Gang; Zhang, Zaoli; Liu, Xiong; He, Yunbin

    2018-03-01

    Core-shell Au-Pt dendritic nanoparticles (Au-Pt NPs) has been synthesized via a facile seed-mediated growth method, in which dendritic Pt nanoparticles as shell grow on the surface of gold nanocores by using ascorbic acid (AA) as "green" reducing reagents. The morphologies and compositions of the as-prepared nanocomposites with core-shell structure are characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Electrochemical experiments, including cyclic voltammetry (CV) and chronoamperometry (CA) are performed to investigate the electrocatalytic properties of the Au-Pt NPs loaded carbon black composites (Au-Pt NPs/V) towards methanol oxidation in an alkaline solution. It is found that the reduction time of AA could regulate the thickness and amount of Pt on the Au nanocores, which significantly affect catalytic activity of the Au-Pt NPs/V toward methanol oxidation. Au-Pt NPs/V with optimum reduction time 4 h exhibit 2.3-times higher electrocatalytic activity than that of a commercial catalyst (Pt/carbon black) and an excellent CO tolerance toward methanol oxidation. This behavior is attributed to large active electrochemical area of the bimetallic nanocomposites and the change in the electronic structure of Pt when Au surface modified with fewer Pt nanoparticles.

  13. Formation conditions of uranium minerals in oxidation zone of uranium deposits

    International Nuclear Information System (INIS)

    Li Youzhu

    2005-01-01

    The paper concerns about the summary and classification of hydrothermal uranium deposit with oxidation zone. Based on the summary of observation results of forty uranium deposits located in CIS and Bulgaria which are of different sizes and industrial-genetic types, analysis on available published information concerning oxidation and uranium mineral enrichment in supergenic zone, oxidation zone classification of hydrothermal uranium had been put forward according to the general system of the exogenetic uranium concentration. (authors)

  14. Template-assisted hydrothermally obtained titania-ceria composites and their application as catalysts in ethyl acetate oxidation and methanol decomposition with a potential for sustainable environment protection

    Czech Academy of Sciences Publication Activity Database

    Tsoncheva, T.; Mileva, A.; Issa, G.; Dimitrov, M.; Kovacheva, D.; Henych, Jiří; Scotti, N.; Kormunda, M.; Atanasova, G.; Štengl, Václav

    2017-01-01

    Roč. 396, FEB (2017), s. 1289-1302 ISSN 0169-4332 R&D Projects: GA MŠk(CZ) LM2015073 Grant - others:AV ČR(CZ) BAS-17-13 Program:Bilaterální spolupráce Institutional support: RVO:61388980 Keywords : Ceria-titania binary oxides * Template assisted hydrothermal synthesis * Methanol decomposition * Ethyl acetate oxidation Subject RIV: CA - Inorganic Chemistry OBOR OECD: Inorganic and nuclear chemistry Impact factor: 3.387, year: 2016

  15. Low content of Pt supported on Ni-MoCx/carbon black as a highly durable and active electrocatalyst for methanol oxidation, oxygen reduction and hydrogen evolution reactions in acidic condition

    Science.gov (United States)

    Zhang, Yan; Zang, Jianbing; Jia, Shaopei; Tian, Pengfei; Han, Chan; Wang, Yanhui

    2017-08-01

    Nickel and molybdenum carbide modified carbon black (Ni-MoCx/C) was synthesized by a two-step microwave-assisted deposition/carbonthermal reduction method and characterized by X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The as-prepared Ni-MoCx/C supported Pt (10 wt%) electrocatalyst (10Pt/Ni-MoCx/C) was synthesized through a microwave-assisted reduction method and 10Pt/Ni-MoCx/C exhibited high electrocatalytic activity for methanol oxidation, oxygen reduction and hydrogen evolution reactions. Results showed that 10Pt/Ni-MoCx/C electrocatalyst had better electrocatalytic activity and stability performance than 20 wt% Pt/C (20Pt/C) electrocatalyst. Among them, the electrochemical surface area of 10Pt/Ni-MoCx/C reached 68.4 m2 g-1, which was higher than that of 20Pt/C (63.2 m2 g-1). The enhanced stability and activity of 10Pt/Ni-MoCx/C electrocatalyst were attributed to: (1) an anchoring effect of Ni and MoCx formed during carbonthermal reduction process; (2) a synergistic effect among Pt, Ni, MoOx and MoCx. These findings indicated that 10Pt/Ni-MoCx/C was a promising electrocatalyst for direct methanol fuel cells.

  16. Molecular analysis of mxbD and mxbM, a putative sensor-regulator pair required for oxidation of methanol in Methylobacterium extorquens AM1.

    Science.gov (United States)

    Springer, A L; Morris, C J; Lidstrom, M E

    1997-05-01

    Five genes are thought to be required for transcription of methanol oxidation genes in Methylobacterium strains. These putative regulatory genes include mxcQE, which encode a putative sensor-regulator pair, and mxbDM and mxaB, whose functions are less well-understood. In this study, mxbDM in Methylobacterium extorquens AM1 were shown to be required for expression of a xylE transcriptional fusion to the structural gene for the large subunit of methanol dehydrogenase (mxaF), confirming the role of these genes in transcriptional regulation of mxaF. The nucleotide sequence suggests that mxbD encodes a histidine protein kinase with two transmembrane domains and that mxbM encodes a DNA-binding response regulator. A xylE transcriptional fusion to the putative mxbD promoter showed low-level expression in wild-type cells grown on one-carbon (C1) compounds and no detectable expression in cells grown on succinate. Deletion analysis of this promoter construct showed that the region 229-129 bp upstream of the start of mxbD is required for expression. The expression of the mxbD-xylE fusion was examined in each of the five known regulatory mutant classes. xylE expression was reduced to non-detectable levels in MxcQ and MxcE mutants, but was not affected in the other regulatory mutants or in non-regulatory mutants defective in methanol oxidation. These results suggest a regulatory hierarchy in which the sensor-regulator pair MxcQE control expression of the sensor-regulator pair MxbDM, and MxbDM in turn control expression of a number of genes involved in methanol oxidation.

  17. The deep-subsurface sulfate reducer Desulfotomaculum kuznetsovii employs two methanol-degrading pathways

    NARCIS (Netherlands)

    Sousa, Diana Z.; Visser, Michael; Gelder, Van Antonie H.; Boeren, Sjef; Pieterse, Mervin M.; Pinkse, Martijn W.H.; Verhaert, Peter D.E.M.; Vogt, Carsten; Franke, Steffi; Kümmel, Steffen; Stams, Alfons J.M.

    2018-01-01

    Methanol is generally metabolized through a pathway initiated by a cobalamine-containing methanol methyltransferase by anaerobic methylotrophs (such as methanogens and acetogens), or through oxidation to formaldehyde using a methanol dehydrogenase by aerobes. Methanol is an important substrate in

  18. The Use of C-MnO2 as Hybrid Precursor Support for a Pt/C-MnxO1+x Catalyst with Enhanced Activity for the Methanol Oxidation Reaction (MOR

    Directory of Open Access Journals (Sweden)

    Alessandro H.A. Monteverde Videla

    2015-07-01

    Full Text Available Platinum (Pt nanoparticles are deposited on a hybrid support (C-MnO2 according to a polyol method. The home-made catalyst, resulted as Pt/C-MnxO1+x, is compared with two different commercial platinum based materials (Pt/C and PtRu/C. The synthesized catalyst is characterized by means of FESEM, XRD, ICP-MS, XPS and μRS analyses. MnO2 is synthesized and deposited over a commercial grade of carbon (Vulcan XC72 by facile reduction of potassium permanganate in acidic solution. Pt nanoparticles are synthesized on the hybrid support by a polyol thermal assisted method (microwave irradiation, followed by an annealing at 600 °C. The obtained catalyst displays a support constituted by a mixture of manganese oxides (Mn2O3 and Mn3O4 with a Pt loading of 19 wt. %. The electro-catalytic activity towards MOR is assessed by RDE in acid conditions (0.5 M H2SO4, evaluating the ability to oxidize methanol in 1 M concentration. The synthesized Pt/C-MnxO1+x catalyst shows good activity as well as good stability compared to the commercial Pt/C based catalyst.

  19. Promotion of Pt-Ru/C catalysts driven by heat treated induced surface segregation for methanol oxidation reaction

    International Nuclear Information System (INIS)

    Wei Yuchen; Liu Chenwei; Chang Weijung; Wang Kuanwen

    2011-01-01

    Research highlights: → Thermal treatments on the Pt-Ru/C induce different extents of surface segregation. → O 2 treatment results in obvious Ru segregation and formation of RuO 2 . → Catalysts treated in H 2 have the excellent CO de-poisoning ability. → N 2 treatment suppresses the surface Pt depletion and hence promotes the MOR. - Abstract: Carbon supported Pt-Ru/C (1:1) alloy catalysts supplied by E-TEK are widely used for fuel cell research. Heat treatments in various atmospheres are conducted for the promotion of the methanol oxidation reaction (MOR) and the investigation of the structure-activity relationship (SAR) of the catalysts. The alloy structures, surface compositions, surface species, and electro-catalytic activities of the alloy catalysts are characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV), respectively. The as-received Pt-Ru/C catalysts have a Ru rich in the inner core and Pt rich on the outer shell structure. Thermal treatments on the catalysts induce Ru surface segregation in different extents and thereby lead to their alteration of the alloying degrees. O 2 treatment results in obvious Ru segregation and formation of RuO 2 . Catalysts treated in H 2 have the highest I f /I b value in the CV scans among all samples, indicating the catalysts have the excellent CO de-poisoning ability as evidenced by anodic CO stripping experiments. N 2 treatment may serve as an adjustment process for the surface composition and structure of the catalysts, which can suppress the surface Pt depletion (∼60% Pt on the surface), make the components stable and hence promote the MOR significantly.

  20. Improved catalytic activity of cobalt core–platinum shell nanoparticles supported on surface functionalized graphene for methanol electro-oxidation

    International Nuclear Information System (INIS)

    Zhang, Mingmei; Li, Yuan; Yan, Zaoxue; Jing, Junjie; Xie, Jimin; Chen, Min

    2015-01-01

    Poly (diallyldimethylammonium chloride) (PDDA) functionalized graphene supported bimetallic catalysts of shell platinum on core cobalt (Co@Pt/PDDA-G) are synthesized using a two-step procedure involving the microwave synthesis method and replacement method. TEM indicate that a uniform dispersion of Co@Pt nanoparticles on PDDA functionalized graphene have the average particle size of 1.9 nm. The composite is applied to electrocatalysis for methanol oxidation. And the electrochemical surface areas of the as-prepared Co@Pt/PDDA-G, Pt supported on PDDA-graphene (Pt/PDDA-G), Co@Pt supported on graphene (Co@Pt/G) are evaluated by cyclic voltammetry, which are calculated to be 105.6 m 2 g −1 Pt , 92.8 m 2 g −1 Pt , and 83.4 m 2 g −1 Pt , with respect to 37.8 m 2 g −1 Pt of commercial Pt/C (TKK) catalyst. The current being examined by chronoamperometry reach a constant at 23 mA mg −1 for Co@Pt/PDDA–G catalyst, which is roughly 3.3-fold higher than that of commercial Pt/C catalyst. The electrochemical tests show that the activity and stability of Co@Pt supported on PDDA-G is highly better than the widely used Pt supported on PDDA-graphene sheets, also better than that of Co@Pt on unfunctional graphene with the same Pt content on the electrode. This improved activity could be attributed to not only the PDDA playing a crucial role in the dispersion and stabilization of Co@Pt on graphene, but also the high use ratio of Pt for its shell structure and the electronic effect of the underlying metal and Pt surface layer

  1. Promotion of Pt-Ru/C catalysts driven by heat treated induced surface segregation for methanol oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Wei Yuchen; Liu Chenwei; Chang Weijung [Institute of Materials Science and Engineering, National Central University, Taoyuan 32001, Taiwan (China); Wang Kuanwen, E-mail: kuanwen.wang@gmail.com [Institute of Materials Science and Engineering, National Central University, Taoyuan 32001, Taiwan (China)

    2011-01-12

    Research highlights: > Thermal treatments on the Pt-Ru/C induce different extents of surface segregation. > O{sub 2} treatment results in obvious Ru segregation and formation of RuO{sub 2}. > Catalysts treated in H{sub 2} have the excellent CO de-poisoning ability. > N{sub 2} treatment suppresses the surface Pt depletion and hence promotes the MOR. - Abstract: Carbon supported Pt-Ru/C (1:1) alloy catalysts supplied by E-TEK are widely used for fuel cell research. Heat treatments in various atmospheres are conducted for the promotion of the methanol oxidation reaction (MOR) and the investigation of the structure-activity relationship (SAR) of the catalysts. The alloy structures, surface compositions, surface species, and electro-catalytic activities of the alloy catalysts are characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV), respectively. The as-received Pt-Ru/C catalysts have a Ru rich in the inner core and Pt rich on the outer shell structure. Thermal treatments on the catalysts induce Ru surface segregation in different extents and thereby lead to their alteration of the alloying degrees. O{sub 2} treatment results in obvious Ru segregation and formation of RuO{sub 2}. Catalysts treated in H{sub 2} have the highest I{sub f}/I{sub b} value in the CV scans among all samples, indicating the catalysts have the excellent CO de-poisoning ability as evidenced by anodic CO stripping experiments. N{sub 2} treatment may serve as an adjustment process for the surface composition and structure of the catalysts, which can suppress the surface Pt depletion ({approx}60% Pt on the surface), make the components stable and hence promote the MOR significantly.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-09-27

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

  3. A deposit model for magmatic iron-titanium-oxide deposits related to Proterozoic massif anorthosite plutonic suites

    Science.gov (United States)

    Woodruff, Laurel G.; Nicholson, Suzanne W.; Fey, David L.

    2013-01-01

    This descriptive model for magmatic iron-titanium-oxide (Fe-Ti-oxide) deposits hosted by Proterozoic age massif-type anorthosite and related rock types presents their geological, mineralogical, geochemical, and geoenvironmental attributes. Although these Proterozoic rocks are found worldwide, the majority of known deposits are found within exposed rocks of the Grenville Province, stretching from southwestern United States through eastern Canada; its extension into Norway is termed the Rogaland Anorthosite Province. This type of Fe-Ti-oxide deposit dominated by ilmenite rarely contains more than 300 million tons of ore, with between 10- to 45-percent titanium dioxide (TiO2), 32- to 45-percent iron oxide (FeO), and less than 0.2-percent vanadium (V). The origin of these typically discordant ore deposits remains as enigmatic as the magmatic evolution of their host rocks. The deposits clearly have a magmatic origin, hosted by an age-constrained unique suite of rocks that likely are the consequence of a particular combination of tectonic circumstances, rather than any a priori temporal control. Principal ore minerals are ilmenite and hemo-ilmenite (ilmenite with extensive hematite exsolution lamellae); occurrences of titanomagnetite, magnetite, and apatite that are related to this deposit type are currently of less economic importance. Ore-mineral paragenesis is somewhat obscured by complicated solid solution and oxidation behavior within the Fe-Ti-oxide system. Anorthosite suites hosting these deposits require an extensive history of voluminous plagioclase crystallization to develop plagioclase-melt diapirs with entrained Fe-Ti-rich melt rising from the base of the lithosphere to mid- and upper-crustal levels. Timing and style of oxide mineralization are related to magmatic and dynamic evolution of these diapiric systems and to development and movement of oxide cumulates and related melts. Active mines have developed large open pits with extensive waste-rock piles, but

  4. A nano-structured Ni(II)-chelidamic acid modified gold nanoparticle self-assembled electrode for electrocatalytic oxidation and determination of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Gholivand, Mohammad Bagher, E-mail: mbgholivand@yahoo.com [Department of Analytical Chemistry, Faculty of Chemistry, Razi University, Kermanshah (Iran, Islamic Republic of); Azadbakht, Azadeh [Department of Chemistry, Faculty of Basic Science, Khorramabad Branch, Islamic Azad University, Khorramabad (Iran, Islamic Republic of)

    2012-10-01

    A nano-structured Ni(II)-chelidamic acid (2,6-dicarboxy-4-hydroxypyridine) film was electrodeposited on a gold nanoparticle-cysteine-gold electrode. The morphology of Ni(II)-chelidamic acid gold nanoparticle self-assembled electrode was investigated by scanning electron microscopy (SEM). Electrocatalytic oxidation of methanol on the surface of modified electrode was studied by cyclic voltammetry and chronoamperometry methods. The hydrodynamic amperometry at a rotating modified electrode at constant potential versus reference electrode was used for detection of methanol. Under optimized conditions the calibration plots are linear in the concentration range 0-50 mM with a detection limit of 15 {mu}M. The formed matrix in our work possessed a 3D porous network structure with a large effective surface area, high catalytic activity and behaved like microelectrode ensembles. The modified electrode indicated reproducible behavior and a high level stability during the experiments, making it particularly suitable for analytical purposes. - Highlights: Black-Right-Pointing-Pointer The Au electrode modified with thin Ni(II)/CHE-AuNP film shows stable and reproducible behavior. Black-Right-Pointing-Pointer Long stability and excellent electrochemical reversibility were observed. Black-Right-Pointing-Pointer This modified electrode shows excellent catalytic activity for methanol oxidation. Black-Right-Pointing-Pointer Combination of unique properties of AuNP and Ni(II)/CHE resulted in improvement of current responses.

  5. Depositing laser-generated nanoparticles on powders for additive manufacturing of oxide dispersed strengthened alloy parts via laser metal deposition

    Science.gov (United States)

    Streubel, René; Wilms, Markus B.; Doñate-Buendía, Carlos; Weisheit, Andreas; Barcikowski, Stephan; Henrich Schleifenbaum, Johannes; Gökce, Bilal

    2018-04-01

    We present a novel route for the adsorption of pulsed laser-dispersed nanoparticles onto metal powders in aqueous solution without using any binders or surfactants. By electrostatic interaction, we deposit Y2O3 nanoparticles onto iron-chromium based powders and obtain a high dispersion of nano-sized particles on the metallic powders. Within the additively manufactured component, we show that the particle spacing of the oxide inclusion can be adjusted by the initial mass fraction of the adsorbed Y2O3 particles on the micropowder. Thus, our procedure constitutes a robust route for additive manufacturing of oxide dispersion-strengthened alloys via oxide nanoparticles supported on steel micropowders.

  6. Depositional characteristics of cretaceous cover in Xiangyangshan area of Heilongjiang province and analysis on prospect for sandstone hosted interlayer oxidation zone type uranium deposits

    International Nuclear Information System (INIS)

    Cai Yuqi; Li Shengxiang; Dong Wenming

    2003-01-01

    The depositional systems and characteristics of Cretaceous Cover depositional facies are discussed. In combination with logging curves in Xiangyangshan area, two depositional systems (namely, alluvial fan depositional system and alluvial plain depositional system) and five types of depositional facies are distinguished. Results of detailed research are given for each depositional facies in aspects of lithology, depositional structure, logging curve and grain size distribution pattern. Temporal and spatial distribution features of the depositional facies and the development features of interlayer oxidation zones of the second member of Quantou Formation are analyzed. Finally, conclusions on prospects for sandstone-hosted interlayer oxidation zone type uranium deposits in the study area are given in the aspect of depositional facies. (authors)

  7. Influences of different oxidants on the characteristics of HfAlOx films deposited by atomic layer deposition

    International Nuclear Information System (INIS)

    Fan Ji-Bin; Liu Hong-Xia; Ma Fei; Zhuo Qing-Qing; Hao Yue

    2013-01-01

    A comparative study of two kinds of oxidants (H 2 O and O 3 ) with the combinations of two metal precursors [trimethylaluminum (TMA) and tetrakis(ethylmethylamino) hafnium (TEMAH)] for atomic layer deposition (ALD) hafnium aluminum oxide (HfAlO x ) films is carried out. The effects of different oxidants on the physical properties and electrical characteristics of HfAlO x films are studied. The preliminary testing results indicate that the impurity level of HfAlO x films grown with both H 2 O and O 3 used as oxidants can be well controlled, which has significant effects on the dielectric constant, valence band, electrical properties, and stability of HfAlO x film. Additional thermal annealing effects on the properties of HfAlO x films grown with different oxidants are also investigated. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  8. Fabrication and Characterization of a Micro Methanol Sensor Using the CMOS-MEMS Technique

    Directory of Open Access Journals (Sweden)

    Chien-Fu Fong

    2015-10-01

    Full Text Available A methanol microsensor integrated with a micro heater manufactured using the complementary metal oxide semiconductor (CMOS-microelectromechanical system (MEMS technique was presented. The sensor has a capability of detecting low concentration methanol gas. Structure of the sensor is composed of interdigitated electrodes, a sensitive film and a heater. The heater located under the interdigitated electrodes is utilized to provide a working temperature to the sensitive film. The sensitive film prepared by the sol-gel method is tin dioxide doped cadmium sulfide, which is deposited on the interdigitated electrodes. To obtain the suspended structure and deposit the sensitive film, the sensor needs a post-CMOS process to etch the sacrificial silicon dioxide layer and silicon substrate. The methanol senor is a resistive type. A readout circuit converts the resistance variation of the sensor into the output voltage. The experimental results show that the methanol sensor has a sensitivity of 0.18 V/ppm.

  9. Fabrication and Characterization of a Micro Methanol Sensor Using the CMOS-MEMS Technique.

    Science.gov (United States)

    Fong, Chien-Fu; Dai, Ching-Liang; Wu, Chyan-Chyi

    2015-10-23

    A methanol microsensor integrated with a micro heater manufactured using the complementary metal oxide semiconductor (CMOS)-microelectromechanical system (MEMS) technique was presented. The sensor has a capability of detecting low concentration methanol gas. Structure of the sensor is composed of interdigitated electrodes, a sensitive film and a heater. The heater located under the interdigitated electrodes is utilized to provide a working temperature to the sensitive film. The sensitive film prepared by the sol-gel method is tin dioxide doped cadmium sulfide, which is deposited on the interdigitated electrodes. To obtain the suspended structure and deposit the sensitive film, the sensor needs a post-CMOS process to etch the sacrificial silicon dioxide layer and silicon substrate. The methanol senor is a resistive type. A readout circuit converts the resistance variation of the sensor into the output voltage. The experimental results show that the methanol sensor has a sensitivity of 0.18 V/ppm.

  10. Characterization of noble metals deposits and oxides in conditions of BWR reactors

    International Nuclear Information System (INIS)

    Arganis J, C.R.; Aguilar T, J.A.; Contreras R, A.

    2008-01-01

    The oxides deposited on steel 304l under normal chemistry conditions (NWC) and hydrogen chemistry (HWC) with presence of Zn, being that the first ones present hexagonal oxides of Hematite and the second bipyramidal crystals possibly Magnetite with traces of Zn. Deposits of Pt on the oxidized surfaces under NWC conditions were obtained, being glasses from 2 to 4 μm and Pt-Rh deposits were obtained on the oxidized surfaces in presence of Zn, by its size its were not possible to observe them by scanning electron microscopy. The kinetics of the surfaces of Hematite and of the deposits of Pt it was measured by means of the Tafel extrapolation technique, being proven the catalytic effect of the Pt, even in sizes of 11 μm. (Author)

  11. Surface electronic and structural properties of nanostructured titanium oxide grown by pulsed laser deposition

    NARCIS (Netherlands)

    Fusi, M.; Maccallini, E.; Caruso, T.; Casari, C. S.; Bassi, A. Li; Bottani, C. E.; Rudolf, P.; Prince, K. C.; Agostino, R. G.

    Titanium oxide nanostructured thin films synthesized by pulsed laser deposition (PLD) were here characterized with a multi-technique approach to investigate the relation between surface electronic, structural and morphological properties. Depending on the growth parameters, these films present

  12. Iron Oxide Deposition from Aqueous Solution and Iron Formations on Mars

    Science.gov (United States)

    Catling, David; Moore, Jeff

    2000-01-01

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

  13. The removal of dimethyl phthalate (DMP) from contaminated water by advanced oxidation processes in the presence of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Al-Tawabini, B.S. [Research Inst., King Fahd Univ. of Petroleum and Minerals, Dhahran (Saudi Arabia)

    2003-07-01

    A bench-scale laboratory study was conducted to investigate the effect of alcohol (i.e. methanol) presence on the removal efficiency of phthalates from water using Fenton's reagent and UV/H{sub 2}O{sub 2} process. Dimethyl phthalate (DMP) was selected as a target compound. In one batch of experiments, only DMP was spiked into pure water, while in the other batch, DMP was initially dissolved in methanol prior to spiking into water samples. A UV lamp of 100 m Watt emitting at a wavelength of approximately 254 nm was used to provide the radiation. Temperature and pH conditions were kept constant at 25 C and 3, respectively. The results showed that Fenton's reagent was effective in reducing the concentration of DMP in water in the absence of the methanol. More than 90% of DMP was removed within 45 minutes at hydrogen peroxide (H{sub 2}O{sub 2}) and ferrous ion (Fe{sup 2+}) concentrations of 1.0 and 0.4 mM respectively. However, Fenton's reagent failed to do so in the presence of methanol. On the other hand, results showed that UV/H{sub 2}O{sub 2} system was effective in removing DMP from both pure, as well as methanol-spiked water. The results clearly indicated that UV radiation plays a fundamental role in the degradation of the target compound. (orig.)

  14. Inhibition of LDL oxidation and oxidized LDL-induced foam cell formation in RAW 264.7 cells show anti-atherogenic properties of a foliar methanol extract of Scoparia dulcis.

    Science.gov (United States)

    Nambiar, Sinjitha S; Shetty, Nandini Prasad; Bhatt, Praveena; Neelwarne, Bhagyalakshmi

    2014-04-01

    Oxidation of low density lipoproteins and their further uptake by macrophages is known to result in the formation of foam cells, which are critical in the initiation of atherosclerosis through activation of inflammatory signalling cascades. Thus, powerful dietary antioxidants are receiving attention for the reversal of such pathological states. Extracts of Scoparia dulcis have been used as tea and health drinks with various health promoting effects. In the present study, we examined the reactive oxygen scavenging potential as well as anti-inflammatory and anti-atherogenic efficacies, using leaf extracts obtained after successive extraction with various solvents. A methanol extract showed potent antioxidant activity with an IC50 value of 570 μg/ml, caused hydrogen peroxide scavenging (28.9 µg/ml) and anti-inflammatory effects by improving human erythrocyte membrane stabilisation (about 86%). The methanol extract also efficiently inhibited lipid peroxidation and oxidation of low density lipoproteins, thus preventing foam cell formation in cultured RAW 264.7 cells. Furthermore, phytochemical screening of the extracts showed high accumulation of flavonoids. The foliar methanol extract of Scoparia dulcis has a strong anti-atherogenic potential and this property could be attributed maybe due to presence of flavonoids since HPLC analysis showed high concentrations of myricetin and rutin in the methanol extract.

  15. Ag2S deposited on oxidized polypropylene as composite material for solar light absorption

    NARCIS (Netherlands)

    Krylovaa, V.; Milbrat, Alexander; Embrachts, A.; Baltrusaitis, Jonas

    2014-01-01

    Thin film metal chalcogenides are superior solar light absorbers and can be combined into a functional material when deposited on polymeric substrates. Ag2S composite materials were synthesized on oxidized polypropylene using chemical bath deposition method and their properties were explored using

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

    NARCIS (Netherlands)

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

    2012-01-01

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

  17. How Gold Deposition Affects Anatase Performance in the Photo-catalytic Oxidation of Cyclohexane

    NARCIS (Netherlands)

    Carneiro, J.T.; Carneiro, Joana T.; Yang, Chieh-Chao; Moma, John A.; Moulijn, Jacob A.; Mul, Guido

    2009-01-01

    Gold deposition on Hombikat UV100 was found to negatively affect the activity of this Anatase catalyst in selective photo-oxidation of cyclohexane. By ammonia TPD and DRIFT spectroscopy it was determined that the Au deposition procedure leads to a significant decrease in OH-group density (mol m−2

  18. Characteristics of indium zinc oxide films deposited using the facing targets sputtering method for OLEDs applications

    International Nuclear Information System (INIS)

    Rim, Y.S.; Kim, H.J.; Kim, K.H.

    2010-01-01

    The amorphous indium zinc oxide (IZO) thin films were deposited on polyethersulfone (PES) and glass substrates using the facing targets sputtering (FTS) system. The electrical, optical and structural properties of the IZO thin films deposited as functions of sputtering parameters on the glass and PES substrates. An optimal IZO deposition condition is fabricated for organic light-emitting device (OLED) based on glass and PES. The amorphous IZO anode-based OLEDs show superior current density and luminance characteristics.

  19. Radiolytic synthesis of carbon-supported PtRu nanoparticles using high-energy electron beam: effect of pH control on the PtRu mixing state and the methanol oxidation activity

    International Nuclear Information System (INIS)

    Ohkubo, Yuji; Kageyama, Satoru; Seino, Satoshi; Nakagawa, Takashi; Kugai, Junichiro; Nitani, Hiroaki; Ueno, Koji; Yamamoto, Takao A.

    2013-01-01

    Electrode catalysts composed of carbon-supported PtRu nanoparticles (PtRu/C) for use as a direct methanol fuel cell anode were synthesized by the reduction of precursor ions in an aqueous solution via irradiation with a high-energy electron beam. The effect of pH control in the precursor solution on the PtRu mixing state and the methanol oxidation activity was studied in order to enhance the catalytic activity for methanol oxidation. The PtRu/C structures were characterized by transmission electron microscopy, inductively coupled plasma atomic emission spectrometry, X-ray fluorescence spectrometry, and X-ray diffraction and X-ray absorption fine structure techniques. The methanol oxidation activity was evaluated by linear sweep voltammetry. The initial pH of the precursor solution has little influence on the average grain size for the metal particles (approximately 3.5 nm) on the carbon particle supports, but the dispersibility of the metal particles, PtRu mixing state, and methanol oxidation activity differed. The maintenance of a low pH in the precursor solution gave the best dispersibility of the PtRu nanoparticles supported on the surface of the carbon particles, whereas, a high pH gave the best PtRu mixing state and the highest oxidation current although a low dispersibility of the PtRu nanoparticles supported on the surface of the carbon particles was obtained. The PtRu mixing state strongly correlated with the methanol oxidation current. In addition, a high pH was more effective for PtRu mixing when using an electron beam irradiation reduction method, because the complexation reaction of the chelating agents was improved, which resulted in an enhancement of the catalytic activity for methanol oxidation.

  20. Radiolytic synthesis of carbon-supported PtRu nanoparticles using high-energy electron beam: effect of pH control on the PtRu mixing state and the methanol oxidation activity

    Energy Technology Data Exchange (ETDEWEB)

    Ohkubo, Yuji, E-mail: okubo@mit.eng.osaka-u.ac.jp; Kageyama, Satoru; Seino, Satoshi; Nakagawa, Takashi; Kugai, Junichiro [Osaka University, Graduate School of Engineering (Japan); Nitani, Hiroaki [High Energy Accelerator Research Organization (KEK), Institute of Materials Structure Science (Japan); Ueno, Koji [Japan Electron Beam Irradiation Service Ltd (Japan); Yamamoto, Takao A. [Osaka University, Graduate School of Engineering (Japan)

    2013-05-15

    Electrode catalysts composed of carbon-supported PtRu nanoparticles (PtRu/C) for use as a direct methanol fuel cell anode were synthesized by the reduction of precursor ions in an aqueous solution via irradiation with a high-energy electron beam. The effect of pH control in the precursor solution on the PtRu mixing state and the methanol oxidation activity was studied in order to enhance the catalytic activity for methanol oxidation. The PtRu/C structures were characterized by transmission electron microscopy, inductively coupled plasma atomic emission spectrometry, X-ray fluorescence spectrometry, and X-ray diffraction and X-ray absorption fine structure techniques. The methanol oxidation activity was evaluated by linear sweep voltammetry. The initial pH of the precursor solution has little influence on the average grain size for the metal particles (approximately 3.5 nm) on the carbon particle supports, but the dispersibility of the metal particles, PtRu mixing state, and methanol oxidation activity differed. The maintenance of a low pH in the precursor solution gave the best dispersibility of the PtRu nanoparticles supported on the surface of the carbon particles, whereas, a high pH gave the best PtRu mixing state and the highest oxidation current although a low dispersibility of the PtRu nanoparticles supported on the surface of the carbon particles was obtained. The PtRu mixing state strongly correlated with the methanol oxidation current. In addition, a high pH was more effective for PtRu mixing when using an electron beam irradiation reduction method, because the complexation reaction of the chelating agents was improved, which resulted in an enhancement of the catalytic activity for methanol oxidation.

  1. Plasma-induced synthesis of Pt nanoparticles supported on TiO{sub 2} nanotubes for enhanced methanol electro-oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Su, Nan [College of Materials Science and Engineering, Nanjing Tech University, Xin-Mo-Fan Road No. 5, 210009, Nanjing, Jiangsu (China); The Synergetic Innovation Center for Advanced Materials, Xin-Mo-Fan Road No. 5, 210009, Nanjing, Jiangsu (China); Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Xin-Mo-Fan Road No. 5, 210009, Nanjing, Jiangsu (China); Hu, Xiulan, E-mail: whoxiulan@163.com [College of Materials Science and Engineering, Nanjing Tech University, Xin-Mo-Fan Road No. 5, 210009, Nanjing, Jiangsu (China); The Synergetic Innovation Center for Advanced Materials, Xin-Mo-Fan Road No. 5, 210009, Nanjing, Jiangsu (China); Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Xin-Mo-Fan Road No. 5, 210009, Nanjing, Jiangsu (China); Zhang, Jianbo; Huang, Huihong; Cheng, Jiexu; Yu, Jinchen; Ge, Chao [College of Materials Science and Engineering, Nanjing Tech University, Xin-Mo-Fan Road No. 5, 210009, Nanjing, Jiangsu (China)

    2017-03-31

    Highlights: • Pt nanoparticles are synthesized by plasma sputtering in water. • Pt/C/TiO{sub 2} nanotubes shows better mass activity and CO-poisoning tolerance than Pt/C. • TiO{sub 2} nanotubes are more suitable for support materials than TiO{sub 2} small particles. • The metal-support interactions between Pt and TiO{sub 2} nanotubes are detected by XPS. - Abstract: A Pt/C/TiO{sub 2} nanotube composite catalyst was successfully prepared for enhanced methanol electro-oxidation. Pt nanoparticles with a particle size of 2 nm were synthesized by plasma sputtering in water, and anatase TiO{sub 2} nanotubes with an inner diameter of approximately 100 nm were prepared by a simple two-step anodization method and annealing process. Field-emission scanning electron microscopy images indicated that the different morphologies of TiO{sub 2} synthesized on the surface of Ti foils were dependent on the different anodization parameters. The electrochemical performance of Pt/C/TiO{sub 2} catalysts for methanol oxidation showed that TiO{sub 2} nanotubes were more suitable for use as Pt nanoparticle support materials than irregular TiO{sub 2} short nanorods due to their tubular morphology and better electronic conductivity. X-ray photoelectron spectroscopy characterization showed that the binding energies of the Pt 4f of the Pt/C/TiO{sub 2} nanotubes exhibited a slightly positive shift caused by the relatively strong interaction between Pt and the TiO{sub 2} nanotubes, which could mitigate the poisoning of the Pt catalyst by CO{sub ads}, and further enhance the electrocatalytic performance. Thus, the as-obtained Pt/C/TiO{sub 2} nanotubes composites may become a promising catalyst for methanol electro-oxidation.

  2. Synthesis of flower-like gold nanoparticles and their electrocatalytic activity towards the oxidation of methanol and the reduction of oxygen.

    Science.gov (United States)

    Jena, Bikash Kumar; Raj, C Retna

    2007-03-27

    This article describes the synthesis of branched flower-like gold (Au) nanocrystals and their electrocatalytic activity toward the oxidation of methanol and the reduction of oxygen. Gold nanoflowers (GNFs) were obtained by a one-pot synthesis using N-2-hydroxyethylpiperazine-N-2-ethanesulphonic acid (HEPES) as a reducing/stabilizing agent. The GNFs have been characterized by UV-visible spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and electrochemical measurements. The UV-visible spectra show two bands corresponding to the transverse and longitudinal surface plasmon (SP) absorption at 532 and 720 nm, respectively, for the colloidal GNFs. The GNFs were self-assembled on a sol-gel-derived silicate network, which was preassembled on a polycrystalline Au electrode and used for electrocatalytic applications. The GNFs retain their morphology on the silicate network; the UV-visible diffuse reflectance spectra (DRS) of GNFs on the silicate network show longitudinal and transverse bands as in the case of colloidal GNFs. The GNFs show excellent electrocatalytic activity toward the oxidation of methanol and the reduction of oxygen. Oxidation of methanol in alkaline solution was observed at approximately 0.245 V, which is much less positive than that on an unmodified polycrystalline gold electrode. Reduction of oxygen to H2O2 and the further reduction of H2O2 to water in neutral pH were observed at less negative potentials on the GNFs electrode. The electrocatalytic activity of GNFs is significantly higher than that of the spherically shaped citrate-stabilized Au nanoparticles (SGNs).

  3. Enhanced photoluminescence and Raman properties of Al-Doped ZnO nanostructures prepared using thermal chemical vapor deposition of methanol assisted with heated brass.

    Directory of Open Access Journals (Sweden)

    Tamil Many K Thandavan

    Full Text Available Vapor phase transport (VPT assisted by mixture of methanol and acetone via thermal evaporation of brass (CuZn was used to prepare un-doped and Al-doped zinc oxide (ZnO nanostructures (NSs. The structure and morphology were characterized by field emission scanning electron microscopy (FESEM and x-ray diffraction (XRD. Photoluminescence (PL properties of un-doped and Al-doped ZnO showed significant changes in the optical properties providing evidence for several types of defects such as zinc interstitials (Zni, oxygen interstitials (Oi, zinc vacancy (Vzn, singly charged zinc vacancy (VZn-, oxygen vacancy (Vo, singly charged oxygen vacancy (Vo+ and oxygen anti-site defects (OZn in the grown NSs. The Al-doped ZnO NSs have exhibited shifted PL peaks at near band edge (NBE and red luminescence compared to the un-doped ZnO. The Raman scattering results provided evidence of Al doping into the ZnO NSs due to peak shift from 145 cm-1 to an anomalous peak at 138 cm-1. Presence of enhanced Raman signal at around 274 and 743 cm-1 further confirmed Al in ZnO NSs. The enhanced D and G band in all Al-doped ZnO NSs shows possible functionalization and doping process in ZnO NSs.

  4. Enhanced photoluminescence and Raman properties of Al-Doped ZnO nanostructures prepared using thermal chemical vapor deposition of methanol assisted with heated brass.

    Science.gov (United States)

    Thandavan, Tamil Many K; Gani, Siti Meriam Abdul; San Wong, Chiow; Md Nor, Roslan

    2015-01-01

    Vapor phase transport (VPT) assisted by mixture of methanol and acetone via thermal evaporation of brass (CuZn) was used to prepare un-doped and Al-doped zinc oxide (ZnO) nanostructures (NSs). The structure and morphology were characterized by field emission scanning electron microscopy (FESEM) and x-ray diffraction (XRD). Photoluminescence (PL) properties of un-doped and Al-doped ZnO showed significant changes in the optical properties providing evidence for several types of defects such as zinc interstitials (Zni), oxygen interstitials (Oi), zinc vacancy (Vzn), singly charged zinc vacancy (VZn-), oxygen vacancy (Vo), singly charged oxygen vacancy (Vo+) and oxygen anti-site defects (OZn) in the grown NSs. The Al-doped ZnO NSs have exhibited shifted PL peaks at near band edge (NBE) and red luminescence compared to the un-doped ZnO. The Raman scattering results provided evidence of Al doping into the ZnO NSs due to peak shift from 145 cm-1 to an anomalous peak at 138 cm-1. Presence of enhanced Raman signal at around 274 and 743 cm-1 further confirmed Al in ZnO NSs. The enhanced D and G band in all Al-doped ZnO NSs shows possible functionalization and doping process in ZnO NSs.

  5. Activation of the oxidative stress regulator PpYap1 through conserved cysteine residues during methanol metabolism in the yeast Pichia pastoris.

    Science.gov (United States)

    Yano, Taisuke; Yurimoto, Hiroya; Sakai, Yasuyoshi

    2009-06-01

    The methylotrophic yeast Pichia pastoris can grow on methanol as sole source of carbon and energy. The first reaction in yeast methanol metabolism, catalyzed by an abundant peroxisomal enzyme, alcohol oxidase, generates high levels of H(2)O(2), but the oxidative stress response during methanol metabolism has not been elucidated. In this study, we isolated the Yap1 homolog of P. pastoris (PpYap1) and analyzed the properties of a PpYAP1-disruption strain. The PpYap1 transcription factor is activated after exposure to various reactive agents, and therefore functions as a regulator of the redox system in P. pastoris. We have also identified PpGPX1, the unique glutathione peroxidase-encoding gene in P. pastoris whose expression is induced by PpYap1. PpGpx1, but not the ScTsa1 or SpTpx1 homolog PpTsa1, functions as a H(2)O(2) sensor and activates PpYap1. This study is the first demonstration of a yeast Yap1 family protein activated during conventional metabolism.

  6. Rhodium based clusters for oxygen reduction and hydrogen oxidation in 0.5 M H2SO4, tolerant to methanol and carbon monoxide, respectively

    Energy Technology Data Exchange (ETDEWEB)

    Uribe-Godinez, J.; Jimenez-Sandoval, O.; Borja-Arco, E.; Altamirano-Gutierrez, A. [Centro de Investigacion y de Estudios Avanzados del Instituto Politecnico Nacional, Queritaro (Mexico); Castellanos, R.H. [Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada-Queretaro, Queretaro (Mexico)

    2008-07-01

    Rhodium (Rh6(CO)16) and novel Rh-based clusters were prepared using thermolysis techniques under different conditions in N2 and H2 reaction media, as well as in n-nonane, o-xylene, 1,2-dichlorobenzene and dimethylsulfoxide. The clusters were used as novel electrocatalysts for oxygen reduction reaction (ORR) in the absence and presence of 1.0 and 2.0 M methanol solutions. The catalysts were also used for hydrogen oxidation reaction (HOR) with pure hydrogen (H2) and in the presence of carbon monoxide (CO). Rotating disk electrode measurements were used to analyze the materials. The study showed that the electrocatalyst support ratio plays a significant role in the electrochemical behaviour of the materials. Rh6(CO)16 and Rh2(1,2-DCB) presented the best electrocatalytic behaviour for ORR and HOR in the absence and presence of methanol and CO. The study demonstrated that the rhodium-based materials are capable of performing ORR and HOR while being tolerant of both methanol and CO. 3 refs., 3 figs.

  7. Facile synthesis of Pt–Pd bimetallic nanoparticles by plasma discharge in liquid and their electrocatalytic activity toward methanol oxidation in alkaline media

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sung-Min; Lee, Yu-Jin [Center for Surface Technology and Applications, Korea Aerospace University, Gyeonggi-do, 412-791 (Korea, Republic of); Department of Materials Engineering, Korea Aerospace University, Gyeonggi-do, 412-791 (Korea, Republic of); Kim, Jung-Wan [Center for Surface Technology and Applications, Korea Aerospace University, Gyeonggi-do, 412-791 (Korea, Republic of); Division of Bioengineering, InCheon National University, Incheon, 406-772 (Korea, Republic of); Lee, Sang-Yul, E-mail: sylee@kau.ac.kr [Center for Surface Technology and Applications, Korea Aerospace University, Gyeonggi-do, 412-791 (Korea, Republic of); Department of Materials Engineering, Korea Aerospace University, Gyeonggi-do, 412-791 (Korea, Republic of)

    2014-12-01

    The Pt–Pd bimetallic nanoparticles for direct methanol fuel cell applications were successfully prepared by plasma discharge in aqueous solution. The obtained nanoparticles were characterized by energy dispersive X-ray spectroscopy, X-ray diffraction spectroscopy, and transmission electron microscopy. During plasma discharge, the nanoparticles were produced from the erosion of electrodes. It was noted that the erosion amount of anode electrodes was much greater than that of cathode electrodes so that the composition of Pt–Pd bimetallic nanoparticles could be changed with different power types and electrode configurations. Diffraction patterns fitted from Gaussian devolution indicated that the crystalline phase of Pt{sub 40}Pd{sub 60} products was composed of pure Pt, pure Pd and Pt–Pd alloy phases. The morphology of synthesized nanoparticles showed that nanowires connected with quasi-spherical nanoparticles with 2–3 nm in diameter were observed and large spherical particles with > 50 nm in diameter were also detected intermittently. The cyclic voltammetric measurement and continuous potential scan demonstrated that Pt{sub 40}Pd{sub 60} had much higher catalytic activity and better resistance to CO poisoning than Pt{sub 94}Pd{sub 6} and Pt{sub 1}Pd{sub 99} for methanol oxidation. These results indicate that the Pt{sub 40}Pd{sub 60} could be an excellent candidate for the direct methanol fuel cell applications.

  8. CuY zeolite catalysts prepared by ultrasonication-assisted ion-exchange for oxidative carbonylation of methanol to dimethyl carbonate.

    Science.gov (United States)

    Woo, Je-Min; Seo, Jung Yoon; Kim, Hyunuk; Lee, Dong-Ho; Park, Young Cheol; Yi, Chang-Keun; Park, Yeong Seong; Moon, Jong-Ho

    2018-06-01

    The influence of ultrasonication treatment on the catalytic performance of CuY zeolite catalysts was investigated for the liquid-phase oxidative carbonylation of methanol to dimethyl carbonate (DMC). The deammoniation method of NH 4 Y into HY zeolites was optimized and characterized by elemental analyzer, derivative thermogravimetry, Brunauer-Emmett-Teller (BET) analyzer, and powder X-ray diffractometry, revealing that the HY zeolite deammoniated at 400 °C presented the highest surface area, complete ammonium/proton ion exchange, and no structure collapse, rendering it the best support from all the prepared zeolites. CuY zeolites were prepared via aqueous phase ion exchange with the aid of ultrasonication. Upon ultrasonication, the Cu + active centers were uniformly dispersed in the Y zeolites, penetrating the core of the zeolite particles in a very short time. In addition to enhancing the Cu dispersity, the ultrasonication treatment influenced the BET surface area, acid amount, Cu + /Cu 2+ ratio, and also had a relatively small impact on the Cu loading. Consequently, adequate exposure to ultrasonication was able to increase the conversion rate of methanol into dimethyl carbonate up to 11.4% with a comparable DMC selectivity of 23.7%. This methanol conversion is 2.65 times higher than that obtained without the ultrasonication treatment. Copyright © 2018 Elsevier B.V. All rights reserved.

  9. Controlling the resistivity gradient in chemical vapor deposition-deposited aluminum-doped zinc oxide

    NARCIS (Netherlands)

    Ponomarev, M. V.; Verheijen, M. A.; Keuning, W.; M. C. M. van de Sanden,; Creatore, M.

    2012-01-01

    Aluminum-doped ZnO (ZnO:Al) grown by chemical vapor deposition (CVD) generally exhibit a major drawback, i.e., a gradient in resistivity extending over a large range of film thickness. The present contribution addresses the plasma-enhanced CVD deposition of ZnO: Al layers by focusing on the control

  10. Pt catalysts on PANI coated WC/C nanocomposites for methanol electro-oxidation and oxygen electro-reduction in DMFC

    International Nuclear Information System (INIS)

    Yaldagard, Maryam; Jahanshahi, Mohsen; Seghatoleslami, Naser

    2014-01-01

    Highlights: • In this work nanosized WC/C were successfully coated by PANI. • Pt particles (10.56 nm) were uniformly dispersed on the surface of PANI/WC/C support. • The Pt/PANI/WC/C exhibited higher MOR activity and CO tolerance than Pt/C. • The Pt/PANI/WC/C exhibited higher activity for ORR than Pt/C in RDE experiments. • Pt/PANI/WC/C showed good stability than that of Pt/C in the presence of methanol. - Abstract: In the present study a Pt/PANI/WC/C electrocatalyst was developed to increase the methanol electro-oxidation and oxygen electro-reduction activity and stability of commercial Pt/C electrocatalyst. WC/C was coated with protonated polyaniline (PANI) in situ during the polymerization of aniline. Fourier transform infrared (FTIR) results illustrate the presence of PANI in the composite. The conductivity of PANI coated – WC/C has been compared with the conductivity of the corresponding mixtures of WC/C and Vulcan XC-72. X-ray diffraction results showed that Pt particles were dispersed on the support with mean particle size of about 10.56 nm. Transition electron microscopy images showed that the nanosized WC/C were successfully coated by PANI. Based on the electrochemical properties characterized by cyclic voltammetry, CO stripping and rotating disk electrode measurements it was found that the as prepared Pt/PANI/WC/C electrocatalyst exhibited a comparable activity for methanol oxidation reaction and oxygen reduction reaction with respect to the commercial one. A significant reduction in the potential of CO electro-oxidation peak from 0.75 V for Pt/C to 0.52 V for Pt/PANI/WC/C electrocatalyst indicates that an increase in the activity for CO electro-oxidation is achieved by replacing the carbon support by PANI coated WC/C. Chronoamerometry results also showed, in the presence of methanol the Pt/PANI/WC/C electrocatalyst still maintains a higher current density than Pt/WC/C and Pt/C

  11. Pt catalysts on PANI coated WC/C nanocomposites for methanol electro-oxidation and oxygen electro-reduction in DMFC

    Energy Technology Data Exchange (ETDEWEB)

    Yaldagard, Maryam, E-mail: m_yaldagard@yahoo.com [Department of Chemical Engineering, Ferdowsi University of Mashhad, P.O. Box 91775-1111 (Iran, Islamic Republic of); Nanotechnology Research Institute, School of Chemical Engineering, Babol University of Technology (Iran, Islamic Republic of); Jahanshahi, Mohsen, E-mail: mjahan@nit.um.ac.ir [Nanotechnology Research Institute, School of Chemical Engineering, Babol University of Technology (Iran, Islamic Republic of); Seghatoleslami, Naser, E-mail: Slami@um.ac.ir [Department of Chemical Engineering, Ferdowsi University of Mashhad, P.O. Box 91775-1111 (Iran, Islamic Republic of)

    2014-10-30

    Highlights: • In this work nanosized WC/C were successfully coated by PANI. • Pt particles (10.56 nm) were uniformly dispersed on the surface of PANI/WC/C support. • The Pt/PANI/WC/C exhibited higher MOR activity and CO tolerance than Pt/C. • The Pt/PANI/WC/C exhibited higher activity for ORR than Pt/C in RDE experiments. • Pt/PANI/WC/C showed good stability than that of Pt/C in the presence of methanol. - Abstract: In the present study a Pt/PANI/WC/C electrocatalyst was developed to increase the methanol electro-oxidation and oxygen electro-reduction activity and stability of commercial Pt/C electrocatalyst. WC/C was coated with protonated polyaniline (PANI) in situ during the polymerization of aniline. Fourier transform infrared (FTIR) results illustrate the presence of PANI in the composite. The conductivity of PANI coated – WC/C has been compared with the conductivity of the corresponding mixtures of WC/C and Vulcan XC-72. X-ray diffraction results showed that Pt particles were dispersed on the support with mean particle size of about 10.56 nm. Transition electron microscopy images showed that the nanosized WC/C were successfully coated by PANI. Based on the electrochemical properties characterized by cyclic voltammetry, CO stripping and rotating disk electrode measurements it was found that the as prepared Pt/PANI/WC/C electrocatalyst exhibited a comparable activity for methanol oxidation reaction and oxygen reduction reaction with respect to the commercial one. A significant reduction in the potential of CO electro-oxidation peak from 0.75 V for Pt/C to 0.52 V for Pt/PANI/WC/C electrocatalyst indicates that an increase in the activity for CO electro-oxidation is achieved by replacing the carbon support by PANI coated WC/C. Chronoamerometry results also showed, in the presence of methanol the Pt/PANI/WC/C electrocatalyst still maintains a higher current density than Pt/WC/C and Pt/C.

  12. Zirconium oxide deposits (ZrO2) and titanium oxide (TiO2) on 304l stainless steel

    International Nuclear Information System (INIS)

    Davila N, M. L.

    2015-01-01

    This research project aims to carry out the surface and electrochemical characterization to obtain the optimum conditions of the hydrothermal deposits of zirconium oxide ZrO 2 (baddeleyite) and titanium oxide TiO 2 (anatase and rutile phases) on 304l stainless steel, simulating an inhibiting protective layer. 304l steel specimens were cut, pre-oxidized in water at a temperature of 288 degrees Celsius and 8 MPa, similar to those of a typical BWR conditions. From the titanium oxide anatase crystalline phase, the rutile phase was obtained by a heat treatment at 1000 degrees Celsius. The Sigma-Aldrich pre-oxidized powders and steel 304l were characterized using techniques of X-ray diffraction, scanning electron microscopy, X-ray dispersive energy, chemical mapping and Raman spectrometry. The pre-oxidized steel has two oxide layers, an inner layer with nano metric crystals and another outer of larger crystals to 1μm, with the formation of hematite and magnetite, this predominating. The surface that contacted the sample holder has larger crystals. Hydrothermal deposits were carry out from suspensions of 10, 100 and 1000 ppm, of the crystal phases of anatase, rutile and baddeleyite, on the pre-oxidized steel at a temperature of 150 degrees Celsius for 2 and 7 days, samples were analyzed by X-ray diffraction, scanning electron microscopy, X-ray dispersive energy, Raman spectrometry and Tafel polarization. The suspension to 1000 ppm for 7 days coated surface most; the baddeleyite deposit is noticed more homogeneous than anatase and rutile. The deposit is favored when hematite and magnetite crystals are larger. The chemical mapping on deposits show that even after being immersed in water to 288 degrees Celsius during 30 days, the deposits are still present although a loss is observed. A reference electrode was assembled to conduct electrochemical tests of Tafel able to withstand a temperature of 288 degrees Celsius and pressure of 8 MPa. The baddeleyite deposit presented

  13. Charging effects during focused electron beam induced deposition of silicon oxide

    NARCIS (Netherlands)

    de Boer, Sanne K.; van Dorp, Willem F.; De Hosson, Jeff Th. M.

    2011-01-01

    This paper concentrates on focused electron beam induced deposition of silicon oxide. Silicon oxide pillars are written using 2, 4, 6, 8, 10-pentamethyl-cyclopenta-siloxane (PMCPS) as precursor. It is observed that branching of the pillar occurs above a minimum pillar height. The branching is

  14. FLAVONOIDS AND ANTI-OXIDANT ACTIVITY MEDIATED GASTROPROTECTIVE ACTION OF LEATHERY MURDAH, TERMINALIA CORIACEA (ROXB. WIGHT & ARN. LEAF METHANOLIC EXTRACT IN RATS

    Directory of Open Access Journals (Sweden)

    Mohammed Safwan ALI KHAN

    2017-05-01

    Full Text Available ABSTRACT BACKGROUND Leathery Murdah, Terminalia coriacea (Roxb. Wight & Arn. from family Combretaceae is used in Ayurveda and Siddha traditional systems of medicine to heal ulcers. OBJECTIVE The present study was conducted to assess the gastroprotective effect and understand the fundamental mechanism of action of Leathery Murdah, Terminalia coriacea (Roxb. Wight & Arn. Leaf Methanolic Extract. METHODS The test extract was screened for anti-ulcer activity by Aspirin induced ulcerogenesis in pyloric ligation and ethanol induced gastric ulcers at three doses - 125, 250, and 500 mg/kg, p.o. using Ranitidine 50 mg/kg and Misoprostol 100 μg/kg as standard drug in respective models. Seven parameters were carefully examined, that is, ulcer index, total protein, mucin, catalase, malondialdehyde, and superoxide dismutase levels and histopathology. High Performance Liquid Chromatographic - Ultra Violet profiling and Liquid Chromatography - Mass Spectral analysis of crude Terminalia coriacea leaves methanolic extract were carried out as a part of chemical characterization to identify bioactive compounds. RESULTS All the test doses exhibited significant gastroprotective function, particularly the higher doses demonstrated improved action. The results revealed a significant increase in the levels of catalase, superoxide dismutase, and Mucin with reduction in ulcer index, the levels of total protein, and malondialdehyde. Histopathological observations also illustrated the gastroprotective effect of Terminalia coriacea leaves methanolic extract. CONCLUSION Terminalia coriacea leaves methanolic extract exhibited strong anti-oxidant and anti-secretory activities mediated gastroprotection besides inducing the gastric mucosal production. The observed pharmacological response can be attributed to the flavonoidal compounds namely - Quercetin-3-O-rutinoside, Luteolin-7-O-glucoside, Myricetin hexoside, Quercetin-3-O-glucoside, Isorhamnetin-3-O-rhamnosylglucoside and

  15. Copper Oxidation through Nucleation Sites of Chemical Vapor Deposited Graphene

    DEFF Research Database (Denmark)

    Luo, Birong; Whelan, Patrick Rebsdorf; Shivayogimath, Abhay

    2016-01-01

    We investigate the nucleation defect-triggered oxidation of Cu covered by CVD graphene during postannealing in air. The results reveal that different growth conditions may induce imperfect nucleation of graphene, and cause creation of defects near the nucleation point such as pin holes...... and amorphous carbon. These defects would serve as a pathway for the diffusion of 02 during thermal annealing, allowing oxidation of Cu to progress gradually from the nucleation center toward the growth edge. The oxidation process follows the graphene morphology closely; the shape of the oxidized area of Cu has...... a striking resemblance to that of the graphene flakes. Our work demonstrates that inferior graphene nucleation in CVD processes can compromise the oxidation resistance of a graphene-coated Cu substrate, and indirectly reveal the structure and integrity of graphene, which is of fundamental importance...

  16. Investigations into the effect of spinel oxide composition on rate of carbon deposition

    International Nuclear Information System (INIS)

    Allen, G.C.; Jutson, J.A.

    1987-11-01

    The deposition of carbon on fuel cladding and other steels results in a reduction in heat transfer efficiency. Methane and carbon monoxide are added to the gaseous coolant in the Advanced Gas Cooled Reactor (AGR) to reduce the radiolytic oxidation of the graphite moderator and this is known to increase the rate of carbon deposition. However, the composition of oxides formed on steel surfaces within the reactor may also influence deposition. In this investigation carefully characterised spinel type oxides of varying composition have been subjected to γ radiation under conditions of temperature, pressure and atmosphere similar to those experienced in the reactor. The rate of carbon deposition has been studied using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Analysis (EDX). (U.K.)

  17. Control of the optical properties of silicon and chromium mixed oxides deposited by reactive magnetron sputtering

    International Nuclear Information System (INIS)

    Vergara, L.; Galindo, R. Escobar; Martinez, R.; Sanchez, O.; Palacio, C.; Albella, J.M.

    2011-01-01

    The development of mixed-oxide thin films allows obtaining materials with better properties than those of the different binary oxides, which makes them suitable for a great number of applications in different fields, such as tribology, optics or microelectronics. In this paper we investigate the deposition of mixed chromium and silicon oxides deposited by reactive magnetron sputtering with a view to use them as optical coatings with an adjustable refractive index. These films have been characterized by means of Rutherford backscattering spectrometry, Auger electron spectroscopy, X-ray diffraction, scanning electron microscopy, Fourier-transform infrared spectroscopy and spectroscopic ellipsometry so as to determine how the deposition conditions influence the characteristics of the material. We have found that the deposition parameter whose influence determines the properties of the films to a greater extent is the amount of oxygen in the reactive sputtering gas.

  18. Generation and oxidation of aerosol deposited PdAg nanoparticles

    Science.gov (United States)

    Blomberg, S.; Gustafson, J.; Martin, N. M.; Messing, M. E.; Deppert, K.; Liu, Z.; Chang, R.; Fernandes, V. R.; Borg, A.; Grönbeck, H.; Lundgren, E.

    2013-10-01

    PdAg nanoparticles with a diameter of 10 nm have been generated by an aerosol particle method, and supported on a silica substrate. By using a combination of X-ray Energy Dispersive Spectroscopy and X-ray Photoelectron Spectroscopy it is shown that the size distribution of the particles is narrow and that the two metals form an alloy with a mixture of 75% Pd and 25% Ag. Under oxidizing conditions, Pd is found to segregate to the surface and a thin PdO like oxide is formed similar to the surface oxide previously reported on extended PdAg and pure Pd surfaces.

  19. Zinc oxide nanorod clusters deposited seaweed cellulose sheet for antimicrobial activity.

    Science.gov (United States)

    Bhutiya, Priyank L; Mahajan, Mayur S; Abdul Rasheed, M; Pandey, Manoj; Zaheer Hasan, S; Misra, Nirendra

    2018-06-01

    Seaweed cellulose was isolated from green seaweed Ulva fasciata using a common bleaching agent. Sheet containing porous mesh was prepared from the extracted seaweed crystalline cellulose along with zinc oxide (ZnO) nanorod clusters grown over the sheet by single step hydrothermal method. Seaweed cellulose and zinc oxide nanorod clusters deposited seaweed cellulose sheet was characterized by FT-IR, XRD, TGA, and SEM-EDX. Morphology showed that the diameter of zinc oxide nanorods were around 70nm. Zinc oxide nanorod clusters deposited on seaweed cellulose sheet gave remarkable antibacterial activity towards gram-positive (Staphylococcus aureus, Bacillus ceresus, Streptococcus thermophilis) and gram-negative (Escherichia coli, Pseudomonas aeruginous) microbes. Such deposited sheet has potential applications in pharmaceutical, biomedical, food packaging, water treatment and biotechnological industries. Copyright © 2018 Elsevier B.V. All rights reserved.

  20. Methanol-Tolerant Cathode Catalyst Composite For Direct Methanol Fuel Cells

    Science.gov (United States)

    Zhu, Yimin; Zelenay, Piotr

    2006-03-21

    A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of a platinum-chromium alloy so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

  1. Rapid synthesis of tantalum oxide dielectric films by microwave microwave-assisted atmospheric chemical vapor deposition

    International Nuclear Information System (INIS)

    Ndiege, Nicholas; Subramanian, Vaidyanathan; Shannon, Mark A.; Masel, Richard I.

    2008-01-01

    Microwave-assisted chemical vapor deposition has been used to generate high quality, high-k dielectric films on silicon at high deposition rates with film thicknesses varying from 50 nm to 110 μm using inexpensive equipment. Characterization of the post deposition products was performed by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Auger electron spectroscopy and Raman spectroscopy. Film growth was determined to occur via rapid formation and accumulation of tantalum oxide clusters from tantalum (v) ethoxide (Ta(OC 2 H 5 ) 5 ) vapor on the deposition surface

  2. In situ deposition of thallium-containing oxides

    International Nuclear Information System (INIS)

    Myers, K.E.

    1996-01-01

    The number and variety of thallium based materials that can be made by in situ methods have grown consistently since the first report of successful thallium cuprate deposition by Face and Nestlerode in 1992. Processes for the deposition of superconductors, normal metals, and insulators have been developed. Most work to date has been done on the Tl-1212 phases, TlBa 2 CaCu 2 O 7 and (Tl,Pb)Sr 2 CaCu 2 O 7 . Recently however, the in situ thallium technique has been extended to other materials. For example, epitaxial thin films of thallium tantalate, an insulator of the pyrochlore structure and a potential buffer layer for thallium cuprate films, have been grown. Multilayers, important in the fabrication of Josephson junctions, have been demonstrated with the thallium lead cuprates. This paper reviews progress in the area of in situ thallium deposition technology which will make more complex thallium cuprate multilayer structures and devices possible

  3. Deposition and characterisation of epitaxial oxide thin films for SOFCs

    KAUST Repository

    Santiso, José ; Burriel, Mó nica

    2010-01-01

    This paper reviews the recent advances in the use of thin films, mostly epitaxial, for fundamental studies of materials for solid oxide fuel cell (SOFC) applications. These studies include the influence of film microstructure, crystal orientation

  4. Morphology-dependent electrocatalytic performance of Fe2(MoO43 for electro-oxidation of methanol in alkaline medium

    Directory of Open Access Journals (Sweden)

    Daoming Zhang

    2017-06-01

    Full Text Available Electrochemically synthesized nanosphere, nanorod and nanotube Fe2(MoO43 at optimized temperature and current density are characterized with XRD, SEM, TEM, XPS. Crystal lattices of the three types Fe2(MoO43 detected by HRTEM are well matched with the simulation analysis results from Materials Studio 6.0 based on the inorganic crystal structure database (ICSD data and the modified XRD lattice parameters. The ratios of Fe/Mo on the surface resulted from XPS analysis are 1.47, 1.63 and 2.22 respectively for nanosphere, nanorod and nanotube. The mixture of Fe2(MoO43 with polytetrafluoroethylene dispersion are coated on glass carbon substrate as electrode for electrocatalytic performance test by cyclic voltammetries in 0.1 mol/L KOH and 1 mol/L methanol electrolyte. Methanol oxidation peak current density of the Nanotube- Fe2(MoO43/GCEs electrode is 3.27 mA/cm2 higher than 2.8 mA/cm2 of platinum foil electrode, which shows enhanced catalytic activity of Nanotube-Fe2(MoO43/GCEs. The cyclic stability in terms of peak current retention are 91%, 92% and 88% respectively for Nanosphere-Fe2(MoO43/GCE, Nanorod-Fe2(MoO43/GCE and Nanotube-Fe2(MoO43/GCE electrode after 220 cycles. It is concluded that nanosized Fe2(MoO43 could be promising alternative non-noble electro-catalysts for electro-oxidation of methanol in alkaline medium.

  5. Progress in the characterisation of structural oxide/oxide ceramic matrix composites fabricated by electrophoretic deposition (EPD)

    Czech Academy of Sciences Publication Activity Database

    Stoll, E.; Mahr, P.; Kruger, H. G.; Kern, H.; Dlouhý, Ivo; Boccaccini, A. R.

    2006-01-01

    Roč. 8, č. 4 (2006), s. 282-285 ISSN 1438-1656 R&D Projects: GA ČR(CZ) GA106/05/0495 Institutional research plan: CEZ:AV0Z20410507 Keywords : electorphoretic deposition * oxid/oxid ceramic matrix composites * flexural strength Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass Impact factor: 1.402, year: 2006 http://www3.interscience.wiley.com/cgi-bin/jissue/112579545

  6. Catalysts development to base of Cu and Ni supported in ZrO2 for the H2 generation by the methanol reformed in oxidizing atmosphere

    International Nuclear Information System (INIS)

    Lopez C, P.; Gutierrez, A.; Gutierrez W, C.; Mendoza A, D.; Martinez, G.; Perez H, R.

    2009-01-01

    The search of new alternating sources of energy is at the present time one of the primordial objectives to world level because of the global heating caused by the high emissions of CO 2 at the atmosphere. In this sense the employment of H 2 through the fuel cells offers a more viable alternative for the use of the energy coming from the connection H-H that can be appointed for use of mobile, industrial and homemade applications. However, to generate H 2 in enough quantities is a great challenge at technological level for the necessity of to count with highly selective and efficient catalysts to low reaction temperatures as well as a source that comes from renewable resources. Under this context the methanol reformed in oxidizing atmosphere offers great ecological as energetics and industrial advantages; inside this investigation plane, the Cu seems to be one of the suitable candidates for this reaction due to its high capacity to generate H 2 , besides the great potential of improvement in its physical-chemical properties when being worked in nano metric size and /or associated with other materials. On the other hand, it is known that the Ni addition improvement the catalytic properties because of a better material dispersion, what offers big possibilities of being applied in the H 2 generation in situ by means of the methanol reformed reaction in oxidizing atmosphere; and that the conformation of bimetallic particles Cu/Ni presented high selectivity and catalytic activity for the reaction in question. (Author)

  7. Functional separation of oxidation–reduction reactions and electron transport in PtRu/ND and conductive additive hybrid electrocatalysts during methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yan; Wang, Yanhui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Bian, Linyan [College of Physics and Chemistry, Henan Polytechnic University, Jiaozuo, Henan 454000 (China); Lu, Rui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Zang, Jianbing, E-mail: jbzang@ysu.edu.cn [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China)

    2016-02-28

    Graphical abstract: - Highlights: • Functional separation of reactions and electron transport in PtRu/ND + AB (or CNT). • A conductive network was formed after the addition of AB or CNT. • PtRu/ND + AB (or CNT) exhibited enhanced activity and stability than PtRu/ND. - Abstract: Undoped nanodiamond (ND) supported PtRu (PtRu/ND) electrocatalyst for methanol oxidation reactions (MOR) in direct methanol fuel cells was prepared by a microwave-assisted polyol reduction method. Sp{sup 3}-bonded ND possesses high electrochemical stability but low conductivity, while sp{sup 2}-bonded carbon nanomaterials with high conductivity are prone to oxidation. Therefore, the functions of the supporting material were separated in this study. ND (sp{sup 3}), as a support, and AB or CNTs (sp{sup 2}), as a conductive additive, were combined to form the hybrid electrocatalysts PtRu/ND + AB and PtRu/ND + CNT for MOR. The morphology of the electrocatalysts was characterized by scanning electron microscopy and electrochemical measurements were performed using an electrochemical workstation. The results indicated that the electrocatalytic activity of PtRu/ND for MOR was improved with the addition of AB or CNTs as a conductive additive. Moreover, adding CNTs to PtRu/ND as a conductive additive showed better electrocatalytic activities than adding AB, which can be ascribed to the better electron-transfer ability of CNTs.

  8. Electrical characterization of low temperature deposited oxide films ...

    Indian Academy of Sciences (India)

    Unknown

    electronics on the same substrate (Water and Chu 2002). Plasma enhanced chemical vapour deposition (PECVD) .... sion in depletion region is due to the presence of inter- face traps. The total capacitance in inversion ... The conductance technique is used to deter- mine the interface state density throughout the depletion.

  9. Spatial Atomic Layer Deposition of transparent conductive oxides

    NARCIS (Netherlands)

    Illiberi, A.; Scherpenborg, R.; Poodt, P.; Roozeboom, F.

    2013-01-01

    Undoped and indium doped ZnO films have been grown by Spatial Atomic Layer Deposition at atmospheric pressure. The electrical properties of ZnO films are controlled by varying the indium content in the range from 0 to 15 %. A minimum resistivity value of 3 mΩ•cm is measured in 180 nm thick films for

  10. Antioxidant efficacy of crude methanol extract of ashitaba green tea against radiation induced oxidative stress in E.coli K12 bacteria

    International Nuclear Information System (INIS)

    Darshan Raj, C.G.; Sindhu Priya, E.S.; Sarojini, B.K.

    2013-01-01

    This study was undertaken to evaluate the antioxidant activity of methanol crude extract of ashitaba green tea (G). The DPPH scavenging assay was evaluated for green tea extract to determine its radical scavenging capacity. The bacteria was pretreated with ashitaba green tea extract, quercetin (Q) and (-) epigallocatechin -3-gallate (E) at below MIC level. Oxidative stress was induced at 0.4 Gy using gamma radiation. The antioxidant efficacy of ashitaba green tea was evaluated through enzyme antioxidant studies like SOD (Superoxidedismutase) and CAT (Catalase). The oxidative stress marker Thiobarbituric acid-reactive substance (TBARS) was also evaluated. Further the protective efficacy of the(G) was confirmed by colony forming units (CFU) study. Among the tested compounds the crude extract of ashitaba (G) exhibited excellent antioxidant activity in comparison with quercetin and (-) epigallocatechin -3-gallate. (abstract)

  11. Influence of the Synthesis Method for Pt Catalysts Supported on Highly Mesoporous Carbon Xerogel and Vulcan Carbon Black on the Electro-Oxidation of Methanol

    Directory of Open Access Journals (Sweden)

    Cinthia Alegre

    2015-03-01

    Full Text Available Platinum catalysts supported on carbon xerogel and carbon black (Vulcan were synthesized with the aim of investigating the influence of the characteristics of the support on the electrochemical performance of the catalysts. Three synthesis methods were compared: an impregnation method with two different reducing agents, sodium borohydride and formic acid, and a microemulsion method, in order to study the effect of the synthesis method on the physico-chemical properties of the catalysts. X-ray diffraction and transmission electron microscopy were applied. Cyclic voltammetry and chronoamperometry were used for studying carbon monoxide and methanol oxidation. Catalysts supported on carbon xerogel presented higher catalytic activities towards CO and CH3OH oxidation than catalysts supported on Vulcan. The higher mesoporosity of carbon xerogel was responsible for the favored diffusion of reagents towards catalytic centers.

  12. Synthesis of electro-active manganese oxide thin films by plasma enhanced chemical vapor deposition

    Energy Technology Data Exchange (ETDEWEB)

    Merritt, Anna R. [Energetics Research Division, Naval Air Warfare Center Weapons Division, China Lake, CA 93555 (United States); Rajagopalan, Ramakrishnan [Department of Engineering, The Pennsylvania State University, Dubois, PA 15801 (United States); Materials Research Institute, The Pennsylvania State University, University Park, PA 16802 (United States); Carter, Joshua D. [Energetics Research Division, Naval Air Warfare Center Weapons Division, China Lake, CA 93555 (United States)

    2014-04-01

    The good stability, cyclability and high specific capacitance of manganese oxide (MnO{sub x}) has recently promoted a growing interest in utilizing MnO{sub x} in asymmetric supercapacitor electrodes. Several literature reports have indicated that thin film geometries of MnO{sub x} provide specific capacitances that are much higher than bulk MnO{sub x} powders. Plasma enhanced chemical vapor deposition (PECVD) is a versatile technique for the production of metal oxide thin films with high purity and controllable thickness. In this work, MnO{sub x} thin films deposited by PECVD from a methylcyclopentadienyl manganese tricarbonyl precursor are presented and the effect of processing conditions on the quality of MnO{sub x} films is described. The film purity and oxidation state of the MnO{sub x} films were studied by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Preliminary electrochemical testing of MnO{sub x} films deposited on carbon fiber electrodes in aqueous electrolytes indicates that the PECVD synthesized films are electrochemically active. - Highlights: • Plasma enhanced chemical vapor deposition of manganese oxide thin films. • Higher plasma power and chamber pressure increase deposition rate. • Manganese oxide thin films are electrochemically active. • Best electrochemical performance observed for pure film with low stress • Lower capacitance observed at higher scan rates despite thin film geometry.

  13. Characterization of photoluminescent europium doped yttrium oxide thin-films prepared by metallorganic chemical vapor deposition

    International Nuclear Information System (INIS)

    McKittrick, J.; Bacalski, C.F.; Hirata, G.A.; Hubbard, K.M.; Pattillo, S.G.; Salazar, K.V.; Trkula, M.

    1998-01-01

    Europium doped yttrium oxide, (Y 1-x Eu x ) 2 O 3 , thin-films were deposited on silicon and sapphire substrates by metallorganic chemical vapor deposition (MOCVD). The films were grown in a MOCVD chamber reacting yttrium and europium tris(2,2,6,6-tetramethyl-3,5,-heptanedionates) precursors in an oxygen atmosphere at low pressures (5 Torr) and low substrate temperatures (500--700 C). The films deposited at 500 C were flat and composed of nanocrystalline regions of cubic Y 2 O 3 , grown in a textured [100] or [110] orientation to the substrate surface. Films deposited at 600 C developed from the flat, nanocrystalline morphology into a plate-like growth morphology oriented in the [111] with increasing deposition time. Monoclinic Y 2 O 3 :Eu 3+ was observed in x-ray diffraction for deposition temperatures ≥600 C on both (111) Si and (001) sapphire substrates. This was also confirmed by the photoluminescent emission spectra

  14. Non-carbon titanium cobalt nitride nanotubes supported platinum catalyst with high activity and durability for methanol oxidation reaction

    Science.gov (United States)

    Chen, Xiaoxiang; Li, Wuyi; Pan, Zhanchang; Xu, Yanbin; Liu, Gen; Hu, Guanghui; Wu, Shoukun; Li, Jinghong; Chen, Chun; Lin, Yingsheng

    2018-05-01

    Titanium cobalt nitride nanotubes (Ti0.95Co0.05N NTs) hybrid support, a novel robust non-carbon support material prepared by solvothermal and post-nitriding processes, is further decorated with Pt nanoparticles for the electrooxidation of methanol. The catalyst is characterized by X-ray diffraction (XRD), nitrogen adsorption/desorption, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. The morphology, structure and composition of the synthesized Ti0.95Co0.05N NTs suggest that the nanotube wall is porous and consists of homogeneous cohesively attached nitrides nanocube particles. Notable, Ti0.95Co0.05N NTs supported Pt catalyst exhibits significantly improved catalytic activity and durability for methanol electrooxidation compared with the conventional JM Pt/C catalyst. The experimental data indicate that enhanced catalytic activity and stability of Pt/Ti0.95Co0.05N NTs towards methanol electrooxidation might be mainly attributed to the tubular nanostructures and synergistic effect introduced by the Co doping. Both of them are playing an important role in improving the activity and durability of the Ti0.95Co0.05N NTs catalyst.

  15. Determination of DPPH Radical Oxidation Caused by Methanolic Extracts of Some Microalgal Species by Linear Regression Analysis of Spectrophotometric Measurements

    Directory of Open Access Journals (Sweden)

    Ulf-Peter Hansen

    2007-10-01

    Full Text Available The demonstrated modified spectrophotometric method makes use of the 2,2-diphenyl-1-picrylhydrazyl (DPPH radical and its specific absorbance properties. Theabsorbance decreases when the radical is reduced by antioxidants. In contrast to otherinvestigations, the absorbance was measured at a wavelength of 550 nm. This wavelengthenabled the measurements of the stable free DPPH radical without interference frommicroalgal pigments. This approach was applied to methanolic microalgae extracts for twodifferent DPPH concentrations. The changes in absorbance measured vs. the concentrationof the methanolic extract resulted in curves with a linear decrease ending in a saturationregion. Linear regression analysis of the linear part of DPPH reduction versus extractconcentration enabled the determination of the microalgae’s methanolic extractsantioxidative potentials which was independent to the employed DPPH concentrations. Theresulting slopes showed significant differences (6 - 34 μmol DPPH g-1 extractconcentration between the single different species of microalgae (Anabaena sp.,Isochrysis galbana, Phaeodactylum tricornutum, Porphyridium purpureum, Synechocystissp. PCC6803 in their ability to reduce the DPPH radical. The independency of the signal on the DPPH concentration is a valuable advantage over the determination of the EC50 value.

  16. Ion beam and dual ion beam sputter deposition of tantalum oxide films

    Science.gov (United States)

    Cevro, Mirza; Carter, George

    1994-11-01

    Ion beam sputter deposition (IBS) and dual ion beam sputter deposition (DIBS) of tantalum oxide films was investigated at room temperature and compared with similar films prepared by e-gun deposition. Optical properties ie refractive index and extinction coefficient of IBS films were determined in the 250 - 1100 nm range by transmission spectrophotometry and at (lambda) equals 632.8 nm by ellipsometry. They were found to be mainly sensitive to the partial pressure of oxygen used as a reactive gas in the deposition process. The maximum value of the refractive index of IBS deposited tantalum oxide films was n equals 2.15 at (lambda) equals 550 nm and the extinction coefficient of order k equals 2 X 10-4. Films deposited by e-gun deposition had refractive index n equals 2.06 at (lambda) equals 550 nm. Films deposited using DIBS ie deposition assisted by low energy Ar and O2 ions (Ea equals 0 - 300 eV) and low current density (Ji equals 0 - 40 (mu) A/cm2) showed no improvement in the optical properties of the films. Preferential sputtering occurred at Ea(Ar) equals 300 eV and Ji equals 20 (mu) A/cm2 and slightly oxygen deficient films were formed. Different bonding states in the tantalum-oxide films were determined by x-ray spectroscopy while composition of the film and contaminants were determined by Rutherford scattering spectroscopy. Tantalum oxide films formed by IBS contained relatively high Ar content (approximately equals 2.5%) originating from the reflected argon neutrals from the sputtering target while assisted deposition slightly increased the Ar content. Stress in the IBS deposited films was measured by the bending technique. IBS deposited films showed compressive stress with a typical value of s equals 3.2 X 109 dyn/cm2. Films deposited by concurrent ion bombardment showed an increase in the stress as a function of applied current density. The maximum was s approximately equals 5.6 X 109 dyn/cm2 for Ea equals 300 eV and Ji equals 35 (mu) A/cm2. All

  17. Ion-beam and dual-ion-beam sputter deposition of tantalum oxide films

    Science.gov (United States)

    Cevro, Mirza; Carter, George

    1995-02-01

    Ion-beam sputter deposition (IBS) and dual-ion-beam sputter deposition (DIBS) of tantalum oxide films was investigated at room temperature and compared with similar films prepared by e-gun deposition. The optical properties, i.e., refractive index and extinction coefficient, of IBS films were determined in the 250- to 1100-nm range by transmission spectrophotometry and at (lambda) equals 632.8 nm by ellipsometry. They were found to be mainly sensitive to the partial pressure of oxygen used as a reactive gas in the deposition process. The maximum value of the refractive index of IBS deposited tantalum oxide films was n equals 2.15 at (lambda) equals 550 nm and the extinction coefficient of order k equals 2 X 10-4. Films deposited by e-gun deposition had refractive index n 2.06 at (lambda) equals 550 nm. Films deposited using DIBS, i.e., deposition assisted by low energy Ar and O2 ions (Ea equals 0 to 300 eV) and low current density (Ji equals 0 to 40 (mu) A/cm2), showed no improvement in the optical properties of the films. Preferential sputtering occurred at Ea(Ar) equals 300 eV and Ji equals 20 (mu) A/cm2 and slightly oxygen deficient films were formed. Different bonding states in the tantalum-oxide films were determined by x-ray spectroscopy, whereas composition of the film and contaminants were determined by Rutherford backscattering spectroscopy (RBS). Tantalum oxide films formed by IBS contained relatively high Ar content (approximately equals 2.5%) originating from the reflected argon neutrals from the sputtering target whereas assisted deposition slightly increased the Ar content. Stress in the IBS-deposited films was measured by the bending technique. IBS-deposited films showed compressive stress with a typical value of s equals 3.2 X 109 dyn/cm2. Films deposited by concurrent ion bombardment showed an increase in the stress as a function of applied current density. The maximum was s approximately equals 5.6 X 109 dyn/cm2 for Ea equals 300 eV and Ji equals

  18. Controlling of morphology and electrocatalytic properties of cobalt oxide nanostructures prepared by potentiodynamic deposition method

    Energy Technology Data Exchange (ETDEWEB)

    Hallaj, Rahman [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Akhtari, Keivan [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Research Center for Nanotechnology, University of Kurdistan, P.O.Box 416, Sanandaj (Iran, Islamic Republic of); Salimi, Abdollah, E-mail: absalimi@uok.ac.ir [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Research Center for Nanotechnology, University of Kurdistan, P.O.Box 416, Sanandaj (Iran, Islamic Republic of); Soltanian, Saied [Department of Physics, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of)

    2013-07-01

    Electrodeposited cobalt oxide nanostructures were prepared by Repetitive Triangular Potential Scans (RTPS) as a simple, remarkably fast and scalable potentiodynamic method. Electrochemical deposition of cobalt oxide nanostructures onto GC electrode was performed from aqueous Co(NO{sub 3}){sub 2}, (pH 6) solution using cyclic voltammetry method. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the morphology of fabricated nanostructures. The evaluation of electrochemical properties of deposited films was performed using cyclic voltametry (CV) and impedance spectroscopy (IS) techniques. The analysis of the experimental data clearly showed that the variations of potential scanning ranges during deposition process have drastic effects on the geometry, chemical structure and particle size of cobalt oxide nanoparticles. In addition, the electrochemical and electrocatalytic properties of prepared nanostructures can be controlled through applying different potential windows in electrodeposition process. The imaging and voltammetric studies suggested to the existence of at least three different shapes of cobalt-oxide nanostructures in various potential windows applied for electrodeposition. With enlarging the applied potential window, the spherical-like cobalt oxide nanoparticles with particles sizes about 30–50 nm changed to the grain-like structures (30 nm × 80 nm) and then to the worm-like cobalt oxide nanostructures with 30 nm diameter and 200–400 nm in length. Furthermore, the roughness of the prepared nanostructures increased with increasing positive potential window. The GC electrodes modified with cobalt oxide nanostructures shows excellent electrocatalytic activity toward H{sub 2}O{sub 2} and As (III) oxidation. The electrocatalytic activity of cobalt oxide nanostructures prepared at more positive potential window toward hydrogen peroxide oxidation was increased, while for As(III) oxidation the electrocatalytic

  19. Controlling of morphology and electrocatalytic properties of cobalt oxide nanostructures prepared by potentiodynamic deposition method

    International Nuclear Information System (INIS)

    Hallaj, Rahman; Akhtari, Keivan; Salimi, Abdollah; Soltanian, Saied

    2013-01-01

    Electrodeposited cobalt oxide nanostructures were prepared by Repetitive Triangular Potential Scans (RTPS) as a simple, remarkably fast and scalable potentiodynamic method. Electrochemical deposition of cobalt oxide nanostructures onto GC electrode was performed from aqueous Co(NO 3 ) 2 , (pH 6) solution using cyclic voltammetry method. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the morphology of fabricated nanostructures. The evaluation of electrochemical properties of deposited films was performed using cyclic voltametry (CV) and impedance spectroscopy (IS) techniques. The analysis of the experimental data clearly showed that the variations of potential scanning ranges during deposition process have drastic effects on the geometry, chemical structure and particle size of cobalt oxide nanoparticles. In addition, the electrochemical and electrocatalytic properties of prepared nanostructures can be controlled through applying different potential windows in electrodeposition process. The imaging and voltammetric studies suggested to the existence of at least three different shapes of cobalt-oxide nanostructures in various potential windows applied for electrodeposition. With enlarging the applied potential window, the spherical-like cobalt oxide nanoparticles with particles sizes about 30–50 nm changed to the grain-like structures (30 nm × 80 nm) and then to the worm-like cobalt oxide nanostructures with 30 nm diameter and 200–400 nm in length. Furthermore, the roughness of the prepared nanostructures increased with increasing positive potential window. The GC electrodes modified with cobalt oxide nanostructures shows excellent electrocatalytic activity toward H 2 O 2 and As (III) oxidation. The electrocatalytic activity of cobalt oxide nanostructures prepared at more positive potential window toward hydrogen peroxide oxidation was increased, while for As(III) oxidation the electrocatalytic activity decreased

  20. Electrochromic and electrochemical capacitive properties of tungsten oxide and its polyaniline nanocomposite films obtained by chemical bath deposition method

    CSIR Research Space (South Africa)

    Nwanya, AC

    2014-05-01

    Full Text Available Polyanine and its nanocomposite WO3/PANI films were deposited on fluorine doped tin oxide (FTO) glassslides by simple chemical bath deposition method. The morphology structure of the composite film wasstudied using atomic force microscopy (AFM...

  1. Improvements of electrocatalytic activity of PtRu nanoparticles on multi-walled carbon nanotubes by a H2 plasma treatment in methanol and formic acid oxidation

    International Nuclear Information System (INIS)

    Jiang Zhongqing; Jiang Zhongjie

    2011-01-01

    Graphical abstract: A H 2 plasma, that aims at reducing the fraction of the oxidized species at the outermost perimeter of metal particles, has been used to treat the PtRu nanoparticles supported on the plasma functionalized multi-walled carbon nanotubes (PtRu/PS-MWCNTs). The plasma treated PtRu/PS-MWCNTs exhibit increased electrochemically active surface area, reduced charge transfer resistance, improved electrocatalytic activity and long term stability toward methanol and formic acid oxidation, and enhanced tolerance to carbonaceous species relative to the sample untreated with the H 2 plasma. Highlights: → A H 2 plasma technique is used to treat the PtRu nanoparticles. → The H 2 plasma treated PtRu/PS-MWCNTs exhibit improved electrocatalytic activity. → The H 2 plasma treated PtRu/PS-MWCNTs have significantly reduced charge transfer resistance. → The H 2 plasma treated PtRu/PS-MWCNTs show the increased stability. → The Pt:Ru atomic ratio of PtRu nanoparticles has a significant effect on the electrochemical activity. - Abstract: A H 2 plasma has been used to treat the PtRu nanoparticles supported on the plasma functionalized multi-walled carbon nanotubes (PtRu/PS-MWCNTs). The plasma treatment does not change the size and crystalline structure of PtRu nanoparticles, but reduces the fraction of the oxidized species at the outermost perimeter of particles. The electrochemical results show that these plasma treated PtRu/PS-MWCNTs exhibit increased electrochemically active surface area, improved electrocatalytic activity and long term stability toward methanol and formic acid oxidation, and enhanced tolerance to carbonaceous species relative to the sample untreated with the H 2 plasma. The electrocatalytic activities of the plasma treated PtRu/PS-MWCNTs are found to be dependent upon the Pt:Ru atomic ratios of PtRu nanoparticles. The catalysts with a Pt:Ru atomic ratio close to 1:1 show superior properties in the electrooxidation of methanol and formic acid

  2. Discussion on the interlayer oxidation and uranium metallogenesis in Qianjiadian uranium deposit, Songliao Basin

    International Nuclear Information System (INIS)

    Pang Yaqing; Chen Xiaolin; Fang Xiheng; Sun Ye

    2010-01-01

    Through systematic drill core observation, section contrast and analysis,it is proved that the ore-controlling interlayer oxidation zone of Qianjiadian uranium deposit is mainly composed by the red oxidized sandstone and locally distributed yellow and off-white sandstones. The red sandstone contains charcoal fragments, pyrite, ilmenite, siderite, which have been oxidized intensively, and it can be deduced that their original color was gray and became red due to the oxidization. The distribution of the oxidation zone is mainly controlled by the sedimentary facies,which also controll uranium metallization. The uranium orebodies mainly developed in the thinning or pinch parts of the red oxidation zone in section. On the plans, the uranium mineralization distributes near the front of the red interlayer oxidation zone. (authors)

  3. Chemical vapor deposition of tin oxide: fundamentals and applications

    NARCIS (Netherlands)

    Mol, A.M.B. van; Chae, Y.; McDaniel, A.H.; Allendorf, M.D.

    2006-01-01

    Tin oxide thin layers have very beneficial properties such as a high transparency for visible light and electrical conductivity making these coatings suitable for a wide variety of applications, such as solar cells, and low-emissivity coatings for architectural glass windows. Each application

  4. Metabolism of methanol in acetogenic bacteria

    International Nuclear Information System (INIS)

    Ivey, D.K.W.

    1987-01-01

    Acetogens can grown on methanol in the presence of a cosubstrate that is more oxidized than methanol. Three mol of acetate is formed from 4 mol methanol and 2 mol CO 2 . One mol of methanol is oxidized to CO 2 . The levels of the tetrahydrofolate enzymes, carbon monoxide dehydrogenase, and corrinoids indicate the presence of the acetyl CoA pathway when growing on methanol. The acetyl-CoA pathway of acetate synthesis as presently understood does not include methanol as a substrate. It is demonstrated that methanol is oxidized to formaldehyde and then to formate by a methanol dehydrogenase. It is also possible that the methyl group of methanol is transferred directly to either a corrinoid-type enzyme, or tetrahydrofolate. When cells of C. thermoautotrophicum are grown on 14 CO 2 , acetate becomes labeled in both carbons with a ratio 14 CH 3 / 14 COOH of 0.7. In addition, methanol gets labeled. When cells are grown on 14 CH 3 OH, label appears in both acetate carbons with a ratio of 3.3, and also appears in CO 2 . Thus methanol is preferentially incorporated into the methyl group of acetate, whereas CO 2 is the preferred source of the carboxyl carbon

  5. Electrochemical Properties of Graphene-vanadium Oxide Composite Prepared by Electro-deposition for Electrochemical Capacitors

    International Nuclear Information System (INIS)

    Jeong, Heeyoung; Jeong, Sang Mun

    2015-01-01

    The nanostructural graphene/vanadium oxide (graphene/V 2 O 5 ) composite with enhanced capacitance was synthesized by the electro-deposition in 0.5 M VOSO 4 solution. The morphology of composites was characterized using scanning electron microscopy (SEM), x-ray diffraction pattern (XRD), and x-ray photoelectron spectroscopy (XPS). The oxidation states of the electro-deposited vanadium oxide was found to be V 5+ and V 4+ . The morphology of the prepared graphene/V 2 O 5 composite exhibits a netlike nano-structure with V 2 O 5 nanorods in about 100 nm diameter, which could lead a better contact between electrolyte an electrode. The composite with a deposition time of 4,000 s exhibits the specific capacitance of 854 mF/cm 2 at a scan rate of 20 mV/s and the capacitance retention of 53% after 1000 CV cycles

  6. Electro-oxidation of methanol and ethanol using PtRu/C, PtSn/C and PtSnRu/C electrocatalysts prepared by an alcohol-reduction process

    Energy Technology Data Exchange (ETDEWEB)

    Neto, Almir Oliveira; Dias, Ricardo R.; Tusi, Marcelo M.; Linardi, Marcelo; Spinace, Estevam V. [Instituto de Pesquisas Energeticas e Nucleares, IPEN-CNEN/SP, Av. Prof. Lineu Prestes 2242, Cidade Universitaria, CEP 05508-900 Sao Paulo, SP (Brazil)

    2007-03-30

    PtRu/C, PtSn/C and PtSnRu/C electrocatalysts were prepared by the alcohol reduction process using ethylene glycol as the solvent and reduction agent and Vulcan Carbon XC72 as the support. The electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The electrochemical oxidation of methanol and ethanol were studied by chronoamperometry using a thin porous coating technique. The PtSn/C electrocatalyst prepared by this methodology showed superior performance compared to the PtRu/C and PtSnRu/C electrocatalysts for methanol and ethanol oxidation at room temperature. (author)

  7. Electro-oxidation of methanol and ethanol using PtRu/C, PtSn/C and PtSnRu/C electrocatalysts prepared by an alcohol-reduction process

    Science.gov (United States)

    Neto, Almir Oliveira; Dias, Ricardo R.; Tusi, Marcelo M.; Linardi, Marcelo; Spinacé, Estevam V.

    PtRu/C, PtSn/C and PtSnRu/C electrocatalysts were prepared by the alcohol reduction process using ethylene glycol as the solvent and reduction agent and Vulcan Carbon XC72 as the support. The electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The electrochemical oxidation of methanol and ethanol were studied by chronoamperometry using a thin porous coating technique. The PtSn/C electrocatalyst prepared by this methodology showed superior performance compared to the PtRu/C and PtSnRu/C electrocatalysts for methanol and ethanol oxidation at room temperature.

  8. Monocrystalline zinc oxide films grown by atomic layer deposition

    International Nuclear Information System (INIS)

    Wachnicki, L.; Krajewski, T.; Luka, G.; Witkowski, B.; Kowalski, B.; Kopalko, K.; Domagala, J.Z.; Guziewicz, M.; Godlewski, M.; Guziewicz, E.

    2010-01-01

    In the present work we report on the monocrystalline growth of (00.1) ZnO films on GaN template by the Atomic Layer Deposition technique. The ZnO films were obtained at temperature of 300 o C using dietylzinc (DEZn) as a zinc precursor and deionized water as an oxygen precursor. High resolution X-ray diffraction analysis proves that ZnO layers are monocrystalline with rocking curve FWHM of the 00.2 peak equals to 0.07 o . Low temperature photoluminescence shows a sharp and bright excitonic line with FWHM of 13 meV.

  9. Defects in zinc oxide grown by pulsed laser deposition

    Energy Technology Data Exchange (ETDEWEB)

    Ling, Francis C.C., E-mail: ccling@hku.hk [Department of Physics, The University of Hong Kong, Pokfulam Road, Hong Kong (China); Wang, Zilan; Ping Ho, Lok; Younas, M. [Department of Physics, The University of Hong Kong, Pokfulam Road, Hong Kong (China); Anwand, W.; Wagner, A. [Institute of Radiation Physics, Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstr. 400, 01328 Dresden (Germany); Su, S.C. [Institute of Optoelectronic Material and Technology, South China Normal University, Guangzhou 510631 (China); Shan, C.X. [State Key Laboratory of Luminescence and Applications, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, Changchun 130033 (China)

    2016-01-01

    ZnO films are grown on c-plane sapphire using the pulsed laser deposition method. Systematic studies on the effects of annealing are performed to understand the thermal evolutions of the defects in the films. Particular attention is paid to the discussions of the ZnO/sapphire interface thermal stability, the Zn-vacancy related defects having different microstructures, the origins of the green luminescence (∼2.4–2.5 eV) and the near band edge (NBE) emission at 3.23 eV.

  10. Geochemistry and genesis of apatite bearing Fe oxide Dizdaj deposit, SE Zanjan

    Directory of Open Access Journals (Sweden)

    Ghasem Nabatian

    2009-09-01

    Full Text Available Sorkheh-Dizaj apatite-iron oxide deposit is located 32 km southeast of Zanjan. The area is situated within the Tarom subzone of Western Alborz-Azarbaijan structural zone. The oldest units at the Sorkheh-Dizaj area are Eocene trachyte, trachyandesite, olivine basalt and volcanoclastic brecciate tuff and lapilli tuff which intruded by a quartz-monzonite, monzonite and granite subvolcanic pluton of Upper Eocene- Early Oligocene age. Subvolcanic plutonic rocks in the area show characteristics of the I-type granites. Magmatism of the area is of synorogenic to postorogenic related to magmatic arc environments. Mineralization at the area is divided into three main zones (A, B and C that all of which are located in the host subvolcanic pluton. These three zones are similar in terms of host rock, mineralogy, alteration, structure, texture and metal content. Mineralization in the volcanic rocks occurs as veins similar to those in three main zones, but less abundant. Geometry of the ore bodies is of vein type and their textures are stockwork, massive, banded, brecciate and vein-veinlet. The most important minerals at Sorkheh-Dizaj deposit are magnetite (low Ti and apatite that associated with them minor sulfide minerals such as chalcopyrite, bornite and pyrite. Minerals such as ilmenite, spinel (titanium magnetite, galena and sphalerite occur in low contents. The supergene minerals like chalcocite, malachite, azurite, covellite, hematite and goethite have been formed due to weathering and supergene processes. The main alterations at the deposit are K-feldspar metasomatism, actinolitization, argillic, sericitization, silicification, tourmalinization, and chlorite-epidotic. Rare earth elements (REE studies demonstrate that the deposit is more enriched in LREE than in HREE. The REE patterns in the apatite, magnetite and host rocks are similar suggesting a magmatic relationship. The REE contents of the apatites are higher than those of the host rocks and

  11. High rate deposition of transparent conducting oxide thin films by vacuum arc plasma evaporation

    Energy Technology Data Exchange (ETDEWEB)

    Minami, Tadatsugu; Ida, Satoshi; Miyata, Toshihiro

    2002-09-02

    Transparent conducting oxide (TCO) thin films have been deposited at a high rate above 370 nm/min by vacuum arc plasma evaporation (VAPE) using sintered oxide fragments as the source material. It was found that the deposition rate of TCO films was strongly dependent on the deposition pressure, whereas the obtained electrical properties were relatively independent of the pressure. Resistivities of 5.6x10{sup -4} and 2.3x10{sup -4} {omega}{center_dot}cm and an average transmittance above 80% (with substrate included) in the visible range were obtained in Ga-doped ZnO (GZO) thin films deposited at 100 and 350 deg. C, respectively. In addition, a resistivity as low as 1.4x10{sup -4} {omega}{center_dot}cm and an average transmittance above 80% were also obtained in indium-tin-oxide (ITO) films deposited at 300 deg. C. The deposited TCO films exhibited uniform distributions of resistivity and thickness on large area substrates.

  12. High rate deposition of transparent conducting oxide thin films by vacuum arc plasma evaporation

    International Nuclear Information System (INIS)

    Minami, Tadatsugu; Ida, Satoshi; Miyata, Toshihiro

    2002-01-01

    Transparent conducting oxide (TCO) thin films have been deposited at a high rate above 370 nm/min by vacuum arc plasma evaporation (VAPE) using sintered oxide fragments as the source material. It was found that the deposition rate of TCO films was strongly dependent on the deposition pressure, whereas the obtained electrical properties were relatively independent of the pressure. Resistivities of 5.6x10 -4 and 2.3x10 -4 Ω·cm and an average transmittance above 80% (with substrate included) in the visible range were obtained in Ga-doped ZnO (GZO) thin films deposited at 100 and 350 deg. C, respectively. In addition, a resistivity as low as 1.4x10 -4 Ω·cm and an average transmittance above 80% were also obtained in indium-tin-oxide (ITO) films deposited at 300 deg. C. The deposited TCO films exhibited uniform distributions of resistivity and thickness on large area substrates

  13. Oxidative dissolution of ruthenium deposits onto stainless steel by permanganate ions in alkaline medium

    Energy Technology Data Exchange (ETDEWEB)

    Floquet, S.; Eysseric, C.; Maurel, D. [Commissariat a l' Energie Atomique (CEA/Valrho), Bagnols-sur-Ceze (France)

    2008-07-01

    During spent nuclear fuel reprocessing ruthenium is liable to form black ruthenium deposits on the stainless steel walls of process equipments. These deposits promote corrosion and can eventually obstruct the off-gas lines. The results of decontamination of 304L stainless steel test specimens covered with RuO(OH){sub 2} . xH{sub 2}O deposits by permanganate ions in alkaline medium are described. The ruthenium deposits were dissolved by oxidation of RuO(OH){sub 2} to RuO{sub 4}{sup 2-} ions, while the permanganate ions were reduced to MnO{sub 4}{sup 2-} ions and then to manganese dioxide MnO{sub 2}. The parameters affecting the kinetics of oxidative dissolution of these deposits were examined. The results indicate that the oxidative dissolution kinetics depends on the instantaneous surface area of the deposit, and that the dissolution rate increases with the concentrations of MnO{sub 4}{sup -} and OH{sup -} ions. (orig.)

  14. Microstructural variation in titanium oxide thin films deposited by DC magnetron sputtering

    International Nuclear Information System (INIS)

    Pandian, Ramanathaswamy; Natarajan, Gomathi; Kamruddin, M.; Tyagi, A.K.

    2013-01-01

    We report on the microstructural evolution of titanium oxide thin films deposited by reactive DC magnetron sputtering using titanium metal target. By varying the ratio of sputter-gas mixture containing argon, oxygen and nitrogen various phases of titanium oxide, almost pure rutile, rutile-rich and anatase-rich nano-crystalline, were deposited on Si substrates at room temperature. Using high-resolution scanning electron microscopy, X-ray diffraction and micro-Raman techniques the microstructure of the films were revealed. The relationship between the microstructure of the films and the oxygen partial pressure during sputtering is discussed

  15. Electrophoretic deposition of PTFE particles on porous anodic aluminum oxide film and its tribological properties

    International Nuclear Information System (INIS)

    Zhang, Dongya; Dong, Guangneng; Chen, Yinjuan; Zeng, Qunfeng

    2014-01-01

    Polytetrafluoroethylene (PTFE) composite film was successfully fabricated by depositing PTFE particles into porous anodic aluminum oxide film using electrophoretic deposition (EPD) process. Firstly, porous anodic aluminum oxide film was synthesized by anodic oxidation process in sulphuric acid electrolyte. Then, PTFE particles in suspension were directionally deposited into the porous substrate. Finally, a heat treatment at 300 °C for 1 h was utilized to enhance PTFE particles adhesion to the substrate. The influence of anodic oxidation parameters on the morphology and micro-hardness of the porous anodic aluminum oxide film was studied and the PTFE particles deposited into the pores were authenticated using energy-dispersive spectrometer (EDS) and scanning electron microscopy (SEM). Tribological properties of the PTFE composite film were investigated under dry sliding. The experimental results showed that the composite film exhibit remarkable low friction. The composite film had friction coefficient of 0.20 which deposited in 15% PTFE emulsion at temperature of 15 °C and current density of 3 A/dm 2 for 35 min. In addition, a control specimen of porous anodic aluminum oxide film and the PTFE composite film were carried out under the same test condition, friction coefficient of the PTFE composite film was reduced by 60% comparing with the control specimen at 380 MPa and 100 mm/s. The lubricating mechanism was that PTFE particles embedded in porous anodic aluminum oxide film smeared a transfer film on the sliding path and the micro-pores could support the supplement of solid lubricant during the sliding, which prolonged the lubrication life of the aluminum alloys.

  16. Deposition of tin oxide doped with fluorine produced by sol-gel method and deposited by spray-pyrolysis

    International Nuclear Information System (INIS)

    Maia, Paulo Herbert Franca; Lima, Francisco Marcone; Sena, Aline Cosmo de; Silva, Alvaro Neuton; Almeida, Ana Fabiola Leite de; Freire, Francisco Nivaldo Aguiar

    2014-01-01

    Solar energy is one of the most important sources of renewable energy today, but its production is based on silicon cells, expensive and difficult to produce, so the research seek new materials to replace them. This work aims to deposit tin oxide doped with fluorine on the glass substrate using the sol-gel method to provide a working solution and spray pyrolysis technique to perform the deposition. F-SnO2 (FTO) were synthesized by sol-gel method, employing NH_4F and SnCl_2 precursor in an ethanol solution. Before the formation of the gel phase, the entire solution was sprayed, with the aid of a pistol aerographic substrate under heated at 600 °C divided by 50 applications and cooled in the furnace. The substrates had resistances between 10 and 30 S.cm. The energy dispersive x-ray (EDS) revealed the presence of fluorine in the SnO_2 network. (author)

  17. Pulsed laser deposition of transparent conductive oxide thin films on flexible substrates

    Science.gov (United States)

    Socol, G.; Socol, M.; Stefan, N.; Axente, E.; Popescu-Pelin, G.; Craciun, D.; Duta, L.; Mihailescu, C. N.; Mihailescu, I. N.; Stanculescu, A.; Visan, D.; Sava, V.; Galca, A. C.; Luculescu, C. R.; Craciun, V.

    2012-11-01

    The influence of target-substrate distance during pulsed laser deposition of indium zinc oxide (IZO), indium tin oxide (ITO) and aluminium-doped zinc oxide (AZO) thin films grown on polyethylene terephthalate (PET) substrates was investigated. It was found that the properties of such flexible transparent conductive oxide (TCO)/PET electrodes critically depend on this parameter. The TCO films that were deposited at distances of 6 and 8 cm exhibited an optical transmittance higher than 90% in the visible range and electrical resistivities around 5 × 10-4 Ω cm. In addition to these excellent electrical and optical characteristics the films grown at 8 cm distance were homogenous, smooth, adherent, and without cracks or any other extended defects, being suitable for opto-electronic device applications.

  18. Effects of oxygen gas pressure on properties of iron oxide films grown by pulsed laser deposition

    International Nuclear Information System (INIS)

    Guo, Qixin; Shi, Wangzhou; Liu, Feng; Arita, Makoto; Ikoma, Yoshifumi; Saito, Katsuhiko; Tanaka, Tooru; Nishio, Mitsuhiro

    2013-01-01

    Highlights: ► Pulsed laser deposition is a promising technique for growing iron oxide films. ► Crystal structure of the iron oxide films strongly depends on oxygen gas pressure. ► Optimum of the oxygen gas pressure leads single phase magnetite films with high crystal quality. -- Abstract: Iron oxide films were grown on sapphire substrates by pulsed laser deposition at oxygen gas pressures between 1 × 10 −5 and 1 × 10 −1 Pa with a substrate temperature of 600 °C. Atomic force microscope, X-ray diffraction, Raman spectroscopy, X-ray absorption fine structure, and vibrational sample magnetometer analysis revealed that surface morphology and crystal structure of the iron oxide films strongly depend on the oxygen gas pressure during the growth and the optimum oxygen gas pressure range is very narrow around 1 × 10 −3 Pa for obtaining single phase magnetite films with high crystal quality

  19. Modification of implant material surface properties by means of oxide nano-structured coatings deposition

    Science.gov (United States)

    Safonov, Vladimir; Zykova, Anna; Smolik, Jerzy; Rogowska, Renata; Lukyanchenko, Vladimir; Kolesnikov, Dmitrii

    2014-08-01

    The deposition of functional coatings on the metal surface of artificial joints is an effective way of enhancing joint tribological characteristics. It is well-known that nanostructured oxide coatings have specific properties advantageous for future implant applications. In the present study, we measured the high hardness parameters, the adhesion strength and the low friction coefficient of the oxide magnetron sputtered coatings. The corrosion test results show that the oxide coating deposition had improved the corrosion resistance by a factor of ten for both stainless steel and titanium alloy substrates. Moreover, the hydrophilic nature of coated surfaces in comparison with the metal ones was investigated in the tensiometric tests. The surfaces with nanostructured oxide coatings demonstrated improved biocompatibility for in vitro and in vivo tests, attributed to the high dielectric constants and the high values of the surface free energy parameters.

  20. Decoupling photochemical Fe(II) oxidation from shallow-water BIF deposition

    DEFF Research Database (Denmark)

    Konhauser, Kurt; Amskold, Larry; Lalonde, Stefan

    2007-01-01

    to the rise of atmospheric oxygen and the development of a protective ozone layer, the Earth's surface was subjected to high levels of ultraviolet radiation. Bulk ocean waters that were anoxic at this time could have supported high concentrations of dissolved Fe(II). Under such conditions, dissolved ferrous...... for biology [Fran??ois, L.M., 1986, Extensive deposition of banded iron formations was possible without photosynthesis. Nature 320, 352-354]. Here, we evaluate the potential importance of photochemical oxidation using a combination of experiments and thermodynamic models. The experiments simulate......-type systems, then we are driven to conclude that oxide-facies BIF are the product of a rapid, non-photochemical oxidative process, the most likely candidates being direct or indirect biological oxidation, and that a significant fraction of BIF could have initially been deposited as ferrous minerals. ?? 2007...

  1. Pt/XC-72 catalysts coated with nitrogen-doped carbon (Pt/XC-72@C–N) for methanol electro-oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Jun; Chu, Yuanyuan; Tan, Xiaoyao, E-mail: cestanxy@aliyun.com

    2014-03-01

    Pt/XC-72 catalysts coated with N-doped carbon (denoted as Pt/XC-72@C–N) for the electro-oxidation of methanol are prepared through a combined microwave-assisted polyol with in-situ carbonization of N-doped carbon coating process using polyvinylpyrrolidone (PVP), 1-vinyl-3-ethylimidazolium nitrate (VEIN) or 1-ethyl-3-methylimidazolium dicyanamide (EMID) ionic liquid as the N-doped carbon precursor. X-ray diffraction, energy dispersive of X-ray, transmission electron microscopy, X-ray photoelectron spectroscopy, cyclic voltammograms and accelerated aging test techniques are applied to characterize the structure and the electro-catalytic activity of the catalysts. The results show that the Pt particles with the average size of around 2.5 nm are highly dispersed in face-centered cubic crystal structure in the carbon support. The structure of the N-doped carbon coating precursor has considerable influence on the electro-catalytic performance of the catalysts. The resultant catalyst with EMID ionic liquid as the N-doped carbon source exhibits 115.9 m{sup 2} g{sup −1}Pt electrochemical surface area (ESA) and 0.66 A mg{sup −1}Pt catalytic activity towards the electro-oxidation of methanol, which are 1.37 times the ESA and 1.35 times the catalytic activity of the PVP-derived catalyst, and 2.02 times the electrochemical surface area and 1.94 times the catalytic activity of the VEIN-derived catalyst. The appropriate amount of the EMID ionic liquid used in the catalyst synthesis process is around 10 uL for 100 mg XC-72 support so as to obtain the highest electro-catalytic activity. - Highlights: • N-doped carbon coated Pt/C catalyst is prepared for methanol electro-oxidation. • Pt/XC-72@C–N exhibits excellent electrocatalytic activity over uncoated catalysts. • Ionic liquid with anionic cyano groups is most suitable as N-doped carbon precursor. • The appropriate amount of ionic liquid for coating is around 10 μL for 100 mg carbon.

  2. Deposition of indium tin oxide films on acrylic substrates by radiofrequency magnetron sputtering

    International Nuclear Information System (INIS)

    Chiou, B.S.; Hsieh, S.T.; Wu, W.F.

    1994-01-01

    Indium tin oxide (ITO) films were deposited onto acrylic substrates by rf magnetron sputtering. Low substrate temperature (< 80 C) and low rf power (< 28 W) were maintained during sputtering to prevent acrylic substrate deformation. The influence of sputtering parameters, such as rf power, target-to-substrate distance, and chamber pressure, on the film deposition rate, the electrical properties, as well as the optical properties of the deposited films was investigated. Both the refractive index and the extinction coefficient were derived. The high reflection at wavelengths greater than 3 μm made these sputtered ITO films applicable to infrared mirrors

  3. Indium oxide deposition on glass by aerosol pyrolysis (Pyrosol (R) process)

    International Nuclear Information System (INIS)

    Blandenet, G.; Lagarde, Y.; Spitz, J.

    1975-01-01

    The pyrosol (R) process involves the pyrolysis of an aerosol generated by ultrasonic nebulisation from a solution of organic or inorganic compounds. This technique was used to deposit transparent n-conducting indium oxide films on glass. The electrical and optical properties of these films were studied as a function of the deposition temperature and doping (using tin or fluorine). A deposition temperature of 480 deg C and a Sn/In ratio of about 5% gave the best results. In this case, the transmission in the visible range was 92%, the infrared reflection 84% and the electrical resistivity 1.7x10 -4 ohm.cm [fr

  4. Direct deposition of aluminum oxide gate dielectric on graphene channel using nitrogen plasma treatment

    International Nuclear Information System (INIS)

    Lim, Taekyung; Kim, Dongchool; Ju, Sanghyun

    2013-01-01

    Deposition of high-quality dielectric on a graphene channel is an essential technology to overcome structural constraints for the development of nano-electronic devices. In this study, we investigated a method for directly depositing aluminum oxide (Al 2 O 3 ) on a graphene channel through nitrogen plasma treatment. The deposited Al 2 O 3 thin film on graphene demonstrated excellent dielectric properties with negligible charge trapping and de-trapping in the gate insulator. A top-gate-structural graphene transistor was fabricated using Al 2 O 3 as the gate dielectric with nitrogen plasma treatment on graphene channel region, and exhibited p-type transistor characteristics

  5. Hydrothermal manganese oxide deposits from the Izu-Ogasawara (Bonin)-Mariana Arc and adjacent areas

    Energy Technology Data Exchange (ETDEWEB)

    Usui, A.; Nishimura, A. (Geological Survey of Japan, Tsukuba (Japan))

    1992-04-27

    Modern and fossil hydrothermal manganese oxide deposits were discovered from a number of locations in the Izu-Ogasawara(Bonin)-Mariana Arc and adjacent areas during the Hakurei-Maru cruises from 1984 to 1989. This paper describes the occurrence and characteristics of these manganese deposits and their geological significance. It was found that the mineralogical and chemical composition and microstructure of the deposits are typically different from manganese nodules and crusts of hydrogenetic or diagenetic origin. Hardpans, veinlets, sheets, and irregular mass of the hydrothermal manganese deposits often cover a large area of sea bed, which suggests possible high-temperature hydrothermal sulfide deposits in their vicinity. On the other hand, the manganese minerals sometimes occur as substrate of younger hydrogenetic crusts and as nucleus of hydrogenetic nodules, which can provide a geological history of low-temperature hydrothermal activity on the past island arcs. 45 refs., 19 figs., 3 tabs.

  6. Optical and electrical characteristics of zirconium oxide thin films deposited on silicon substrates by spray pyrolysis

    International Nuclear Information System (INIS)

    Aguilar-Frutis, M.; Araiza, J.J.; Falcony, C.; Garcia, M.

    2002-01-01

    The optical and electrical characteristics of zirconium oxide thin films deposited by spray pyrolysis on silicon substrates are reported. The films were deposited from a spraying solution of zirconium acetylacetonate in N,N-dimethylformamide using an ultrasonic mist generator on (100) Si substrates. The substrate temperature during deposition was in the range of 400 to 600 grad C. Deposition rates up to 16 A/sec were obtained depending on the spraying solution concentration and on the substrate temperature. A refraction index of the order of 2.0 was measured on these films by ellipsometry. The electrical characteristics of the films were determined from the capacitance and current versus voltage measurements. The addition of water mist during the spraying deposition process was also studied in the characteristics of the films. (Authors)

  7. Oxidation Kinetics of Chemically Vapor-Deposited Silicon Carbide in Wet Oxygen

    Science.gov (United States)

    Opila, Elizabeth J.

    1994-01-01

    The oxidation kinetics of chemically vapor-deposited SiC in dry oxygen and wet oxygen (P(sub H2O) = 0.1 atm) at temperatures between 1200 C and 1400 C were monitored using thermogravimetric analysis. It was found that in a clean environment, 10% water vapor enhanced the oxidation kinetics of SiC only very slightly compared to rates found in dry oxygen. Oxidation kinetics were examined in terms of the Deal and Grove model for oxidation of silicon. It was found that in an environment containing even small amounts of impurities, such as high-purity Al2O3 reaction tubes containing 200 ppm Na, water vapor enhanced the transport of these impurities to the oxidation sample. Oxidation rates increased under these conditions presumably because of the formation of less protective sodium alumino-silicate scales.

  8. Hepatoprotective efficiency of methanol extract of red algae against chromium-induced oxidative damage in Wistar rats

    Directory of Open Access Journals (Sweden)

    Murugesan Subbiah

    2016-07-01

    Full Text Available Objective: To investigate the hepatoprotective activity of red algae Portieria hornemannii (Lyngbye Silva (P. hornemannii and Spyridia fusiformis Boergesen (S. fusiformis by using the chromium treated rat liver as the animal model. Methods: The extract of red algae at a dosage of 0.200 g/kg of whole body weight was orally administrated to Cr (VI intoxicated rats for 28 consecutive days. The effect of drug in rats was evaluated by comparing the degree of the production of enzymes responsible for antioxidant activity such lipid peroxidase, superoxide dismutase, catalase and reduced glutathione with Cr (VI analogs in the absence of any secondary treatment. The overall damage of liver was detected by measuring serum enzymes such as aspartate amino transferase and alanine aminotransferase activities which released into the blood from the damaged cells. Results: It was observed that these enzyme levels were noticed in the animals treated with methanol extracts of red algae (200 mg/kg through preventing the leakage of the above enzymes into the blood. The hepatoprotection obtained using LIV 52 (standard reference drug appeared relatively higher. The antihepatotoxic potential of red algae P. hornemannii and S. fusiformis might be due to their antioxidative and membrane stabilizing activities. Conclusions: Our results indicated that the extract of P. hornemannii and S. fusiformis obtained from methanol could be a promising hepatoprotective agent against chromium (VI-induced liver damage.

  9. Effect of Co deposition on oxidation behavior and electrical properties of ferritic steel for solid oxide fuel cell interconnects

    Energy Technology Data Exchange (ETDEWEB)

    Kruk, A.; Adamczyk, A.; Gil, A. [AGH University of Science and Technology, Faculty of Materials Science and Ceramics, al. Mickiewicza 30, 30-059 Krakow (Poland); Kąc, S. [AGH University of Science and Technology, Faculty of Metals Engineering and Industrial Computer Science, al. Mickiewicza 30, 30-059 Krakow (Poland); Dąbek, J.; Ziąbka, M. [AGH University of Science and Technology, Faculty of Materials Science and Ceramics, al. Mickiewicza 30, 30-059 Krakow (Poland); Brylewski, T., E-mail: brylew@agh.edu.pl [AGH University of Science and Technology, Faculty of Materials Science and Ceramics, al. Mickiewicza 30, 30-059 Krakow (Poland)

    2015-09-01

    In this work, a Co layer deposited on DIN 50049 steel by means of pulsed laser deposition was applied for the protection of solid oxide fuel cell (SOFC) interconnects operating on the cathode side. The coated and uncoated steel samples were oxidized in air at 1073 K for 500 h, and their microstructures as well as electrical resistances were evaluated using X-ray diffraction, atomic force microscopy, scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, and the 2-probe 4-point direct current method. It was demonstrated that the Co coating had reduced the oxidation rate of the steel by nearly a half. The area-specific resistance value of the coated steel was 5 × 10{sup −6} Ω·m{sup 2}, which was significantly lower than that of bare steel after 350 h of oxidation at 1073 K. Cr vaporization tests showed that the Co coating was efficient at blocking the outward diffusion of Cr. The obtained results prove that steel coated with a thin film of cobalt was suitable for use as metallic interconnect material in SOFCs operating at intermediate temperatures. - Highlights: • Co layer was deposited on ferritic steel by means of pulsed laser deposition. • Coated and bare ferritic steel samples were exposed to air at 1073 K for 500 h. • Scale growth rate on bare steel is higher than that on coated steel. • Electrical resistance for oxidized coated steel was lower than for bare steel. • Co-coated steel effectively reduced the formation of volatile Cr species.

  10. Process and catalysts for the gasification of methanol. [German Patent

    Energy Technology Data Exchange (ETDEWEB)

    Harris, N.; Dennis, A.J.; Shevels, T.F.

    1975-02-13

    The invention concerns catalysts and catalytic processes for the gasification of methanol which is used to manufacture methane from methanol. Mixtures of iron and chromium oxide, phosphate, phosphoric acid, tungstate, tungstic acid, aluminium phosphate, aluminium oxide are suitable as dehydrating catalysts. Gasification takes place together with steam and dehydrogenating catalysts at high temperature. The molar ratios steam: methanol are described.

  11. l-Glutamic acid assisted eco-friendly one-pot synthesis of sheet-assembled platinum-palladium alloy networks for methanol oxidation and oxygen reduction reactions.

    Science.gov (United States)

    Shi, Ya-Cheng; Mei, Li-Ping; Wang, Ai-Jun; Yuan, Tao; Chen, Sai-Sai; Feng, Jiu-Ju

    2017-10-15

    In this work, bimetallic platinum-palladium sheet-assembled alloy networks (PtPd SAANs) were facilely synthesized by an eco-friendly one-pot aqueous approach under the guidance of l-glutamic acid at room temperature, without any additive, seed, toxic or organic solvent involved. l-Glutamic acid was served as the green shape-director and weak-stabilizing agent. A series of characterization techniques were employed to examine the morphology, structure and formation mechanism of the product. The architectures exhibited improved electrocatalytic activity and durable ability toward methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) in contrast with commercial Pt black and Pd black catalysts. This is ascribed to the unique structures of the obtained PtPd SAANs and the synergistic effects of the bimetals. These results demonstrate the potential application of the prepared catalyst in fuel cells. Copyright © 2017 Elsevier Inc. All rights reserved.

  12. Constraining the role of anoxygenic phototrophic Fe(II)-oxidizing bacteria in deposition of BIFs

    Science.gov (United States)

    Kappler, A.; Posth, N. R.; Hegler, F.; Wartha, E.; Huelin, S.

    2007-12-01

    Banded Iron Formations (BIFs) are Precambrian sedimentary deposits of alternating iron oxide and silica mineral layers. Their presence in the rock record ca.3.8-2.2 Ga makes them particularly intriguing formations for the debate over when oxygen became dominant on Earth. The mechanism(s) of BIF deposition is still unclear; suggestions including both abiotic and biotic processes. We are interested in constraining one of these proposed mechanisms; the direct biological oxidation of Fe(II) via anoxygenic Fe(II)-oxidizing autophototrophs. In order to find the limitations of photoferrotrophic BIF deposition, we take a holistic approach, investigating the oxidation of Fe(II) by modern Fe(II)-oxidizing phototrophs, the precipitation of Fe(III) (hydr)oxides, and the fate of the cell-mineral aggregates in the water column and at the basin floor. Specifically, physiology experiments with Fe(II)-oxidizing phototrophs under various conditions of light intensity, pH, Fe(II) concentration and temperature allow us to determine the environmental limits of such organisms. We carry out precipitation experiments to characterize the sedimentation rates, aggregate size and composition in order to resolve the effect of reactions in the water column. Finally, we simulate the diagenetic fate of these aggregates on the basin floor by placing them in gold capsules under T and P conditions relevant for the Transvaal Supergroup BIFs of South Africa. Recently, we have developed a tank simulating the Archean ocean in which the strains grow in continuous culture and collect the aggregates formed under various geochemical conditions. We aim to model the extent of and limitations to photoferrotrophs in BIF deposition. This information will help constrain whether biotic processes were dominant in the Archean ocean and will offer insight to the evolution of the early biogeosphere.

  13. Transient oxidation of Al-deposited Fe-Cr-Al alloy foil

    International Nuclear Information System (INIS)

    Andoh, A.

    1997-01-01

    The oxide phases formed on an Al-deposited Fe-Cr-Al alloy foil and an Fe-Cr-Al alloy foil of the same levels of Al and (La+Ce) contents, and their oxidation kinetics have been studied in air at 1173 and 1373 K using TGA, XRD and SEM. Al deposition promotes the growth of metastable aluminas (θ-Al 2 O 3 , γ-Al 2 O 3 ). Scales consisting of θ-Al 2 O 3 and a small amount of α-Al 2 O 3 develop on the Al-deposited foil at 1173 K and exhibit the whisker-type morphology. In the early stage of oxidation at 1373 K, thick scales consisting of θ-Al 2 O 3 and α-Al 2 O 3 grow rapidly on the Al-deposited foil. The transformation from θ-Al 2 O 3 to α-Al 2 O 3 is very fast, and the scales result in only α-Al 2 O 3 . In contrast, α-Al 2 O 3 scales containing a minor amount of FeAl 2 O 4 develop on the alloy foil. The growth rate of α-Al 2 O 3 scales on the Al-deposited foil is smaller than that on the alloy foil and very close to that on NiAl at 1373 K. (orig.)

  14. Electro-oxidation of methanol in alkaline conditions using Pd–Ni nanoparticles prepared from organometallic precursors and supported on carbon vulcan

    Energy Technology Data Exchange (ETDEWEB)

    Manzo-Robledo, A., E-mail: amanzor@ipn.mx [UPALM, Laboratorio de Electroquímica y Corrosión, Escuela Superior de Ingeniería Química e Industrias Extractivas-IPN (Mexico); Costa, Natália J. S. [Universidade de São Paulo, Instituto de Química (Brazil); Philippot, K. [CNRS, LCC, Laboratoire de Chimie de Coordination (France); Rossi, Liane M. [Universidade de São Paulo, Instituto de Química (Brazil); Ramírez-Meneses, E. [Universidad Iberoamericana, Departamento de Ingeniería y Ciencias Químicas (Mexico); Guerrero-Ortega, L. P. A. [UPALM, Laboratorio de Electroquímica y Corrosión, Escuela Superior de Ingeniería Química e Industrias Extractivas-IPN (Mexico); Ezquerra-Quiroga, S. [Universidad Iberoamericana, Departamento de Ingeniería y Ciencias Químicas (Mexico)

    2015-12-15

    Oxidation of low-molecular weight alcohols as energy sources using metal nanoparticles has attracted considerable interest for use as a power source in portable electronic devices. In this work, a series of mono- and bimetallic nanoparticles based on palladium and nickel (Pd, Pd{sub 90}Ni{sub 10}, Pd{sub 50}Ni{sub 50}, Pd{sub 10}Ni{sub 90}, and Ni) have been synthesized from organometallic precursors, namely tris(dibenzylideneacetone) dipalladium(0), Pd{sub 2}(dba){sub 3}, and bis(1,5-cyclooctadiene)nickel(0), Ni(cod){sub 2}. Well-defined metal particles in the nanometric scale from 4.2 to 6.3 nm were observed by transmission electron microscopy. The as-prepared nanoparticles were mixed with a carbon Vulcan matrix (10 % wt. of the catalyst in turn) for investigation as electrocatalysts in methanol oxidation reaction (MOR) in alkaline conditions. The i–E profiles from cyclic voltammetry for the monometallic systems indicated a redox process attributed only to palladium or nickel, as expected. With the bimetallic nanomaterials, the redox process and the i–E characteristics are functions of the amount of nickel associated to palladium. From a fundamental point of view, it has been established that the OH ions’ interfacial interaction and the MOR kinetics are affected by the presence of nickel (decreasing the faradic current) as supported by the current versus potential profiles obtained as a function of methanol concentration and with temperature variation.

  15. Metal oxide targets produced by the polymer-assisted deposition method

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, Mitch A., E-mail: mitch@berkeley.ed [Department of Chemistry, Room 446 Latimer Hall, University of California Berkeley, Berkeley, CA 94720-1460 (United States); Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Ali, Mazhar N.; Chang, Noel N.; Parsons-Moss, T. [Department of Chemistry, Room 446 Latimer Hall, University of California Berkeley, Berkeley, CA 94720-1460 (United States); Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Ashby, Paul D. [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Gates, Jacklyn M. [Department of Chemistry, Room 446 Latimer Hall, University of California Berkeley, Berkeley, CA 94720-1460 (United States); Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Stavsetra, Liv [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Gregorich, Kenneth E.; Nitsche, Heino [Department of Chemistry, Room 446 Latimer Hall, University of California Berkeley, Berkeley, CA 94720-1460 (United States); Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States)

    2010-02-11

    The polymer-assisted deposition (PAD) method was used to create crack-free homogenous metal oxide films for use as targets in nuclear science applications. Metal oxide films of europium, thulium, and hafnium were prepared as models for actinide oxides. Films produced by a single application of PAD were homogenous and uniform and ranged in thickness from 30 to 320 nm. Reapplication of the PAD method (six times) with a 10% by weight hafnium(IV) solution resulted in an equally homogeneous and uniform film with a total thickness of 600 nm.

  16. Metal oxide targets produced by the polymer-assisted deposition method

    International Nuclear Information System (INIS)

    Garcia, Mitch A.; Ali, Mazhar N.; Chang, Noel N.; Parsons-Moss, T.; Ashby, Paul D.; Gates, Jacklyn M.; Stavsetra, Liv; Gregorich, Kenneth E.; Nitsche, Heino

    2010-01-01

    The polymer-assisted deposition (PAD) method was used to create crack-free homogenous metal oxide films for use as targets in nuclear science applications. Metal oxide films of europium, thulium, and hafnium were prepared as models for actinide oxides. Films produced by a single application of PAD were homogenous and uniform and ranged in thickness from 30 to 320 nm. Reapplication of the PAD method (six times) with a 10% by weight hafnium(IV) solution resulted in an equally homogeneous and uniform film with a total thickness of 600 nm.

  17. Self-catalytic growth of tin oxide nanowires by chemical vapor deposition process

    CSIR Research Space (South Africa)

    Thabethe, BS

    2013-01-01

    Full Text Available The authors report on the synthesis of tin oxide (SnO(sub2)) nanowires by a chemical vapor deposition (CVD) process. Commercially bought SnO nanopowders were vaporized at 1050°C for 30 minutes with argon gas continuously passing through the system...

  18. Optoelectronic properties of expanding thermal plasma deposited textured zinc oxide : effect of aluminum doping

    NARCIS (Netherlands)

    Groenen, R.; Kieft, E.R.; Linden, J.L.; Sanden, van de M.C.M.

    2006-01-01

    Aluminum-doped zinc oxide films exhibiting a rough surface morphol. are deposited on glass substrates utilizing expanding thermal plasma. Spectroscopic ellipsometry is used to evaluate optical and electronic film properties. The presence of aluminum donors in doped films is confirmed by a shift in

  19. Atomic layer deposition of high-mobility hydrogen-doped zinc oxide

    NARCIS (Netherlands)

    Macco, B.; Knoops, H.C.M.; Verheijen, M.A.; Beyer, W.; Creatore, M.; Kessels, W.M.M.

    2017-01-01

    In this work, atomic layer deposition (ALD) has been employed to prepare high-mobility H-doped zinc oxide (ZnO:H) films. Hydrogen doping was achieved by interleaving the ZnO ALD cycles with H2 plasma treatments. It has been shown that doping with H2 plasma offers key advantages over traditional

  20. Deposition of zinc oxide thin films by reactive pulsed laser ablation

    Czech Academy of Sciences Publication Activity Database

    Bílková, Petra; Zemek, Josef; Mitu, B.; Marotta, V.; Orlando, S.

    2006-01-01

    Roč. 252, - (2006), s. 4604-4609 ISSN 0169-4332 Grant - others:NATO-CNR Outreach Fellowships Programm 2001(XE) 219.34 Institutional research plan: CEZ:AV0Z10100521 Keywords : reactive pulsed laser deposition * zinc oxide * thin films Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.436, year: 2006

  1. Plasma-deposited aluminum-doped zinc oxide : controlling nucleation, growth and electrical properties

    NARCIS (Netherlands)

    Ponomarev, M.

    2012-01-01

    In this work, the Expanding Thermal Plasma (ETP) deposition technique was employed to study the growth development of ZnO:Al thin film as a transparent conductive oxide layer for sustainable applications. Characteristic for ETP-grown ZnO:Al is a gradually reducing resistivity of the growing layer

  2. Plasma processes and film growth of expanding thermal plasma deposited textured zinc oxide

    NARCIS (Netherlands)

    Groenen, R.; Linden, J.L.; Sanden, van de M.C.M.

    2005-01-01

    Plasma processes and film growth of textured zinc oxide deposited from oxygen and diethyl zinc utilizing expanding thermal argon plasma created by a cascaded arc is discussed. In all conditions explored, an excess of argon ions and low temperature electrons is available, which represent the

  3. Low temperature growth of gallium oxide thin films via plasma enhanced atomic layer deposition

    NARCIS (Netherlands)

    O'Donoghue, R.; Rechmann, J.; Aghaee, M.; Rogalla, D.; Becker, H.-W.; Creatore, M.; Wieck, A.D.; Devi, A.P.K.

    2017-01-01

    Herein we describe an efficient low temperature (60–160 °C) plasma enhanced atomic layer deposition (PEALD) process for gallium oxide (Ga2O3) thin films using hexakis(dimethylamido)digallium [Ga(NMe2)3]2 with oxygen (O2) plasma on Si(100). The use of O2 plasma was found to have a significant

  4. Oxide deposition in the orifices of AGR boiler inlet ferrule assemblies

    International Nuclear Information System (INIS)

    Thomas, D.M.

    1988-08-01

    In experiments designed to study the erosion-corrosion behaviour of AGR boiler inlet ferrules using the CERL high velocity circulating isothermal water rig, oxide deposition was frequently found within the flow control orifices. The present investigation was carried out as a preliminary to a programme of experiments addressed specifically to this problem. Analysis shows the deposits to be predominantly magnetite (or possible maghemite) with traces of α-haematite. Calculations indicate that the maximum rate of magnetite deposition is mass transfer limited, although in some experiments no deposition occurred in cases where mass transfer would have allowed substantial deposition. Thus the occurrence of deposition is thought to depend on the rig potential as this varies with experimental conditions. In these experiments the surface potential is not found to be governed by the hydrogen level. Metallographic cross-sections through the ferrule control bores show the deposits to be found in regions of separated flow, and the flow markings in the deposits show that the flow is turbulent in these zones. The exact morphology is thought to be influenced by machining marks within the control bore. (author)

  5. The effect of substrate temperature on atomic layer deposited zinc tin oxide

    Energy Technology Data Exchange (ETDEWEB)

    Lindahl, Johan, E-mail: johan.lindahl@angstrom.uu.se; Hägglund, Carl, E-mail: carl.hagglund@angstrom.uu.se; Wätjen, J. Timo, E-mail: timo.watjen@angstrom.uu.se; Edoff, Marika, E-mail: marika.edoff@angstrom.uu.se; Törndahl, Tobias, E-mail: tobias.torndahl@angstrom.uu.se

    2015-07-01

    Zinc tin oxide (ZTO) thin films were deposited on glass substrates by atomic layer deposition (ALD), and the film properties were investigated for varying deposition temperatures in the range of 90 to 180 °C. It was found that the [Sn]/([Sn] + [Zn]) composition is only slightly temperature dependent, while properties such as growth rate, film density, material structure and band gap are more strongly affected. The growth rate dependence on deposition temperature varies with the relative number of zinc or tin containing precursor pulses and it correlates with the growth rate behavior of pure ZnO and SnO{sub x} ALD. In contrast to the pure ZnO phase, the density of the mixed ZTO films is found to depend on the deposition temperature and it increases linearly with about 1 g/cm{sup 3} in total over the investigated range. Characterization by transmission electron microscopy suggests that zinc rich ZTO films contain small (~ 10 nm) ZnO or ZnO(Sn) crystallites embedded in an amorphous matrix, and that these crystallites increase in size with increasing zinc content and deposition temperature. These crystallites are small enough for quantum confinement effects to reduce the optical band gap of the ZTO films as they grow in size with increasing deposition temperature. - Highlights: • Zinc tin oxide thin films were deposited by atomic layer deposition. • The structure and optical properties were studied at different growth temperatures. • The growth temperature had only a small effect on the composition of the films. • Small ZnO or ZnO(Sn) crystallites were observed by TEM in zinc rich ZTO films. • The growth temperature affects the crystallite size, which influences the band gap.

  6. The effect of substrate temperature on atomic layer deposited zinc tin oxide

    International Nuclear Information System (INIS)

    Lindahl, Johan; Hägglund, Carl; Wätjen, J. Timo; Edoff, Marika; Törndahl, Tobias

    2015-01-01

    Zinc tin oxide (ZTO) thin films were deposited on glass substrates by atomic layer deposition (ALD), and the film properties were investigated for varying deposition temperatures in the range of 90 to 180 °C. It was found that the [Sn]/([Sn] + [Zn]) composition is only slightly temperature dependent, while properties such as growth rate, film density, material structure and band gap are more strongly affected. The growth rate dependence on deposition temperature varies with the relative number of zinc or tin containing precursor pulses and it correlates with the growth rate behavior of pure ZnO and SnO x ALD. In contrast to the pure ZnO phase, the density of the mixed ZTO films is found to depend on the deposition temperature and it increases linearly with about 1 g/cm 3 in total over the investigated range. Characterization by transmission electron microscopy suggests that zinc rich ZTO films contain small (~ 10 nm) ZnO or ZnO(Sn) crystallites embedded in an amorphous matrix, and that these crystallites increase in size with increasing zinc content and deposition temperature. These crystallites are small enough for quantum confinement effects to reduce the optical band gap of the ZTO films as they grow in size with increasing deposition temperature. - Highlights: • Zinc tin oxide thin films were deposited by atomic layer deposition. • The structure and optical properties were studied at different growth temperatures. • The growth temperature had only a small effect on the composition of the films. • Small ZnO or ZnO(Sn) crystallites were observed by TEM in zinc rich ZTO films. • The growth temperature affects the crystallite size, which influences the band gap

  7. Remote sensing technology prospecting methods of interlayer oxidation zone type sandstone uranium deposit in Yili basin

    International Nuclear Information System (INIS)

    Huang Xianfang; Huang Shutao; Pan Wei; Feng Jie; Liu Dechang; Zhang Jingbo; Xuan Yanxiu; Rui Benshan

    1998-12-01

    Taking Yili Basin as an example, remote sensing technology and method of interlayer oxidation zone type sandstone uranium deposit have systematically been summarized. Firstly, principle, methods and procedures of the second development of scientific experimental satellite photograph have been elaborated in detail. Three dimensional stereo simulation, display, and multi-parameters extraction have been recommended. Secondarily, the research is focused on prospective section image features in different type images and their geological implications and on establishing recognition keys of promising areas. Finally, based on above research results, three graded predictions, i.e. regional prospect, promising sections and favourable location in the deposit have been made step by step and reconnaissance and prospecting range are gradually reduced. The practice has indicated that breakthrough progress has been made in application to prospect prognosis of interlayer oxidation zone type sandstone uranium deposit and good verified results have been obtained

  8. Study on metallogenetic prospect of interlayer oxidation zone sandstone type uranium deposit in Shanganning basin

    International Nuclear Information System (INIS)

    Wang Jinping

    1998-01-01

    As Compared with orogenic zone basin, which the interlayer oxidation zone sandstone type uranium deposits are found, the Shanganning basin a continental platform type basin is distinct either in the geodynamic background and the post-basin hydrogeological evolution or in the appearance of the metallogenetic dynamics-orogenesis. The prediction criteria summarized for interlayer oxidation zone type U-deposits in Middle Asia therefore can not be completely applied in such a basin. Based on analysis of the typical regional geological setting, the hydrogeology of the Meso-Cenozoic cover is studied in detail. Three hydrogeological cycles have been divided, and prospects of uranium deposits have been clarified and the most promising target have been proposed

  9. Deposition of an Ultraflat Graphene Oxide Nanosheet on Atomically Flat Substrates

    Science.gov (United States)

    Khan, M. Z. H.; Shahed, S. M. F.; Yuta, N.; Komeda, T.

    2017-07-01

    In this study, graphene oxide (GO) sheets produced in the form of stable aqueous dispersions were deposited on Au (111), freshly cleaved mica, and highly oriented pyrolytic graphite (HOPG) substrates. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to study the presence and distinct contact of GO sheets on the substrates. It was revealed from the topography images that high-quality ultraflat GO monolayer sheets formed on the substrates without distinct cracking/wrinkling or folding. GO sheets with apparent height variation observed by microscopy also indicate ultraflat deposition with clear underlying steps. It was observed that ultrasonication and centrifuge steps prior to deposition were very effective for getting oxidation debris (OD)-free ultraflat single monolayer GO nanosheets onto substrates and that the process depends on the concentration of supplied GO solutions.

  10. The selectivity of catalysts composed of V/sub 2/O/sub 5/ supported on ZrO/sub 2/-Y/sub 2/O/sub 3/ mixed oxides for methanol oxidation

    International Nuclear Information System (INIS)

    VanOmmen, J.G.; Gellings, P.J.; Ross, J.R.H.

    1988-01-01

    V/sub 2/O/sub 5/ monolayer catalysts were prepared on ZrO/sub 2/ and ZrO/sub 2/ doped with Y/sub 2/O/sub 3/ by two methods. The coverages obtained are only half a monolayer and did not depend on the preparation method or type of support. The selectivity for oxidation of methanol over these V/sub 2/O/sub 5/ catalysts changes from a predominance of formaldehyde to a predominance of methyl formate when the support is doped with Y/sub 2/C/sub 3/, independent of the amount of Y/sub 2/O/sub 3/

  11. Occurrence and prevention of enhanced oxide deposition in boiler flow control orifices

    International Nuclear Information System (INIS)

    Woolsey, I.S.; Thomas, D.M.; Garbett, K.; Bignold, G.J.

    1989-10-01

    Once-through boilers, such as those of the AGRs, incorporate flow control orifices at the boiler inlet to ensure a satisfactory flow distribution and stability in the parallel flow paths of the boiler. Deposition of corrosion products in the flow control orifice leads to changes in the orifice pressure loss characteristics, which could lead to problems of flow maldistribution within the boiler, and any adverse consequences resulting from this, such as tube overheating. To date, AGR boiler inlet orifices have not suffered significant fouling due to corrosion products in the boiler feedwater. However, oxide deposition in orifices has been observed in other plants, and in experimental loops operating under conditions very similar to those at inlet to AGR boilers. The lack of deposition in AGR flow control orifices is therefore somewhat surprising. This Report describes studies carried out to examine the factors controlling oxide deposition in flow control orifices, the intention of the work being to explain why deposition has not occurred in AGR boilers to date, and to provide means of preventing deposition in the future should this prove necessary. (author)

  12. Deposition of low sheet resistance indium tin oxide directly onto functional small molecules

    KAUST Repository

    Franklin, Joseph B.

    2014-11-01

    © 2014 Elsevier B.V. All rights reserved. We outline a methodology for depositing tin-doped indium oxide (ITO) directly onto semiconducting organic small molecule films for use as a transparent conducting oxide top-electrode. ITO films were grown using pulsed laser deposition onto copper(II)phthalocyanine (CuPc):buckminsterfullerene (C60) coated substrates. The ITO was deposited at a substrate temperature of 150 °C over a wide range of background oxygen pressures (Pd) (0.67-10 Pa). Deposition at 0.67 ≤ Pd ≤ 4.7 Pa led to delamination of the organic films owing to damage induced by the high energy ablated particles, at intermediate 4.7 ≤ Pd < 6.7 Pa pressures macroscopic cracking is observed in the ITO. Increasing Pd further, ≥ 6.7 Pa, supports the deposition of continuous, polycrystalline and highly transparent ITO films without damage to the CuPc:C60. The free carrier concentration of ITO is strongly influenced by Pd; hence growth at > 6.7 Pa induces a significant decrease in conductivity; with a minimum sheet resistance (Rs) of 145 /□ achieved for 300 nm thick ITO films. To reduce the Rs a multi-pressure deposition was implemented, resulting in the formation of polycrystalline, highly transparent ITO with an Rs of - 20/□ whilst maintaining the inherent functionality and integrity of the small molecule substrate.

  13. Deposition of low sheet resistance indium tin oxide directly onto functional small molecules

    KAUST Repository

    Franklin, Joseph B.; Fleet, Luke R.; Burgess, Claire H.; McLachlan, Martyn A.

    2014-01-01

    © 2014 Elsevier B.V. All rights reserved. We outline a methodology for depositing tin-doped indium oxide (ITO) directly onto semiconducting organic small molecule films for use as a transparent conducting oxide top-electrode. ITO films were grown using pulsed laser deposition onto copper(II)phthalocyanine (CuPc):buckminsterfullerene (C60) coated substrates. The ITO was deposited at a substrate temperature of 150 °C over a wide range of background oxygen pressures (Pd) (0.67-10 Pa). Deposition at 0.67 ≤ Pd ≤ 4.7 Pa led to delamination of the organic films owing to damage induced by the high energy ablated particles, at intermediate 4.7 ≤ Pd < 6.7 Pa pressures macroscopic cracking is observed in the ITO. Increasing Pd further, ≥ 6.7 Pa, supports the deposition of continuous, polycrystalline and highly transparent ITO films without damage to the CuPc:C60. The free carrier concentration of ITO is strongly influenced by Pd; hence growth at > 6.7 Pa induces a significant decrease in conductivity; with a minimum sheet resistance (Rs) of 145 /□ achieved for 300 nm thick ITO films. To reduce the Rs a multi-pressure deposition was implemented, resulting in the formation of polycrystalline, highly transparent ITO with an Rs of - 20/□ whilst maintaining the inherent functionality and integrity of the small molecule substrate.

  14. Vapor deposition of molybdenum oxide using bis(ethylbenzene) molybdenum and water

    International Nuclear Information System (INIS)

    Drake, Tasha L.; Stair, Peter C.

    2016-01-01

    Three molybdenum precursors—bis(acetylacetonate) dioxomolybdenum, molybdenum isopropoxide, and bis(ethylbenzene) molybdenum—were tested for molybdenum oxide vapor deposition. Quartz crystal microbalance studies were performed to monitor growth. Molybdenum isopropoxide and bis(ethylbenzene) molybdenum achieved linear growth rates 0.01 and 0.08 Å/cycle, respectively, using atomic layer deposition techniques. Negligible MoO_x growth was observed on alumina powder using molybdenum isopropoxide, as determined by inductively coupled plasma optical emission spectroscopy. Bis(ethylbenzene) molybdenum achieved loadings of 0.5, 1.1, and 1.9 Mo/nm"2 on alumina powder after one, two, and five cycles, respectively, using atomic layer deposition techniques. The growth window for bis(ethylbenzene) molybdenum is 135–150 °C. An alternative pulsing strategy was also developed for bis(ethylbenzene) molybdenum that results in higher growth rates in less time compared to atomic layer deposition techniques. The outlined process serves as a methodology for depositing molybdenum oxide for catalytic applications. All as-deposited materials undergo further calcination prior to characterization and testing.

  15. Corrosion Behavior of Pipeline Carbon Steel under Different Iron Oxide Deposits in the District Heating System

    Directory of Open Access Journals (Sweden)

    Yong-Sang Kim

    2017-05-01