WorldWideScience

Sample records for surface reactions lead

  1. Reduced Heat Flux Through Preferential Surface Reactions Leading to Vibrationally and Electronically Excited Product States

    Science.gov (United States)

    2016-03-04

    an ideal gas at a given temperature, pressure, and composition. A more detailed description of this method can be found in: Norman...are generated at random points on a plane above the surface with a frequency corresponding to the flux of an ideal gas through that plane. This plane...to a dissociated gas at a given temperature and pressure. Examples of steady state surfaces for both amorphous SiO2 and crystalline SiO2 (quartz

  2. Computed potential energy surfaces for chemical reactions

    Science.gov (United States)

    Walch, Stephen P.

    1994-01-01

    Quantum mechanical methods have been used to compute potential energy surfaces for chemical reactions. The reactions studied were among those believed to be important to the NASP and HSR programs and included the recombination of two H atoms with several different third bodies; the reactions in the thermal Zeldovich mechanism; the reactions of H atom with O2, N2, and NO; reactions involved in the thermal De-NO(x) process; and the reaction of CH(squared Pi) with N2 (leading to 'prompt NO'). These potential energy surfaces have been used to compute reaction rate constants and rates of unimolecular decomposition. An additional application was the calculation of transport properties of gases using a semiclassical approximation (and in the case of interactions involving hydrogen inclusion of quantum mechanical effects).

  3. Potential energy surfaces for chemical reactions

    International Nuclear Information System (INIS)

    Schaefer, H.F. III.

    1976-01-01

    Research into potential energy surfaces for chemical reactions at Lawrence Berkeley Laboratory during 1976 is described. Topics covered include: the fuzzy interface between surface chemistry catalysis and organometallic chemistry; potential energy surfaces for elementary fluorine hydrogen reactions; structure, energetics, and reactivity of carbenes; and the theory of self-consistent electron pairs

  4. Theoretical aspects of surface reactions

    Science.gov (United States)

    Nørskov, J. K.; Stoltze, P.

    1987-10-01

    A short review is given of our present understanding of the trends in the chemisorption energies and activation energies for dissociation of simple gas molecules on the transition metals. The effect of adsorbed alkali atoms on the activation energy for dissociation is also discussed. This is then used to explain the trends in activity along the transition metal rows and the promoting effect of K for the ammonia synthesis reaction. The basis for the description is the development of a kinetic model for the ammonia synthesis which can describe quantitatively the macroscopic kinetics of a commercial catalyst under industrial conditions. The model relates the reaction rate directly to the properties of the chemisorbed reactants, intermediates and product as measured for model single crystal systems under ultrahigh vacuum conditions.

  5. Computed potential energy surfaces for chemical reactions

    Science.gov (United States)

    Walch, Stephen P.; Levin, Eugene

    1993-01-01

    A new global potential energy surface (PES) is being generated for O(P-3) + H2 yields OH + H. This surface is being fit using the rotated Morse oscillator method, which was used to fit the previous POL-CI surface. The new surface is expected to be more accurate and also includes a much more complete sampling of bent geometries. A new study has been undertaken of the reaction N + O2 yields NO + O. The new studies have focused on the region of the surface near a possible minimum corresponding to the peroxy form of NOO. A large portion of the PES for this second reaction has been mapped out. Since state to state cross sections for the reaction are important in the chemistry of high temperature air, these studies will probably be extended to permit generation of a new global potential for reaction.

  6. Chemical Reactions at Surfaces. Final Progress Report

    Energy Technology Data Exchange (ETDEWEB)

    Freud, Hans-Joachim [Max-Planck-Gesellschaft, Berlin (Germany). Fritz-Haber-Inst.

    2003-02-21

    The Gordon Research Conference (GRC) on Chemical Reactions at Surfaces was held at Holiday Inn, Ventura, California, 2/16-21/03. Emphasis was placed on current unpublished research and discussion of the future target areas in this field.

  7. Screened Thermonuclear Reaction Rates on Magnetar Surfaces

    International Nuclear Information System (INIS)

    Hong-Lin, Liu; Zhi-Quan, Luo; Jing-Jing, Liu; Xiang-Jun, Lai

    2008-01-01

    Improving Salpeter's method, we discuss the effect of superstrong magnetic fields (such as those of magnetars) on thermonuclear reaction rates. These most interesting reactions, including the hydrogen burning by the CNO cycle and the helium burning by the triple alpha reaction, are investigated as examples on the magnetar surfaces. The obtained result shows that the superstrong magnetic fields can increase the thermonuclear reaction rates by many orders of magnitude. The enhancement may have significant influence for further study research of the magnetars, especially for the x-ray luminosity observation and the evolution of magnetars. (geophysics, astronomy, and astrophysics)

  8. Fundamental study on reaction of lead-bismuth eutectic and sodium. Identification of reaction products and examination of reaction behavior

    International Nuclear Information System (INIS)

    Saito, Jun-ichi; Hirakawa, Yasushi

    2003-09-01

    A simplified secondary sodium cooling system utilizing lead-bismuth eutectic as an intermediate coolant has been selected as one of candidate systems for the 'Feasibility Studies on Commercialized Fast Reactor System'. In this study, fundamental reaction experiments have been performed to understand a reaction behavior between sodium and lead-bismuth. In order to identify the reaction products and to elucidate a reaction process, sampling and X-ray diffraction analysis of the reaction products are carried out. Following results are obtained. (1) The principal reaction products which formed in sodium and lead-bismuth ternary system are BiNa 3 and Pb 4 Na 15 intermetallic compounds. These two reaction products are identified irrespective of either primary sample content or sampling temperature. (2) Pb 3 Na intermetallic compound is identified in the reaction products for the first time. (3) The principal reaction product which formed in sodium and bismuth binary system is BiNa 3 intermetallic compound. (4) The reaction products which formed in sodium and lead binary system consist of various intermetallic compounds of sodium and lead system. Single phase of an intermetallic compound can not be obtained in this system. Based on these X-ray diffraction analyses, reaction process models of formation and dissolution are proposed. (author)

  9. Quasi-elastic neutrino reactions on carbon and lead nuclei

    Science.gov (United States)

    Hedayatipoor, Mohammad; Finlay, James; Massoudi, Soheyl; Nokes, Charles; de Montigny, Marc

    2018-02-01

    We examine neutral-current quasi-elastic neutrino-nucleus reactions on 12C and 208Pb targets. We use the relativistic mean field theory approach to describe the nuclear dynamics. We compute the cross sections for the scattering of 150, 500 and 1000 MeV neutrinos on a 12C target and study the effect of the strange-quark content of the nucleon which appears in these reactions via the isoscalar weak current. We compare our results with the data of the MiniBooNE experiment for mineral oil (CH2). We also calculate the cross section for the quasi-elastic neutron knockout reaction of 20-60 MeV neutrinos on a 208Pb target which is relevant to plans to use lead as a target material in future supernova neutrino detectors.

  10. Ozone-surface reactions in five homes: surface reaction probabilities, aldehyde yields, and trends.

    Science.gov (United States)

    Wang, H; Morrison, G

    2010-06-01

    Field experiments were conducted in five homes during three seasons (summer 2005, summer 2006 and winter 2007) to quantify ozone-initiated secondary aldehyde yields, surface reaction probabilities, and trends any temporal over a 1.5-year interval. Surfaces examined include living room carpets, bedroom carpets, kitchen floors, kitchen counters, and living room walls. Reaction probabilities for all surfaces for all seasons ranged from 9.4 x 10(-8) to 1.0 x 10(-4). There were no significant temporal trends in reaction probabilities for any surfaces from summer 2005 to summer 2006, nor over the entire 1.5-year period, indicating that it may take significantly longer than this period for surfaces to exhibit any 'ozone aging' or lowering of ozone-surface reactivity. However, all surfaces in three houses exhibited a significant decrease in reaction probabilities from summer 2006 to winter 2007. The total yield of aldehydes for the summer of 2005 were nearly identical to that for summer of 2006, but were significantly higher than for winter 2007. We also observed that older carpets were consistently less reactive than in newer carpets, but that countertops remained consistently reactive, probably because of occupant activities such as cooking and cleaning. Ozone reactions taking place at indoor surfaces significantly influence personal exposure to ozone and volatile reaction products. These field studies show that indoor surfaces only slowly lose their ability to react with ozone over several year time frames, and that this is probably because of a combination of large reservoirs of reactive coatings and periodic additions of reactive coatings in the form of cooking, cleaning, and skin-oil residues. When considering exposure to ozone and its reaction products and in the absence of dramatic changes in occupancy, activities or furnishings, indoor surface reactivity is expected to change very slowly.

  11. Elementary Chemical Reactions in Surface Photocatalysis.

    Science.gov (United States)

    Guo, Qing; Zhou, Chuanyao; Ma, Zhibo; Ren, Zefeng; Fan, Hongjun; Yang, Xueming

    2018-02-28

    Photocatalytic hydrogen evolution and organic degradation on oxide materials have been extensively investigated in the last two decades. Great efforts have been dedicated to the study of photocatalytic reaction mechanisms of a variety of molecules on TiO 2 surfaces by using surface science methods under ultra-high vacuum (UHV) conditions, providing fundamental understanding of surface chemical reactions in photocatalysis. In this review, we summarize the recent progress in the study of photocatalysis of several important species (water, methanol, and aldehydes) on different TiO 2 surfaces. The results of these studies have provided us deep insights into the elementary processes of surface photocatalysis and stimulated a new frontier of research in this area. Based on the results of these studies, a new dynamics-based photocatalysis model is also discussed. Expected final online publication date for the Annual Review of Physical Chemistry Volume 69 is April 20, 2018. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

  12. Confining domains lead to reaction bursts: reaction kinetics in the plasma membrane.

    Directory of Open Access Journals (Sweden)

    Ziya Kalay

    Full Text Available Confinement of molecules in specific small volumes and areas within a cell is likely to be a general strategy that is developed during evolution for regulating the interactions and functions of biomolecules. The cellular plasma membrane, which is the outermost membrane that surrounds the entire cell, was considered to be a continuous two-dimensional liquid, but it is becoming clear that it consists of numerous nano-meso-scale domains with various lifetimes, such as raft domains and cytoskeleton-induced compartments, and membrane molecules are dynamically trapped in these domains. In this article, we give a theoretical account on the effects of molecular confinement on reversible bimolecular reactions in a partitioned surface such as the plasma membrane. By performing simulations based on a lattice-based model of diffusion and reaction, we found that in the presence of membrane partitioning, bimolecular reactions that occur in each compartment proceed in bursts during which the reaction rate is sharply and briefly increased even though the asymptotic reaction rate remains the same. We characterized the time between reaction bursts and the burst amplitude as a function of the model parameters, and discussed the biological significance of the reaction bursts in the presence of strong inhibitor activity.

  13. Reactions between monolayer Fe and Si(001) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Hasegawa, M.; Kobayashi, N.; Hayashi, N. [Electrotechnical Lab., Tsukuba, Ibaraki (Japan)

    1997-03-01

    Reactions between 1.5 monolayer(ML) Fe deposited on Si(001)-2x1 and -dihydride surfaces were studied in situ by reflection high-energy electron diffraction and time-of-flight ion scattering spectrometry with the use of 25 keV H ions. The reactions between Fe and Si which were successively deposited on Si(001)-dihydride surface were also studied. After the room temperature deposition Fe reacted with Si(001)-2x1 substrate resulting in the formation of polycrystalline Fe5Si3. By annealing to 560-650degC composite heteroepitaxial layer of both type A and type B {beta}-FeSi2 was formed. On the dihydride surface polycrystalline Fe was observed after 1.5ML Fe deposition at room temperature, and reaction between Fe and Si(001)-dihydride surface is not likely at room temperature. We observed 3D rough surface when we deposited only Fe layer on the dihydride surface and annealed above 700degC. The hydrogen termination of Si(001) surface prevents the deposited Fe from diffusing into the substrate below 500degC, however the annealing above 710degC leads to the diffusion. We obtained 2D ordered surface, which showed 3x3 RHEED pattern as referenced to the primitive unreconstructed Si(001) surface net, when we deposited 2.5ML Fe and 5.8ML Si successively onto Si(001)-dihydride surface and annealed to 470degC. (author)

  14. Removal of lead contaminated dusts from hard surfaces.

    Science.gov (United States)

    Lewis, Roger D; Condoor, Sridhar; Batek, Joe; Ong, Kee Hean; Backer, Denis; Sterling, David; Siria, Jeff; Chen, John J; Ashley, Peter

    2006-01-15

    Government guidelines have widely recommended trisodium phosphate (TSP) or "lead-specific" cleaning detergents for removal of lead-contaminated dust (LCD) from hard surfaces, such as floors and window areas. The purpose of this study was to determine if low-phosphate, non-lead-specific cleaners could be used to efficiently remove LCD from 3 types of surfaces (vinyl flooring, wood, and wallpaper). Laboratory methods were developed and validated for simulating the doping, embedding, and sponge cleaning of the 3 surface types with 4 categories of cleaners: lead-specific detergents, nonionic cleaners, anionic cleaners, and trisodium phosphate (TSP). Vinyl flooring and wood were worn using artificial means. Materials were ashed, followed by ultrasound extraction, and anodic stripping voltammetry (ASV). One-way analysis of variance approach was used to evaluate the surface and detergent effects. Surface type was found to be a significant factor in removal of lead (p < 0.001). Vinyl flooring cleaned better than wallpaper by over 14% and wood cleaned better than wallpaper by 13%. There was no difference between the cleaning action of vinyl flooring and wood. No evidence was found to support the use of TSP or lead-specific detergents over all-purpose cleaning detergents for removal of lead-contaminated dusts. No-phosphate, non-lead-specific detergents are effective in sponge cleaning of lead-contaminated hard surfaces and childhood lead prevention programs should consider recommending all-purpose household detergents for removal of lead-contaminated dust after appropriate vacuuming.

  15. Computed potential energy surfaces for chemical reactions

    Science.gov (United States)

    Walch, Stephen P.

    1988-01-01

    The minimum energy path for the addition of a hydrogen atom to N2 is characterized in CASSCF/CCI calculations using the (4s3p2d1f/3s2p1d) basis set, with additional single point calculations at the stationary points of the potential energy surface using the (5s4p3d2f/4s3p2d) basis set. These calculations represent the most extensive set of ab initio calculations completed to date, yielding a zero point corrected barrier for HN2 dissociation of approx. 8.5 kcal mol/1. The lifetime of the HN2 species is estimated from the calculated geometries and energetics using both conventional Transition State Theory and a method which utilizes an Eckart barrier to compute one dimensional quantum mechanical tunneling effects. It is concluded that the lifetime of the HN2 species is very short, greatly limiting its role in both termolecular recombination reactions and combustion processes.

  16. Surface chemical reactions probed with scanning force microscopy

    NARCIS (Netherlands)

    Werts, M.P L; van der Vegte, E.W.; Hadziioannou, G

    1997-01-01

    In this letter we report the study of surface chemical reactions with scanning force microscopy (SFM) with chemical specificity. Using chemically modified SFM probes, we can determine the local surface reaction conversion during a chemical surface modification. The adhesion forces between a

  17. Highly reversible lead-carbon battery anode with lead grafting on the carbon surface

    KAUST Repository

    Yin, Jian

    2018-03-27

    A novel C/Pb composite has been successfully prepared by electroless plating to reduce the hydrogen evolution and achieve the high reversibility of the anode of lead-carbon battery (LCB). The deposited lead on the surface of C/Pb composite was found to be uniform and adherent to carbon surface. Because lead has been stuck on the surface of C/Pb composite, the embedded structure suppresses the hydrogen evolution of lead-carbon anode and strengthens the connection between carbon additive and sponge lead. Compared with the blank anode, the lead-carbon anode with C/Pb composite displays excellent charge–discharge reversibility, which is attributed to the good connection between carbon additives and lead that has been stuck on the surface of C/Pb composite during the preparation process. The addition of C/Pb composite maintains a solid anode structure with high specific surface area and power volume, and thereby, it plays a significant role in the highly reversible lead-carbon anode.

  18. Aging of residual surface resistance of superconducting lead cavities

    DEFF Research Database (Denmark)

    Danielsen, M.

    1972-01-01

    Measurements of the residual surface resistance of superconducting lead cavities as a function of time during a period of a month showed an oscillating variation. An explanation of the ageing curves is proposed. ©1972 The American Institute of Physics......Measurements of the residual surface resistance of superconducting lead cavities as a function of time during a period of a month showed an oscillating variation. An explanation of the ageing curves is proposed. ©1972 The American Institute of Physics...

  19. Electronic dissipation processes during chemical reactions on surfaces

    CERN Document Server

    Stella, Kevin

    2012-01-01

    Hauptbeschreibung Every day in our life is larded with a huge number of chemical reactions on surfaces. Some reactions occur immediately, for others an activation energy has to be supplied. Thus it happens that though a reaction should thermodynamically run off, it is kinetically hindered. Meaning the partners react only to the thermodynamically more stable product state within a mentionable time if the activation energy of the reaction is supplied. With the help of catalysts the activation energy of a reaction can be lowered. Such catalytic processes on surfaces are widely used in industry. A

  20. Surface ordering during underpotential deposition of lead on copper

    Science.gov (United States)

    Vasiljevic, Natasa

    Recently there has been an increased fundamental and practical interest in studies of ultra-thin films in systems with large atomic size mismatch. For those systems interesting surface stress-driven phenomena are observed, such as surface-confined alloying resulting in self-assembly and ordering of domain structures. The system of interest in the present study is the electrochemical deposition of lead on copper that has an atomic size mismatch of 37%. This system shows no bulk alloying and has been thoroughly examined in ultra high vacuum (UHV). Electrodeposition of lead on copper starts by formation of one epitaxial monolayer in the potential region positive with respect to the reversible potential of bulk lead deposition, a phenomenon known in electrochemistry as underpotential deposition (UPD). On copper (111), in-situ STM results have shown (4 x 4) Moire structure of the complete lead monolayer, a structure identical to that observed in UHV. Following stripping of the lead monolayer, STM results revealed nano-organization of the topmost copper layer. Depending on the solution pH value, different types of nanoscale organization have been observed: (i) a Moire pattern of anion-induced reconstruction of the top copper layer, and (ii) a star pattern dislocation network. Additional experiments in lead-free aerated and deaerated solutions at different pH values suggest that observed structures are results of lead-assisted oxy-anion adsorption in which lead plays a catalytic role. On copper (100), the lead UPD process features coverage-dependent phase behavior identical to that observed in UHV. As a function of lead coverage, phases corresponding to a dilute random alloy phase and ordered surface alloy phase that appears at a surface coverage ratio of three lead atoms to eight copper atoms are observed. With increasing lead coverage, lead dealloys from this ordered phase resulting in the formation of a c(2 x 2) lead overlayer phase that transforms with increasing lead

  1. Investigations on organolead compounds V. Lead---lead bond cleavage reactions of hexaphenyldilead

    NARCIS (Netherlands)

    Willemsens, L.C.; Kerk, G.J.M. van der

    1968-01-01

    It has been shown that a number of nucleophilic and weakly electrophilic reagents (organolithium and organomagnesium compounds, metallic lithium, potassium permanganate, sodium ethoxide, diaryl disulphides, sulphur, ozone, hypochlorous acid and iodine/iodide) selectively cleave the lead---lead bond

  2. CHEMICAL REACTIONS ON ADSORBING SURFACE: KINETIC LEVEL OF DESCRIPTION

    Directory of Open Access Journals (Sweden)

    P.P.Kostrobii

    2003-01-01

    Full Text Available Based on the effective Hubbard model we suggest a statistical description of reaction-diffusion processes for bimolecular chemical reactions of gas particles adsorbed on the metallic surface. The system of transport equations for description of particles diffusion as well as reactions is obtained. We carry out the analysis of the contributions of all physical processes to the formation of diffusion coefficients and chemical reactions constants.

  3. Steric Effects in the Reaction of Aryl Radicals on Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Combellas, Catherine [CNRS-ESPCI; Jiang, Deen [ORNL; Kanoufi, Frederic [CNRS-ESPCI; Pinson, Jean [Alchimer; Podvorica, Fetah [University of Prishtina, Kosovo

    2009-01-01

    Steric effects are investigated in the reaction of aryl radicals with surfaces. The electrochemical reduction of 2-, 3-, 4-methyl, 2-methoxy, 2-ethyl, 2,6-, 2,4-, and 3,5-dimethyl, 4-tert-butyl, 3,5-bis-tert-butyl benzenediazonium, 3,5-bis(trifluoromethyl), and pentafluoro benzenediazonium tetrafluoroborates is examined in acetonitrile solutions. It leads to the formation of grafted layers only if the steric hindrance at the 2- or 2,6-position(s) is small. When the 3,5-positions are crowded with tert-butyl groups, the growth of the organic layer is limited by steric effects and a monolayer is formed. The efficiency of the grafting process is assessed by cyclic voltammetry, X-ray photoelectron spectroscopy, infrared, and ellipsometry. These experiments, together with density functional computations of bonding energies of substituted phenyl groups on a copper surface, are discussed in terms of the reactivity of aryl radicals in the electrografting reaction and in the growth of the polyaryl layer.

  4. A novel surface cleaning method for chemical removal of fouling lead layer from chromium surfaces

    Science.gov (United States)

    Gholivand, Kh.; Khosravi, M.; Hosseini, S. G.; Fathollahi, M.

    2010-10-01

    Most products especially metallic surfaces require cleaning treatment to remove surface contaminations that remain after processing or usage. Lead fouling is a general problem which arises from lead fouling on the chromium surfaces of bores and other interior parts of systems which have interaction with metallic lead in high temperatures and pressures. In this study, a novel chemical solution was introduced as a cleaner reagent for removing metallic lead pollution, as a fouling metal, from chromium surfaces. The cleaner aqueous solution contains hydrogen peroxide (H 2O 2) as oxidizing agent of lead layer on the chromium surface and acetic acid (CH 3COOH) as chelating agent of lead ions. The effect of some experimental parameters such as acetic acid concentration, hydrogen peroxide concentration and temperature of the cleaner solution during the operation on the efficiency of lead cleaning procedure was investigated. The results of scanning electron microscopy (SEM) showed that using this procedure, the lead pollution layer could be completely removed from real chromium surfaces without corrosion of the original surface. Finally, the optimum conditions for the complete and fast removing of lead pollution layer from chromium surfaces were proposed. The experimental results showed that at the optimum condition (acetic acid concentration 28% (V/V), hydrogen peroxide 8% (V/V) and temperature 35 °C), only 15-min time is needed for complete removal of 3 g fouling lead from a chromium surface.

  5. Dynamics of Surface Exchange Reactions Between Au and Pt for HER and HOR

    DEFF Research Database (Denmark)

    Abrams, Billie; Vesborg, Peter Christian Kjærgaard; Bonde, Jacob Lindner

    2009-01-01

    Cyclic voltammetric analysis of the Pt-on-Au system for hydrogen evolution and oxidation reactions (HER/HOR) indicates that dynamic surface exchange reactions occur between Pt and Au. HER/HOR activities depend on the dominant surface species present, which is controllable by the potential applied...... to the system. Bulk Au is not very active for HER/HOR; however, when Pt is deposited onto the Au surface, the system becomes active. The Pt-on-Au system can subsequently be deactivated by cycling to potentials cathodic of the OH-adsorption and Pt-dissolution potentials (~+1.18 V vs normal hydrogen electrode...... reaction is attributed to the lower surface energy of Au relative to Pt causing Au to migrate to the surface. When the system is deactivated, Au is present at the surface. However, Pt migrates back to the surface at higher positive potentials, where PtOx/PtOHx is formed, leading to adsorbate...

  6. Reaction mechanisms for on-surface synthesis of covalent nanostructures

    International Nuclear Information System (INIS)

    Björk, J

    2016-01-01

    In recent years, on-surface synthesis has become an increasingly popular strategy to form covalent nanostructures. The approach has great prospects for facilitating the manufacture of a range of fascinating materials with atomic precision. However, the on-surface reactions are enigmatic to control, currently restricting its bright perspectives and there is a great need to explore how the reactions are governed. The objective of this topical review is to summarize theoretical work that has focused on comprehending on-surface synthesis protocols through studies of reaction mechanisms. (topical review)

  7. Study on the surface reaction of uranium metal in hydrogen atmosphere with XPS

    International Nuclear Information System (INIS)

    Wang Xiaolin; Fu Yibei; Xie Renshou; Zuo Changming; Zhao Chunpei; Chen Hong

    1998-01-01

    The surface reactions of uranium metal in hydrogen atmosphere at 25 degree C and 200 degree C and effects of temperature and carbon monoxide to the hydriding reaction have been studied by X-ray photoelectron spectroscopy (XPS). The reaction between H 2 and uranium metal at 25 degree C leads to the further oxidation of surface layer of metal due to traces of water vapor. At 200 degree C, it may lead to the hydriding reaction of uranium and the hydriding increases with increasing exposure to H 2 in the initial stages. The U4f 7/2 binding energy of UH 3 has been found to be 378.6 eV. Investigation indicates carbon monoxide inhibits both the hydriding reaction and oxidation on the condition of H 2 -CO atmosphere

  8. Centrality in Hadron-Carbon, Hadron-Lead, and Lead-Lead Reactions at 158 GeV/c

    International Nuclear Information System (INIS)

    Rybicki, A.

    2006-08-01

    A study of centrality in p + C, π + C, p + Pb, π + Pb, and Pb + Pb reactions is made. The analysis is performed by means of a simple geometrical model. The mean number of elementary collisions, , is estimated in minimum bias p + C reactions. For the specific case of the carbon nucleus, estimates on appear to depend strongly on assumed nuclear densities. Most realistic of the presented assumptions result in a value of 1.71 ± 0.05. Additional quantities, like predictions for the total inelastic cross-section in p + C reactions, or the number of participants in minimum bias C + C collisions, are given. The analysis is subsequently extended to minimum bias π + C, π + Pb, and p + Pb reactions. Estimates are given for the mean number of elementary collisions as well as for the contribution of single collisions P(1). A comparison with experimental data is made. Finally, the impact parameter dependence of p + Pb and Pb + Pb collisions is discussed. In view of future studies, various aspects of the analysis are discussed in detail; a bibliography of used references is included. (author)

  9. Bond-selective control of a gas-surface reaction

    Science.gov (United States)

    Killelea, Daniel R.

    The prospect of using light to selectively control chemical reactions has tantalized chemists since the development of the laser. Unfortunately, the realization of laser-directed chemistry is frequently thwarted by the randomization of energy within the molecule through intramolecular vibrational energy distribution (IVR). However, recent results showing vibrational mode-specific reactivity on metal surfaces suggest that IVR may not always be complete for gas-surface reactions. Here, we combine molecular beam techniques and direct laser excitation to characterize the bond-specific reactivity of trideuteromethane on a Ni(111) surface. Our results reveal important details about how vibrational energy is distributed in the reactive molecule. We use a molecular beam to direct state-selected trideuteromethane (CHD 3) molecules onto a nickel single crystal sample and use the results we obtain to describe the flow of vibrational energy in the methane-surface reaction complex. We show that CHD3 molecules initially excited to v=1, J=2, K=0 of the v 1 symmetric C-H stretching mode will dissociate exclusively via C-H cleavage on Ni(111). This result highlights the localization of vibrational energy in the reaction complex, despite the presence of many energy exchange channels with the high state-density surface. We demonstrate, for the first time, highly parallel bond-selective control of a heterogeneously catalyzed reaction. We place our results in the context of recent experiments investigating IVR for molecules in both the gas phase and liquid solutions. If IVR is fast on the reaction timescale, vibrational energy would be randomly distributed throughout the nascent methane-surface reaction complex and vibrational mode-specific behavior would not occur. The short timescale of a direct gas-surface collision may explain how the exchange of energy via IVR is limited to only a small subset of the energetic configurations available to the reaction complex. This framework

  10. XPS study on the surface reaction of uranium metal in H2 and H2-CO atmospheres

    International Nuclear Information System (INIS)

    Wang Xiaolin; Fu Yibei; Xie Renshou

    1996-04-01

    The surface reactions of uranium metal in H 2 and H 2 -CO atmospheres and the effects of temperature and CO on the hydriding reaction have been studied by X-ray photoelectron spectroscopy (XPS). The reaction between commercial H 2 and uranium metal at 25 degree C leads mainly to the further oxidation of surface layer of metal due to traces of water vapour. At 200 degree C, it may lead to the hydriding reaction of uranium and the hydriding increases with increasing the exposure of H 2 . Investigation indicates CO inhibits both the hydriding reaction and oxidation on the condition of H 2 -CO atmospheres. (13 refs., 10 figs.)

  11. Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Polo-Garzon, Felipe [Chemical Sciences Division and Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA; Yang, Shi-Ze [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA; Fung, Victor [Department of Chemistry, University of California, Riverside CA 92521 USA; Foo, Guo Shiou [Chemical Sciences Division and Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA; Bickel, Elizabeth E. [Department of Chemical Engineering, Tennessee Technological University, Cookeville TN 38505 USA; Chisholm, Matthew F. [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA; Jiang, De-en [Department of Chemistry, University of California, Riverside CA 92521 USA; Wu, Zili [Chemical Sciences Division and Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA

    2017-07-19

    Although well known in the material science field, surface reconstruction of perovskites has not been implemented in heterogeneous catalysis. In this work, we employ multiple surface sensitive techniques to characterize the surface reconstruction of SrTiO3 (STO) after thermal pretreatment (Sr-enrichment) and chemical etching (Ti-enrichment). We show, using the conversion of 2-propanol as a probe reaction, that the surface reconstruction of STO can be controlled to greatly tune catalytic acid/base properties and consequently the reaction selectivities in a wide range, which are inaccessible using single metal oxides, either SrO or TiO2. Density functional theory (DFT) calculations well explain the selectivity tuning and reaction mechanism on differently reconstructed surfaces of STO. Similar catalytic tunability is also observed on BaZrO3, highlighting the generality of the finding from this work.

  12. Surface sampling concentration and reaction probe

    Science.gov (United States)

    Van Berkel, Gary J; Elnaggar, Mariam S

    2013-07-16

    A method of analyzing a chemical composition of a specimen is described. The method can include providing a probe comprising an outer capillary tube and an inner capillary tube disposed co-axially within the outer capillary tube, where the inner and outer capillary tubes define a solvent capillary and a sampling capillary in fluid communication with one another at a distal end of the probe; contacting a target site on a surface of a specimen with a solvent in fluid communication with the probe; maintaining a plug volume proximate a solvent-specimen interface, wherein the plug volume is in fluid communication with the probe; draining plug sampling fluid from the plug volume through the sampling capillary; and analyzing a chemical composition of the plug sampling fluid with an analytical instrument. A system for performing the method is also described.

  13. Lead isotopes in marine surface sediments reveal historical use of leaded fuel.

    Science.gov (United States)

    Larsen, Martin M; Blusztajn, Jerzy S; Andersen, Ole; Dahllöf, Ingela

    2012-11-01

    Analyses of lead (Pb) isotopes have been performed in terrestrial and fresh water environments to estimate historical uses of leaded fuel, but so far this method has not been employed in studies of world-wide marine surface sediments. We analyzed Pb and its isotopes in 23 surface sediments from four continents collected during the Galathea 3 expedition in 2006-2007. To enhance the anthropogenic signal, a partial digestion using nitric acid was performed. The concentrations of Pb, Th, U and Al were determined with an ICP-Quadrupole MS, and Pb-isotope ratios with an ICP-multi-collector MS. The samples could be divided into three groups: Harbor areas in larger cities with concentrations of 150 to 265 mg kg(-1) dry weight, smaller towns with concentrations between 20 and 40 mg kg(-1) dry weight, and remotely located sites with concentrations below 15 mg kg(-1) dry weight. Pb-isotope ratios were compared to literature values for gasoline and local or geological background values, and the contribution of leaded-gasoline to total concentrations was calculated for contaminated sites using both a one-dimensional and a novel two-dimensional (vector) method. The North American sites had Pb-isotope ratios corresponding to the US leaded gasoline, with 24-88% of the Pb from leaded gasoline. Samples from Oceania showed Pb-isotope ratios corresponding to Australian gasoline, with 60% attributed to leaded gasoline in Sydney and 21% in Christchurch. Outside Cape Town, 15 to 46% of Pb in sediments was from leaded gasoline.

  14. 2011 Chemical Reactions at Surfaces Gordon Research Conference

    Energy Technology Data Exchange (ETDEWEB)

    Peter Stair

    2011-02-11

    The Gordon Research Conference on Chemical Reactions at Surfaces is dedicated to promoting and advancing the fundamental science of interfacial chemistry and physics by providing surface scientists with the foremost venue for presentation and discussion of research occurring at the frontiers of their fields.

  15. Supersonic molecular beam experiments on surface chemical reactions.

    Science.gov (United States)

    Okada, Michio

    2014-10-01

    The interaction of a molecule and a surface is important in various fields, and in particular in complex systems like biomaterials and their related chemistry. However, the detailed understanding of the elementary steps in the surface chemistry, for example, stereodynamics, is still insufficient even for simple model systems. In this Personal Account, I review our recent studies of chemical reactions on single-crystalline Cu and Si surfaces induced by hyperthermal oxygen molecular beams and by oriented molecular beams, respectively. Studies of oxide formation on Cu induced by hyperthermal molecular beams demonstrate a significant role of the translational energy of the incident molecules. The use of hyperthermal molecular beams enables us to open up new chemical reaction paths specific for the hyperthermal energy region, and to develop new methods for the fabrication of thin films. On the other hand, oriented molecular beams also demonstrate the possibility of understanding surface chemical reactions in detail by varying the orientation of the incident molecules. The steric effects found on Si surfaces hint at new ways of material fabrication on Si surfaces. Controlling the initial conditions of incoming molecules is a powerful tool for finely monitoring the elementary step of the surface chemical reactions and creating new materials on surfaces. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Lead concentrations and risk exposure assessment in surface soils ...

    African Journals Online (AJOL)

    This study investigated lead concentrations in < 250 μm and < 75 μm of deposited dust and< 2000 μm, < 250 μm, and < 75 μm of surface soils at undeveloped residential lands leased to auto-mechanic artisans for a minimum of ten years and estimated exposure risk for children that will reside on the polluted lands after the ...

  17. Photogenerated carrier-induced reactions on uhv semiconductor surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Osgood, R.M. Jr.

    1992-05-28

    The objective for this experimental work was to examine the reaction mechanisms, half-collision dynamics, and other optically induced chemical effects, that are operable on a well characterized single-crystal semiconductor surface. Of particular interest were reactions induced by charge transfer from the semiconductor surface including hot carrier and thermalized carrier processes. The primary technique to measure the desorbed fragment translational energies was time-of-flight mass-spectroscopy, used in conjunction with a pulsed tunable laser source. The work was carried out in ultrahigh vacuum, thus other surface spectroscopies such as temperature-programmed desorption, (TPD), (LEED), etc. were used as needed. In the project, the photoreactions of several halogen-containing molecules on GaAs(110) surfaces have been investigated. The studies have made the first observations of several new photochemical processes on uhv prepared surfaces including intermolecular charge transfer; desorption by thermal-carrier-induced reactions (including the measurement of coverage-dependent changes in the translational energies of the desorbed products); interferometric oscillation of photoinduced reactions; and self-quenching of thermal carrier reactions on surfaces.

  18. Modeling adsorption and reactions of organic molecules at metal surfaces.

    Science.gov (United States)

    Liu, Wei; Tkatchenko, Alexandre; Scheffler, Matthias

    2014-11-18

    CONSPECTUS: The understanding of adsorption and reactions of (large) organic molecules at metal surfaces plays an increasingly important role in modern surface science and technology. Such hybrid inorganic/organic systems (HIOS) are relevant for many applications in catalysis, light-emitting diodes, single-molecule junctions, molecular sensors and switches, and photovoltaics. Obviously, the predictive modeling and understanding of the structure and stability of such hybrid systems is an essential prerequisite for tuning their electronic properties and functions. At present, density-functional theory (DFT) is the most promising approach to study the structure, stability, and electronic properties of complex systems, because it can be applied to both molecules and solids comprising thousands of atoms. However, state-of-the-art approximations to DFT do not provide a consistent and reliable description for HIOS, which is largely due to two issues: (i) the self-interaction of the electrons with themselves arising from the Hartree term of the total energy that is not fully compensated in approximate exchange-correlation functionals, and (ii) the lack of long-range part of the ubiquitous van der Waals (vdW) interactions. The self-interaction errors sometimes lead to incorrect description of charge transfer and electronic level alignment in HIOS, although for molecules adsorbed on metals these effects will often cancel out in total energy differences. Regarding vdW interactions, several promising vdW-inclusive DFT-based methods have been recently demonstrated to yield remarkable accuracy for intermolecular interactions in the gas phase. However, the majority of these approaches neglect the nonlocal collective electron response in the vdW energy tail, an effect that is particularly strong in condensed phases and at interfaces between different materials. Here we show that the recently developed DFT+vdW(surf) method that accurately accounts for the collective electronic

  19. Synthesis and Characterization of New Surface Active Azo Initiators for Radical Reactions

    Directory of Open Access Journals (Sweden)

    Klaus Tauer

    2000-04-01

    Full Text Available The synthesis of a water soluble azo initiators from 2,2’-azodiisobutyronitrile (AIBN was performed in three steps: reaction of dinitrile with aromatic alcohols in the presence of HCl to form bisiminoesters hydrochlorides which are hydrolyzed to the esters and final regioselective sulfonation of the aromatic esters. The thermal decomposition of the azo initiators obtained leads to formation of two surface active radicals which can start the chain reaction.

  20. Surface passivation of high purity granular metals: zinc, cadmium, lead

    Directory of Open Access Journals (Sweden)

    Pirozhenko L. A.

    2017-10-01

    Full Text Available For the high purity metals (99.9999%, such as zinc, cadmium, and lead, which are widely used as initial components in growing semiconductor and scintillation crystals (CdTe, CdZnTe, ZnSe, (Cd, Zn, Pb WO4, (Cd, Zn, Pb MoO4 et al., it is very important to ensure reliable protection of the surface from oxidation and adsorption of impurities from the atmosphere. The specific features of surface passivation of high purity cadmium, lead and zinc are not sufficiently studied and require specific methodologies for further studies. The use of organic solutions in the schemes of chemical passivation of the investigated metals avoids hydrolysis of the obtained protective films. The use of organic solvents with pure cation and anion composition as the washing liquid prevents chemisorption of ions present in the conventionally used distilled water. This keeps the original purity of the granular metals. Novel compositions of etchants and etching scheme providing simultaneous polishing and passivation of high purity granular Zn, Cd and Pb are developed. Chemical passivation allows storing metals in the normal atmospheric conditions for more than half a year for Zn and Cd and up to 30 days for Pb without changing the state of the surface. The use of the glycerol-DMF solution in the processes for obtaining Pb granules provides self-passivation of metal surfaces and eliminates the additional chemical processing while maintaining the quality of corrosion protection.

  1. Molecular extinction coefficients of lead sulfide and polymerized diaminobenzidine as final reaction products of histochemical phosphatase reactions

    NARCIS (Netherlands)

    van Noorden, C. J.; Jonges, G. N.

    1992-01-01

    Molar extinction coefficients of precipitated lead sulfide (PbS) and polymerized diaminobenzidine (polyDAB) have been determined at wavelengths of 450 nm and 480 nm, respectively, for quantitative histochemical analysis of phosphatase reactions. These values are essential for the conversion of

  2. Ultrafast Coherent Control and Characterization of Surface Reactions using FELs

    International Nuclear Information System (INIS)

    Ogasawara, Hirohito

    2005-01-01

    The microscopic understanding of reactions at surfaces requires an in-depth knowledge of the dynamics of elementary processes on an ultrafast timescale. This can be accomplished using an ultrafast excitation to initiate a chemical reaction and then probe the progression of the reaction with an ultrashort x-ray pulse from the FEL. There is a great potential to use atom-specific spectroscopy involving core levels to probe the chemical nature, structure and bonding of species on surfaces. The ultrashort electron pulse obtained in the linear accelerator to feed the X-ray FEL can also be used for generation of coherent synchrotron radiation in the low energy THz regime to be used as a pump. This radiation has an energy close to the thermal excitations of low-energy vibrational modes of molecules on surfaces and phonons in substrates. The coherent THz radiation will be an electric field pulse with a certain direction that can collectively manipulate atoms or molecules on surfaces. In this respect a chemical reaction can be initiated by collective atomic motion along a specific reaction coordinate. If the coherent THz radiation is generated from the same source as the X-ray FEL radiation, full-time synchronization for pump-probe experiments will be possible. The combination of THz and X-ray spectroscopy could be a unique opportunity for FEL facilities to conduct ultrafast chemistry studies at surfaces

  3. Theoretical Study of Sodium-Water Surface Reaction Mechanism

    Science.gov (United States)

    Kikuchi, Shin; Kurihara, Akikazu; Ohshima, Hiroyuki; Hashimoto, Kenro

    Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using the ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule on the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. It was found that the estimated rate constant of the former was much larger than the latter. The results are the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by Japan Atomic Energy Agency (JAEA) toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR).

  4. Theoretical study of sodium-water surface reaction mechanism

    International Nuclear Information System (INIS)

    Kikuchi, Shin; Kurihara, Akikazu; Ohshima, Hiroyuki; Hashimoto, Kenro

    2012-01-01

    Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using the ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule on the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. It was found that the estimated rate constant of the former was much larger than the latter. The results are the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by Japan Atomic Energy Agency (JAEA) toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR). (author)

  5. Reaction of water vapor with a clean liquid uranium surface

    International Nuclear Information System (INIS)

    Siekhaus, W.

    1985-01-01

    To study the reaction of water vapor with uranium, we have exposed clean liquid uranium surfaces to H 2 O under UHV conditions. We have measured the surface concentration of oxygen as a function of exposure, and determined the maximum attainable surface oxygen concentration X 0 /sup s/ as a function of temperature. We have used these measurements to estimate, close to the melting point, the solubility of oxygen (X 0 /sup b/, -4 ) and its surface segregation coefficient β/sup s/(> 10 3 ). 8 refs., 5 figs., 1 tab

  6. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    International Nuclear Information System (INIS)

    Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing; Gong, Yongkuan

    2016-01-01

    Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH 2 ) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

  7. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing, E-mail: shisq@nwu.edu.cn; Gong, Yongkuan

    2016-11-15

    Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH{sub 2}) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

  8. Ultrafast Coherent Control and Characterization of Surface Reactions using FELs

    CERN Document Server

    Ogasawara, Hirohito; Nordlund, Dennis

    2005-01-01

    The microscopic understanding of surface chemistry requires a detailed understanding of the dynamics of elementary processes at surfaces. The ultrashort electron pulse obtained in the linear accelerator to feed the FEL can be used for generation of coherent synchrotron radiation in the low energy THz regime. With the current parameters for LCLS this corresponds to radiation with energy corresponding to excitations of low-energy vibrational modes of molecules on surfaces or phonons in substrates. The coherent radiation can coherently manipulate atoms or molecules on surfaces. In this respect a chemical reaction can be initiated by coherent atomic motion along a specific reaction coordinate. Since the THz radiation is generated from the same source as the FEL radiation full-time synchronization for pump-probe experiments will be possible. The possibility to perform time-resolved X-ray Emission Spectroscopy (XES) and X-ray Photoelectron Spectroscopy (XPS) measurements as a probe of chemical dynamics is an exciti...

  9. Chemical reaction on solid surface observed through isotope tracer technique

    International Nuclear Information System (INIS)

    Tanaka, Ken-ichi

    1983-01-01

    In order to know the role of atoms and ions on solid surfaces as the partners participating in elementary processes, the literatures related to the isomerization and hydrogen exchanging reaction of olefines, the hydrogenation of olefines, the metathesis reaction and homologation of olefines based on solid catalysts were reviewed. Various olefines, of which the hydrogen atoms were substituted with deuterium at desired positions, were reacted using various solid catalysts such as ZnO, K 2 CO 3 on C, MoS 2 (single crystal and powder) and molybdenum oxide (with various carriers), and the infra-red spectra of adsorbed olefines on catalysts, the isotope composition of reaction products and the production rate of the reaction products were measured. From the results, the bonding mode of reactant with the atoms and ions on solid surfaces, and the mechanism of the elementary process were considered. The author emphasized that the mechanism of the chemical reaction on solid surfaces and the role of active points or catalysts can be made clear to the considerable extent by combining isotopes suitably. (Yoshitake, I.)

  10. Surface reactivity and layer analysis of chemisorbed reaction films in ...

    Indian Academy of Sciences (India)

    Administrator

    Studies on surface reactivity of substrate iron (Fe-particles) were made in the tribo-chemical environment of alkyl octadecenoates. Two alkyl octadecenoates namely ethyl octadecenoate and methyl. 12-hydroxy octadecenoate, slightly different in their chemical nature, were taken for preparing the chemisorbed reaction films ...

  11. Evidence concerning oxidation as a surface reaction in Baltic amber

    DEFF Research Database (Denmark)

    Shashoua, Yvonne

    2012-01-01

    The aim of this study was to provide evidence about oxidation as a surface reaction during degradation of Baltic amber. A clear understanding of the amber-oxygen interaction modalities is essential to develop conservation techniques for museum collections of amber objects. Pellet-shaped samples...

  12. Canard Phenomena in Oscillations of a Surface Oxidation Reaction

    Science.gov (United States)

    Xie, Feng; Han, Maoan; Zhang, Weijiang

    2005-12-01

    In this paper we investigate canard phenomena occurring in oscillations of a surface oxidation reaction which can be modeled by a three-dimensional singularly perturbed system of ordinary differential equations with two fast variables. By using asymptotic methods, we prove the existence of the maximal canard of the mentioned model, and provide sufficient conditions for the existence of stable canard cycles.

  13. Oxygen reduction reaction over silver particles with various morphologies and surface chemical states

    Science.gov (United States)

    Ohyama, Junya; Okata, Yui; Watabe, Noriyuki; Katagiri, Makoto; Nakamura, Ayaka; Arikawa, Hidekazu; Shimizu, Ken-ichi; Takeguchi, Tatsuya; Ueda, Wataru; Satsuma, Atsushi

    2014-01-01

    The oxygen reduction reaction (ORR) in an alkaline solution was carried out using Ag powders having various particle morphologies and surface chemical states (Size: ca. 40-110 nm in crystalline size. Shape: spherical, worm like, and angular. Surface: smooth with easily reduced AgOx, defective with AgOx, and Ag2CO3 surface layer). The various Ag powders were well characterized by X-ray diffraction, X-ray photoelectron spectroscopy, N2 adsorption, scanning electron microscopy, Raman spectroscopy, cyclic voltammetry, and stripping voltammetry of underpotential-deposited lead. Defective and oxidized surfaces enhanced the Ag active surface area during the ORR. The ORR activity was affected by the morphology and surface chemical state: Ag particles with defective and angular surfaces showed smaller electron exchange number between three and four but showed higher specific activity compared to Ag particles with smooth surfaces.

  14. Competitive reactions of organophosphorus radicals on coke surfaces.

    Science.gov (United States)

    Catak, Saron; Hemelsoet, Karen; Hermosilla, Laura; Waroquier, Michel; Van Speybroeck, Veronique

    2011-10-17

    The efficacy of organophosphorus radicals as anticoking agents was subjected to a computational study in which a representative set of radicals derived from industrially relevant organophosphorus additives was used to explore competitive reaction pathways on the graphene-like coke surface formed during thermal cracking. The aim was to investigate the nature of the competing reactions of different organophosphorus radicals on coke surfaces, and elucidate their mode of attack and inhibiting effect on the forming coke layer by use of contemporary computational methods. Density functional calculations on benzene and a larger polyaromatic hydrocarbon, namely, ovalene, showed that organophosphorus radicals have a high propensity to add to the periphery of the coke surface, inhibiting methyl radical induced hydrogen abstraction, which is known to be a key step in coke growth. Low addition barriers reported for a phosphatidyl radical suggest competitive aptitude against coke formation. Moreover, organophosphorus additives bearing aromatic substituents, which were shown to interact with the coke surface through dispersive π-π stacking interactions, are suggested to play a nontrivial role in hindering further stacking among coke surfaces. This may be the underlying rationale behind experimental observation of softer coke in the presence of organophosphorus radicals. The ultimate goal is to provide information that will be useful in building single-event microkinetic models. This study presents pertinent information on potential reactions that could be taken up in these models. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Polymer surface engineering via thiol-mediated reactions

    Science.gov (United States)

    Hensarling, Ryan Matthew

    Synthesis of polymer brushes to decorate a surface with desired functionality typically involves surface-initiated polymerization (SIP) of functional, but non-reactive monomers. This approach suffers major drawbacks associated with synthesizing sufficiently thick polymer brushes containing surface-attached polymer chains of high molecular weight at high grafting density (i.e. cost, synthetic effort and functional group intolerance during polymerization). The research herein seeks to circumvent these limitations by the decoration of surfaces with polymer chains bearing specific pendent functional groups amenable to post-polymerization modification (PPM). In particular, this dissertation leverages PPM via a specific class of click reactions - thiol-click - that 1) enables the rapid generation of a diverse library of functional surfaces from a single substrates precursor, 2) utilizes a structurally diverse range of commercially available or easily attainable reagents, 3) proceeds rapidly to quantitative conversions under mild conditions and 4) opens the door to orthogonal and site-selective functionalization. In the first two studies, radical-mediated thiol-yne and base-catalyzed thiol-isocyanate reactions are demonstrated as modular platforms for the rapid and practical fabrication of highly functional, multicomponent surfaces under ambient conditions. Brush surfaces expressing a three-dimensional configuration of alkyne or isocyanate functionalities were modified with high efficiency and short reaction times using a library of commercially available thiols. In the third study, two routes to multifunctional brush surfaces were demonstrated utilizing orthogonal thiol-click reactions. In the first approach, alkyne-functionalized homopolymer brushes were modified with multiple thiols via a statistical, radical-mediated thiol-yne co-click reaction; and in the second approach, statistical copolymer brushes carrying two distinctly-addressable reactive moieties were

  16. Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons.

    Science.gov (United States)

    Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A; Wäckerlin, Aneliia; Meyer, Ernst

    2017-03-22

    Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C 18 H 12 ) on a Gd 2 O 3 . Our study evidences a novel effect - oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level.

  17. Recyclable surfaces for amine conjugation chemistry via redox reaction

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Inseong; Yeo, Woon Seok [Dept. of Bioscience and Biotechnology, Bio/Molecular Informatics Center, Konkuk University, Seoul (Korea, Republic of); Bae, Se Won [Green Materials and Process Group, Research Institute of Sustainable Manufacturing System, Korea Institute of Industrial Technology, Cheonan (Korea, Republic of)

    2017-02-15

    In this study, we extended this strategy to present a switchable surface that allows surface functionalization and removal of functional groups repeatedly. The substrate presenting a benzoquinone acid group is first used to immobilize with an amine-containing (bio)molecule using well-known conjugation chemistry. The benzoquinone group is then converted to the corresponding hydroquinone by treating with a reducing agent. We have described a strategy for the dynamic control of surface properties with recyclability via a simple reduction/ oxidation reaction. A stimuli-responsive quinone derivative was harnessed for the repeated immobilization and release of (bio)molecules, and thus, for the repeated dynamic change of the surface properties according to the characteristics of the immobilized (bio)molecules.

  18. Method of determining paper-deposited materials, eg. lead, by their reaction with radioactive krypton

    International Nuclear Information System (INIS)

    Tolgyessy, J.; Pruzinec, J.

    1976-01-01

    The invention claims a method of determining substances on a paper carrier based on the substance reaction with 85 Kr gas and the measurement of radioactivity of the kryptonate formed. Lead is shown as an example. Different amounts of lead acetate were deposited on Whatman 2 chromatographic paper as was an unknown sample of Pb salt. The paper was exposed to a 2.5 mCi 85 Kr atmosphere for 48 hours. The activity of the individual spots was then measured, a calibration curve established and the amount of lead in the analyzed sample read-out. (Ha)

  19. Solid-state reactions to synthesize nanostructured lead selenide semiconductor powders by high-energy milling

    Energy Technology Data Exchange (ETDEWEB)

    Rojas-Chavez, H., E-mail: uu_gg_oo@yahoo.com.mx [Centro de Investigacion e Innovacion Tecnologica - IPN, Cerrada de CECATI s/n, Col. Santa Catarina, Del. Azcapotzalco (Mexico) and Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada - IPN, Legaria 694, Col. Irrigacion, Del. Miguel Hidalgo (Mexico); Reyes-Carmona, F. [Facultad de Quimica - UNAM, Circuito de la Investigacion Cientifica s/n, C.U. Del. Coyoacan (Mexico); Jaramillo-Vigueras, D. [Centro de Investigacion e Innovacion Tecnologica - IPN, Cerrada de CECATI s/n, Col. Santa Catarina, Del. Azcapotzalco (Mexico)

    2011-10-15

    Highlights: {yields} PbSe synthesized from PbO instead of Pb powder do not require an inert atmosphere. {yields} During high-energy milling oxygen has to be chemically reduced from the lead oxide. {yields} Solid-state and solid-gas chemical reactions promote both solid and gaseous products. -- Abstract: Both solid-solid and gas-solid reactions have been traced during high-energy milling of Se and PbO powders under vial (P, T) conditions in order to synthesize the PbSe phase. Chemical and thermodynamic arguments are postulated to discern the high-energy milling mechanism to transform PbO-Se micropowders onto PbSe-nanocrystals. A set of reactions were evaluated at around room temperature. Therefore an experimental campaign was designed to test the nature of reactions in the PbO-Se system during high-energy milling.

  20. Computed Potential Energy Surfaces and Minimum Energy Pathway for Chemical Reactions

    Science.gov (United States)

    Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

    1994-01-01

    Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NO and soot formation in hydrocarbon combustion are discussed.

  1. Effect of surface structure on catalytic reactions: A sum frequency generation surface vibrational spectroscopy study

    Energy Technology Data Exchange (ETDEWEB)

    McCrea, Keith Ryan [Univ. of California, Berkeley, CA (United States)

    2001-01-01

    In the results discussed above, it is clear that Sum Frequency Generation (SFG) is a unique tool that allows the detection of vibrational spectra of adsorbed molecules present on single crystal surfaces under catalytic reaction conditions. Not only is it possible to detect active surface intermediates, it is also possible to detect spectator species which are not responsible for the measured turnover rates. By correlating high-pressure SFG spectra under reaction conditions and gas chromatography (GC) kinetic data, it is possible to determine which species are important under reaction intermediates. Because of the flexibility of this technique for studying surface intermediates, it is possible to determine how the structures of single crystal surfaces affect the observed rates of catalytic reactions. As an example of a structure insensitive reaction, ethylene hydrogenation was explored on both Pt(111) and Pt(100). The rates were determined to be essentially the same. It was observed that both ethylidyne and di-σ bonded ethylene were present on the surface under reaction conditions on both crystals, although in different concentrations. This result shows that these two species are not responsible for the measured turnover rate, as it would be expected that one of the two crystals would be more active than the other, since the concentration of the surface intermediate would be different on the two crystals. The most likely active intermediates are weakly adsorbed molecules such as π-bonded ethylene and ethyl. These species are not easily detected because their concentration lies at the detection limit of SFG. The SFG spectra and GC data essentially show that ethylene hydrogenation is structure insensitive for Pt(111) and Pt(100). SFG has proven to be a unique and excellent technique for studying adsorbed species on single crystal surfaces under high-pressure catalytic reactions. Coupled with kinetic data obtained from gas chromatography measurements, it can give

  2. Computed Potential Energy Surfaces and Minimum Energy Pathways for Chemical Reactions

    Science.gov (United States)

    Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

    1994-01-01

    Computed potential energy surfaces are often required for computation of such parameters as rate constants as a function of temperature, product branching ratios, and other detailed properties. For some dynamics methods, global potential energy surfaces are required. In this case, it is necessary to obtain the energy at a complete sampling of all the possible arrangements of the nuclei, which are energetically accessible, and then a fitting function must be obtained to interpolate between the computed points. In other cases, characterization of the stationary points and the reaction pathway connecting them is sufficient. These properties may be readily obtained using analytical derivative methods. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method to obtain accurate energetics, gives usefull results for a number of chemically important systems. The talk will focus on a number of applications including global potential energy surfaces, H + O2, H + N2, O(3p) + H2, and reaction pathways for complex reactions, including reactions leading to NO and soot formation in hydrocarbon combustion.

  3. Effects of Chronic Exposure to Lead Acetate on the Reactions to Painful Stimuli in Mice

    Directory of Open Access Journals (Sweden)

    MK Koohi

    2016-12-01

    Full Text Available Introduction: Influences of lead on functions of many organ systems are known, but less experimental studies has been done on influences over the behavior, including pain sensation. This study was carried out to reveal possible changes in the onset and intensity of reactions to painful stimuli in mice, after long-term exposure to lead acetate. Methods: In this experimental study, 24 adult male albino mice were divided randomly into 3 groups of 8 each. Control group received fresh water ad lib and 2 treated groups received drinking water contaminated by either 5 ppm or 500 ppm of LA for 90 consecutive days. On the day of 91, nociceptive were performed using a hot plate and formalin, to evaluate onset and intensity of  reaction in response to the thermal and chemical pain, respectively. At the end, the animals were euthanized and blood samples were collected for determination of cortisol levels using an ELISA assay. Results: The animals exposed to LA showed a delay in reaction to painful stimuli induced by thermal stimulus by 52% and 59% with low and high doses, respectively. Thermal pain intensity of reactions to was declined by 63% with LA 5 ppm and by 82% with LA 500 ppm (P<0.05. Delayed reaction to chemical stimulus was also prominent in treated groups up to 68% and the pain intensity was declined by 80%, but they were not statistically significant. Blood cortisol levels remained almost unchanged. Conclusion: Delayed reaction to painful stimuli after chronic LA exposure may be considered as a complication which weaken the alarming role of the pain. Further studies regarding the mechanism of action and the extent of the importance of these effects are warranted.

  4. Response Surface Optimization of Lead Azide for Explosive Detonators

    National Research Council Canada - National Science Library

    McCulloh, Ian; Massie, Darrell; Cordaro, Emily

    2006-01-01

    The Armament Research, Development and Engineering Center, Picatinny (ARDEC) has been tasked with developing a new chemical process to produce lead azide, the key explosive ingredient in detonators...

  5. Electrocatalysis of anodic oxygen-transfer reactions at modified lead dioxide electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Hsiao, Yun-Lin.

    1990-09-21

    The electrocatalytic activities were compared for pure and chloride-doped beta-PbO{sub 2} (Cl-PbO{sub 2}) films on gold and platinum substrates. Rate constants were increased significantly for oxidations of Mn{sup 2+}, toluene, benzyl alcohol, dimethylsulphoxide (DMSO) and benzaldehyde in acidic media by the incorporation of Cl{sup {minus}} into the oxide films. These reactions are concluded to occur by the electrocatalytic transfer of oxygen from H{sub 2}O to the reaction products. Results of x-ray diffraction studies indicate the Cl-PbO{sub 2} film continues to have the slightly distorted rutile structure of pure beta-PbO{sub 2}. The observed electrocatalytic phenomena are concluded to be the beneficial consequence of surface defects generated when Cl{sup {minus}} serves for charge compensation within the surface matrix and, thereby, increases the number of surface sites capable of adsorbing hydroxyl radicals which are transferred in the electrocatalytic O-transfer reactions. 91 refs., 44 figs., 10 tabs.

  6. Excitation functions of (n,2n) reactions for stable lead isotopes from reaction threshold to 20 MeV

    International Nuclear Information System (INIS)

    Joseph Jeremiah, J.; Suchiang, Damewan; Jyrwa, B.M.

    2013-01-01

    Highlights: ► Good agreement between the calculated and measured data. ► The Talys code has been used exclusively. ► Effective imaginary potential and level density has been adjusted to obtain an excellent fit. - Abstract: The excitation functions for (n,2n) reactions from reaction threshold to 20 MeV on four stable lead isotopes 204 Pb, 206 Pb, 207 Pb and 208 Pb were calculated using Talys-1.2 nuclear model code, this essentially involves fitting a set of global parameters. An excellent agreement between the calculated and experimental data is obtained. The level densities and effective imaginary potential were studied to obtain the best fit of the excitation functions. The cross sections were calculated by invoking suitable options for global optical model potential, microscopic level densities from Goriely’s Table, Hauser–Feshbach model for equilibrium calculations, the two-component exciton model by Kalbach for pre-equilibrium calculations in the Talys input file. The results of the present study reveal that the theoretical estimation of the cross sections match fairly well with the experimental data (EXFOR database) as well as with the evaluated data files (ENDF/VII.0, JENDL-4.0, CENDL-3.1). This is of importance to the validation of nuclear model approaches with increased predictive power

  7. Double Charged Surface Layers in Lead Halide Perovskite Crystals

    KAUST Repository

    Sarmah, Smritakshi P.

    2017-02-01

    Understanding defect chemistry, particularly ion migration, and its significant effect on the surface’s optical and electronic properties is one of the major challenges impeding the development of hybrid perovskite-based devices. Here, using both experimental and theoretical approaches, we demonstrated that the surface layers of the perovskite crystals may acquire a high concentration of positively charged vacancies with the complementary negatively charged halide ions pushed to the surface. This charge separation near the surface generates an electric field that can induce an increase of optical band gap in the surface layers relative to the bulk. We found that the charge separation, electric field, and the amplitude of shift in the bandgap strongly depend on the halides and organic moieties of perovskite crystals. Our findings reveal the peculiarity of surface effects that are currently limiting the applications of perovskite crystals and more importantly explain their origins, thus enabling viable surface passivation strategies to remediate them.

  8. Potential energy surface of the reaction of imidazole with peroxynitrite: Density functional theory study

    Science.gov (United States)

    Gogonea, Valentin

    This article presents a theoretical investigation of the reaction mechanism of imidazole nitration by peroxynitrite using density functional theory calculations. Understanding this reaction mechanism will help in elucidating the mechanism of guanine nitration by peroxynitrite, which is one of the assumed chemical pathways for damaging DNA in cells. This work focuses on the analysis of the potential energy surface (PES) for this reaction in the gas phase. Calculations were carried out using Hartree-Fock (HF) and density functional theory (DFT) Hamiltonians with double-zeta basis sets ranging from 6-31G(d) to 6-31++G(d,p), and the triple-zeta basis set 6-311G(d). The computational results reveal that the reaction of imidazole with peroxynitrite in gas phase produces the following species: (i) hydroxide ion and 2-nitroimidazole, (ii) hydrogen superoxide ion and 2-nitrosoimidazole, and (iii) water and 2-nitroimidazolide. The rate-determining step is the formation of a short-lived intermediate in which the imidazole C2 carbon is covalently bonded to peroxynitrite nitrogen. Three short-lived intermediates were found in the reaction path. These intermediates are involved in a proton-hopping transport from C2 carbon to the terminal oxygen of the OO moiety of peroxynitrite via the nitroso (ON) oxygen. Both HF and DFT calculations (using the Becke3-Lee-Yang-Parr functional) lead to similar reaction paths for proton transport, but the landscape details of the PES for HF and DFT calculations differ. This investigation shows that the reaction of imidazole with peroxynitrite produces essentially the same types of products (nitro- and nitroso-) as observed experimentally in the reaction of guanine with peroxynitrite, which makes the former reaction a good model to study by computation the essential characteristics of the latter reaction. Nevertheless, the computationally determined activation energy for imidazole nitration by peroxynitrite in the gas phase is 84.1 kcal

  9. Nucleation of reaction-diffusion waves on curved surfaces

    International Nuclear Information System (INIS)

    Kneer, Frederike; Schöll, Eckehard; Dahlem, Markus A

    2014-01-01

    We study reaction-diffusion waves on curved two-dimensional surfaces, and determine the influence of curvature upon the nucleation and propagation of spatially localized waves in an excitable medium modelled by the generic FitzHugh–Nagumo model. We show that the stability of propagating wave segments depends crucially on the curvature of the surface. As they propagate, they may shrink to the uniform steady state, or expand, depending on whether they are smaller or larger, respectively, than a critical nucleus. This critical nucleus for wave propagation is modified by the curvature acting like an effective space-dependent local spatial coupling, similar to diffuson, thus extending the regime of propagating excitation waves beyond the excitation threshold of flat surfaces. In particular, a negative gradient of Gaussian curvature Γ, as on the outside of a torus surface (positive Γ), when the wave segment symmetrically extends into the inside (negative Γ), allows for stable propagation of localized wave segments remaining unchanged in size and shape, or oscillating periodically in size. (paper)

  10. Redox reactions and weak buffering capacity lead to acidification in the Chesapeake Bay.

    Science.gov (United States)

    Cai, Wei-Jun; Huang, Wei-Jen; Luther, George W; Pierrot, Denis; Li, Ming; Testa, Jeremy; Xue, Ming; Joesoef, Andrew; Mann, Roger; Brodeur, Jean; Xu, Yuan-Yuan; Chen, Baoshan; Hussain, Najid; Waldbusser, George G; Cornwell, Jeffrey; Kemp, W Michael

    2017-08-28

    The combined effects of anthropogenic and biological CO 2 inputs may lead to more rapid acidification in coastal waters compared to the open ocean. It is less clear, however, how redox reactions would contribute to acidification. Here we report estuarine acidification dynamics based on oxygen, hydrogen sulfide (H 2 S), pH, dissolved inorganic carbon and total alkalinity data from the Chesapeake Bay, where anthropogenic nutrient inputs have led to eutrophication, hypoxia and anoxia, and low pH. We show that a pH minimum occurs in mid-depths where acids are generated as a result of H 2 S oxidation in waters mixed upward from the anoxic depths. Our analyses also suggest a large synergistic effect from river-ocean mixing, global and local atmospheric CO 2 uptake, and CO 2 and acid production from respiration and other redox reactions. Together they lead to a poor acid buffering capacity, severe acidification and increased carbonate mineral dissolution in the USA's largest estuary.The potential contribution of redox reactions to acidification in coastal waters is unclear. Here, using measurements from the Chesapeake Bay, the authors show that pH minimum occurs at mid-depths where acids are produced via hydrogen sulfide oxidation in waters mixed upward from anoxic depths.

  11. Surface tension and density of binary lead and lead-free Sn-based solders

    Science.gov (United States)

    Kaban, I.; Mhiaoui, S.; Hoyer, W.; Gasser, J.-G.

    2005-12-01

    The surface tension and density of the liquid Sn60Pb40, Sn90Pb10, Sn96.5Ag3.5 and Sn97Cu3 solder alloys (wt%) have been determined experimentally over a wide temperature interval. It is established that the surface tension of liquid Sn90Pb10 is about 7% higher than that of a traditional Sn60Pb40 solder and that the surface tension of Sn96.5Ag3.5 and Sn97Cu3 alloys is about 12% higher than that of Sn60Pb40. The analytical expressions for the temperature dependences of the surface tension and density are given.

  12. Determination of the shapes and sizes of the regions in which in hadron-nucleus collisions reactions leading to the nucleon emission, particle production, and fragment evaporation occur

    International Nuclear Information System (INIS)

    Strugalski, Z.

    1985-01-01

    Shapes and sizes of the regions in target-nuclei in which reactions leading to the nucleon emission, particle production and fragment evaporation occur are determined. The region of nucleon emission is of cylindrical shape, with the diameter as large as two nucleon diameters, centered on the incident hadron course. The reactions leading to the particle production happen predominantly along the incident hadron course in nuclear matter. The fragment evaporation goes from the surface layer of the part of the target-nucleus damaged in nucleon emission process

  13. Some Theoretical and Experimental Insights on the Mechanistic Routes Leading to the Spontaneous Grafting of Gold Surfaces by Diazonium Salts.

    Science.gov (United States)

    Berisha, Avni; Combellas, Catherine; Kanoufi, Frédéric; Decorse, Philippe; Oturan, Nihal; Médard, Jérôme; Seydou, Mahamadou; Maurel, François; Pinson, Jean

    2017-09-05

    The spontaneous grafting of diazonium salts on gold may involve the carbocation obtained by heterolytic dediazonation and not necessarily the radical, as usually observed on reducing surfaces. The mechanism is addressed on the basis of DFT calculations and experiments carried out under conditions where the carbocation and the radical are produced selectively. The calculations indicate that the driving force of the reaction leading from a gold cluster, used as a gold model surface, and the carbocation to the modified cluster is higher than that of the analogous reaction starting from the radical. The experiments performed under conditions of heterolytic dediazonation show the formation of thin films on the surface of gold. The grafting of a carbocation is therefore possible, but a mechanism where the cleavage of the Ar-N bond is catalyzed by the surface of gold cannot be excluded.

  14. Asian industrial lead inputs to the North Pacific evidenced by lead concentrations and isotopic compositions in surface waters and aerosols.

    Science.gov (United States)

    Gallon, Céline; Ranville, Mara A; Conaway, Christopher H; Landing, William M; Buck, Clifton S; Morton, Peter L; Flegal, A Russell

    2011-12-01

    Recent trends of atmospheric lead deposition to the North Pacific were investigated with analyses of lead in aerosols and surface waters collected on the fourth Intergovernmental Oceanographic Commission Contaminant Baseline Survey from May to June, 2002. Lead concentrations of the aerosols varied by 2 orders of magnitude (0.1-26.4 pmol/m(3)) due in part to variations in dust deposition during the cruise. The ranges in lead aerosol enrichment factors relative to iron (1-119) and aluminum (3-168) were similar, evidencing the transport of Asian industrial lead aerosols across the North Pacific. The oceanic deposition of some of those aerosols was substantiated by the gradient of lead concentrations of North Pacific waters, which varied 3-fold (32.7-103.5 pmol/kg), were highest along with the Asian margin of the basin, and decreased eastward. The hypothesized predominance of Asian industrial lead inputs to the North Pacific was further corroborated by the lead isotopic composition of ocean surface waters ((206)Pb/(207)Pb = 1.157-1.169; (208)Pb/(206)Pb = 2.093-2.118), which fell within the range of isotopic ratios reported in Asian aerosols that are primarily attributed to Chinese industrial lead emissions.

  15. Chemical surface reactions by click chemistry: coumarin dye modification of 11-bromoundecyltrichlorosilane monolayers

    International Nuclear Information System (INIS)

    Haensch, Claudia; Hoeppener, Stephanie; Schubert, Ulrich S

    2008-01-01

    The functionalization of surfaces and the ability to tailor their properties with desired physico-chemical functions is an important field of research with a broad spectrum of applications. These applications range from the modification of wetting properties, over the alteration of optical properties, to the fabrication of molecular electronic devices. In each of these fields, it is of specific importance to be able to control the quality of the layers with high precision. The present study demonstrates an approach that utilizes the 1,3-dipolar cycloaddition of terminal acetylenes to prepare triazole-terminated monolayers on different substrates. The characterization of the precursor monolayers, the optimization of the chemical surface reactions as well as the clicking of a fluorescent dye molecule on such azide-terminated monolayers was carried out. A coumarin 343 derivative was utilized to discuss the aspects of the functionalization approach. Based on this approach, a number of potential surface reactions, facilitated via the acetylene-substituted functional molecules, for a broad range of applications is at hand, thus leading to numerous possibilities where surface modifications are concerned. These modifications can be applied on non-structured surfaces of silicon or glass or can be used on structured surfaces. Various possibilities are discussed

  16. Pacing Lead-Induced Granuloma in the Atrium: A Foreign Body Reaction to Polyurethane

    Directory of Open Access Journals (Sweden)

    Shinagawa Yoko

    2013-01-01

    Full Text Available We described a case of an 82-year-old male who presented with a granuloma entrapping the polyurethane-coated pacing lead at the site of contact on the atrium. He had been paced for 8 years without symptoms or signs suggestive of an allergic reaction to the pacemaker system and died from thrombosis of the superior mesenteric artery and heart failure. A histological examination of the nodule showed an incidental granuloma with multinucleated giant cells. No granuloma was found in the heart or the lung.

  17. Lead Concentrations and Risk Exposure Assessment in Surface ...

    African Journals Online (AJOL)

    ADOWIE PERE

    µm, < 250 µm, and < 75 µm of surface soils at undeveloped residential lands leased to auto-mechanic artisans for a minimum of ten years and estimated exposure risk for children that will reside on the polluted lands after the lease periods. Soil-Pb levels ranges obtained were ... Other factors considered were closeness to.

  18. Self-activated, self-limiting reactions on Si surfaces

    DEFF Research Database (Denmark)

    Morgen, Per; Hvam, Jeanette; Bahari, Ali

    , and the temperatures vary from room temperature to 10000C.The growth is in these cases self-limiting, with the optimal oxide thickness around 0.7-0.8 nm, at 5000C, and up to a few nm for nitride. The self-limiting oxide case was recently predicted by Alex Demkov in a structural optimization to minimise the total...... energy of an oxide system, which happened for an ordered structure, at a thickness of 0.7-0.8 nm. Thus this thin oxide structure has definite crystalline features. We have closely monitored the reaction kinetics with normal x-ray induced photoelectron spectroscopies, and also the structure, composition...... and electrical properties of the system, with surface sensitive, high resolution core level photoelectron spectroscopy. The growth kinetics is well fitted by a Hill function, with parameters, which give information about the character of the process. This function describes a self-activated process. Thus...

  19. Reactions of substituted aromatic molecules on the silicon(001) surface

    Science.gov (United States)

    Coutler, Sarah Kathryn

    Organic molecules possess unique physical and electronic properties that could be incorporated as components in new technologies, such as molecular electronics, biosensors and DNA chip arrays. While the properties of individual molecules often can be measured and predicted, the technological value of organic molecules for these types of applications requires the ability to understand and manipulate how physical and electronic properties are affected by bonding to a surface. Consequently, integration of organic systems with existing silicon-based technology necessitates a thorough investigation of the interfacial chemistry involved in adsorption processes. On a molecular scale, the delocalized electrons of a conjugated system could be used to carry charge from one point to another. Therefore, the interaction of pi-conjugated molecules with the technologically important Si(001) surface is of particular interest. X-ray Photoelectron Spectroscopy (XPS), Scanning Tunneling Microscopy (STM) and Fourier Transform Infrared (FTIR) Spectroscopy were used to investigate the bonding selectivity of several model aromatic molecules. Analysis of the infrared spectra of benzene, toluene and xylene suggest that these simple aromatic molecules covalently bond with the Si(001) surface, resulting in a loss of aromaticity. Studies of aromatic rings with other, more reactive substituent groups containing sulfur, oxygen, nitrogen, iodine or carbon atoms, indicate that the majority of these molecules preferentially adsorb to the surface through the substituent group. Careful consideration of the role played by both the electron-rich substituent groups and the silicon dimers in controlling selectivity leads to new insights regarding adsorption mechanisms. This knowledge, in turn, provides a method for selecting and designing molecules that will preferentially chemisorb on the Si(001) surface in a highly predictable manner. Preliminary studies correlating the chemical identity of the

  20. Lead

    Science.gov (United States)

    ... about the health effects of lead in drinking water The law mandates no-lead products for drinking water after ... Waste, and Cleanup Lead Mold Pesticides Radon Science Water A-Z Index Laws & Regulations By Business Sector By Topic Compliance Enforcement ...

  1. [Influence of Reaction Time on Titanate Nanomaterials and Its Adsorptioi Capability for Lead in Aqueous Solutions].

    Science.gov (United States)

    Fan, Gong-duan; Chen, Li-ru; Lin, Ru-jing; Lin, Qian; Su, Zhao-yue; Lin, Xiu-yong

    2016-02-15

    Titanate nanomaterials (TNs) were synthesized via a simple hydrothermal method using TiO2 (ST-01) and NaOH as the raw materials, and presented different morphologies by adjusting the reaction time. The physico-chemical properties of the as-prepared TNs, such as morphology, structure, surface area, and chemical composition were characterized by XRD, SEM and BET. The adsorption capability and rules of Pb(II) in aqueous solutions were tested in the static system. The results showed that the TNs prepared with 12-72 h reaction time were pure monoclinic phase titanate and their specific surface areas were in the range from 243.05 m2 x g(-1) to 286.20 m2 x g(-1). TNs with reaction time between 12-36 h mainly showed sheet structure, and those with reaction time higher than 48 h showed linear structure. The adsorption capacity of Pb(II) by TNs-12, TNs-24, TNs-36, TNs-48, TNs-60 and TNs-72 was 479.40, 504.12, 482.00, 388.10, 364.60 and 399.00 mg x g(-1), respectively. The sheet TNs had a better adsorption capacity than the linear TNs. TNs-24 had the highest adsorbing capacity. The adsorption kinetics of Pb(II) by TNs-24 followed the pseudo-second-order model, and the equilibrium data was best fitted with the Langmuir isotherm model. The equilibrium adsorption time of TNs-24 was 120 min, and the adsorption was an exothermic process, with a high adsorption capacity at low temperature or room temperature; the optimal adsorption pH was 5.0. When pH was 1.0, the desorption rate of TNs-24 could reach 99.00%, and the removal efficiency of Pb(II) by regenerated TNs was still more than 97% after six times of usage. Therefore, TNs could efficiently remove Pb(II) in aqueous solutions, and the optimal reaction time should be controlled to 12-24 h. When Cd(II) or Ni(II) existed in the solution, the equilibrium adsorption capacity and removal rate of TNs-24 were decreased. The adsorption mechanism was mainly ion-exchanged between Pb(II) and H+/Na+ in TNs.

  2. Ultralow friction induced by tribochemical reactions: a novel mechanism of lubrication on steel surfaces.

    Science.gov (United States)

    Li, Ke; Amann, Tobias; Walter, Michael; Moseler, Michael; Kailer, Andreas; Rühe, Jürgen

    2013-04-30

    The tribological properties of two steel surfaces rubbing against each other are measured while they are in contact with 1,3-diketones of varying structure. Such systems show after a short running-in period ultralow friction properties with a coefficient of friction of as low as μ = 0.005. It is suggested that the extremely favorable friction properties are caused by a tribochemical reaction between the 1,3-diketones and the steel surfaces, leading to formation of a chelated iron-diketo complex. The influence of temperature and the molecular structure of the 1,3 diketo-lubricants onto the friction properties of the system is elucidated under both static and dynamic conditions. With progression of the tribochemical reaction, the sliding surfaces become very conformal and smooth, so that the pressure is greatly reduced and further wear is strongly reduced. All iron particles potentially generated by wear during the initial running-in period are completely dissolved through complex formation. It is proposed that the tribochemical polishing reaction causes a transition from boundary lubrication to fluid lubrication.

  3. The synthesis of PdPt/carbon paper via surface limited redox replacement reactions for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Motsoeneng, RG

    2015-09-01

    Full Text Available Surface-limited redox replacement reactions using the electrochemical atomic layer deposition (EC-ALD) technique were used to synthesize PdPt bimetallic electrocatalysts on carbon paper substrate. Electrocatalysts having different Pd:Pt ratio were...

  4. Stochastic surface walking reaction sampling for resolving heterogeneous catalytic reaction network: A revisit to the mechanism of water-gas shift reaction on Cu

    Science.gov (United States)

    Zhang, Xiao-Jie; Shang, Cheng; Liu, Zhi-Pan

    2017-10-01

    Heterogeneous catalytic reactions on surface and interfaces are renowned for ample intermediate adsorbates and complex reaction networks. The common practice to reveal the reaction mechanism is via theoretical computation, which locates all likely transition states based on the pre-guessed reaction mechanism. Here we develop a new theoretical method, namely, stochastic surface walking (SSW)-Cat method, to resolve the lowest energy reaction pathway of heterogeneous catalytic reactions, which combines our recently developed SSW global structure optimization and SSW reaction sampling. The SSW-Cat is automated and massively parallel, taking a rough reaction pattern as input to guide reaction search. We present the detailed algorithm, discuss the key features, and demonstrate the efficiency in a model catalytic reaction, water-gas shift reaction on Cu(111) (CO + H2O → CO2 + H2). The SSW-Cat simulation shows that water dissociation is the rate-determining step and formic acid (HCOOH) is the kinetically favorable product, instead of the observed final products, CO2 and H2. It implies that CO2 and H2 are secondary products from further decomposition of HCOOH at high temperatures. Being a general purpose tool for reaction prediction, the SSW-Cat may be utilized for rational catalyst design via large-scale computations.

  5. Interfacial Reaction of Sn-Ag-Cu Lead-Free Solder Alloy on Cu: A Review

    Directory of Open Access Journals (Sweden)

    Liu Mei Lee

    2013-01-01

    Full Text Available This paper reviews the function and importance of Sn-Ag-Cu solder alloys in electronics industry and the interfacial reaction of Sn-Ag-Cu/Cu solder joint at various solder forms and solder reflow conditions. The Sn-Ag-Cu solder alloys are examined in bulk and in thin film. It then examines the effect of soldering conditions to the formation of intermetallic compounds such as Cu substrate selection, structural phases, morphology evolution, the growth kinetics, temperature and time is also discussed. Sn-Ag-Cu lead-free solder alloys are the most promising candidate for the replacement of Sn-Pb solders in modern microelectronic technology. Sn-Ag-Cu solders could possibly be considered and adapted in miniaturization technologies. Therefore, this paper should be of great interest to a large selection of electronics interconnect materials, reliability, processes, and assembly community.

  6. Radionuclide production from lead by neutron-induced reactions up to 175 MeV

    CERN Document Server

    Glasser, W; Neumann, S; Schuhmacher, H; Dangendorf, V; Nolte, R; Herpers, U; Smirnov, A N; Ryzhov, I; Prokofiev, A V; Malmborg, P; Kollar, D; Meulders, J P

    2002-01-01

    Activation experiments with quasi mono-energetic neutrons produced by the /sup 7/Li(p, n)/sup 7/Be reaction with proton-energies between 36.4 and 178.8 MeV were performed at UCL and TSL in order to determine cross sections for the production of residual nuclides from 13 target elements. The targets were irradiated in well-characterized neutron fields monitored by various measuring techniques. Residual nuclide abundances were determined by gamma -spectrometry. Cross sections were derived from them by an iterative method based on measured and calculated neutron spectra inside the target stacks and starting from "guess" excitation functions calculated by the ALICE- IPPE code. First results for the target element lead are presented. (20 refs).

  7. Oxygen isotope exchange between metabolites and water during biochemical reactions leading to cellulose synthesis

    International Nuclear Information System (INIS)

    Sternberg, L. da S.L.; DeNiro, M.J.; Savidge, R.A.

    1986-01-01

    Cellulose was produced heterotrophically from different carbon substrates by carrot tissue cultures and Acetobacter xylinum (a cellulose-producing bacterium) and by castor bean seeds germinated in the dark, in each case in the presence of water having known concentration of oxygen-18 ( 18 O). We used the relationship between the amount of 18 O in the water and in the cellulose that was synthesized to determine the number and 18 O content of the substrate oxygens that exchanged with water during the reactions leading to cellulose synthesis. Our observations support the hypothesis that oxygen isotope ratios of plant cellulose are determined by isotopic exchange occurring during hydration of carbonyl groups of the intermediates of cellulose synthesis. (author)

  8. Pd-catalyzed coupling reaction on the organic monolayer: Sonogashira reaction on the silicon (1 1 1) surfaces

    International Nuclear Information System (INIS)

    Qu Mengnan; Zhang Yuan; He Jinmei; Cao Xiaoping; Zhang Junyan

    2008-01-01

    Iodophenyl-terminated organic monolayers were prepared by thermally induced hydrosilylation on hydrogen-terminated silicon (1 1 1) surfaces. The films were characterized by ellipsometry, contact-angle goniometry, and X-ray photoelectron spectroscopy (XPS). To modify the surface chemistry and the structure of the monolayers, the Sonogashira coupling reaction was performed on the as-prepared monolayers. The iodophenyl groups on the film surfaces reacted with 1-ethynyl-4-fluorobenzene or the 1-chloro-4-ethynylbenzene under the standard Sonogashira reaction conditions for attaching conjugated molecules via the formation of C-C bonds. It is expected that this surface coupling reaction will present a new method to modify the surface chemistry and the structure of monolayers

  9. Theoretical Study on Reaction Pathways Leading to CO and CO2in the Pyrolysis of Resorcinol.

    Science.gov (United States)

    Furutani, Yuki; Kudo, Shinji; Hayashi, Jun-Ichiro; Norinaga, Koyo

    2017-01-26

    Possible pathways for the pyrolysis of resorcinol with the formation of CO and CO 2 as final products were proposed and evaluated using ab initio calculations. Our experimental study revealed that large quantities of CO 2 are generated in the pyrolysis of 1,3-dihydroxybenzene (resorcinol), while the pyrolysis of the dihydroxybenzene isomers 1,2-dihydroxybenzene (catechol) and 1,4-dihydroxybenzene (hydroquinone) produces little CO 2 . The fate of oxygen atoms in catechol and hydroquinone was essentially the formation of CO. In the proposed pathways, the triplet ground state m-benzoquinone was generated initially from simultaneous cleavage of the two O-H bonds in resorcinol. Subsequently, the direct cleavage of a C-C bond of the m-benzoquinone diradical yields 2-oxidanylcyclopenta-2,4-dien-1-yl-methanone, which can be converted via two channels: release of CO from the aldehyde radical group and combination of the ketone radical and carbon atom in the aldehyde radical group to form the 6-oxabicyclo[3.2.0]hepta-2,4-dien-7-one, resulting in the release of CO 2 . Potential energy surfaces along the proposed reaction pathways were calculated employing the CBS-QB3 method, and the rate constants at the high-pressure limit were also evaluated based on transition-state theory to assess the feasibility of the proposed reaction pathways.

  10. Nicotiana tabacum as model for ozone - plant surface reactions

    Science.gov (United States)

    Jud, Werner; Fischer, Lukas; Wohlfahrt, Georg; Tissier, Alain; Canaval, Eva; Hansel, Armin

    2015-04-01

    Elevated tropospheric ozone concentrations are considered a toxic threat to plants, responsible for global crop losses with associated economic costs of several billion dollars per year. The ensuing injuries have been related to the uptake of ozone through the stomatal pores and oxidative effects damaging the internal leaf tissue. A striking question of current research is the environment and plant specific partitioning of ozone loss between gas phase, stomatal or plant surface sink terms. Here we show results from ozone fumigation experiments using various Nicotiana Tabacum varieties, whose surfaces are covered with different amounts of unsaturated diterpenoids exuded by their glandular trichomes. Exposure to elevated ozone levels (50 to 150 ppbv) for 5 to 15 hours in an exceptionally clean cuvette system did neither result in a reduction of photosynthesis nor caused any visible leaf damage. Both these ozone induced stress effects have been observed previously in ozone fumigation experiments with the ozone sensitive tobacco line Bel-W3. In our case ozone fumigation was accompanied by a continuous release of oxygenated volatile organic compounds, which could be clearly associated to their condensed phase precursors for the first time. Gas phase reactions of ozone were avoided by choosing a high enough gas exchange rate of the plant cuvette system. In the case of the Ambalema variety, that is known to exude only the diterpenoid cis-abienol, ozone fumigation experiments yield the volatiles formaldehyde and methyl vinyl ketone (MVK). The latter could be unequivocally separated from isomeric methacrolein (MACR) by the aid of a Selective Reagent Ion Time-of-Flight Mass Spectrometer (SRI-ToF-MS), which was switched every six minutes from H3O+ to NO+ primary ion mode and vice versa. Consistent with the picture of an ozone protection mechanism caused by reactive diterpenoids at the leaf surface are the results from dark-light experiments. The ozone loss obtained from the

  11. Chemical reaction surface vibrational frequencies evaluated in curvilinear internal coordinates: Application to H + CH(4) H(2) + CH(3).

    Science.gov (United States)

    Banks, Simon T; Clary, David C

    2009-01-14

    We consider the general problem of vibrational analysis at nonglobally optimized points on a reduced dimensional reaction surface. We discuss the importance of the use of curvilinear internal coordinates to describe molecular motion and derive a curvilinear projection operator to remove the contribution of nonzero gradients from the Hessian matrix. Our projection scheme is tested in the context of a two-dimensional quantum scattering calculation for the reaction H + CH(4) --> H(2) + CH(3) and its reverse H(2) + CH(3) --> H + CH(4). Using zero-point energies calculated via rectilinear and curvilinear projections we construct two two-dimensional, adiabatically corrected, ab initio reaction surfaces for this system. It is shown that the use of curvilinear coordinates removes unphysical imaginary frequencies observed with rectilinear projection and leads to significantly improved thermal rate constants for both the forward and reverse reactions.

  12. Reliable and efficient reaction path and transition state finding for surface reactions with the growing string method.

    Science.gov (United States)

    Jafari, Mina; Zimmerman, Paul M

    2017-04-15

    The computational challenge of fast and reliable transition state and reaction path optimization requires new methodological strategies to maintain low cost, high accuracy, and systematic searching capabilities. The growing string method using internal coordinates has proven to be highly effective for the study of molecular, gas phase reactions, but difficulties in choosing a suitable coordinate system for periodic systems has prevented its use for surface chemistry. New developments are therefore needed, and presented herein, to handle surface reactions which include atoms with large coordination numbers that cannot be treated using standard internal coordinates. The double-ended and single-ended growing string methods are implemented using a hybrid coordinate system, then benchmarked for a test set of 43 elementary reactions occurring on surfaces. These results show that the growing string method is at least 45% faster than the widely used climbing image-nudged elastic band method, which also fails to converge in several of the test cases. Additionally, the surface growing string method has a unique single-ended search method which can move outward from an initial structure to find the intermediates, transition states, and reaction paths simultaneously. This powerful explorative feature of single ended-growing string method is demonstrated to uncover, for the first time, the mechanism for atomic layer deposition of TiN on Cu(111) surface. This reaction is found to proceed through multiple hydrogen-transfer and ligand-exchange events, while formation of H-bonds stabilizes intermediates of the reaction. Purging gaseous products out of the reaction environment is the driving force for these reactions. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  13. Uniform surface modification of diatomaceous earth with amorphous manganese oxide and its adsorption characteristics for lead ions

    Science.gov (United States)

    Li, Song; Li, Duanyang; Su, Fei; Ren, Yuping; Qin, Gaowu

    2014-10-01

    A novel method to produce composite sorbent material compromising porous diatomaceous earth (DE) and surface functionalized amorphous MnO2 is reported. Via a simple in situ redox reaction over the carbonized DE powders, a uniform layer of amorphous MnO2 was anchored onto the DE surface. The hybrid adsorbent was characterized by X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. The batch method has been employed to investigate the effects of surface coating on adsorption performance of DE. According to the equilibrium studies, the adsorption capacity of DE for adsorbing lead ions after MnO2 modification increased more than six times. And the adsorption of Pb2+ on the MnO2 surface is based on ion-exchange mechanism. The developed strategy presents a novel opportunity to prepare composite adsorbent materials by integrating nanocrystals with porous matrix.

  14. How Reactive Metabolites Induce an Immune Response That Sometimes Leads to an Idiosyncratic Drug Reaction.

    Science.gov (United States)

    Cho, Tiffany; Uetrecht, Jack

    2017-01-17

    Little is known with certainty about the mechanisms of idiosyncratic drug reactions (IDRs); however, there is substantive evidence that reactive metabolites are involved in most, but not all, IDRs. In addition, evidence also suggests that most IDRs are immune mediated. That raises the question of how reactive metabolites induce an immune response that can lead to an IDR. The dominant hypotheses are the hapten and danger hypotheses. These are complementary hypotheses: a reactive metabolite can act as a hapten to produce neoantigens, and it can also cause cell damage leading to the release of danger-associated molecular pattern molecules that activate antigen presenting cells. Both are required for an immune response. In addition, drugs may induce an immune response through inflammasome activation. We have found examples in which the ability to activate inflammasomes differentiated drugs that cause IDRs from similar drugs that do not. There are other hypotheses that do not involve an immune mechanism such as mitochondrial injury and bile salt export pump (BSEP) inhibition. With some possible exceptions, these hypotheses are unlikely to be able to completely explain IDRs. However, some types of mitochondrial injury or BSEP inhibition could produce danger signals. The major mechanism that protects us from IDRs appears to be immune tolerance. Consistent with this hypothesis, we used checkpoint inhibition to develop the first animal model of idiosyncratic drug-induced liver injury that has the same characteristics as the idiosyncratic injury in humans. This was accomplished by treating Pd-1 -/- mice with anti-CTLA-4 antibodies and amodiaquine. The combination of the Pd-1 -/- mouse and anti-CTLA-4 also unmasks the ability of other drugs such as isoniazid to cause delayed type liver injury. This model should allow rigorous testing of mechanistic hypotheses that was impossible in the past.

  15. Using the Surface ECG to Identify Right Ventricular Pacing Lead Position: A Cautionary Tale.

    Science.gov (United States)

    Kaye, Gerald C; Rowe, Matthew K; Gould, Paul A

    2017-09-01

    Chronic right ventricular (RV) apical pacing may lead to the development of heart failure in some patients. Although pacing of the RV septum has been proposed as an alternative, positioning a lead in the true septum has proven challenging. In addition to fluoroscopy at implant, it has been suggested that 12-lead surface electrocardiogram (ECG) can be used to determine septal lead position; however, studies show this may be inaccurate. We present a case where a change in the ECG QRS axis late after pacemaker insertion with an active fixation lead highlights the difficulties of ECG localization of pacing leads. © 2017 Wiley Periodicals, Inc.

  16. In vitro lead bioaccessibility and phosphate leaching as affected by surface application of phosphoric acid in lead-contaminated soil.

    Science.gov (United States)

    Yang, J; Mosby, D E; Casteel, S W; Blanchar, R W

    2002-11-01

    Phosphate treatment of lead-contaminated soil may be a cost-effective remedial alternative for in situ stabilizing soil Pb and reducing Pb toxicology to human. The leaching behaviors of the P added to soil surface and the effect on subsurface Pb bioaccessibility must be addressed for this remedial technology to be acceptable. A smelter-contaminated soil containing an average of 2,670 mg Pb kg(-1), collected from the Jasper County Superfund Site located in Jasper County, Missouri, was surface treated with 10 g P kg(-1) as phosphoric acid (H(3)PO(4)). Following a simulated column leaching and 90-day treatment of field plots, respectively, bioaccessible Pb, P, and pH in soil profile were measured. Surface treatment using H(3)PO(4) effectively stabilized soil Pb and reduced leachable Pb and the bioaccessibility. Phosphate leached into deeper profile significantly lowered bioaccessible Pb in subsurface. Reduction of Pb bioaccessibility increased as a linear function of increasing soil P. Although surface H(3)PO(4) treatment resulted in an enhanced leaching of added P and may increase potential risk of surface and groundwater pollution, the P leaching under field conditions is very limited. Lime addition following the treatment may reduce the leachability of added P and further immobilize soil Pb.

  17. Quantitative surface analysis using deuteron-induced nuclear reactions

    International Nuclear Information System (INIS)

    Afarideh, Hossein

    1991-01-01

    The nuclear reaction analysis (NRA) technique consists of looking at the energies of the reaction products which uniquely define the particular elements present in the sample and it analysis the yield/energy distribution to reveal depth profiles. A summary of the basic features of the nuclear reaction analysis technique is given, in particular emphasis is placed on quantitative light element determination using (d,p) and (d,alpha) reactions. The experimental apparatus is also described. Finally a set of (d,p) spectra for the elements Z=3 to Z=17 using 2 MeV incident deutrons is included together with example of more applications of the (d,alpha) spectra. (author)

  18. Energy Accommodation from Surface Catalyzed Reactions in Air Plasmas

    Data.gov (United States)

    National Aeronautics and Space Administration — Understanding energy transport at the gas-surface interface between catalytic/reacting surfaces exposed to highly dissociated plasmas remains a significant research...

  19. Capability of LEP-type surfaces to describe noncollinear reactions 2 - Polyatomic systems

    CERN Document Server

    Espinosa-Garcia, Joaquin

    2001-01-01

    In this second article of the series, the popular LEP-type surface for collinear reaction paths and a "bent" surface, which involves a saddle point geometry with a nonlinear central angle, were used to examine the capacity of LEP-type surfaces to describe the kinetics and dynamics of noncollinear reaction paths in polyatomic systems. Analyzing the geometries, vibrational frequencies, curvature along the reaction path (to estimate the tunneling effect and the reaction coordinate-bound modes coupling), and the variational transition- state theory thermal rate constants for the NH//3 + O(**3P) reaction, we found that the "collinear" LEP-type and the "bent" surfaces for this polyatomic system show similar behavior, thus allowing a considerable saving in time and computational effort. This agreement is especially encouraging for this polyatomic system because in the Cs symmetry the reaction proceeds via two electronic states of symmetries **3A prime and **3A double prime , which had to be independently calibrated....

  20. Eight-dimensional quantum reaction rate calculations for the H+CH4 and H2+CH3 reactions on recent potential energy surfaces.

    Science.gov (United States)

    Zhou, Yong; Zhang, Dong H

    2014-11-21

    Eight-dimensional (8D) transition-state wave packet simulations have been performed on two latest potential energy surfaces (PES), the Zhou-Fu-Wang-Collins-Zhang (ZFWCZ) PES [Y. Zhou, B. Fu, C. Wang, M. A. Collins, and D. H. Zhang, J. Chem. Phys. 134, 064323 (2011)] and the Xu-Chen-Zhang (XCZ)-neural networks (NN) PES [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. Reaction rate constants for both the H+CH4 reaction and the H2+CH3 reaction are calculated. Simulations of the H+CH4 reaction based on the XCZ-NN PES show that the ZFWCZ PES predicts rate constants with reasonable high accuracy for low temperatures while leads to slightly lower results for high temperatures, in line with the distribution of interpolation error associated with the ZFWCZ PES. The 8D H+CH4 rate constants derived on the ZFWCZ PES compare well with full-dimensional 12D results based on the equivalent m-ZFWCZ PES, with a maximum relative difference of no more than 20%. Additionally, very good agreement is shown by comparing the 8D XCZ-NN rate constants with the 12D results obtained on the ZFWCZ-WM PES, after considering the difference in static barrier height between these two PESs. The reaction rate constants calculated for the H2+CH3 reaction are found to be in good consistency with experimental observations.

  1. Preparation and Support of a Tap Test on the Leading Edge Surfaces of the Space Shuttle

    Science.gov (United States)

    Bohr, Jerry

    2009-01-01

    This slide presentation reports on a Tap test for the leading edge surfaces of the Space Shuttle. A description of the Wing Leading Edge Impact Detection System (WLEIDS) flight system is given, and the rationale and approach for improving the WLEIDS system. The three phases of the strategy of the test project amd the results of the tests are reviewed.

  2. Performing chemical reactions in virtual capillary of surface tension ...

    Indian Academy of Sciences (India)

    In this article, we report for the first time the performance of a few common laboratory chemical reactions inside such capillaries of STCM. The substrate is of glass slides with lines of ink of permanent marker pen (colored) or clear nail polish. Two such slides placed one against the other and separated by a spacer makes the.

  3. Performing chemical reactions in virtual capillary of surface tension ...

    Indian Academy of Sciences (India)

    The flow paths were fabricated by making parallel lines using permanent marker pen ink or other polymer on glass surfaces. Two mirror image patterned glass plates were then sandwiched one on top of the other, separated by a thin gap - created using a spacer. The aqueous liquid moves between the surfaces by capillary ...

  4. 2013 Chemical reactions at surfaces. Surfaces in Energy and the Environment. Gordon Research Conference and Gordon Research Seminar (April 28 - May 3, 2013 - Les Diablerets, Switzerland)

    Energy Technology Data Exchange (ETDEWEB)

    Stair, Peter C. [Northwestern Univ., Evanston, IL (United States)

    2013-02-03

    presentations on chemistry at solid and liquid surfaces of relevance to catalysis, synthesis, photochemistry, environmental science, and tribology. Topics include: Fundamental Surface Chemistry; Catalysis; Solid Liquid and Aerosol Interfaces; Surface Photochemistry; Synthesis of Surfaces; Environmental Interfaces; Hot Topics in Surface Chemical Reactions; Tribology; Gas-Surface Scattering and Reactions; Novel Materials and Environments.

  5. NATO Advanced Research Workshop on the Mechanisms of Reactions of Organometallic Compounds with Surfaces

    CERN Document Server

    Williams, J

    1989-01-01

    A NATO Advanced Research Workshop on the "Mechanisms of Reactions of Organometallic Compounds with Surfaces" was held in St. Andrews, Scotland in June 1988. Many of the leading international researchers in this area were present at the workshop and all made oral presentations of their results. In addition, significant amounts of time were set aside for Round Table discussions, in which smaller groups considered the current status of mechanistic knowledge, identified areas of dispute or disagreement, and proposed experiments that need to be carried out to resolve such disputes so as to advance our understanding of this important research area. All the papers presented at the workshop are collected in this volume, together with summaries of the conclusions reached at the Round Table discussions. The workshop could not have taken place without financial support from NATO, and donations were also received from Associated Octel, Ltd., STC Ltd., and Epichem Ltd., for which the organisers are very grateful. The orga...

  6. Chemical reactions on platinum-group metal surfaces studied by synchrotron-radiation-based spectroscopy

    International Nuclear Information System (INIS)

    Kondoh, Hiroshi; Nakai, Ikuyo; Nagasaka, Masanari; Amemiya, Kenta; Ohta, Toshiaki

    2009-01-01

    A new version of synchrotron-radiation-based x-ray spectroscopy, wave-length-dispersive near-edge x-ray absorption fine structure (dispersive-NEXAFS), and fast x-ray photoelectron spectroscopy have been applied to mechanistic studies on several surface catalytic reactions on platinum-group-metal surfaces. In this review, our approach using above techniques to understand the reaction mechanism and actual application studies on three well-known catalytic surface reactions, CO oxidation on Pt(111) and Pd(111), NO reduction on Rh(111), and H 2 O formation on Pt(111), are introduced. Spectroscopic monitoring of the progress of the surface reactions enabled us to detect reaction intermediates and analyze the reaction kinetics quantitatively which provides information on reaction order, rate constant, pre-exponential factor, activation energy and etc. Such quantitative analyses combined with scanning tunneling microscopy and kinetic Monte Carlo simulations revealed significant contribution of the adsorbate configurations and their dynamic changes to the reaction mechanisms of the above fundamental catalytic surface reactions. (author)

  7. Skin and surface lead contamination, hygiene programs, and work practices of bridge surface preparation and painting contractors.

    Science.gov (United States)

    Virji, M Abbas; Woskie, Susan R; Pepper, Lewis D

    2009-02-01

    A 2005 regulatory review of the lead in construction standard by the Occupational Safety and Health Administration (OSHA) noted that alternative pathways of exposure can be as significant as inhalation exposure and that noncompliance with the standard pertaining to hygiene facilities and practices was the second most commonly violated section of the standard. Noncompliance with provisions of the standard and unhealthy work and hygiene practices likely increase the likelihood of take-home lead via contaminated clothing, automobiles, and skin, thus contributing to elevated blood lead levels (BLL) among construction workers and their family members. We performed a cross-sectional study of bridge painters working for small contractors in Massachusetts to investigate causes of persistent elevated BLLs and to assess lead exposures. Thirteen work sites were evaluated for a 2-week period during which surface and skin wipe samples were collected and qualitative information was obtained on personal hygiene practices, decontamination and hand wash facilities, and respiratory protection programs. Results showed lead contamination on workers' skin, respirators, personal automobiles, and the decontamination unit, indicating a significant potential for take-home lead exposure. Overall, the geometric mean (GM) skin lead levels ranged from 373 microg on workers' faces at end of shift to 814 microg on hands at break time. The overall GM lead level inside respirators was 143 microg before work and 286 microg after work. Lead contamination was also present inside workers' personal vehicles as well as on surfaces inside the clean side of the decontamination unit. Review of the respiratory protection programs, work site decontamination and hand wash facilities, and personal hygiene practices indicated that these factors had significant impact on skin and surface contamination levels and identified significant opportunities for improving work site facilities and personal practices

  8. High-pressure catalytic reactions over single-crystal metal surfaces

    Science.gov (United States)

    Rodriguez, JoséA.; Wayne Goodman, D.

    1991-11-01

    Studies dealing with high-pressure catalytic reactions over single-crystal surfaces are reviewed. The coupling of an apparatus for the measurement of reaction kinetics at elevated pressures with an ultrahigh vacuum system for surface analysis allows detailed study of structure sensitivity, the effects of promoters and inhibitors on catalytic activity, and, in certain cases, identification of reaction intermediates by post-reaction surface analysis. Examples are provided which demonstrate the relevance of single-crystal studies for modeling the behaviour of high-surface-area supported catalysts. Studies of CO methanation and CO oxidation over single-crystal surfaces provide convincing evidence that these reactions are structure insensitive. For structure-sensitive reactions (ammonia synthesis, alkane hydrogenolysis, alkane isomerization, water-gas shift reaction, etc.) model single-crystal studies allow correlations to be established between surface structure and catalytic activity. The effects of both electronegative (S and P) and electropositive (alkali metals) impurities upon the catalytic activity of metal single crystals for ammonia synthesis, CO methanation, alkane hydrogenolysis, ethylene epoxidation and water-gas shift are discussed. The roles of "ensemble" and "ligand" effects in bimetallic catalysts are examined in light of data obtained using surfaces prepared by vapor-depositing one metal onto a crystal face of a dissimilar metal.

  9. Laser Induced Reaction for Prebond Surface Preparation of Aluminum Alloys

    National Research Council Canada - National Science Library

    Rotel, M

    1994-01-01

    .... These adhesives are normally used in bonding and repairing processes for aerospace application. Surface treatment for bonding Al adherends with structural adhesives involve the sue of harsh chemicals such as acids bases and organic solvents...

  10. Fundamental Studies of Diamond Growth and Surface Reactions

    Science.gov (United States)

    1994-07-01

    deposition ( PACVD ) have been observed as a function of growth temperature, substrate identity and surface condition. Our highest microwave PACVD growth...The rate of growth of PACVD diamond films is intimately tied to the availability of low energy growth sites. Such low energy sites will be associated...oriented diamond film. m Fig. I Scanning electron micrograph of a random polycrystalline diamond film surface grown at 1000°C by micro- wave PACVD

  11. Reaction chemistry and ligand exchange at cadmium selenide nanocrystal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Owen, Jonathan; Park, Jungwon; Trudeau, Paul-Emile; Alivisatos, A. Paul

    2008-12-02

    Chemical modification of nanocrystal surfaces is fundamentally important to their assembly, their implementation in biology and medicine, and greatly impacts their electrical and optical properties. However, it remains a major challenge owing to a lack of analytical tools to directly determine nanoparticle surface structure. Early nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) studies of CdSe nanocrystals prepared in tri-n-octylphosphine oxide (1) and tri-n-octylphosphine (2), suggested these coordinating solvents are datively bound to the particle surface. However, assigning the broad NMR resonances of surface-bound ligands is complicated by significant concentrations of phosphorus-containing impurities in commercial sources of 1, and XPS provides only limited information about the nature of the phosphorus containing molecules in the sample. More recent reports have shown the surface ligands of CdSe nanocrystals prepared in technical grade 1, and in the presence of alkylphosphonic acids, include phosphonic and phosphinic acids. These studies do not, however, distinguish whether these ligands are bound datively, as neutral, L-type ligands, or by X-type interaction of an anionic phosphonate/phosphinate moiety with a surface Cd{sup 2+} ion. Answering this question would help clarify why ligand exchange with such particles does not proceed generally as expected based on a L-type ligand model. By using reagents with reactive silicon-chalcogen and silicon-chlorine bonds to cleave the ligands from the nanocrystal surface, we show that our CdSe and CdSe/ZnS core-shell nanocrystal surfaces are likely terminated by X-type binding of alkylphosphonate ligands to a layer of Cd{sup 2+}/Zn{sup 2+} ions, rather than by dative interactions. Further, we provide spectroscopic evidence that 1 and 2 are not coordinated to our purified nanocrystals.

  12. Leading coordinate analysis of reaction pathways in proton chain transfer: Application to a two-proton transfer model for the green fluorescent protein

    International Nuclear Information System (INIS)

    Wang Sufan; Smith, Sean C.

    2006-01-01

    The 'leading coordinate' approach to computing an approximate reaction pathway, with subsequent determination of the true minimum energy profile, is applied to a two-proton chain transfer model based on the chromophore and its surrounding moieties within the green fluorescent protein (GFP). Using an ab initio quantum chemical method, a number of different relaxed energy profiles are found for several plausible guesses at leading coordinates. The results obtained for different trial leading coordinates are rationalized through the calculation of a two-dimensional relaxed potential energy surface (PES) for the system. Analysis of the 2-D relaxed PES reveals that two of the trial pathways are entirely spurious, while two others contain useful information and can be used to furnish starting points for successful saddle-point searches. Implications for selection of trial leading coordinates in this class of proton chain transfer reactions are discussed, and a simple diagnostic function is proposed for revealing whether or not a relaxed pathway based on a trial leading coordinate is likely to furnish useful information

  13. Olefin metathesis reaction on GaN (0 0 0 1) surfaces

    International Nuclear Information System (INIS)

    Makowski, Matthew S.; Zemlyanov, Dmitry Y.; Ivanisevic, Albena

    2011-01-01

    Proof-of-concept reactions were performed on GaN (0 0 0 1) surfaces to demonstrate surface termination with desired chemical groups using an olefin cross-metathesis reaction. To prepare the GaN surfaces for olefin metathesis, the surfaces were hydrogen terminated with hydrogen plasma, chlorine terminated with phosphorous pentachloride, and then terminated with an alkene group via a Grignard reaction. The olefin metathesis reaction then bound 7-bromo-1-heptene. The modified surfaces were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and water contact angle measurements following each step in the reaction scheme. The XPS data was used to qualitatively identify surface chemical species and to quantitatively determine molecular surface coverage. The bromine atom in 7-bromo-1-heptene served as a heteroatom for identification with XPS. The reaction scheme resulted in GaN substrates with a surface coverage of 0.10 monolayers and excellent stability towards oxidation when exposed to oxygen plasma.

  14. Olefin metathesis reaction on GaN (0 0 0 1) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Makowski, Matthew S. [Weldon School of Biomedical Engineering, Purdue University, West Lafayette, IN 47907 (United States); Zemlyanov, Dmitry Y. [Birck Nanotechnology Center, Purdue University, West Lafayette, IN 47907 (United States); Ivanisevic, Albena, E-mail: albena@purdue.edu [Weldon School of Biomedical Engineering, Purdue University, West Lafayette, IN 47907 (United States); Department of Chemistry, Purdue University, West Lafayette, IN 47907 (United States)

    2011-03-01

    Proof-of-concept reactions were performed on GaN (0 0 0 1) surfaces to demonstrate surface termination with desired chemical groups using an olefin cross-metathesis reaction. To prepare the GaN surfaces for olefin metathesis, the surfaces were hydrogen terminated with hydrogen plasma, chlorine terminated with phosphorous pentachloride, and then terminated with an alkene group via a Grignard reaction. The olefin metathesis reaction then bound 7-bromo-1-heptene. The modified surfaces were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and water contact angle measurements following each step in the reaction scheme. The XPS data was used to qualitatively identify surface chemical species and to quantitatively determine molecular surface coverage. The bromine atom in 7-bromo-1-heptene served as a heteroatom for identification with XPS. The reaction scheme resulted in GaN substrates with a surface coverage of 0.10 monolayers and excellent stability towards oxidation when exposed to oxygen plasma.

  15. A facile and expedient one-pot three-component reaction leading to ...

    Indian Academy of Sciences (India)

    pot multicomponent reactions have emerged as a forceful tool in synthetic organic chemistry due to their significant advantages.7,8 A prac- tical and expedient construction of highly functiona- lized and diversified molecules from simple starting.

  16. A mechanistic study on the reaction pathways leading to benzene and naphthalene in cellulose vapor phase cracking

    International Nuclear Information System (INIS)

    Norinaga, Koyo; Yang, Huamei; Tanaka, Ryota; Appari, Srinivas; Iwanaga, Keita; Takashima, Yuka; Kudo, Shinji; Shoji, Tetsuya; Hayashi, Jun-ichiro

    2014-01-01

    The reaction pathways leading to aromatic hydrocarbons such as benzene and naphthalene in gas-phase reactions of multi-component mixtures derived from cellulose fast pyrolysis were studied both experimentally and numerically. A two-stage tubular reactor was used for evaluating the reaction kinetics of secondary vapor phase cracking of the nascent pyrolysates at temperature ranging from 400 to 900 °C, residence time from 0.2 to 4.3 s, and at 241 kPa. The products of alkyne and diene were identified from the primary pyrolysis of cellulose even at low temperature range 500–600 °C. These products include acetylene, propyne, propadiene, vinylacetylene, and cyclopentadiene. Experiments were also numerically validated by a detailed chemical kinetic model consisting of more than 8000 elementary step-like reactions with over 500 chemical species. Acceptable capabilities of the kinetic model in predicting concentration profiles of the products enabled us to assess reaction pathways leading to benzene and naphthalene via the alkyne and diene from primary pyrolysates of cellulose. C 3 alkyne and diene are primary precursors of benzene at 650 °C, while combination of ethylene and vinylacetylene produces benzene dominantly at 850 °C. Cyclopentadiene is a prominent precursor of naphthalene. Combination of acetylene with propyne or allyl radical leads to the formation of cyclopentadiene. Furan and acrolein are likely important alkyne precursors in cellulose pyrolysis at low temperature, whereas dehydrogenations of olefins are major route to alkyne at high temperatures. - Highlights: • Analytical pyrolysis experiments provided data for kinetic modeling. • Detailed chemical kinetic model was used and evaluated. • Alkyne and diene were important intermediates for aromatic hydrocarbon formation. • Reaction pathways leading to aromatic hydrocarbons were proposed

  17. Reaction 12C(16O,α)24Mg leading to nuclear molecular resonances

    International Nuclear Information System (INIS)

    Nagatani, K.; Shimoda, T.; Tanner, D.; Tribble, R.; Yamaya, T.

    1979-01-01

    The reactions 12 C( 16 O,α) 24 Mg and 13 C( 16 O,α) 25 Mg were investigated at an incident energy of 145 MeV. In the reaction with the 12 C target, broad peaks are observed at forward angles which correspond to the molecular resonance states of the 12 C+ 12 C system, while the spectra with 13 C target show only a smooth continuum

  18. Dosimetric perturbations of a lead shield for surface and interstitial high-dose-rate brachytherapy

    International Nuclear Information System (INIS)

    Candela-Juan, Cristian; Granero, Domingo; Vijande, Javier; Ballester, Facundo; Perez-Calatayud, Jose; Rivard, Mark J

    2014-01-01

    In surface and interstitial high-dose-rate brachytherapy with either 60 Co, 192 Ir, or 169 Yb sources, some radiosensitive organs near the surface may be exposed to high absorbed doses. This may be reduced by covering the implants with a lead shield on the body surface, which results in dosimetric perturbations. Monte Carlo simulations in Geant4 were performed for the three radionuclides placed at a single dwell position. Four different shield thicknesses (0, 3, 6, and 10 mm) and three different source depths (0, 5, and 10 mm) in water were considered, with the lead shield placed at the phantom surface. Backscatter dose enhancement and transmission data were obtained for the lead shields. Results were corrected to account for a realistic clinical case with multiple dwell positions. The range of the high backscatter dose enhancement in water is 3 mm for 60 Co and 1 mm for both 192 Ir and 169 Yb. Transmission data for 60 Co and 192 Ir are smaller than those reported by Papagiannis et al (2008 Med. Phys. 35 4898–4906) for brachytherapy facility shielding; for 169 Yb, the difference is negligible. In conclusion, the backscatter overdose produced by the lead shield can be avoided by just adding a few millimetres of bolus. Transmission data provided in this work as a function of lead thickness can be used to estimate healthy organ equivalent dose saving. Use of a lead shield is justified. (paper)

  19. Reaction dynamics of molecular hydrogen on silicon surfaces

    DEFF Research Database (Denmark)

    Bratu, P.; Brenig, W.; Gross, A.

    1996-01-01

    Experimental and theoretical results on the dynamics of dissociative adsorption and recombinative desorption of hydrogen on silicon are presented. Using optical second-harmonic generation, extremely small sticking probabilities in the range 10(-9)-10(-5) could be measured for H-2 and D-2 on Si(111......)7X7 and Si(100)2X1. Strong phonon-assisted sticking was observed for gases at 300 K and surface temperatures between 550 K and 1050 K. The absolute values as well as the temperature variation of the adsorption and desorption rates show surprisingly little isotope effect, and they differ only little...... between the two surfaces. These results indicate that tunneling, molecular vibrations, and the structural details of the surface play only a minor role for the adsorption dynamics. Instead, they appear to be governed by the localized H-Si bonding and Si-Si lattice vibrations. Theoretically, an effective...

  20. Calculation of excitation functions of 1H and 3,4He induced reactions leading to 123I

    International Nuclear Information System (INIS)

    Rurarz, E.; Rymuza, P.

    1992-01-01

    About 25 nuclear reactions leading directly or indirectly (via parent 123 Xe or grandparent 123 Cs formation) to 123 I production have been suggested. However, no detailed study, especially on the cross section measurements for a large group of reactions potentially useful for 123 I production has been reported. On the basis of the good reproduction of the measured cross section values for the 123 Te(p,n) 123 I, 124 Te(p,2n) 123 I, 127 I(p,5n) 123 Xe → 123 I and 124 Xe(p,2n) 123 Cs → 123 Xe → 123 I reactions, we can conclude that the hybrid model of nuclear reactions in the form of the well developed computer code Overlaid ALICE makes it possible to calculate unknown cross sections even at intermediate bombarding energies. The code can be useful for estimating cross sections in order to plan experiments. The calculated data can be used for predictions of the reaction yields with a reasonable degree of confidence even when no measured data are available. For production of 123 I through different nuclear reactions we have computed excitation functions of the following reactions over a wide range of incident energies. Excitation functions have been plotted and the cross section values can be directly read from the plots for given bombarding energies. (author). 32 refs, 17 figs

  1. Blaming for a better future: future orientation and associated intolerance of personal uncertainty lead to harsher reactions toward innocent victims.

    Science.gov (United States)

    Bal, Michèlle; van den Bos, Kees

    2012-07-01

    People are often encouraged to focus on the future and strive for long-term goals. This noted, the authors argue that this future orientation is associated with intolerance of personal uncertainty, as people usually cannot be certain that their efforts will pay off. To be able to tolerate personal uncertainty, people adhere strongly to the belief in a just world, paradoxically resulting in harsher reactions toward innocent victims. In three experiments, the authors show that a future orientation indeed leads to more negative evaluations of an innocent victim (Study 1), enhances intolerance of personal uncertainty (Study 2), and that experiencing personal uncertainty leads to more negative evaluations of a victim (Study 3). So, while a future orientation enables people to strive for long-term goals, it also leads them to be harsher toward innocent victims. One underlying mechanism causing these reactions is intolerance of personal uncertainty, associated with a future orientation.

  2. Reaction Kinetic Parameters and Surface Thermodynamic Properties of Cu2O Nanocubes

    Directory of Open Access Journals (Sweden)

    Xingxing Li

    2015-07-01

    Full Text Available Cuprous oxide (Cu2O nanocubes were synthesized by reducing Cu(OH2 in the presence of sodium citrate at room temperature. The samples were characterized in detail by field-emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray powder diffraction, and N2 absorption (BET specific surface area. The equations for acquiring reaction kinetic parameters and surface thermodynamic properties of Cu2O nanocubes were deduced by establishment of the relations between thermodynamic functions of Cu2O nanocubes and these of the bulk Cu2O. Combined with thermochemical cycle, transition state theory, basic theory of chemical thermodynamics, and in situ microcalorimetry, reaction kinetic parameters, specific surface enthalpy, specific surface Gibbs free energy, and specific surface entropy of Cu2O nanocubes were successfully determined. We also introduced a universal route for gaining reaction kinetic parameters and surface thermodynamic properties of nanomaterials.

  3. Surface reactivity and layer analysis of chemisorbed reaction films in ...

    Indian Academy of Sciences (India)

    Administrator

    Abstract. Studies on surface reactivity of substrate iron (Fe-particles) were made in the tribo-chemical environment of alkyl octadecenoates. Two alkyl octadecenoates namely ethyl octadecenoate and methyl. 12-hydroxy octadecenoate, slightly different in their chemical nature, were taken for preparing the chemisorbed ...

  4. Reaction dynamics of small molecules at metal surfaces

    CERN Document Server

    Samson, P A

    1999-01-01

    directed angular distributions suggest the influence of a trapping mechanism, recombining molecules scattering through a molecularly adsorbed state, with a transition state of large d sub N sub N responsible for the product vibrational excitation. Although N sub 2 dissociation on Fe(100) forms a simple overlayer structure, on Fe(110), molecular chemisorption does not occur at or above room temperature and the sticking is extremely small (approx 10 sup - sup 6 to 10 sup - sup 7). Activated nitrogen bombardment can be used to prepare a 'surface nitride' with a structure related to the geometry of bulk Fe sub 4 N. Scanning tunnelling microscopy yields atomic scale features that cannot be explained by simple overlayers. It is proposed that the uppermost iron layer reconstructs to generate quasi-octahedral sites between the top two layers, with sub-surface nitrogen in these sites forming a model for the 'surface nitride' structure. The dissociation-desorption dynamics of D sub 2 upon the Sn/Pt(111) surface alloy a...

  5. Performing chemical reactions in virtual capillary of surface tension ...

    Indian Academy of Sciences (India)

    Two mirror image patterned glass plates were then sandwiched one on top of the other, separated by a thin gap - created using a spacer. The aqueous liquid moves between the surfaces by capillary forces, confined to the hydrophilic areas without wetting the hydrophobic lines, achieving liquid confinement without physical ...

  6. Reaction of [3H]-taurine maleimide with platelet surface thiols

    International Nuclear Information System (INIS)

    Karl, D.W.; Mills, D.C.B.

    1986-01-01

    Taurine Maleimide (2-maleimidoethanesulfonate, TM) was synthesized from [2- 3 H]-taurine and methoxycarbonylmaleimide (MCM). The yield of a 1 μmol synthesis approached 100% (based on taurine) when MCM was used in 4-fold excess. The product (TM*) was purified by ion exchange chromatography. TM* reacted irreversibly with thiol groups on the surface of washed human platelets, leading to incorporation of radioactivity into platelet pellets. Incorporation was blocked by cysteine, mercuribenzenesulfonate (MBS), dithiobisnitrobenzoate, and N-ethylmaleimide, but not by taurine or by inhibitors of anion transport. Reaction of TM* with platelets showed the dependence on time and concentration characteristics of a bimolecular reaction. The number of reactive sites ranged from 1 to 5 x 10 5 /platelet, and the apparent rate constant from 1 to 3 x 10 3 /(M x min). TM was less effective than MBS as an inhibitor of platelet aggregation induced by several agents. TM had no effect on the uptake of serotonin, taurine, or phosphate by the platelets, processes which are sensitive to MBS. These differences, considered with the similarity in size and charge of TM and MBS, suggest that classes of thiols defined as exofacial by their accessibility to MBS can differ substantially in their reactivity with other impermeant reagents

  7. Optimization of lead adsorption of mordenite by response surface methodology: characterization and modification

    OpenAIRE

    Turkyilmaz, Havva; Kartal, Tolga; Yigitarslan Yildiz, Sibel

    2014-01-01

    Background In order to remove heavy metals, water treatment by adsorption of zeolite is gaining momentum due to low cost and good performance. In this research, the natural mordenite was used as an adsorbent to remove lead ions in an aqueous solution. Methods The effects of adsorption temperature, time and initial concentration of lead on the adsorption yield were investigated. Response surface methodology based on Box-Behnken design was applied for optimization. Adsorption data were analyzed...

  8. Lessons learned from surface wipe sampling for lead in three workplaces.

    Science.gov (United States)

    Beaucham, Catherine; Ceballos, Diana; King, Bradley

    2017-08-01

    Surface wipe sampling in the occupational environment is a technique widely used by industrial hygienists. Although several organizations have promulgated standards for sampling lead and other metals, uncertainty still exists when trying to determine an appropriate wipe sampling strategy and how to interpret sampling results. Investigators from the National Institute for Occupational Safety and Health (NIOSH) Health Hazard Evaluation Program have used surface wipe sampling as part of their exposure assessment sampling strategies in a wide range of workplaces. This article discusses wipe sampling for measuring lead on surfaces in three facilities: (1) a battery recycling facility; (2) a firing range and gun store; and (3) an electronic scrap recycling facility. We summarize our findings from the facilities and what we learned by integrating wipe sampling into our sampling plan. Wiping sampling demonstrated lead in non-production surfaces in all three workplaces and that the potential that employees were taking lead home to their families existed. We also found that the presence of metals such as tin can interfere with the colorimetric results. We also discuss the advantages and disadvantages of colorimetric analysis of surface wipe samples and the challenges we faced when interpreting wipe sampling results.

  9. [The surface ECG in the diagnosis of cardiac arrhythmias: the value of the right precordial leads].

    Science.gov (United States)

    Richter, S

    2007-03-01

    The surface electrocardiogram (ECG) is a simple noninvasive method to assess the electrical activity of the heart and provides important information to identify patients with cardiac arrhythmias and increased arrhythmic risk. This brief review highlights cardiac conditions in which the right precordial leads recorded on the surface ECG during sinus rhythm or tachycardia are of important diagnostic and prognostic value. Epsilon waves seen in the right precordial ST segments are the electrocardiographic hallmark of arrhythmogenic right ventricular cardiomyopathy. The diagnosis of Brugada syndrome and risk stratification of affected patients are based on a coved-type >or=2 mm ST-segment elevation in the right precordial leads. This typical ECG pattern may be present persistently, intermittently or only after administration of sodium-channel blockers. The early repolarization syndrome, most commonly seen in healthy young individuals, is characterized by a ST-segment elevation of 1 to 4 mm in the mid-precordial leads with a notched and elevated J point in lead V4. The precordial ECG T-wave repolarization pattern may be helpful in identifying the genotype in patients with suspected long QT syndrome. In patients with overt preexcitation, the surface leads V1 and V2 play a key role in localizing the site of bypass-tract insertion. Finally, the right precordial lead V1 is often crucial in the diagnosis of narrow and broad QRS-complex tachycardias.

  10. The Role of Electronic Excitations on Chemical Reaction Dynamics at Metal, Semiconductor and Nanoparticle Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Tully, John C. [Yale Univ., New Haven, CT (United States)

    2017-06-10

    Chemical reactions are often facilitated and steered when carried out on solid surfaces, essential for applications such as heterogeneous catalysis, solar energy conversion, corrosion, materials processing, and many others. A critical factor that can determine the rates and pathways of chemical reactions at surfaces is the efficiency and specificity of energy transfer; how fast does energy move around and where does it go? For reactions on insulator surfaces energy transfer generally moves in and out of vibrations of the adsorbed molecule and the underlying substrate. By contrast, on metal surfaces, metallic nanoparticles and semiconductors, another pathway for energy flow opens up, excitation and de-excitation of electrons. This so-called “nonadiabatic” mechanism often dominates the transfer of energy and can directly impact the course of a chemical reaction. Conventional computational methods such as molecular dynamics simulation do not account for this nonadiabatic behavior. The current DOE-BES funded project has focused on developing the underlying theoretical foundation and the computational methodology for the prediction of nonadiabatic chemical reaction dynamics at surfaces. The research has successfully opened up new methodology and new applications for molecular simulation. In particular, over the last three years, the “Electronic Friction” theory, pioneered by the PI, has now been developed into a stable and accurate computational method that is sufficiently practical to allow first principles “on-the-fly” simulation of chemical reaction dynamics at metal surfaces.

  11. Uniform surface modification of diatomaceous earth with amorphous manganese oxide and its adsorption characteristics for lead ions

    International Nuclear Information System (INIS)

    Li, Song; Li, Duanyang; Su, Fei; Ren, Yuping; Qin, Gaowu

    2014-01-01

    Graphical abstract: - Highlights: • A uniform MnO 2 layer was anchored onto diatomite surface. • Kinetics and isotherms over MnO 2 modified diatomite were studied. • The Pb(II) adsorption is based on ion-exchange mechanism. - Abstract: A novel method to produce composite sorbent material compromising porous diatomaceous earth (DE) and surface functionalized amorphous MnO 2 is reported. Via a simple in situ redox reaction over the carbonized DE powders, a uniform layer of amorphous MnO 2 was anchored onto the DE surface. The hybrid adsorbent was characterized by X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. The batch method has been employed to investigate the effects of surface coating on adsorption performance of DE. According to the equilibrium studies, the adsorption capacity of DE for adsorbing lead ions after MnO 2 modification increased more than six times. And the adsorption of Pb 2+ on the MnO 2 surface is based on ion-exchange mechanism. The developed strategy presents a novel opportunity to prepare composite adsorbent materials by integrating nanocrystals with porous matrix

  12. Uniform surface modification of diatomaceous earth with amorphous manganese oxide and its adsorption characteristics for lead ions

    Energy Technology Data Exchange (ETDEWEB)

    Li, Song; Li, Duanyang; Su, Fei; Ren, Yuping; Qin, Gaowu, E-mail: lis@atm.neu.edu.cn

    2014-10-30

    Graphical abstract: - Highlights: • A uniform MnO{sub 2} layer was anchored onto diatomite surface. • Kinetics and isotherms over MnO{sub 2} modified diatomite were studied. • The Pb(II) adsorption is based on ion-exchange mechanism. - Abstract: A novel method to produce composite sorbent material compromising porous diatomaceous earth (DE) and surface functionalized amorphous MnO{sub 2} is reported. Via a simple in situ redox reaction over the carbonized DE powders, a uniform layer of amorphous MnO{sub 2} was anchored onto the DE surface. The hybrid adsorbent was characterized by X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. The batch method has been employed to investigate the effects of surface coating on adsorption performance of DE. According to the equilibrium studies, the adsorption capacity of DE for adsorbing lead ions after MnO{sub 2} modification increased more than six times. And the adsorption of Pb{sup 2+} on the MnO{sub 2} surface is based on ion-exchange mechanism. The developed strategy presents a novel opportunity to prepare composite adsorbent materials by integrating nanocrystals with porous matrix.

  13. One-pot reaction for the preparation of biofunctionalized self-assembled monolayers on gold surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Raigoza, Annette F.; Fies, Whitney; Lim, Amber; Onyirioha, Kristeen; Webb, Lauren J., E-mail: lwebb@cm.utexas.edu

    2017-02-01

    Highlights: • One-pot synthesis of α-helical-terminated self-assembled monolayers on Au(111). • Synthesis of high density, structured, and covalently bound α-helices on Au(111). • Characterization by surface-averaged and single molecule techniques. • Peptide-terminated surfaces for fabrication of biomaterials and sensors. - Abstract: The Huisgen cycloaddition reaction (“click” chemistry) has been used extensively to functionalize surfaces with macromolecules in a straightforward manner. We have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to a well-ordered azide-terminated alkanethiol self-assembled monolayer (SAM) on a Au(111) surface. While convenient, click-based strategies potentially pose significant problems from reagents, solvents, and reaction temperatures that may irreversibly damage some molecules or substrates. Tuning click chemistry conditions would allow individual optimization of reaction conditions for a wide variety of biomolecules and substrate materials. Here, we explore the utility of simultaneous SAM formation and peptide-attachment chemistry in a one-pot reaction. We demonstrate that a formerly multistep reaction can be successfully carried out concurrently by mixing azide-terminated alkanethiols, CuCl, and a propargylglycine-containing peptide over a bare gold surface in ethanol and reacting at 70 °C. X-ray photoelectron spectroscopy (XPS), surface infrared spectroscopy, surface circular dichroic (CD) spectroscopy, and scanning tunneling microscopy (STM) were used to determine that this one-pot reaction strategy resulted in a high density of surface-bound α-helices without aggregation. This work demonstrates the simplicity and versatility of a SAM-plus-click chemistry strategy for functionalizing Au surfaces with structured biomolecules.

  14. Reaction rates of ozone and terpenes adsorbed to model indoor surfaces.

    Science.gov (United States)

    Springs, M; Wells, J R; Morrison, G C

    2011-08-01

    Reaction rates and reaction probabilities have been quantified on model indoor surfaces for the reaction of ozone with two monoterpenes (Δ(3) -carene and d-limonene). Molar surface loadings were obtained by performing breakthrough experiments in a plug-flow reactor (PFR) packed with beads of glass, polyvinylchloride or zirconium silicate. Reaction rates and probabilities were determined by equilibrating the PFR with both the terpene and the ozone and measuring the ozone consumption rate. To mimic typical indoor conditions, temperatures of 20, 25, and 30°C were used in both types of experiments along with a relative humidity ranging from 10% to 80%. The molar surface loading decreased with increased relative humidity, especially on glass, suggesting that water competed with the terpenes for adsorption sites. The ozone reactivity experiments indicate that higher surface loadings correspond with higher ozone uptake. The reaction probability for Δ(3) -carene with ozone ranged from 2.9 × 10(-6) to 3.0 × 10(-5) while reaction probabilities for d-limonene ranged from 2.8 × 10(-5) to 3.0 × 10(-4) . These surface reaction probabilities are roughly 10-100 times greater than the corresponding gas-phase values. Extrapolation of these results to typical indoor conditions suggests that surface conversion rates may be substantial relative to gas-phase rates, especially for lower volatility terpenoids. At present, it is unclear how important heterogeneous reactions will be in influencing indoor concentrations of terpenes, ozone and their reaction products. We observe that surface reaction probabilities were 10 to 100 times greater than their corresponding gas-phase values. Thus indoor surfaces do enhance effective reaction rates and adsorption of terpenes will increase ozone flux to otherwise low-reactivity surfaces. Extrapolation of these results to typical indoor conditions suggests that surface conversion rates may be substantial relative to gas-phase rates, especially

  15. Lead extraction from waste funnel cathode-ray tubes glasses by reaction with silicon carbide and titanium nitride.

    Science.gov (United States)

    Yot, Pascal G; Méar, François O

    2009-12-15

    As a possibility to clean waste CRT glass, treatment of lead-containing glass with a reducing agent, SiC or TiN, leads to a porous material containing metallic lead, Pb(0), located on the surface of the pore, and unreduced lead, Pb(II). The influences of reducing agent content, of the time, and at last of the temperature on lead reduction were analysed. Our investigations have pointed out significant differences as a function of the used reducing agent. CRT glass heat treated with SiC lead to less Pb(0), compared to TiN as shown by X-ray diffraction, and differential scanning calorimetry (DSC). It has been also evidenced that lead reduction occurs on randomized zones inside the sample leading to macroscopic lead beads inside glassy samples. XPS and XAS measurements were also carried out to investigate the local structure of lead and have evidenced a change of role of lead inside the glassy framework in function of the used conditions.

  16. Surface-Assisted Self-Assembly Strategies Leading to Supramolecular Hydrogels.

    Science.gov (United States)

    Vigier-Carrière, Cécile; Boulmedais, Fouzia; Schaaf, Pierre; Jierry, Loïc

    2018-02-05

    Localized molecular self-assembly processes leading to the growth of nanostructures exclusively from the surface of a material is one of the great challenges in surface chemistry. In the last decade, several works have been reported on the ability of modified or unmodified surfaces to manage the self-assembly of low-molecular-weight hydrogelators (LMWH) resulting in localized supramolecular hydrogel coatings mainly based on nanofiber architectures. This Minireview highlights all strategies that have emerged recently to initiate and localize LMWH supramolecular hydrogel formation, their related fundamental issues and applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Dissipative effects in fission investigated with proton-on-lead reactions

    Directory of Open Access Journals (Sweden)

    Rodríguez-Sánchez J. L.

    2016-01-01

    Full Text Available The complete kinematic measurement of the two fission fragments permitted us to investigate dissipative effects at large deformations, between the saddle-point and the corresponding scission configurations. Up to now, this kind of study has only been performed with fusionfission reactions using a limited number of observables, such as the mass distribution of the fission fragments or the neutron multiplicities. However, the large angular momenta gained by the compound nucleus could affect the conclusions drawn from such experiments. In this work, the use of spallation reactions, where the fissioning systems are produced with low angular momentum, small deformations and high excitation energies, favors the study of dissipation, and allowed us to define new observables, such as postscission neutron multiplicities and the neutron excess of the final fission fragments as a function of the atomic number of the fissioning system. These new observables are used to investigate the dissipation at large deformations.

  18. Halogen substitutions leading to enhanced oxygen evolution and oxygen reduction reactions in metalloporphyrin frameworks.

    Science.gov (United States)

    Wannakao, Sippakorn; Maihom, Thana; Kongpatpanich, Kanokwan; Limtrakul, Jumras; Promarak, Vinich

    2017-11-08

    The oxygen evolution and oxygen reduction reactions (OER and ORR, respectively) are important in the field of renewable and clean energy, particularly for hydrogen production and fuel cells. These applications have so far been limited because of the high price of the catalysts and the energy loss due to overpotentials. Hence, non-precious metal catalysts with high efficiency toward the OER/ORR are desirable. In this work, we employ density functional theory (DFT) calculations to study the OER/ORR on metalloporphyrin and halogenated metalloporphyrin frameworks. The free energies of the reaction intermediates, including OH, O and OOH, were measured on 14 metal sites (Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Ir, Pt and Au) of the metalloporphyrin frameworks. Adsorption free energy relations were found and used to establish the reaction trend. The group 9 metals, namely Co, Rh and Ir, turn out to be potential candidates for both the OER and ORR because they provide intermediate free energies close to those of an ideal catalyst. The substitution of halogen atoms at the beta-positions of the metalloporphyrins of group 9 metals modifies the adsorption free energies of the intermediates so that they become closer to the ideal values and in turn reduce the OER and ORR overpotentials. After functionalization, Co-Por-F provides the lowest ORR overpotential and reduces the OER overpotential, approaching the value for an expensive Ir catalyst. Analysis of the electronic structure shows that controlling the d-band splitting by chemical manipulation of the single active site catalyst can be the key to enhancing the efficiency of these reactions.

  19. Surface chemistry of tribochemical reactions explored in ultrahigh vacuum conditions

    International Nuclear Information System (INIS)

    Lara-Romero, Javier; Maya-Yescas, Rafael; Rico-Cerda, Jose Luis; Rivera-Rojas, Jose Luis; Castillo, Fernando Chinas; Kaltchev, Matey; Tysoe, Wilfred T.

    2006-01-01

    The thermal decomposition of model extreme-pressure lubricant additives on clean iron was studied in ultrahigh vacuum conditions using molecular beam strategies. Methylene chloride and chloroform react to deposit a solid film consisting of FeCl 2 and carbon, and evolve only hydrogen into the gas phase. No gas-phase products and less carbon on the surface are detected in the case of carbon tetrachloride. Dimethyl and diethyl disulfide react on clean iron to deposit a saturated sulfur plus carbon layer at low temperatures (∼600 K) and an iron sulfide film onto a Fe + C underlayer at higher temperatures (∼950 K). Methane is the only gas-phase product when dimethyl disulfide reacts with iron. Ethylene and hydrogen are detected when diethyl disulfide is used

  20. Production of specific structured lipids by enzymatic interesterification: optimization of the reaction by response surface design

    DEFF Research Database (Denmark)

    Xu, Xuebing; Skands, Anja Rebecca Havegaard; Adler-Nissen, Jens

    1998-01-01

    Rapeseed oil and capric acid were interesterified in solvent-free media catalyzed by Lipozyme IM (Rhizomucor miehei) to produce specific-structured lipids (SSLs). The process was optimized by response surface design concerning the effects of acyl migration and the by-products of diacylglycerols...... (DAGs). A five-factor response surface design was used to evaluate the influences of five major factors and their relationships. The five factors were water content (Wc, wt% based on enzyme used), reaction temperature (Te,°C), enzyme load (El, wt% based on substrates), reaction time (Tr, hour....... Thus we conclude that the quadratic response models adequately expressed the reaction. Based on the models, the reaction was optimized for the maximum net incorporation and minimum DAG content. The reaction and the control of water content or water activity (Aw) was also discussed....

  1. Prediction of Tetraoxygen Reaction Mechanism with Sulfur Atom on the Singlet Potential Energy Surface

    Directory of Open Access Journals (Sweden)

    Ashraf Khademzadeh

    2014-01-01

    Full Text Available The mechanism of S+O4 (D2h reaction has been investigated at the B3LYP/6-311+G(3df and CCSD levels on the singlet potential energy surface. One stable complex has been found for the S+O4 (D2h reaction, IN1, on the singlet potential energy surface. For the title reaction, we obtained four kinds of products at the B3LYP level, which have enough thermodynamic stability. The results reveal that the product P3 is spontaneous and exothermic with −188.042 and −179.147 kcal/mol in Gibbs free energy and enthalpy of reaction, respectively. Because P1 adduct is produced after passing two low energy level transition states, kinetically, it is the most favorable adduct in the 1S+1O4 (D2h atmospheric reactions.

  2. Production of specific structured lipids by enzymatic interesterification: optimization of the reaction by response surface design

    DEFF Research Database (Denmark)

    Xu, Xuebing; Skands, Anja Rebecca Havegaard; Adler-Nissen, Jens

    1998-01-01

    (DAGs). A five-factor response surface design was used to evaluate the influences of five major factors and their relationships. The five factors were water content (Wc, wt% based on enzyme used), reaction temperature (Te,°C), enzyme load (El, wt% based on substrates), reaction time (Tr, hour....... Thus we conclude that the quadratic response models adequately expressed the reaction. Based on the models, the reaction was optimized for the maximum net incorporation and minimum DAG content. The reaction and the control of water content or water activity (Aw) was also discussed.......Rapeseed oil and capric acid were interesterified in solvent-free media catalyzed by Lipozyme IM (Rhizomucor miehei) to produce specific-structured lipids (SSLs). The process was optimized by response surface design concerning the effects of acyl migration and the by-products of diacylglycerols...

  3. Sorption of oxygen on Cu(111)-Ni surfaces and its reaction with hydrogen

    NARCIS (Netherlands)

    Mesters, C.M.A.M.; Koster, A. de; Gijzeman, O.L.J.; Geus, John W.

    1984-01-01

    The interaction of O2 with a Cu(111)-Ni alloy and the reaction of sorbed oxygen with H2 has been investigated with ellipsometry and AES. The surface alloys were prepared by dissociation of nickel carbonyl on a clean Cu(111) surface. Sorption of O2 can be described by a precursor state model for

  4. Ab initio molecular dynamics calculations on reactions of molecules with metal surfaces

    NARCIS (Netherlands)

    Nattino, Francesco

    2015-01-01

    Reactions on metal surfaces are of scientific interest due to the tremendous relevance of heterogeneous catalysis. Single crystal surfaces under controlled physical conditions are generally employed as a model for the real catalysts, with the aim of improving the fundamental understanding of the

  5. Reconstruction of an 8-lead surface ECG from two subcutaneous ICD vectors.

    Science.gov (United States)

    Wilson, David G; Cronbach, Peter L; Panfilo, D; Greenhut, Saul E; Stegemann, Berthold P; Morgan, John M

    2017-06-01

    Techniques exist which allow surface ECGs to be reconstructed from reduced lead sets. We aimed to reconstruct an 8-lead ECG from two independent S-ICD sensing electrodes vectors as proof of this principle. Participants with ICDs (N=61) underwent 3minute ECGs using a TMSi Porti7 multi-channel signal recorder (TMS international, The Netherlands) with electrodes in the standard S-ICD and 12-lead positions. Participants were randomised to either a training (N=31) or validation (N=30) group. The transformation used was a linear combination of the 2 independent S-ICD vectors to each of the 8 independent leads of the 12-lead ECG, with coefficients selected that minimized the root mean square error (RMSE) between recorded and derived ECGs when applied to the training group. The transformation was then applied to the validation group and agreement between the recorded and derived lead pairs was measured by Pearson correlation coefficient (r) and normalised RMSE (NRMSE). In total, 27 patients with complete data sets were included in the validation set consisting of 57,888 data points from 216 full lead sets. The distribution of the r and NRMSE were skewed. Mean r=0.770 (SE 0.024), median r=0.925. NRMSE mean=0.233 (SE 0.015) median=0.171. We have demonstrated that the reconstruction of an 8-lead ECG from two S-ICD vectors is possible. If perfected, the ability to generate accurate multi-lead surface ECG data from an S-ICD would potentially allow recording and review of clinical arrhythmias at follow-up. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Effect of atmospheric oxidative plasma treatments on polypropylenic fibers surface: Characterization and reaction mechanisms

    International Nuclear Information System (INIS)

    Nisticò, Roberto; Magnacca, Giuliana; Faga, Maria Giulia; Gautier, Giovanna; D’Angelo, Domenico; Ciancio, Emanuele; Lamberti, Roberta; Martorana, Selanna

    2013-01-01

    Atmospheric pressure plasma-dielectric barrier discharge (APP-DBD, open chamber configuration) was used to functionalize polypropylene (PP) fibers surface in order to generate oxidized-reactive groups such as hydroperoxides, alcohols and carbonyl species (i.e. ketones and others). Such a species increased the surface polarity, without causing material degradation. Three different types of plasma mixture (He, He/O 2 , He/O 2 /H 2 O) under three different values of applied power (750, 1050, 1400 W) were investigated. The formed plasma species (O 2 + , O single atom and OH radical) and their distribution were monitored via optical emission spectrometry (OES) measurements, and the plasma effects on PP surface species formation were followed by X-ray photoemission spectroscopy (XPS). Results allowed to better understand the reaction pathways between plasma phase and PP fibers. In fact, two reaction mechanisms were proposed, the first one concerning the plasma phase reactions and the second one involving material surface modifications.

  7. The effect of Fermi energy on reaction of water with oxide surfaces

    Science.gov (United States)

    Mullins, W. M.

    1989-07-01

    The experimental relationship found between oxide Fermi level and aqueous point of zero charge (pzc) is modeled by the generalized Lewis acid-base theory. This model describes a nearly linear relationship between the position of the Fermi level in the band gap and the net charge transferred in a surface acid-base reaction. The situation of a water molecule adsorbed onto an uncharged, insulator (alumina) surface is examined. The charge in the reaction is assumed to shift the dissociation equilibrium of the water molecule, resulting in a net surface charge on the insulator. The pzc of the surface is calculated as a function of insulator Fermi level from these equilibria. This model predicts very strong effects of doping, surface states and surface space charges on pzc of insulators but possibly small effects of structure and stoichiometry.

  8. Reaction of winter oilseed rape varieties to elevated concentrations of lead

    Directory of Open Access Journals (Sweden)

    Oreščanin Bojana

    2012-01-01

    Full Text Available Remediation methods allow the removal of metals from contaminated soil, and phytoremediation a technology for cleaning contaminated soil and waste material by plants, is becoming increasingly used. Brassica napus L., as one of the main oilcrops and high-biomass producing species, is becoming more and more interesting for the use in phytoextraction as it is proved to be tolerant to higher concentrations of heavy metals. The aim of this study was to examine the specific responses of three commercial winter rapeseed varieties, Banaćanka, Slavica and Kata, to the increased concentrations of lead in vitro. Significant reduction in root length of plants treated with lead was observed only in the variety Slavica, indicating susceptibility of this variety to the increased concentrations of this heavy metal. As in variety Kata a significant reduction in the length of the above-ground part due to the treatment with lead was detected, it could be concluded that the variety Banaćanka is the most tolerant to the applied concentrations of lead since there were no significant changes in the growth and biomass accumulation in all treatments except one, and could be recommended for further use in phytoremediation studies. [Projekat Ministarstva nauke Republike Srbije, br. TR31025 i br. III43007

  9. Surface Electronic Structure of Hybrid Organo Lead Bromide Perovskite Single Crystals

    KAUST Repository

    Komesu, Takashi

    2016-08-24

    The electronic structure and band dispersion of methylammonium lead bromide, CH3NH3PbBr3, has been investigated through a combination of angle-resolved photoemission spectroscopy (ARPES) and inverse photoemission spectroscopy (IPES), as well as theoretical modeling based on density functional theory. The experimental band structures are consistent with the density functional calculations. The results demonstrate the presence of a dispersive valence band in MAPbBr3 that peaks at the M point of the surface Brillouin zone. The results also indicate that the surface termination of the CH3NH3PbBr3 is the methylammonium bromide (CH3NH3Br) layer. We find our results support models that predict a heavier hole effective mass in the region of -0.23 to -0.26 me, along the Γ (surface Brillouin center) to M point of the surface Brillouin zone. The surface appears to be n-type as a result of an excess of lead in the surface region. © 2016 American Chemical Society.

  10. The significance of surface complexation reactions in hydrologic systems: a geochemist's perspective

    Science.gov (United States)

    Koretsky, C.

    2000-05-01

    Complexation reactions at the mineral-water interface affect the transport and transformation of metals and organic contaminants, nutrient availability in soils, formation of ore deposits, acidification of watersheds and the global cycling of elements. Such reactions can be understood by quantifying speciation reactions in homogeneous aqueous solutions, characterizing reactive sites at mineral surfaces and developing models of the interactions between aqueous species at solid surfaces. In this paper, the application of thermodynamic principles to quantify aqueous complexation reactions is described. This is followed by a brief overview of a few of the methods that have been used to characterize reactive sites on mineral surfaces. Next, the application of empirical and semi-empirical models of adsorption at the mineral-water interface, including distribution coefficients, simple ion exchange models, and Langmuir and Freundlich isotherms is discussed. Emphasis is placed on the limitations of such models in providing an adequate representation of adsorption in hydrological systems. These limitations arise because isotherms do not account for the structure of adsorbed species, nor do they account for the development of surface charge with adsorption. This is contrasted with more sophisticated models of adsorption, termed 'surface complexation models', which include the constant capacitance model, the diffuse layer model, the triple layer model and the MUSIC model. In these models, speciation reactions between surface functional groups and dissolved species control the variable surface charge build-up and the specific adsorption properties of minerals in aqueous solutions. Next, the influence of mineral surface speciation on the reactivity of adsorbed species and on far from equilibrium dissolution rates of minerals is discussed. Finally, the applicability of microscopic models of surface complexation to field-scale systems is explored and the need to integrate

  11. Scanning Tunneling Microscopy Applied to the Electrochemical Deposition of Lead on the GOLD(111) Surface.

    Science.gov (United States)

    Green, Michael Philip

    1990-01-01

    A scanning tunneling microscope (STM) was developed and used to study the atomic scale structure of two types of metal surfaces. Operating both in air and through an electrolytic bath, the STM was used to investigate electrochemical deposition on the gold(111) surface. For the study in air, images were taken of both uncoated gold(111) films and those with monolayer and submonolayer deposits of lead and copper, prepared by underpotential deposition (UPD). Comparison between STM images of the bare gold substrates and those with the UPD adlayers reveals no difference. Oxidation of the UPD films is blamed for rendering the overlayers invisible to the STM. The common surface structure of these samples in air is discussed. Dominant features include: planar regions or terraces separated by monoatomic steps; monolayer deep pits; and monolayer high platforms. Room temperature surface diffusion has been monitored and can be seen to produce an overall smoothing of the topography. A second type of diffusion, more rapid and less common, produces finger-like ridges which are related to the gold(111) 1 x 23 reconstruction. In-situ experiments involved real-time STM monitoring of the surface topography during the electrochemical deposition and subsequent removal of a UPD lead monolayer. For the deposition process, step edges show the earliest and most extensive activity; however, nucleation of small lead islands on apparently flat terraces also provides growth sites. The lead coated surfaces are found to be smoother than the underlying gold. Subsequent removal of the UPD overlayer proceeds from the dissolution of lead platforms to the formation and expansion of a network of pits in the adlayer. The topography of the gold substrate is altered by the deposition/stripping process. Design of the STM and Modifications necessary to operate in an electrochemical environment are discussed. The STM has also been used in air to investigate the surface topography of x-ray reflecting optics

  12. Production of He-, Ne-, Ar-, Kr-, and Xe-isotopes by proton-induced reactions on lead

    International Nuclear Information System (INIS)

    Leya, I.; Michel, R.

    2003-01-01

    We measured integral thin target cross sections for the proton-induced production of He-, Ne-, Ar-, Kr-, and Xe-isotopes from lead from the respective reaction thresholds up to 2.6 GeV. The production of noble gas isotopes in lead by proton-induced reactions is of special importance for design studies of accelerator driven systems and energy amplifiers. In order to minimise the influences of secondary particles on the production of residual nuclides a new Mini-Stack approach was used instead of the well-known stacked-foil techniques for all experiments with proton energies above 200 MeV. With some exceptions our database for the proton-induced production of noble gas isotopes from lead is consistent and nearly complete. In contradistinction to the production of He from Al and Fe, where the cross sections obtained by thin-target irradiation experiments are up to a factor of 2 higher than the NESSI data, both datasets agree for the He production from lead. (orig.)

  13. The dynamics of molecular interactions and chemical reactions at metal surfaces: testing the foundations of theory.

    Science.gov (United States)

    Golibrzuch, Kai; Bartels, Nils; Auerbach, Daniel J; Wodtke, Alec M

    2015-04-01

    We review studies of molecular interactions and chemical reactions at metal surfaces, emphasizing progress toward a predictive theory of surface chemistry and catalysis. For chemistry at metal surfaces, a small number of central approximations are typically made: (a) the Born-Oppenheimer approximation of electronic adiabaticity, (b) the use of density functional theory at the generalized gradient approximation level, (c) the classical approximation for nuclear motion, and (d) various reduced-dimensionality approximations. Together, these approximations constitute a provisional model for surface chemical reactivity. We review work on some carefully studied examples of molecules interacting at metal surfaces that probe the validity of various aspects of the provisional model.

  14. Effects of reaction conditions on the emission behaviors of arsenic, cadmium and lead during sewage sludge pyrolysis.

    Science.gov (United States)

    Han, Hengda; Hu, Song; Syed-Hassan, Syed Shatir A; Xiao, Yiming; Wang, Yi; Xu, Jun; Jiang, Long; Su, Sheng; Xiang, Jun

    2017-07-01

    Sewage sludge is an important class of bioresources whose energy content could be exploited using pyrolysis technology. However, some harmful trace elements in sewage sludge can escape easily to the gas phase during pyrolysis, increasing the potential of carcinogenic material emissions to the atmosphere. This study investigates emission characteristics of arsenic, cadmium and lead under different pyrolysis conditions for three different sewage sludge samples. The increased temperature (within 723-1123K) significantly promoted the cadmium and lead emissions, but its influence on arsenic emission was not pronounced. The releasing rate order of the three trace elements is volatile arsenic compounds>cadmium>lead in the beginning of pyrolysis. Fast heating rates promoted the emission of trace elements for the sludge containing the highest amount of ash, but exhibited an opposite effect for other studied samples. Overall, the high ash sludge released the least trace elements almost under all reaction conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. From Lead to Drug Utilizing a Mannich Reaction: The Topotecan Story.

    Science.gov (United States)

    Bracher, Franz; Tremmel, Tim

    2017-07-01

    Natural products are a rich source of bioactive compounds, and numerous natural compounds have found application in cancer chemotherapy. However, unfavorable physicochemical properties often prevent the use of the original natural product as a drug. A prominent example is camptothecin from the Chinese tree Camptotheca acuminata, which shows extraordinary cytotoxic activity based on a specific molecular mode of action (inhibition of human topoisomerase I). Due to its extremely poor solubility, the original natural product cannot be used as a drug. The marketed drug topotecan was developed from this lead structure by semi-synthesis utilizing a Mannich aminomethylation as the crucial step. In this review, the long-distance run leading to this drug and further perspectives are summarized. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Can in vivo surface dental enamelmicrobiopsies be used to measure remote lead exposure?

    Science.gov (United States)

    Olympio, Kelly Polido Kaneshiro; Huila, Manuel Fernando Gonzalez; de Almeida Baldini Cardoso, Cristiane; da Silva Ferreira, Ana Paula Sacone; Ortiz, Adrielly Garcia; Toma, Henrique Eisi; da Silva, Ricardo Henrique Alves; Luz, Maciel Santos; Cardoso, Maria Regina Alves; Kelmer, Gislayne Aparecida Rodrigues; de Oliveira, Pedro Vitoriano; Bechara, Etelvino José Henriques; Günhter, Wanda Maria Risso; Buzalaf, Marília Afonso Rabelo

    2017-12-20

    Measuring lead in the surface dental enamel (SDE) using biopsies is a rapid, safe, and painless procedure. The dental enamel lead levels (DELLs) decrease from the outermost superficial layer to the inner layer of dental enamel, which becomes crucial for the biopsy depth (BD) measurement. However, whether the origin of lead found in SDE is fully endogenous is not yet established. There is also controversy about the biopsy protocol. The aims of this study were to investigate if DELLs are altered by extrinsic contamination (A) and to evaluate the real geometric figure formed by the erosion provoked by biopsy procedure and the respective BD in SDE (B). To accomplish the aim A, lead from 90 bovine incisor crowns lead was determined by graphite furnace atomic absorption spectrometer as a function of exposure time and lead concentration. Two biopsies were performed in each tooth, before and after lead exposure. Six 15-tooth groups differed by exposure time (1 or 30 min) and lead concentrations (A. 0 mg/L-placebo, B. 0.01 mg/L-standard for drinking water, or C. 0.06 mg/L-concentration found in contaminated groundwater). Phosphorus was determined by an inductively coupled plasm optical emission spectrometer to quantify the enamel removed. To compare intakes/losses of lead in SDE among the groups, values of DELL differences between before and after lead exposure were compared by ANOVA (p bottom surface area, analyzed by microscopy, showed an irregular area, with regions of peaks and valleys, where areas with depth ranging from 0.2 (peaks) to 1.8 μm (valleys) (± 0.1 μm) could be found. BD carried out in vivo is commonly calculated using the cylinder height formula. The real BD was shown to be very similar to already published data. In conclusion, the SDE of erupted teeth does not seem to be susceptible to environmental lead intake, being thus reliable to measure remote exposures to lead.

  17. Photoelectron spectroscopy: a strategy for the study of reactions at solid surfaces

    Science.gov (United States)

    Au, C. T.; Carley, A. F.; Roberts, M. W.

    The development of X-ray photoelectron spectroscopy for the study of the nature of chemisorbed species and the mechanisms of surface reactions is described. The methodology of data analysis and the establishment of data banks which enable photoelectron spectra to be assigned to specific surface species is discussed by reference to examples from recent studies. Although in the first instance the primary aim was to establish a qualitative logic in a well defined area of surface chemistry, this was then developed quantitatively and extended to studies of the mechanism of surface catalysed reactions. Emphasis is given here to the activation of molecules at metal surfaces either by surface modification or through chemical specificity which is associated with coadsorbed molecules. As illustration we discuss the activation of O-H and N-H bonds by `oxygen' resulting in reaction pathways being followed which would not have been predicted on the basis of the known reactivities of the individual molecules. The examples chosen also illustrate the severe limitations of mechanistic studies in surface chemistry based (a) on the study of the individual reactants separately; (b) on a post-mortem type of analysis of the surface and (c) on just a gaseous product analysis. An important concept that has emerged is the dual role of surface `oxygen'. It may either act as a promoter in activating an otherwise unreactive adsorbate molecule, or it may form an unreactive oxide overlayer. Parallel studies of metal oxides per se provide information on the defect nature of both oxide overlayers at metal surfaces and also bulk oxide surfaces. Close similarities are shown to exist between the `oxygen' activation of molecules at metal surfaces and the catalytic reactivity of defective bulk oxides. A common theme is that the dominant mechanism involves hydrogen abstraction by oxygen adatoms, which are assigned as O-(s) both at metal surfaces (by XPS) and at bulk oxide surfaces (by E.P.R. and XPS).

  18. Theory of the reaction dynamics of small molecules on metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Jackson, Bret [Univ. of Massachusetts, Amherst, MA (United States)

    2016-09-09

    The objective of this project has been to develop realistic theoretical models for gas-surface interactions, with a focus on processes important in heterogeneous catalysis. The dissociative chemisorption of a molecule on a metal is a key step in many catalyzed reactions, and is often the rate-limiting step. We have explored the dissociative chemisorption of H2, H2O and CH4 on a variety of metal surfaces. Most recently, our extensive studies of methane dissociation on Ni and Pt surfaces have fully elucidated its dependence on translational energy, vibrational state and surface temperature, providing the first accurate comparisons with experimental data. We have explored Eley-Rideal and hot atom reactions of H atoms with H- and C-covered metal surfaces. H atom interactions with graphite have also been explored, including both sticking and Eley-Rideal recombination processes. Again, our methods made it possible to explain several experiments studying these reactions. The sticking of atoms on metal surfaces has also been studied. To help elucidate the experiments that study these processes, we examine how the reaction dynamics depend upon the nature of the molecule-metal interaction, as well as experimental variables such as substrate temperature, beam energy, angle of impact, and the internal states of the molecules. Electronic structure methods based on Density Functional Theory are used to compute each molecule-metal potential energy surface. Both time-dependent quantum scattering techniques and quasi-classical methods are used to examine the reaction or scattering dynamics. Much of our effort has been directed towards developing improved quantum methods that can accurately describe reactions, as well as include the effects of substrate temperature (lattice vibration).

  19. Screening hydroxyapatite for cadmium and lead immobilization in aqueous solution and contaminated soil: The role of surface area.

    Science.gov (United States)

    Li, Hongying; Guo, Xisheng; Ye, Xinxin

    2017-02-01

    Hydroxyapatite (HAP) has been widely used to immobilize many cationic metals in water and soils. The specific reason why an increase in the surface area of HAP enhances cadmium (Cd) uptake, but has no effect on lead (Pb) uptake, is not clear. The aim of this study was to determine the factors causing the differences in sorption behavior between Cd and Pb by evaluating HAPs with different surface areas. We synthesized HAPs with two different surface areas, which were characterized by X-ray diffraction, N 2 adsorption, and scanning electron microscopy, and then evaluated them as sorbents for Cd and Pb removal by testing in single and binary systems. The sorption capacity of large surface area HAP (1.85mmol/g) for Cd in the single-metal system was higher than that of small surface area HAP (0.64mmol/g), but there were no differences between single- and binary-metal solutions containing Pb. After the Cd experiments, the HAP retained a stable structure and intact morphology, which promotes the accessibility of reactive sites for Cd. However, a newly formed precipitate covered the surface and blocked the channels in the presence of Pb, which reduced the number of potential adsorption sites on HAP for Cd and Pb. Remediation experiments using Cd- and Pb-contaminated soil produced similar results to the solution tests. These results indicate that alterations of the structure and morphology during the reaction is an important factor influencing metal sorption to HAP. Copyright © 2016. Published by Elsevier B.V.

  20. Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry

    International Nuclear Information System (INIS)

    Osborn, David L.

    2017-01-01

    Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low temperature combustion and the oxidation of volatile organic compounds in earth’s atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization make characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, while master equation methods enable a holistic treatment of both sequential and well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.

  1. Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry

    Science.gov (United States)

    Osborn, David L.

    2017-05-01

    Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low-temperature combustion and in the oxidation of volatile organic compounds in Earth's atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization makes characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, and master equation methods enable a holistic treatment of both sequential and well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.

  2. Studies of the surface of titanium dioxide. IV. The hydrogen-deuterium equilibration reaction

    International Nuclear Information System (INIS)

    Iwaki, T.; Katsuta, K.; Miura, M.

    1981-01-01

    The interaction of hydrogen with the surface of titanium dioxide has been studied in connection with the hydrogen-reduction mechanism of titanium dioxide, by means of such measurements as weight decrease, magnetic susceptibility, hydrogen uptake, and electrical conductance. It was postulated in the previous study that the rate-determining step of the hydrogen-reduction reaction may be the formation of surface hydroxyl groups, followed by the rapid removal of water molecules from the surface. In this study, the interactions between hydrogen and the surface of titanium dioxide were investigated by measuring the hydrogen-deuterium equilibration reaction, H 2 + D 2 = 2HD, at temperatures above 200 0 C on both surfaces before and after hydrogen reduction to compare the differences in the reactivities

  3. Lead-free, bronze-based surface layers for wear resistance in axial piston hydraulic pumps

    Energy Technology Data Exchange (ETDEWEB)

    Vetterick, Gregory Alan [Iowa State Univ., Ames, IA (United States)

    2010-01-01

    Concerns regarding the safety of lead have provided sufficient motivation to develop substitute materials for the surface layer on a thrust bearing type component known as a valve plate in axial piston hydraulic pumps that consists of 10% tin, 10% lead, and remainder cooper (in wt. %). A recently developed replacement material, a Cu-10Sn-3Bi (wt.%) P/M bronze, was found to be unsuitable as valve plate surface layer, requiring the development of a new alloy. A comparison of the Cu-1-Sn-10Pb and Cu-10Sn-3Bi powder metal valve plates showed that the differences in wear behavior between the two alloys arose due to the soft phase bismuth in the alloy that is known to cause both solid and liquid metal embrittlement of copper alloys.

  4. Ab initio potential energy surfaces and quantum dynamics for polyatomic bimolecular reactions.

    Science.gov (United States)

    Fu, Bina; Zhang, Donghui

    2018-03-26

    There has been great progress in the development of potential energy surfaces (PESs) and quantum dynamics calculations in the gas phase. The establishment of fitting procedure for highly accurate PESs and new developments in quantum reactive scattering on reliable PESs allow accurate characterization of reaction dynamics beyond triatomic systems. This review will give the recent development in our group in constructing ab initio PESs based on the neural networks, and the time-dependent wave packet calculations for bimolecular reactions beyond three atoms. Bimolecular reactions of current interest to the community, namely, OH+H2, H+H2O, OH+CO, H+CH4 and Cl+CH4 are focused on. Quantum mechanical characterization of these reactions uncovers interesting dynamical phenomena with an unprecedented level of sophistication, and has greatly advanced our understanding of polyatomic reaction dynamics.

  5. A Light-Induced Reaction with Oxygen Leads to Chromophore Decomposition and Irreversible Photobleaching in GFP-Type Proteins.

    Science.gov (United States)

    Grigorenko, Bella L; Nemukhin, Alexander V; Polyakov, Igor V; Khrenova, Maria G; Krylov, Anna I

    2015-04-30

    Photobleaching and photostability of proteins of the green fluorescent protein (GFP) family are crucially important for practical applications of these widely used biomarkers. On the basis of simulations, we propose a mechanism for irreversible bleaching in GFP-type proteins under intense light illumination. The key feature of the mechanism is a photoinduced reaction of the chromophore with molecular oxygen (O2) inside the protein barrel leading to the chromophore's decomposition. Using quantum mechanics/molecular mechanics (QM/MM) modeling we show that a model system comprising the protein-bound Chro(-) and O2 can be excited to an electronic state of the intermolecular charge-transfer (CT) character (Chro(•)···O2(-•)). Once in the CT state, the system undergoes a series of chemical reactions with low activation barriers resulting in the cleavage of the bridging bond between the phenolic and imidazolinone rings and disintegration of the chromophore.

  6. Nonenzymatic Reactions above Phospholipid Surfaces of Biological Membranes: Reactivity of Phospholipids and Their Oxidation Derivatives

    Science.gov (United States)

    Solís-Calero, Christian; Ortega-Castro, Joaquín; Frau, Juan; Muñoz, Francisco

    2015-01-01

    Phospholipids play multiple and essential roles in cells, as components of biological membranes. Although phospholipid bilayers provide the supporting matrix and surface for many enzymatic reactions, their inherent reactivity and possible catalytic role have not been highlighted. As other biomolecules, phospholipids are frequent targets of nonenzymatic modifications by reactive substances including oxidants and glycating agents which conduct to the formation of advanced lipoxidation end products (ALEs) and advanced glycation end products (AGEs). There are some theoretical studies about the mechanisms of reactions related to these processes on phosphatidylethanolamine surfaces, which hypothesize that cell membrane phospholipids surface environment could enhance some reactions through a catalyst effect. On the other hand, the phospholipid bilayers are susceptible to oxidative damage by oxidant agents as reactive oxygen species (ROS). Molecular dynamics simulations performed on phospholipid bilayers models, which include modified phospholipids by these reactions and subsequent reactions that conduct to formation of ALEs and AGEs, have revealed changes in the molecular interactions and biophysical properties of these bilayers as consequence of these reactions. Then, more studies are desirable which could correlate the biophysics of modified phospholipids with metabolism in processes such as aging and diseases such as diabetes, atherosclerosis, and Alzheimer's disease. PMID:25977746

  7. Optimization of Maillard Reaction in Model System of Glucosamine and Cysteine Using Response Surface Methodology

    Science.gov (United States)

    Arachchi, Shanika Jeewantha Thewarapperuma; Kim, Ye-Joo; Kim, Dae-Wook; Oh, Sang-Chul; Lee, Yang-Bong

    2017-01-01

    Sulfur-containing amino acids play important roles in good flavor generation in Maillard reaction of non-enzymatic browning, so aqueous model systems of glucosamine and cysteine were studied to investigate the effects of reaction temperature, initial pH, reaction time, and concentration ratio of glucosamine and cysteine. Response surface methodology was applied to optimize the independent reaction parameters of cysteine and glucosamine in Maillard reaction. Box-Behnken factorial design was used with 30 runs of 16 factorial levels, 8 axial levels and 6 central levels. The degree of Maillard reaction was determined by reading absorption at 425 nm in a spectrophotometer and Hunter’s L, a, and b values. ΔE was consequently set as the fifth response factor. In the statistical analyses, determination coefficients (R2) for their absorbance, Hunter’s L, a, b values, and ΔE were 0.94, 0.79, 0.73, 0.96, and 0.79, respectively, showing that the absorbance and Hunter’s b value were good dependent variables for this model system. The optimum processing parameters were determined to yield glucosamine-cysteine Maillard reaction product with higher absorbance and higher colour change. The optimum estimated absorbance was achieved at the condition of initial pH 8.0, 111°C reaction temperature, 2.47 h reaction time, and 1.30 concentration ratio. The optimum condition for colour change measured by Hunter’s b value was 2.41 h reaction time, 114°C reaction temperature, initial pH 8.3, and 1.26 concentration ratio. These results can provide the basic information for Maillard reaction of aqueous model system between glucosamine and cysteine. PMID:28401086

  8. Optimization of Maillard Reaction in Model System of Glucosamine and Cysteine Using Response Surface Methodology.

    Science.gov (United States)

    Arachchi, Shanika Jeewantha Thewarapperuma; Kim, Ye-Joo; Kim, Dae-Wook; Oh, Sang-Chul; Lee, Yang-Bong

    2017-03-01

    Sulfur-containing amino acids play important roles in good flavor generation in Maillard reaction of non-enzymatic browning, so aqueous model systems of glucosamine and cysteine were studied to investigate the effects of reaction temperature, initial pH, reaction time, and concentration ratio of glucosamine and cysteine. Response surface methodology was applied to optimize the independent reaction parameters of cysteine and glucosamine in Maillard reaction. Box-Behnken factorial design was used with 30 runs of 16 factorial levels, 8 axial levels and 6 central levels. The degree of Maillard reaction was determined by reading absorption at 425 nm in a spectrophotometer and Hunter's L, a, and b values. ΔE was consequently set as the fifth response factor. In the statistical analyses, determination coefficients (R 2 ) for their absorbance, Hunter's L, a, b values, and ΔE were 0.94, 0.79, 0.73, 0.96, and 0.79, respectively, showing that the absorbance and Hunter's b value were good dependent variables for this model system. The optimum processing parameters were determined to yield glucosamine-cysteine Maillard reaction product with higher absorbance and higher colour change. The optimum estimated absorbance was achieved at the condition of initial pH 8.0, 111°C reaction temperature, 2.47 h reaction time, and 1.30 concentration ratio. The optimum condition for colour change measured by Hunter's b value was 2.41 h reaction time, 114°C reaction temperature, initial pH 8.3, and 1.26 concentration ratio. These results can provide the basic information for Maillard reaction of aqueous model system between glucosamine and cysteine.

  9. Effect of cadmium and lead on the membrane potential and photoelectric reaction of Nitellopsis obtusa cells.

    Science.gov (United States)

    Kurtyka, Renata; Burdach, Zbigniew; Karcz, Waldemar

    2011-03-01

    The effects of Cd and Pb on membrane potential (E(m)) and photoelectric reaction of Nitellopsis obtusa cells were investigated. It was found that Cd and Pb at 1.0 mM caused a depolarization of the E(m), whereas both metals at lower concentrations changed the E(m) in a different way. Pb at 0.1 mM and 0.01 mM hyperpolarized the E(m), whereas Cd at the same concentrations depolarized and did not change the E(m), respectively. In the presence of 0.01 mM Pb, the light-induced hyperpolarization of the E(m) was by 18% higher as compared to the control, whereas at 1.0 mM Pb it was by 40% lower. Pb at 0.1 mM and Cd at 0.01 mM or 5 × 0.01 mM did not change the light-induced membrane hyperpolarization. However, in the presence of Cd at 0.1 mM and 1.0 mM this hyperpolarization was 2-fold lower or was completely abolished, respectively. These results suggest that at high Cd and Pb concentrations both depolarization of the E(m) and decrease of light-induced membrane hyperpolarization in Nitellopsis obtusa cells are probably due to inhibition of the plasma membrane H(+)-ATPase activity, whereas both metals at lower concentrations differ in mechanism of membrane potential changes.

  10. The effect of oxygen molecule adsorption on lead iodide perovskite surface by first-principles calculation

    Science.gov (United States)

    Ma, Xia-Xia; Li, Ze-Sheng

    2018-01-01

    Oxygen molecule has a negative effect on perovskite solar cells, which has been investigated experimentally. However, detailed theoretical research is still rare. This study presents a microscopic view to reveal the interaction mechanism between O2 and perovskite based on the first-principles calculation. The results show that O2 is adsorbed on the (100) surface of MAPbI3 perovskite mainly by Van der Waals force. O2 adsorption makes the MAPbI3 surface generate a small number of positive charges, which leads to the increase of the work function of the MAPbI3 surface. This is in agreement with the experimental measurement. And increased work function of MAPbI3 surface is not beneficial to electron transfer from perovskite to electronic extraction layer (such as TiO2). Comparison of the density of states (DOS) of the clean (100) surface and the adsorbed system shows that an in-gap state belonging to O2 appears, which can explain the phenomenon observed from experiments that electron transfers from the surface of perovskite to O2 to form superoxide. The theoretical power conversion efficiency of the system with and without O2 adsorption is evaluated, and it turns out that the power conversion efficiency of the system with O2 adsorption is slightly lower than that of the system without O2 adsorption. This result indicates that avoiding the introduction of O2 molecules between perovskite and electronic extraction layer is beneficial to the perovskite solar cell.

  11. Reaction of water vapour with a clean liquid uranium surface. Revised 1

    International Nuclear Information System (INIS)

    McLean, W. II; Siekhaus, W.

    1986-01-01

    To study the reaction of water vapour with uranium, we have exposed clean liquid uranium surfaces to H 2 O under UHV conditions. We have measured the surface concentration of oxygen as a function of exposure, and determined the maximum attainable surface oxygen concentration X/sup s//sub O/ as a function of temperature. We have used these measurements to estimate, close to the melting point, the solubility of oxygen (X/sup b//sub O/, -4 ) and its surface segregation coefficient β/sup s/(> 10 3 ). 11 refs., 5 figs

  12. XPS study on the surface reaction of uranium metal with carbon monoxide at 200 degree C

    International Nuclear Information System (INIS)

    Wang Xiaoling; Fu Yibei; Xie Renshou; Huang Ruiliang

    1996-12-01

    The surface reaction of uranium metal with carbon monoxide at 200 degree C has been studied by X-ray photoelectron spectroscopy (XPS). The carbon monoxide adsorption on the surface oxide layer resulted in U4f peak shifting to the lower binding energy and the content of oxygen in the oxide is decreased. O/U radio decreases with increasing the exposure of carbon monoxide to the surface layer. The investigation indicated the surface layer of uranium metal was further reduced in the atmosphere of carbon monoxide at high temperature. (3 refs., 5 figs.)

  13. Surface dust wipes are the best predictors of blood leads in young children with elevated blood lead levels

    Energy Technology Data Exchange (ETDEWEB)

    Gulson, Brian, E-mail: brian.gulson@mq.edu.au [Graduate School of the Environment, Macquarie University, North Ryde NSW 2109 (Australia); CSIRO Earth Science and Resource Engineering, North Ryde NSW 2113 (Australia); Anderson, Phil [Information and Statistics Group, Australian Institute of Health and Welfare, Canberra ACT 2601 (Australia); Faculty of Health, University of Canberra, Canberra ACT 2601 (Australia); Taylor, Alan [Department of Psychology, Macquarie University, Sydney NSW 2109 (Australia)

    2013-10-15

    Background: As part of the only national survey of lead in Australian children, which was undertaken in 1996, lead isotopic and lead concentration measurements were obtained from children from 24 dwellings whose blood lead levels were ≥15 µg/dL in an attempt to determine the source(s) of their elevated blood lead. Comparisons were made with data for six children with lower blood lead levels (<10 µg/dL). Methods: Thermal ionisation and isotope dilution mass spectrometry were used to determine high precision lead isotopic ratios ({sup 208}Pb/{sup 206}Pb, {sup 207}Pb/{sup 206}Pb and {sup 206}Pb/{sup 204}Pb) and lead concentrations in blood, dust from floor wipes, soil, drinking water and paint (where available). Evaluation of associations between blood and the environmental samples was based on the analysis of individual cases, and Pearson correlations and multiple regression analyses based on the whole dataset. Results and discussion: The correlations showed an association for isotopic ratios in blood and wipes (r=0.52, 95% CI 0.19–0.74), blood and soil (r=0.33, 95% CI −0.05–0.62), and blood and paint (r=0.56, 95% CI 0.09–0.83). The regression analyses indicated that the only statistically significant relationship for blood isotopic ratios was with dust wipes (B=0.65, 95% CI 0.35–0.95); there were no significant associations for lead concentrations in blood and environmental samples. There is a strong isotopic correlation of soils and house dust (r=0.53, 95% CI 0.20–0.75) indicative of a common source(s) for lead in soil and house dust. In contrast, as with the regression analyses, no such association is present for bulk lead concentrations (r=−0.003, 95% CI −0.37–0.36), the most common approach employed in source investigations. In evaluation of the isotopic results on a case by case basis, the strongest associations were for dust wipes and blood. -- Highlights: • Children with elevated blood lead ≥15 µg/dL compared with a group with <10

  14. Adsorption and reaction of propanal, 2-propenol and 1-propanol on Ni/Pt(111) bimetallic surfaces

    Science.gov (United States)

    Murillo, Luis E.; Chen, Jingguang G.

    2008-07-01

    The hydrogenation of acrolein (CH 2dbnd CH sbnd CH dbnd O) can lead to the formation of three hydrogenation products, 2-propenol (CH 2dbnd CH sbnd CH 2sbnd OH), propanal (CH 3sbnd CH 2sbnd CH dbnd O), and 1-propanol (CH 3sbnd CH 2sbnd CH 2sbnd OH). In the current study the adsorption and reaction of these three molecules were investigated on Ni/Pt(111) surfaces to understand the different hydrogenation pathways of acrolein, using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). TPD experiments showed that 2-propenol underwent isomerization toward propanal on Pt(111) and the Pt sbnd Ni sbnd Pt(111) bimetallic surface, with a dominant decarbonylation pathway on the Pt(111) surface. A self-hydrogenation (disproportionation) pathway toward 1-propanol was observed on the Ni(111) film, however, the decarbonylation pathway was found to be the most dominant on this surface. Unlike 2-propenol, propanal did not undergo isomerization or self-hydrogenation pathways on any of the surfaces, with the dominant pathway being primarily the decarbonylation on Pt(111) and Ni(111). In contrast, 1-propanol underwent mainly molecular desorption from all three surfaces. These results provided additional understanding of previous studies of hydrogenation pathways of acrolein on the Ni/Pt(111) surfaces.

  15. Laser-based surface preparation of composite laminates leads to improved electrodes for electrical measurements

    KAUST Repository

    Almuhammadi, Khaled

    2015-10-19

    Electrical impedance tomography (EIT) is a low-cost, fast and effective structural health monitoring technique that can be used on carbon fiber reinforced polymers (CFRP). Electrodes are a key component of any EIT system and as such they should feature low resistivity as well as high robustness and reproducibility. Surface preparation is required prior to bonding of electrodes. Currently this task is mostly carried out by traditional sanding. However this is a time consuming procedure which can also induce damage to surface fibers and lead to spurious electrode properties. Here we propose an alternative processing technique based on the use of pulsed laser irradiation. The processing parameters that result in selective removal of the electrically insulating resin with minimum surface fiber damage are identified. A quantitative analysis of the electrical contact resistance is presented and the results are compared with those obtained using sanding.

  16. Insect Residue Contamination on Wing Leading Edge Surfaces: A Materials Investigation for Mitigation

    Science.gov (United States)

    Lorenzi, Tyler M.; Wohl, Christopher J.; Penner, Ronald K.; Smith, Joseph G.; Siochi, Emilie J.

    2011-01-01

    Flight tests have shown that residue from insect strikes on aircraft wing leading edge surfaces may induce localized transition of laminar to turbulent flow. The highest density of insect populations have been observed between ground level and 153 m during light winds (2.6 -- 5.1 m/s), high humidity, and temperatures from 21 -- 29 C. At a critical residue height, dependent on the airfoil and Reynolds number, boundary layer transition from laminar to turbulent results in increased drag and fuel consumption. Although this represents a minimal increase in fuel burn for conventional transport aircraft, future aircraft designs will rely on maintaining laminar flow across a larger portion of wing surfaces to reduce fuel burn during cruise. Thus, insect residue adhesion mitigation is most critical during takeoff and initial climb to maintain laminar flow in fuel-efficient aircraft configurations. Several exterior treatments investigated to mitigate insect residue buildup (e.g., paper, scrapers, surfactants, flexible surfaces) have shown potential; however, implementation has proven to be impractical. Current research is focused on evaluation of wing leading edge surface coatings that may reduce insect residue adhesion. Initial work under NASA's Environmentally Responsible Aviation Program focused on evaluation of several commercially available products (commercial off-the-shelf, COTS), polymers, and substituted alkoxy silanes that were applied to aluminum (Al) substrates. Surface energies of these coatings were determined from contact angle data and were correlated to residual insect excrescence on coated aluminum substrates using a custom-built "bug gun." Quantification of insect excrescence surface coverage was evaluated by a series of digital photographic image processing techniques.

  17. Surface dust wipes are the best predictors of blood leads in young children with elevated blood lead levels

    International Nuclear Information System (INIS)

    Gulson, Brian; Anderson, Phil; Taylor, Alan

    2013-01-01

    Background: As part of the only national survey of lead in Australian children, which was undertaken in 1996, lead isotopic and lead concentration measurements were obtained from children from 24 dwellings whose blood lead levels were ≥15 µg/dL in an attempt to determine the source(s) of their elevated blood lead. Comparisons were made with data for six children with lower blood lead levels ( 208 Pb/ 206 Pb, 207 Pb/ 206 Pb and 206 Pb/ 204 Pb) and lead concentrations in blood, dust from floor wipes, soil, drinking water and paint (where available). Evaluation of associations between blood and the environmental samples was based on the analysis of individual cases, and Pearson correlations and multiple regression analyses based on the whole dataset. Results and discussion: The correlations showed an association for isotopic ratios in blood and wipes (r=0.52, 95% CI 0.19–0.74), blood and soil (r=0.33, 95% CI −0.05–0.62), and blood and paint (r=0.56, 95% CI 0.09–0.83). The regression analyses indicated that the only statistically significant relationship for blood isotopic ratios was with dust wipes (B=0.65, 95% CI 0.35–0.95); there were no significant associations for lead concentrations in blood and environmental samples. There is a strong isotopic correlation of soils and house dust (r=0.53, 95% CI 0.20–0.75) indicative of a common source(s) for lead in soil and house dust. In contrast, as with the regression analyses, no such association is present for bulk lead concentrations (r=−0.003, 95% CI −0.37–0.36), the most common approach employed in source investigations. In evaluation of the isotopic results on a case by case basis, the strongest associations were for dust wipes and blood. -- Highlights: • Children with elevated blood lead ≥15 µg/dL compared with a group with <10 µg/dL. • High precision lead isotopic ratios in blood, house dust wipes, soil, water, paint. • Associations for isotopic measures of blood and dust, blood and

  18. Ni- and Mn-Promoted Mesoporous Co3O4: A Stable Bifunctional Catalyst with Surface-Structure-Dependent Activity for Oxygen Reduction Reaction and Oxygen Evolution Reaction.

    Science.gov (United States)

    Song, Wenqiao; Ren, Zheng; Chen, Sheng-Yu; Meng, Yongtao; Biswas, Sourav; Nandi, Partha; Elsen, Heather A; Gao, Pu-Xian; Suib, Steven L

    2016-08-17

    Efficient bifunctional catalysts for electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are highly desirable due to their wide applications in fuel cells and rechargeable metal air batteries. However, the development of nonprecious metal catalysts with comparable activities to noble metals is still challenging. Here we report a one-step wet-chemical synthesis of Ni-/Mn-promoted mesoporous cobalt oxides through an inverse micelle process. Various characterization techniques including powder X-ray diffraction (PXRD), N2 sorption, transmission electron microscopy (TEM), and scanning electron microscopy (SEM) confirm the successful incorporation of Ni and Mn leading to the formation of Co-Ni(Mn)-O solid solutions with retained mesoporosity. Among these catalysts, cobalt oxide with 5% Ni doping demonstrates promising activities for both ORR and OER, with an overpotential of 399 mV for ORR (at -3 mA/cm(2)) and 381 mV (at 10 mA/cm(2)) for OER. Furthermore, it shows better durability than precious metals featuring little activity decay throughout 24 h continuous operation. Analyses of cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), Raman, and O2-temperature-programmed desorption (O2-TPD) reveal that redox activity of Co(3+) to Co(4+) is crucial for OER performance, while the population of surface oxygen vacancies and surface area determine ORR activities. The comprehensive investigation of the intrinsic active sites for ORR and OER by correlating different physicochemical properties to the electrochemical activities is believed to provide important insight toward the rational design of high-performance electrocatalysts for ORR and OER reactions.

  19. A comparison of surface wipe media for sampling lead on hands.

    Science.gov (United States)

    Boeniger, Mark

    2006-08-01

    Hand contamination by toxic agents such as lead presents a potentially significant health hazard to workers if the contamination is transferred to the mouth by food, smoking, or touching the mouth. One method to sample the mass of contamination on hands is to wipe the skin and analyze the wipe media for the analyte. Several commercially available, prewetted wipe media were evaluated and compared. The Palintest and Wash'n Dri media are made of cellulose fiber; the Ghost wipe is made of a nonwoven polyvinyl alcohol fiber. ASTM test method E1792 for surface lead sampling provides some specified minimum requirements and some general, nonspecific criteria that these media should meet. However, no objective determination of the performance or characteristics of these different wiping media were found in the open literature for sampling lead on hands, particularly relating to typical collection efficiency. To test the recovery of lead oxide dust collected from two hands, two different loading levels were used for each wipe medium. Four successive wipes were collected and analyzed individually. The results of this study indicate that only about 52-62% of the total lead loading is recovered with the first wipe, but that up to 75% recovery could be obtained by combining all three successive wipes. This study also describes testing several physical aspects of these wipes that included tensile strength, wetness, and drying rate, which are characteristics that are not specified by ASTM E1792. The results indicate a higher fragility among the cellulosic wipes, less moisture content, and higher drying rates than the Ghost wipe. This information should be helpful when selecting a wipe material that is best suited for an environmental or industrial hygiene surface or skin sampling task and might also be useful for improving such media in the future.

  20. Measurement of activation reaction rate distributions in a lead assembly bombarded with 500-MeV protons

    CERN Document Server

    Takada, H; Sasa, T; Tsujimoto, K; Yasuda, H

    2000-01-01

    Reaction rate distributions of various activation detectors such as the /sup nat/Ni(n, x)/sup 58/Co, /sup 197/Au(n,2n)/sup 196/Au, and /sup 197/Au(n,4n)/sup 194/Au reactions were measured to study the production and the transport of spallation neutrons in a lead assembly bombarded with protons of 500 MeV. The measured data were analyzed with the nucleon-meson transport code NMTC/JAERI combined with the MCNP4A code using the nuclide production cross sections based on the JENDL Dosimetry File and those calculated with the ALICE-F code. It was found that the NMTC/JAERI-MCNP4A calculations agreed well with the experiments for the low-energy-threshold reaction of /sup nat/Ni(n, x)/sup 58/Co. With the increase of threshold energy, however, the calculation underestimated the experiments, especially above 20 MeV. The reason for the disagreement can be attributed to the underestimation of the neutron yield in the tens of mega-electron-volt regions by the NMTC/JAERI code. (32 refs).

  1. Combined Thermodynamic-Kinetic Analysis of the Interfacial Reactions between Ni Metallization and Various Lead-Free Solders

    Directory of Open Access Journals (Sweden)

    Tomi Laurila

    2009-11-01

    Full Text Available In this paper we will demonstrate how a thermodynamic-kinetic method can be utilized to rationalize a wide range of interfacial phenomena between Sn-based lead-free solders and Ni metallizations. First, the effect of P on the interfacial reactions, and thus on the reliability, between Sn-based solders and electroless Ni/immersion Au (ENIG metallizations, will be discussed. Next, the effect of small amounts of Cu in Sn-based solders on the intermetallic compound (IMC, which forms first on top of Ni metallization, will be covered. With the help of thermodynamic arguments a so called critical Cu concentration for the formation of (Cu,Ni6Sn5 can be determined as a function of temperature. Then the important phenomenon of redeposition of (Au,NiSn4 layer on top of Ni3Sn4 IMC will be discussed in detail. The reasons leading to this behaviour will be rationalized with the help of thermodynamic information and an explanation of why this phenomenon does not occur when an appropriate amount of Cu is present in the soldering system will be given. Finally, interfacial reaction issues related to low temperature Sn-Zn and Sn-Bi based solders and Ni metallization will be discussed.

  2. Surface chemical reactions induced by molecules electronically-excited in the gas

    DEFF Research Database (Denmark)

    Petrunin, Victor V.

    2011-01-01

    and alignment are taking place, guiding all the molecules towards the intersections with the ground state PES, where transitions to the ground state PES will occur with minimum energy dissipation. The accumulated kinetic energy may be used to overcome the chemical reaction barrier. While recombination chemical...... beams inducing the reaction can be used to distinguish the new process we try to investigate from chemical reactions induced by photoexcitation within adsorbed molecules and/or gas phase photolysis.......We present a model suggesting high chemical activity of electronically-excited molecules colliding with an isolator surface. Initial photochemical event is accounted for as the result of molecular evolution on the electronically-excited potential energy surface (PES), where acceleration...

  3. Surface concentration nonuniformities resulting from chronoamperometry of a reversible reaction at an ultramicrodisk electrode

    DEFF Research Database (Denmark)

    Britz, Dieter H.; Strutwolf, Jörg

    2016-01-01

    The chronoamperometric experiment at a disk electrode was simulated, assuming a reversible reaction. When the diffusion coefficients of the two substances involved are different, there appears a surface concentration non- uniformity in the radial direction, exhibiting a maximum effect in time...

  4. Surface bond contraction and its effect on the nanometric sized lead zirconate titanate

    International Nuclear Information System (INIS)

    Haitao Huang; Sun, Chang Q.; Hing, Peter

    2000-01-01

    The grain size effect of lead zirconate titanate PbZr 1-x Ti x O 3 (PZT, x≥0.6) caused by surface bond contraction has been investigated by using the Landau-Ginsburg-Devonshire (LGD) phenomenological theory. It has been shown that, due to the surface bond contraction, both the Curie temperature and the spontaneous polarization of tetragonal PZT decrease with decreasing grain size. These effects become more significant when the grain size is in the nanometre range. A dielectric anomaly appears with decreasing grain size, which corresponds to a size dependent phase transformation. The ferroelectric critical size below which a loss of ferroelectricity will happen is estimated from the results obtained. (author). Letter-to-the-editor

  5. Effect of zinc, lead, and cadmium pollution on the leaf surface mircoflora

    Energy Technology Data Exchange (ETDEWEB)

    Gingell, S.M.; Campbell, R.; Martin, M.H.

    1976-01-01

    A leaf-washing method was used to compare the phylloplane microflora of cabbages and pine saplings exposed to surface contamination by zinc, lead and cadmium from a smelter with that of similar uncontaminated plants. The microflora of contaminated plants was reduced in both abundance and species diversity; pigmented yeasts and bacteria seemed particularly sensitive. The isolates from contaminated plants were more tolerant to heavy metals in artificial media than the isolates from uncontaminated plants. Artificially contaminated and inoculated plants also showed a reduction in the phylloplane microflora.

  6. Theoretical investigation of lead vapor adsorption on kaolinite surfaces with DFT calculations.

    Science.gov (United States)

    Wang, Xinye; Huang, Yaji; Pan, Zhigang; Wang, Yongxing; Liu, Changqi

    2015-09-15

    Kaolinite can be used as the in-furnace sorbent/additive to adsorb lead (Pb) vapor at high temperature. In this paper, the adsorptions of Pb atom, PbO molecule and PbCl2 molecule on kaolinie surfaces were investigated by density functional theory (DFT) calculation. Si surface is inert to Pb vapor adsorption while Al surfaces with dehydroxylation are active for the unsaturated Al atoms and the O atoms losing H atoms. The adsorption energy of PbO is much higher than that of Pb atom and PbCl2. Considering the energy barriers, it is easy for PbO and PbCl2 to adsorb on Al surfaces but difficult to escape. The high energy barriers of de-HCl process cause the difficulties of PbCl2 to form PbO·Al2O3·2SiO2 with kaolinite. Considering the inertia of Si atoms and the activity of Al atoms after dehydroxylation, calcination, acid/alkali treatment and some other treatment aiming at amorphous silica producing and Al activity enhancement can be used as the modification measures to improve the performance of kaolinite as the in-furnace metal capture sorbent. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Probing the Surface of Platinum during the Hydrogen Evolution Reaction in Alkaline Electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Stoerzinger, Kelsey A. [Physical; Favaro, Marco [Advanced; Joint; Chemical; Ross, Philip N. [Materials; Yano, Junko [Joint; Molecular; Liu, Zhi [State; Division; Hussain, Zahid [Advanced; Crumlin, Ethan J. [Advanced; Joint Center

    2017-11-02

    Understanding the surface chemistry of electrocatalysts in operando can bring insight into the reaction mechanism, and ultimately the design of more efficient materials for sustainable energy storage and conversion. Recent progress in synchrotron based X-ray spectroscopies for in operando characterization allows us to probe the solid/liquid interface directly while applying an external potential, applied here to the model system of Pt in alkaline electrolyte for the hydrogen evolution reaction (HER). We employ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to identify the oxidation and reduction of Pt-oxides and hydroxides on the surface as a function of applied potential, and further assess the potential for hydrogen adsorption and absorption (hydride formation) during and after the HER. This new window into the surface chemistry of Pt in alkaline brings insight into the nature of the rate limiting step, the extent of H ad/absorption and it’s persistence at more anodic potentials.

  8. Investigation of reaction mechanisms during electroreduction of carbon dioxide on lead electrode for the production of organic compounds

    International Nuclear Information System (INIS)

    Innocent, B.

    2008-09-01

    The aim of this work was to promote the reduction of CO 2 through its electrochemical conversion (electro-synthesis) on a lead electrode into high added value products. Depending on the nature of electrolyte, the electro-reduction of carbon dioxide leads to different products. Various electrolytes (aqueous or organic, protic or aprotic) were used to study two mechanisms: hydrogenation (formation of formate) and electro-dimerization (synthesis of oxalate). Cyclic voltammetry studies have been carried out for electrochemically characterizing CO 2 reduction on Pb. The electrochemical investigation of the electrode electrolyte interface has shown that the process of CO 2 electro-reduction is a mass transfer control both in the organic and aqueous media. Electrochemical experiments (cyclic voltammetry, chrono-amperometry) coupled with in situ infrared reflectance spectroscopic techniques (SPAIRS, SNIFTIRS) have also shown that in aqueous medium (7 ≤pH≤9) hydrogeno-carbonate ions were reduced to formate. The modification of solvent (propylene carbonate) leads selectively to oxalate as the main reaction product. Long-term electrolyses were performed in a filter-press cell to deal large volumes. In aqueous medium, the reduction of HCO 3 - to HCOO - (R F = 89% at -2.5 mA cm -2 and 4 C) is always accompanied by the production of H 2 . (author)

  9. Oxidation of elemental mercury by chlorine: Gas phase, Surface,and Photo-induced reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Nai-Qiang; Liu, Shou-Heng; Chang, Shih-Ger

    2004-10-22

    Accurate oxidation rate constants of mercury gas are needed for determining its dispersion and lifetime in the atmosphere. They would also help in developing a technology for the control of mercury emissions from coal-fired power plants. However, it is difficult to establish the accurate rate constants primarily due to the fact that mercury easily adsorbs on solid surface and its reactions can be catalyzed by the surface. We have demonstrated a procedure that allows the determination of gas phase, surface-induced, and photo-induced contributions in the kinetic study of the oxidation of mercury by chlorine gas. The kinetics was studied using reactors with various surface to volume ratios. The effect of the surface and the photo irradiation on the reaction was taken into consideration. The pressure dependent study revealed that the gas phase oxidation was a three-body collision process. The third order rate constant was determined to be 7.5({+-}0.2) x 10{sup -39} mL{sup 2} molecules{sup -2}s{sup -1} with N{sub 2} as the third body at 297 {+-} 1 K. The surface induced reaction on quartz window was second order and the rate constant was 2.7 x 10{sup -17} mL{sup 2} molecules{sup -1} cm{sup -2} sec. Meanwhile, the 253.7 nm photon employed for mercury detection was found to accelerate the reaction. The utilization efficiency of 253.7 nm photon for Hg{sup 0} oxidation was 6.7 x 10{sup -4} molecules photon{sup -1} under the conditions employed in this study.

  10. Use of molecular beams for kinetic measurements of chemical reactions on solid surfaces

    Science.gov (United States)

    Zaera, Francisco

    2017-05-01

    In this review we survey the contributions that molecular beam experiments have provided to our understanding of the dynamics and kinetics of chemical interactions of gas molecules with solid surfaces. First, we describe the experimental details of the different instrumental setups and approaches available for the study of these systems under the ultrahigh vacuum conditions and with the model planar surfaces often used in modern surface-science experiments. Next, a discussion is provided of the most important fundamental aspects of the dynamics of chemical adsorption that have been elucidated with the help of molecular beam experiments, which include the development of potential energy surfaces, the determination of the different channels for energy exchange between the incoming molecules and the surface, the identification of adsorption precursor states, the understanding of dissociative chemisorption, the determination of the contributions of corrugation, steps, and other structural details of the surface to the adsorption process, the effect to molecular steering, the identification of avenues for assisting adsorption, and the molecular details associated with the kinetics of the uptake of adsorbates as a function of coverage. We follow with a summary of the work directed at the determination of kinetic parameters and mechanistic details of surface reactions associated with catalysis, mostly those promoted by late transition metals. This discussion we initiate with an overview of what has been learned about simple bimolecular reactions such as the oxidation of CO and H2 with O2 and the reaction of CO with NO, and continue with the review of the studies of more complex systems such as the oxidation of alcohols, the conversion of organic acids, the hydrogenation and isomerization of olefins, and the oxidative activation of alkanes under conditions of short contact times. Sections 6 and 7 of this review deal with the advances made in the use of molecular beams with

  11. Small leak detection by measuring surface oscillation during sodium-water reaction in steam generator

    International Nuclear Information System (INIS)

    Nei, Hiromichi; Hori, Masao

    1977-01-01

    Small leak sodium-water reaction tests were conducted to develop various kinds of leak detectors for the sodium-heated steam generator in FBR. The super-heated steam was injected into sodium in a reaction vessel having a sodium free surface, simulating the steam generator. The level gauge in the reaction vessel generated the most reliable signal among detectors, as long as the leak rates were relatively high. The level gauge signal was estimated to be the sodium surface oscillation caused by hydrogen bubbles produced in sodium-water reaction. Experimental correlation was derived, predicting the amplitude as a function of leak rate, hydrogen dissolution ratio, bubble rise velocity and other parameters concerned, assuming that the surface oscillation is in proportion to the gas hold-up. The noise amplitude under normal operation without water leak was increased with sodium flow rate and found to be well correlated with Froud number. These two correlations predict that a water leak in a ''MONJU'' class (300 MWe) steam generator could possibly be detected by level gauges at a leak rate above 2 g/sec. (auth.)

  12. Surface photo reaction processes using synchrotron radiation; Hoshako reiki ni yoru hyomenko hanno process

    Energy Technology Data Exchange (ETDEWEB)

    Imaizumi, Y. [Tohoku University, Sendai (Japan). Institute for Materials Research; Yoshigoe, A. [Toyohashi University of Technology, Aichi (Japan); Urisu, T. [Toyohashi University of Technology, Aichi (Japan). Institute for Molecular Science

    1997-08-20

    This paper introduces the surface photo reaction processes using synchrotron radiation, and its application. A synchrotron radiation process using soft X-rays contained in electron synchrotron radiated light as an excited light source has a possibility of high-resolution processing because of its short wave length. The radiated light can excite efficiently the electronic state of a substance, and can induce a variety of photochemical reactions. In addition, it can excite inner shell electrons efficiently. In the aspect of its application, it has been found that, if radiated light is irradiated on surfaces of solids under fluorine-based reaction gas or Cl2, the surfaces can be etched. This technology is utilized practically. With regard to radiated light excited CVD process, it may be said that anything that can be deposited by the ordinary plasma CVD process can be deposited. Its application to epitaxial crystal growth may be said a nano processing application in thickness direction, such as forming an ultra-lattice structure, the application being subjected to expectation. In micromachine fabricating technologies, a possibility is searched on application of a photo reaction process of the radiated light. 5 refs., 6 figs.

  13. Optimization of lead adsorption of mordenite by response surface methodology: characterization and modification.

    Science.gov (United States)

    Turkyilmaz, Havva; Kartal, Tolga; Yigitarslan Yildiz, Sibel

    2014-01-06

    In order to remove heavy metals, water treatment by adsorption of zeolite is gaining momentum due to low cost and good performance. In this research, the natural mordenite was used as an adsorbent to remove lead ions in an aqueous solution. The effects of adsorption temperature, time and initial concentration of lead on the adsorption yield were investigated. Response surface methodology based on Box-Behnken design was applied for optimization. Adsorption data were analyzed by isotherm models. The process was investigated by batch experiments; kinetic and thermodynamic studies were carried out. Adsorption yields of natural and hexadecyltrimethylammonium-bromide-modified mordenite were compared. The optimum conditions of maximum adsorption (nearly 84 percent) were found as follows: adsorption time of 85-90 min, adsorption temperature of 50°C, and initial lead concentration of 10 mg/L. At the same optimum conditions, modification of mordenite produced 97 percent adsorption yield. The most appropriate isotherm for the process was the Freundlich. Adsorption rate was found as 4.4. Thermodynamic calculations showed that the adsorption was a spontaneous and an exothermic process. Quadratic model and reduced cubic model were developed to correlate the variables with the adsorption yield of mordenite. From the analysis of variance, the most influential factor was identified as initial lead concentration. At the optimum conditions modification increased the adsorption yield up to nearly 100 percent. Mordenite was found an applicable adsorbent for lead ions especially in dilute solutions and may also be applicable in more concentrated ones with lower yields.

  14. Electro-deposition of Pd on Carbon paper and Ni foam via surface limited redox-replacement reaction for oxygen reduction reaction: Presentation

    CSIR Research Space (South Africa)

    Modibedi, M

    2013-03-01

    Full Text Available during the catalyst preparation process, Pd nanosturctures are grown directly on fuel cell gas diffusion layers and evaluated for the ORR. Pd nanostructures were synthesized via surface-limited redox replacement (SLRR) reaction employing...

  15. Electro-deposition of Pd on carbon paper and Ni foam via surface limited redox-replacement reaction for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Modibedi, RM

    2014-05-01

    Full Text Available Pd nanostructured catalysts were electrodeposited by surface-limited redox replacement reactions usingthe electrochemical atomic layer deposition technique. Carbon paper and Ni foam were used as substratesfor the electrodeposition of the metal...

  16. TEM monitoring of silver nanoparticles formation on the surface of lead crystal glass

    Energy Technology Data Exchange (ETDEWEB)

    Gil, C. [Fundacion Centro Nacional del Vidrio, Real Fabrica de Cristales, Po Pocillo, 1. 40100 La Granja de San Ildefonso, Segovia (Spain); Villegas, M.A. [Centro Nacional de Investigaciones Metalurgicas, CSIC, Avda. Gregorio del Amo, 8. 28040 Madrid (Spain)]. E-mail: mavillegas@cenim.csic.es; Navarro, J.M. Fernandez [Instituto de Optica Daza de Valdes, CSIC, C. Serrano, 121. 28006 Madrid (Spain)

    2006-12-15

    Silver nanoparticles have been formed on the surface of lead crystal glass by means of (i) ion-exchange of alkaline ions from the glass by Ag{sup +} ions from a molten salts bath, and (ii) silica based sol-gel coatings containing silver. All experimental variables concerning both ion-exchange process and sol-gel coatings application were combined and studied as main parameters governing the reduction of Ag{sup +} ions to Ag{sup 0} atoms and further aggregation to form nanosized colloids. The content of thermoreducing agents (arsenic or antimony oxides) in the lead crystal glass was essential to favour the reduction of silver ions to form nanoparticles. Optimal experimental conditions to be used for the obtaining of surface silver nanoparticles were determined. TEM was used as the principal characterisation technique for direct observation of the nanoparticles generated. The size of silver colloids varied in the 20-300 nm range for ion-exchanged samples and in the 10-80 nm range for sol-gel coated samples.

  17. Surface reaction and transport in mixed conductors with electrochemically-active surfaces: a 2-D numerical study of ceria.

    Science.gov (United States)

    Ciucci, Francesco; Chueh, William C; Goodwin, David G; Haile, Sossina M

    2011-02-14

    A two-dimensional, small-bias model has been developed for describing transport through a mixed ionic and electronic conductor (MIEC) with electrochemically-active surfaces, a system of particular relevance to solid oxide fuel cells. Utilizing the h-adaptive finite-element method, we solve the electrochemical potential and flux for both ionic and electronic species in the MIEC, taking the transport properties of Sm(0.15)Ce(0.85)O(1.925-δ) (SDC15). In addition to the ionic flux that flows between the two sides of the cell, there are two types of electronic fluxes: (1) cross-plane current that flows in the same general direction as the ionic current, and (2) in-plane current that flows between the catalytically-active MIEC surface and the metal current collectors. From an evaluation of these fluxes, the macroscopic interfacial resistance is decomposed into an electrochemical reaction resistance and an electron diffusion-drift resistance, the latter associated with the in-plane electronic current. Analysis of the experimental data for the interfacial resistance for hydrogen electro-oxidation on SDC15 having either Pt or Au current collectors (W. Lai and S. M. Haile, J. Am. Ceram. Soc., 2005, 88, 2979-2997; W. C. Chueh, W. Lai and S. M. Haile, Solid State Ionics, 2008, 179, 1036-1041) indicates that surface reaction rather than electron migration is the overall rate-limiting step, and suggests furthermore that the surface reaction rate, which has not been directly measured in the literature, scales with pO2(-1/4). The penetration depth for the in-plane electronic current is estimated at 0.6 μm for the experimental conditions of interest to SDC15, and is found to attain a value as high as 4 μm within the broader range of computational conditions.

  18. Molecular resonances, fusion reactions and surface transparency of interaction between heavy ions

    International Nuclear Information System (INIS)

    Abe, Yasuhisa.

    1980-01-01

    A review of the Band Crossing Model is given, including recent results on the 16 O + 16 O system. Surface Transparency is discussed in the light of the recent development in our understanding of the fusion reaction mechanisms and by calculating the number of open channels available to direct reactions. The existence of the Molecular Resonance Region is suggested in several systems by the fact that Band Crossing Region overlaps with the Transparent Region. A systematic study predicts molecular resonances in the 14 C + 14 C and 12 C + 14 C systems as prominent as those observed in the 16 O + 16 O and 12 C + 16 O systems

  19. Surface Modification Reaction of Photocatalytic Titanium Dioxide with Triethoxysilane for Improving Dispersibility

    International Nuclear Information System (INIS)

    Lee, Myung Jin; Kim, Ji Ho; Park, Young Tae

    2010-01-01

    We have carried out the surface modification of photocatalytic TiO 2 with triethoxysilane through dehydrogenation reaction and characterized the modified photocatalyst by spectroscopic methods, such as FT-IR, solid-state 29 Si MAS NMR, XPS, and XRF, etc. We also examined photocatalytic activity of the immobilized photocatalytic titanium dioxide with triethoxysilane by decolorization reaction of dyes such as cong red and methylene blue under visible light. Dispersion test showed that the photocatalytic titanium dioxide immobilized with triethoxysilane group has kept higher dispersibility than titanium dioxide itself. No appreciable precipitation takes place even after standing for 24 h in the 4:6 mixture ratio of ethanol and water

  20. Plasma-Engraved Co3 O4 Nanosheets with Oxygen Vacancies and High Surface Area for the Oxygen Evolution Reaction.

    Science.gov (United States)

    Xu, Lei; Jiang, Qianqian; Xiao, Zhaohui; Li, Xingyue; Huo, Jia; Wang, Shuangyin; Dai, Liming

    2016-04-18

    Co3 O4 , which is of mixed valences Co(2+) and Co(3+) , has been extensively investigated as an efficient electrocatalyst for the oxygen evolution reaction (OER). The proper control of Co(2+) /Co(3+) ratio in Co3 O4 could lead to modifications on its electronic and thus catalytic properties. Herein, we designed an efficient Co3 O4 -based OER electrocatalyst by a plasma-engraving strategy, which not only produced higher surface area, but also generated oxygen vacancies on Co3 O4 surface with more Co(2+) formed. The increased surface area ensures the Co3 O4 has more sites for OER, and generated oxygen vacancies on Co3 O4 surface improve the electronic conductivity and create more active defects for OER. Compared to pristine Co3 O4 , the engraved Co3 O4 exhibits a much higher current density and a lower onset potential. The specific activity of the plasma-engraved Co3 O4 nanosheets (0.055 mA cm(-2) BET at 1.6 V) is 10 times higher than that of pristine Co3 O4 , which is contributed by the surface oxygen vacancies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Investigations of the Fundamental Surface Reactions Involved in the Sorption and Desorption of Radionuclides

    International Nuclear Information System (INIS)

    Czerwinski, Ken; Heske, Clemens; Moser, Duane; Misra, Mnoranjan; McMillion, Glen

    2011-01-01

    Models for describing solution- and surface-phase reactions have been used for 30 years, but only recently applicable to complex surfaces. Duff et al., using micro-XANES, found that Pu was concentrated on Mn-oxide and smectite phases of zeolitic tuff, providing an evaluation of contaminant speciation on surfaces for modeling. Experiments at Los Alamos demonstrated that actinides display varying surface residence time distributions, probably reflective of mineral surface heterogeneity. We propose to investigate the sorption/desorption behavior of radionuclides from mineral surfaces, as effected by microorganisms, employing isolates from Nevada Test Site deep alluvium as a model system. Characterizations will include surface area, particle size distribution, x-ray diffraction (XRD), microprobe analysis, extractions, and microbiology. Surface interactions will be assessed by electron spectroscopy (XPS), x-ray absorption fine structure spectroscopy (XAFS), X-ray emission spectroscopy, transmission electron microscopy (TEM) and Scanning electron microscopy (SEM). Desert Research Institute (DRI), University of Nevada, Reno (UNR), and University of Nevada, Las Vegas (UNLV) researchers will collaborate to enhance scientific infrastructure and the understanding of contaminant behavior on surfaces, with broader implications for the management of DOE sites.

  2. Investigations of the Fundamental Surface Reactions Involved in the Sorption and Desorption of Radionuclides

    Energy Technology Data Exchange (ETDEWEB)

    Czerwinski, Ken; Heske, Clemens; Moser, Duane; Misra, Mnoranjan; McMillion, Glen

    2011-04-20

    Models for describing solution- and surface-phase reactions have been used for 30 years, but only recently applicable to complex surfaces. Duff et al., using micro-XANES, found that Pu was concentrated on Mn-oxide and smectite phases of zeolitic tuff, providing an evaluation of contaminant speciation on surfaces for modeling. Experiments at Los Alamos demonstrated that actinides display varying surface residence time distributions, probably reflective of mineral surface heterogeneity. We propose to investigate the sorption/desorption behavior of radionuclides from mineral surfaces, as effected by microorganisms, employing isolates from Nevada Test Site deep alluvium as a model system. Characterizations will include surface area, particle size distribution, x-ray diffraction (XRD), microprobe analysis, extractions, and microbiology. Surface interactions will be assessed by electron spectroscopy (XPS), x-ray absorption fine structure spectroscopy (XAFS), X-ray emission spectroscopy, transmission electron microscopy (TEM) and Scanning electron microscopy (SEM). Desert Research Institute (DRI), University of Nevada, Reno (UNR), and University of Nevada, Las Vegas (UNLV) researchers will collaborate to enhance scientific infrastructure and the understanding of contaminant behavior on surfaces, with broader implications for the management of DOE sites.

  3. Surface plasmon resonance sensing detection of mercury and lead ions based on conducting polymer composite.

    Directory of Open Access Journals (Sweden)

    Mahnaz M Abdi

    Full Text Available A new sensing area for a sensor based on surface plasmon resonance (SPR was fabricated to detect trace amounts of mercury and lead ions. The gold surface used for SPR measurements were modified with polypyrrole-chitosan (PPy-CHI conducting polymer composite. The polymer layer was deposited on the gold surface by electrodeposition. This optical sensor was used for monitoring toxic metal ions with and without sensitivity enhancement by chitosan in water samples. The higher amounts of resonance angle unit (ΔRU were obtained for PPy-CHI film due to a specific binding of chitosan with Pb(2+ and Hg(2+ ions. The Pb(2+ ion bind to the polymer films most strongly, and the sensor was more sensitive to Pb(2+ compared to Hg(2+. The concentrations of ions in the parts per million range produced the changes in the SPR angle minimum in the region of 0.03 to 0.07. Data analysis was done by Matlab software using Fresnel formula for multilayer system.

  4. 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.

  5. Effect of trace elements on the interface reactions between two lead-free solders and copper or nickel substrates

    Directory of Open Access Journals (Sweden)

    Soares D.

    2007-01-01

    Full Text Available Traditional Sn-Pb solder alloys are being replaced, because of environmental and health concerns about lead toxicity. Among some alternative alloy systems, the Sn-Zn and Sn-Cu base alloy systems have been studied and reveal promising properties. The reliability of a solder joint is affected by the solder/substrate interaction and the nature of the layers formed at the interface. The solder/substrate reactions, for Sn-Zn and Sn-Cu base solder alloys, were evaluated in what concerns the morphology and chemical composition of the interface layers. The effect of the addition of P, at low levels, on the chemical composition of the layers present at the interface was studied. The phases formed at the interface between the Cu or Ni substrate and a molten lead-free solder at 250ºC, were studied for different stage times and alloy compositions. The melting temperatures, of the studied alloys, were determined by Differential Scanning Calorimetry (DSC. Identification of equilibrium phases formed at the interface layer, and the evaluation of their chemical composition were performed by Scanning Electron Microscopy (SEM/EDS. Different interface characteristics were obtained, namely for the alloys containing Zn. The obtained IML layer thickness was compared, for both types of alloy systems.

  6. Versatile gas-phase reactions for surface to bulk esterification of cellulose microfibrils aerogels.

    Science.gov (United States)

    Fumagalli, Matthieu; Ouhab, Djamila; Boisseau, Sonia Molina; Heux, Laurent

    2013-09-09

    Aqueous suspensions of microfibrillated cellulose obtained by a high pressure homogenization process were freeze-dried after solvent exchange into tert-butanol. The resulting aerogels, which displayed a remarkable open morphology with a surface area reaching 100 m(2)/g, were subjected to a gas-phase esterification with palmitoyl chloride. Under these conditions, variations of the reaction temperature from 100 to 200 °C, of the reaction time from 0.5 to 2 h, and of the initial quantity of reagent, led to the preparation of a library of cellulose palmitates with DS varying from zero to 2.36. These products were characterized by gravimetry, FTIR, and (13)C solid-state NMR spectroscopy. Of special interest were the cellulose palmitate samples of low DS in the range of 0.1-0.4, which corresponded to hydrophobic cellulose microfibrils exclusively esterified at their surface while keeping intact their inner structure.

  7. Deuterium isotopic exchange reaction on the surface of promoted nickel catalysts+

    International Nuclear Information System (INIS)

    Abou EL-Nour, F.; Abdel-Badei, M.M.; Belacy, N.

    1987-01-01

    Nickel catalysts promoted with different metal oxides proved to be efficient for the isotopic exchange of deuterium between hydrogen and water in the vapour phase. Estimation of the surface properties of this type of catalysts led to the correlation of the specific catalytic activity with their surface characteristics. The particle size of nickel content of the catalysts under investigation was determined from the surface area measurements. The equation used for particle size determination is a corrected one. The correction is based on the probability of sharing the 6-faces of cubic nickel crystals, present in the promoted catalyst, in the isotopic exchange process. It may be also due to the increased porosity of the components of the catalyst mixture. The results demonstrate the probability of migration of nickel crystals during the isotopic exchange reaction of deuterium between hydrogen and water in the vapour state on the surface of nickel catalysis promoted with different metal oxides

  8. Heterogeneous reaction of SO2 with soot: The roles of relative humidity and surface composition of soot in surface sulfate formation

    Science.gov (United States)

    Zhao, Yan; Liu, Yongchun; Ma, Jinzhu; Ma, Qingxin; He, Hong

    2017-03-01

    The conversion of SO2 to sulfates on the surface of soot is still poorly understood. Soot samples with different fractions of unsaturated hydrocarbons and oxygen-containing groups were prepared by combusting n-hexane under well-controlled conditions. The heterogeneous reaction of SO2 with soot was investigated using in situ attenuated total internal reflection infrared (ATR-IR) spectroscopy, ion chromatography (IC) and a flow tube reactor at the ambient pressure and relative humidity (RH). Water promoted SO2 adsorption and sulfate formation at the RH range from 6% to 70%, while exceeded water condensed on soot was unfavorable for sulfate formation due to inhibition of SO2 adsorption when RH was higher than 80%. The surface composition of soot, which was governed by combustion conditions, also played an important role in the heterogeneous reaction of SO2 with soot. This effect was found to greatly depend on RH. At low RH of 6%, soot with the highest fuel/oxygen ratio of 0.162 exhibited a maximum uptake capacity for SO2 because it contained a large amount of aromatic Csbnd H groups, which acted as active sites for SO2 adsorption. At RH of 54%, soot produced with a fuel/oxygen ratio of 0.134 showed the highest reactivity toward SO2 because it contained appropriate amounts of aromatic Csbnd H groups and oxygen-containing groups, subsequently leading to the optimal surface concentrations of both SO2 and water. These results suggest that variation in the surface composition of soot from different sources and/or resulting from chemical aging in the atmosphere likely affects the conversion of SO2 to sulfates.

  9. Detection of submonolayer oxygen-18 on a gold surface by nuclear reaction analysis

    Energy Technology Data Exchange (ETDEWEB)

    Wielunski, L.S.; Kenny, M.J.; Wieczorek, L. [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Lindfield, NSW (Australia). Div. of Applied Physics

    1993-12-31

    A gold substrate is the preferred solid surface for formation of an organic self-assembled monolayer ( SAM ). Device fabrication process may require the gold film to be exposed to photolithographic processing and plasma treatment prior to molecular assembly. It has been observed that oxygen plasma treatment prevents the formation of SAMs; however, subsequent treatment with an argon plasma allows assembly of the organic monolayers. To understand the mechanisms involved, a plasma containing 98% {sup 18}O was used and the film surface was analysed using the {sup 18}O (p,{alpha}){sup 15}N nuclear reaction. 5 refs., 1 tab., 3 figs.

  10. Modeling of Transmittance Degradation Caused by Optical Surface Contamination by Atomic Oxygen Reaction with Adsorbed Silicones

    Science.gov (United States)

    Snyder, Aaron; Banks, Bruce; Miller, Sharon; Stueber, Thomas; Sechkar, Edward

    2001-01-01

    A numerical procedure is presented to calculate transmittance degradation caused by contaminant films on spacecraft surfaces produced through the interaction of orbital atomic oxygen (AO) with volatile silicones and hydrocarbons from spacecraft components. In the model, contaminant accretion is dependent on the adsorption of species, depletion reactions due to gas-surface collisions, desorption, and surface reactions between AO and silicone producing SiO(x), (where x is near 2). A detailed description of the procedure used to calculate the constituents of the contaminant layer is presented, including the equations that govern the evolution of fractional coverage by specie type. As an illustrative example of film growth, calculation results using a prototype code that calculates the evolution of surface coverage by specie type is presented and discussed. An example of the transmittance degradation caused by surface interaction of AO with deposited contaminant is presented for the case of exponentially decaying contaminant flux. These examples are performed using hypothetical values for the process parameters.

  11. Measuring the Electrode Kinetics of Surface Confined Electrode Reactions at a Constant Scan Rate

    OpenAIRE

    Guziejewski, Dariusz; Mirceski, Valentin; Jadresko, Dijana

    2014-01-01

    Abstract: The kinetics of surface confined electrode reactions of alizarin, vitamin B12, and vitamin K2 is measured with square-wave voltammetry over a wide pH interval, by applying the recent methodology for kinetic analysis at a constant scan rate [V. Mirceski, D. Guziejewski, K. Lisichkov, Electrochim. Acta 2013, 114, 667–673]. The reliability and the simplicity of the recent methodology is confirmed. The methodology requires analysis of the peak potential separation o...

  12. Generating Converged Accurate Free Energy Surfaces for Chemical Reactions with a Force-Matched Semiempirical Model.

    Science.gov (United States)

    Kroonblawd, Matthew P; Pietrucci, Fabio; Saitta, Antonino Marco; Goldman, Nir

    2018-03-22

    We demonstrate the capability of creating robust density functional tight binding (DFTB) models for chemical reactivity in prebiotic mixtures through force matching to short time scale quantum free energy estimates. Molecular dynamics using density functional theory (DFT) is a highly accurate approach to generate free energy surfaces for chemical reactions, but the extreme computational cost often limits the time scales and range of thermodynamic states that can feasibly be studied. In contrast, DFTB is a semiempirical quantum method that affords up to a thousandfold reduction in cost and can recover DFT-level accuracy. Here, we show that a force-matched DFTB model for aqueous glycine condensation reactions yields free energy surfaces that are consistent with experimental observations of reaction energetics. Convergence analysis reveals that multiple nanoseconds of combined trajectory are needed to reach a steady-fluctuating free energy estimate for glycine condensation. Predictive accuracy of force-matched DFTB is demonstrated by direct comparison to DFT, with the two approaches yielding surfaces with large regions that differ by only a few kcal mol -1 .

  13. Surface Treatment to Improve Corrosion Resistance in Lead-Alloy Coolants

    International Nuclear Information System (INIS)

    Todd R. Allen; Kumar Sridharan; McLean T. Machut; Lizhen Tan

    2007-01-01

    One of the six proposed advanced reactor designs of the Generation IV Initiative, the Lead-cooled Fast Reactor (LFR) possesses many characteristics that make it a desirable candidate for future nuclear energy production and responsible actinide management. These characteristics include favorable heat transfer, fluid dynamics, and neutronic performance compared to other candidate coolants. However, the use of a heavy liquid metal coolant presents a challenge for reactor designers in regards to reliable structural and fuel cladding materials in both a highly corrosive high temperature liquid metal and an intense radiation field. Flow corrosion studies at the University of Wisconsin have examined the corrosion performance of candidate materials for application in the LFR concept as well as the viability of various surface treatments to improve the materials compatibility. To date this research has included several focus areas, which include the formulation of an understanding of corrosion mechanisms and the examination of the effects of chemical and mechanical surface modifications on the materials performance in liquid lead-bismuth by experimental testing in Los Alamos National Laboratory's DELTA Loop, as well as comparison of experimental findings to numerical and physical models for long term corrosion prediction. This report will first review the literature and introduce the experiments and data that will be used to benchmark theoretical calculations. The experimental results will be followed by a brief review of the underlying theory and methodology for the physical and theoretical models. Finally, the results of theoretical calculations as well as experimentally obtained benchmarks and comparisons to the literature are presented

  14. Theoretical study on the initial reaction mechanisms of ansa-metallocene zirconium precursor on hydroxylated Si(1 0 0) surface.

    Science.gov (United States)

    Zhou, Guangfen; Ren, Jie; Zhang, Shaowen

    2016-05-01

    The initial reaction mechanisms for depositing ZrO2 thin films using ansa-metallocene zirconium (Cp2CMe2)ZrMe2 precursor were studied by density functional theory (DFT) calculations. The (Cp2CMe2)ZrMe2 precursor could be absorbed on the hydroxylated Si(1 0 0) surface via physisorption. Possible reaction pathways of (Cp2CMe2)ZrMe2 were proposed. For each reaction, the activation energies and reaction energies were compared, and stationary points along the reaction pathways were shown. In addition, the influence of dispersion effects on the reactions was evaluated by non-local dispersion corrected DFT calculations.

  15. Heterogeneous Reactions of Polycyclic Aromatic Hydrocarbons on Atmospheric and Terrestrial Surfaces

    Science.gov (United States)

    Simonich, S. L.

    2014-12-01

    The heterogeneous reactions of five higher molecular weight polycyclic aromatic hydrocarbons (PAHs), benzo[a]pyrene-d12 (BaP-d12), benzo(k)fluoranthene-d12 (BkF-d12), benzo[g,h,i]perylene-d12 (BghiP-d12), dibenzo(a,i)pyrene-d14 (DBaiP-d14), and dibenzo[a,l]pyrene (DalP), with NO2, NO3/N2O5, O3, and OH radicals were investigated in a 7000 L indoor Teflon chamber. Quartz fiber filters (QFF) were used as the reaction surface and substrate and the analyses of parent PAHs and Nitro-PAH (NPAH) products was conducted using electron impact gas chromatographic mass spectrometry (GC/MS) and negative chemical ionization GC/MS. In parallel to the laboratory experiments, a theoretical study was conducted to assist in determining the formation of NPAH isomers based on the OH-radical initiated reaction. The thermodynamic stability of OH-PAH intermediates was used to indicate the position of highest electron density and the most stable NPAH products were synthesized to confirm their identity. NO2 and NO3/N2O5 were the most effective oxidizing agents in transforming PAHs deposited on filters to NPAHs, under the experimental conditions. Reaction of BaP-d12, BkF-d12 and BghiP-d12 resulted in the formation of several mono-nitro PAH isomer product, while the reaction of DalP and DaiP-d14 resulted in the formation of only one mono-nitro PAH isomer product. The direct-acting mutagenicity of the products increased the most after NO3/N2O5 exposure, particularly for BkF-d12 in which the formation of dinitro- PAHs was observed. In addition, the degradation of particulate matter (PM)-bound PAHs by heterogeneous reaction with OH radicals, O3, NO3/N2O5 was also studied. Ambient PM samples collected from Beijing, China and Riverside, California were exposed in an indoor chamber under simulated trans-Pacific atmospheric transport conditions and the formation of NPAHs was studied. NPAHs were most effectively formed during the NO3/N2O5 exposure and, for all exposures, there was no significant

  16. Non-thermal desorption from interstellar dust grains via exothermic surface reactions

    Science.gov (United States)

    Garrod, R. T.; Wakelam, V.; Herbst, E.

    2007-06-01

    Aims:The gas-phase abundance of methanol in dark quiescent cores in the interstellar medium cannot be explained by gas-phase chemistry. In fact, the only possible synthesis of this species appears to be production on the surfaces of dust grains followed by desorption into the gas. Yet, evaporation is inefficient for heavy molecules such as methanol at the typical temperature of 10 K. It is necessary then to consider non-thermal mechanisms for desorption. But, if such mechanisms are considered for the production of methanol, they must be considered for all surface species. Methods: Our gas-grain network of reactions has been altered by the inclusion of a non-thermal desorption mechanism in which the exothermicity of surface addition reactions is utilized to break the bond between the product species and the surface. Our estimated rate for this process derives from a simple version of classical unimolecular rate theory with a variable parameter only loosely constrained by theoretical work. Results: Our results show that the chemistry of dark clouds is altered slightly at times up to 106 yr, mainly by the enhancement in the gas-phase abundances of hydrogen-rich species such as methanol that are formed on grain surfaces. At later times, however, there is a rather strong change. Instead of the continuing accretion of most gas-phase species onto dust particles, a steady-state is reached for both gas-phase and grain-surface species, with significant abundances for the former. Nevertheless, most of the carbon is contained in an undetermined assortment of heavy surface hydrocarbons. Conclusions: The desorption mechanism discussed here will be better constrained by observational data on pre-stellar cores, where a significant accretion of species such as CO has already occurred.

  17. Non-adiabatic effects in elementary reaction processes at metal surfaces

    Science.gov (United States)

    Alducin, M.; Díez Muiño, R.; Juaristi, J. I.

    2017-12-01

    Great success has been achieved in the modeling of gas-surface elementary processes by the use of the Born-Oppenheimer approximation. However, in metal surfaces low energy electronic excitations are generated even by thermal and hyperthermal molecules due to the absence of band gaps in the electronic structure. This shows the importance of performing dynamical simulations that incorporate non-adiabatic effects to analyze in which way they affect most common gas-surface reactions. Here we review recent theoretical developments in this problem and their application to the study of the effect of electronic excitations in the adsorption and relaxation of atoms and molecules in metal surfaces, in scattering processes, and also in recombinative processes between impinging atoms and adsorbates at the surface. All these studies serve us to establish what properties of the gas-surface interaction favor the excitation of low-energy electron-hole pairs. A general observation is that the nature of these excitations usually requires long lasting interactions at the surface in order to observe deviations from the adiabatic behaviour. We also provide the basis of the local density friction approximation (LDFA) that have been used in all these studies, and show how it has been employed to perform ab initio molecular dynamics with electronic friction (AIMDEF). As a final remark, we will shortly review on recent applications of the LDFA to successfully simulate desorption processes induced by intense femtosecond laser pulses.

  18. Nanoparticle-Programmed Surface for Drug Release and Cell Regulation via Reversible Hybridization Reaction.

    Science.gov (United States)

    Jiang, Pinliang; Li, Shihui; Lai, Jinping; Zheng, Hong; Lin, Changjian; Shi, Peng; Wang, Yong

    2017-02-08

    A surface directly connects the bulk of a material to its surroundings. The ability to dynamically regulate the surface without affecting the bulk of a material holds great potential for new applications. The purpose of this work was to demonstrate that the surface can be dynamically changed using nanoparticles and oligonucleotides (ODNs) in a reversible and reiterative manner. A dual-functional nanogel was synthesized as the model of nanoparticles using miniemulsion polymerization and click chemistry. The nanogel can not only adsorb drugs for sustained drug release but also bind a surface functionalized with complementary ODNs. Importantly, hybridization reaction and ODN degradation can drive reversible and reiterative nanogel binding to the surface for dynamic change, which in principle is unlimited. Moreover, nanogel-mediated dynamic change offers the surface with the drug-releasing function for inhibiting the growth of surrounding cells. Because nanogels can be replaced by any functional nanoparticles with a diverse array of properties, nanoparticle-programmed surface change constitutes a promising platform for various applications such as drug delivery and stent implantation.

  19. Understanding the mechanisms of solid-water reactions through analysis of surface topography.

    Science.gov (United States)

    Bandstra, Joel Z; Brantley, Susan L

    2015-12-01

    The topography of a reactive surface contains information about the reactions that form or modify the surface and, therefore, it should be possible to characterize reactivity using topography parameters such as surface area, roughness, or fractal dimension. As a test of this idea, we consider a two-dimensional (2D) lattice model for crystal dissolution and examine a suite of topography parameters to determine which may be useful for predicting rates and mechanisms of dissolution. The model is based on the assumption that the reactivity of a surface site decreases with the number of nearest neighbors. We show that the steady-state surface topography in our model system is a function of, at most, two variables: the ratio of the rate of loss of sites with two neighbors versus three neighbors (d(2)/d(3)) and the ratio of the rate of loss of sites with one neighbor versus three neighbors (d(1)/d(3)). This means that relative rates can be determined from two parameters characterizing the topography of a surface provided that the two parameters are independent of one another. It also means that absolute rates cannot be determined from measurements of surface topography alone. To identify independent sets of topography parameters, we simulated surfaces from a broad range of d(1)/d(3) and d(2)/d(3) and computed a suite of common topography parameters for each surface. Our results indicate that the fractal dimension D and the average spacing between steps, E[s], can serve to uniquely determine d(1)/d(3) and d(2)/d(3) provided that sufficiently strong correlations exist between the steps. Sufficiently strong correlations exist in our model system when D>1.5 (which corresponds to D>2.5 for real 3D reactive surfaces). When steps are uncorrelated, surface topography becomes independent of step retreat rate and D is equal to 1.5. Under these conditions, measures of surface topography are not independent and any single topography parameter contains all of the available mechanistic

  20. Reactions of BBr(n)(+) (n = 0--2) at fluorinated and hydrocarbon self-assembled monolayer surfaces: observations of chemical selectivity in ion--surface scattering.

    Science.gov (United States)

    Wade, N; Shen, J; Koskinen, J; Cooks, R G

    2001-07-01

    Ion-surface reactions involving BBr(n)(+) (n = 0--2) with a fluorinated self-assembled monolayer (F-SAM) surface were investigated using a multi-sector scattering mass spectrometer. Collisions of the B(+) ion yield BF(2)(+) at threshold energy with the simpler product ion BF(+)* appearing at higher collision energies and remaining of lower abundance than BF(2)(+) at all energies examined. In addition, the reactively sputtered ion CF(+) accompanies the formation of BF(2)(+) at low collision energies. These results stand in contrast with previous data on the ion-surface reactions of atomic ions with the F-SAM surface in that the threshold and most abundant reaction products in those cases involved the abstraction of a single fluorine atom. Gas-phase enthalpy data are consistent with BF(2)(+) being the thermodynamically favored product. The fact that the abundance of BF(2)(+) is relatively low and relatively insensitive to changes in collision energy suggests that this reaction proceeds through an entropically demanding intermediate at the vacuum--surface interface, one which involves interaction of the B(+) ion simultaneously with two fluorine atoms. By contrast with the reaction of B(+), the odd-electron species BBr(+)* reacts with the F-SAM surface to yield an abundant single-fluorine abstraction product, BBrF(+). Corresponding gas-phase ion--molecule experiments involving B(+) and BBr(+)* with C(6)F(14) also yield the products BF(+)* and BF(2)(+), but only in extremely low abundances and with no preference for double fluorine abstraction. Ion--surface reactions were also investigated for BBr(n)(+) (n = 0-2) with a hydrocarbon self-assembled monolayer (H-SAM) surface. Reaction of the B(+) ion and dissociative reactions of BBr(+)* result in the formation of BH(2)(+), while the thermodynamically less favorable product BH(+)* is not observed. Collisions of BBr(2)(+) with the H-SAM surface yield the dissociative ion-surface reaction products, BBrH(+) and BBrCH(3

  1. Interfacial Cu+ promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts

    Science.gov (United States)

    Senanayake, Sanjaya D.; Pappoe, Naa Adokaley; Nguyen-Phan, Thuy-Duong; Luo, Si; Li, Yuanyuan; Xu, Wenqian; Liu, Zongyuan; Mudiyanselage, Kumudu; Johnston-Peck, Aaron C.; Frenkel, Anatoly I.; Heckler, Ilana; Stacchiola, Dario; Rodriguez, José A.

    2016-10-01

    We have studied the catalytic carbon monoxide (CO) oxidation (CO + 0.5O2 → CO2) reaction using a powder catalyst composed of both copper (5 wt.% loading) and titania (CuOx-TiO2). Our study was focused on revealing the role of Cu, and the interaction between Cu and TiO2, by systematic comparison between two nanocatalysts, CuOx-TiO2 and pure CuOx. We interrogated these catalysts under in situ conditions using X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to probe the structure and electronic properties of the catalyst at all stages of the reaction and simultaneously probe the surface states or intermediates of this reaction. With the aid of several ex situ characterization techniques including transmission electron microscopy (TEM), the local catalyst morphology and structure were also studied. Our results show that a CuOx-TiO2 system is more active than bulk CuOx for the CO oxidation reaction due to its lower onset temperature and better stability at higher temperatures. Our results also suggest that surface Cu+ species observed in the CuOx-TiO2 interface are likely to be a key player in the CO oxidation mechanism, while implicating that the stabilization of this species is probably associated with the oxide-oxide interface. Both in situ DRIFTS and XAFS measurements reveal that there is likely to be a Cu(Ti)-O mixed oxide at this interface. We discuss the nature of this Cu(Ti)-O interface and interpret its role on the CO oxidation reaction.

  2. Iodinated Contrast Media and the Alleged "Iodine Allergy": An Inexact Diagnosis Leading to Inferior Radiologic Management and Adverse Drug Reactions.

    Science.gov (United States)

    Böhm, Ingrid; Nairz, Knud; Morelli, John N; Keller, Patricia Silva Hasembank; Heverhagen, Johannes T

    2017-04-01

    Purpose  To test the hypothesis that the incomplete diagnosis "iodine allergy" is a possibly dangerous concept for patients under routine radiologic conditions. Materials and Methods  300 patients with a history of an "iodine allergy" were retrospectively screened and compared with two age-, sex-, and procedure-matched groups of patients either diagnosed with a nonspecific "iodine contrast medium (ICM) allergy" or an allergy to a specific ICM agent. For all groups, the clinical symptoms of the most recent past adverse drug reaction (ADR), prophylactic actions taken for subsequent imaging, and ultimate outcome were recorded and analyzed. Results  The diagnosis "iodine allergy" was not otherwise specified in 84.3 % patients. For this group, in most cases, the symptoms of the previous ADRs were not documented. In contrast, the type of ADR was undocumented in only a minority of patients in the comparison groups. In the group of patients with an "iodine allergy" the percentage of unenhanced CT scans was greater than within the other two groups (36.7 % vs. 28.7 %/18.6 %). ADRs following prophylactic measures were only observed in the "iodine allergy" group (OR of 9.24 95 % CI 1.16 - 73.45; p contrast media containing covalently bound iodine.. · There is a clear correlation between the exactness of the diagnosis - from the alleged "iodine allergy" to "contrast media allergy" to naming the exact culprit CM - and the quality of documentation of the symptoms.. · Management of patients diagnosed with "iodine allergy" was associated with uncertainty leading to unenhanced scans and sometimes unnecessary prophylactic actions.. · The term "iodine allergy" should be omitted, because it is potentially dangerous and can decrease the quality of radiology exams.. Citation Format · Böhm Ingrid, Nairz Knud, Morelli John N et al. Iodinated Contrast Media and the Alleged "Iodine Allergy": An Inexact Diagnosis Leading to Inferior Radiologic Management and

  3. Harnessing surface-bound enzymatic reactions to organize microcapsules in solution.

    Science.gov (United States)

    Shklyaev, Oleg E; Shum, Henry; Sen, Ayusman; Balazs, Anna C

    2016-03-01

    By developing new computational models, we examine how enzymatic reactions on an underlying surface can be harnessed to direct the motion and organization of reagent-laden microcapsules in a fluid-filled microchannel. In the presence of appropriate reagents, surface-bound enzymes can act as pumps, which drive large-scale fluid flows. When the reagents diffuse through the capsules' porous shells, they can react with enzymatic sites on the bottom surface. The ensuing reaction generates fluid density variations, which result in fluid flows. These flows carry the suspended microcapsules and drive them to aggregate into "colonies" on and near the enzyme-covered sites. This aggregation continues until the reagent has been depleted and the convection stops. We show that the shape of the assembled colonies can be tailored by patterning the distribution of enzymes on the surface. This fundamental physicochemical mechanism could have played a role in the self-organization of early biological cells (protocells) and can be used to regulate the autonomous motion and targeted delivery of microcarriers in microfluidic devices.

  4. Effect of Reaction Conditions on the Surface Modification of Cellulose Nanofibrils with Aminopropyl Triethoxysilane

    Directory of Open Access Journals (Sweden)

    Eduardo Robles

    2018-04-01

    Full Text Available Nine different surface modifications of cellulose nanofibrils (CNF with 3-aminopropyl triethoxysilane (ATS by using three different solvent systems (water, ethanol, and a mixture of both were investigated. The effect of reaction conditions, such as silane to cellulose ratio and solvent type were evaluated to determine their contribution to the extent of the silane modification. Nanofibril properties were evaluated by infrared spectroscopy, powder X-ray diffraction, surface free energy, thermogravimetry, 13C and 29Si nuclear magnetic resonance, and electronic microscopy. The influence of the solvent in the solvolysis of the silane was reflected in the presence or absence of ethoxy groups in the silane. On the other hand, whereas the surface modification was increased directly proportionally to silane ratio on the reaction, the aggregation of nanofibrils was also increased, which can play a negative role in certain applications. The increment of silane modification also had substantial repercussions on the crystallinity of the nanofibrils by the addition of amorphous components to the crystalline unit; moreover, silane surface modifications enhanced the hydrophobic character of the nanofibrils.

  5. Synchrotron Spectroscopic Studies of the Reaction of Cleaved Pyrite ( {FeS2}) Surfaces with Cr(VI) Solutions

    Science.gov (United States)

    Doyle, C. S.; Kendelewicz, T.; Bostick, B. C.; Brown, G. E.

    2002-12-01

    Pyrite is one of the most common sulfide ores, and the separation of valuable sulfide minerals from it has been an area of considerable interest for a long time. This extraction has led to a large quantity of pyrite waste, typically remaining in mine tailings piles which can interact with oxygen and surface water. The oxidation of pyrite under these conditions leads to the commonly known environmental problem of acid mine drainage, with acidification of surface waters, and the release of potentially toxic metals remaining within the pyrite matrix. A microscopic understanding of this oxidation process is extremely important and has been the aim of a number of studies. We apply the methods of synchrotron based surface science to this problem, utilizing surface sensitive photoemission and X-ray absorption spectroscopy to study the surface species present on the pyrite surface at the initial stages of oxidation. We have reacted pyrite surfaces with solutions containing chromate. Chromium exists in solution in two principal valence states, trivalent Cr(III) and hexavalent Cr(VI). Hexavalent chromium is itself considered an environmental problem due to its high toxicity and solubility, and thus mobility, whilst trivalent chromium is much less toxic and relatively insoluble. Hexavalent chromate is a strong oxidizing agent, and will react rapidly with the pyrite surface allowing the identification of oxidized iron and sulfur surface species. The possibility of using pyrite as a means of reducing chromate, and at the same time using chromate to passivate the pyrite surface to further oxidation through the buildup of a non-reactive iron-chromium (oxy)hydroxide layer will be investigated. The work was performed on rods cut from a natural pyrite single crystal from the Logroño region of Spain. The rods were then fractured over a reaction vessel, producing a fresh (100) surface for each experiment. The pyrite surfaces were reacted with 50 μM Cr(VI) solutions for 5 minutes at

  6. How have new bearing surfaces altered the local biological reactions to byproducts of wear and modularity?

    Science.gov (United States)

    Bauer, Thomas W; Campbell, Patricia A; Hallerberg, Gretchen

    2014-12-01

    The biologic reactions to byproducts of wear or corrosion can involve innate and adaptive processes and are dependent on many factors, including the composition, size, surface properties, shape, and concentration of debris. We used a systematic literature review to compare the reported patterns of inflammation in tissues around total hip implants with the goal of identifying whether there are unique or characteristic patterns associated with the newer bearing options or modular components. A search of the Ovid Medline database between 1996 and early December 2013 identified articles that compared the histology around six implant groups: (1) metal-on-metal; (2) ceramic-on-ceramic; (3) metal-on-crosslinked polyethylene; (4) metal-on-conventional polyethylene with or (5) without modularity; and (6) tissue obtained at primary arthroplasty. Our initial search yielded 865 citations. After excluding articles that lacked a quantitative or semiquantitative description of histologic findings in periprosthetic tissue, we reviewed 34 articles. No pattern of inflammation is specific for any given bearing combination. Histologic features suggestive of an adaptive immune response appear to be more frequent and of greater magnitude in failed metal-on-metal implants, but tissues around many failed metal-on-metal implants show features of an "innate" foreign body reaction without lymphocytes. Occasional nonmetal-on-metal implants show features of an immune reaction, possibly associated with metal particles. Modular connections are one source of metal debris in nonmetal-on-metal implants. Features of an immune reaction appear rare in ceramic-on-ceramic implants that lack corrosion. Insufficient reports are available to characterize the biologic response to crosslinked polyethylene. All total hip bearing combinations will wear in vivo, and modular interfaces are a likely source of metal that may be associated with a biological response regardless of the composition of the bearing

  7. Surface area-burnoff correlation for the steam--graphite reaction

    International Nuclear Information System (INIS)

    Stark, W.A. Jr.; Malinauskas, A.P.

    1977-01-01

    The oxidation of core graphite by steam of air represents a problem area of significant concern in safety analyses for the high temperature gas cooled reactor (HTGR). Core and core-support graphite integrity and strength deteriorate with oxidation of the graphite, and oxidation furthermore could affect the rate of fission product release under upset conditions. Consequently, modeling of core response during steam or air ingress conditions requires an expression for the rate of graphite interaction with those impurities. The steam--graphite reaction in particular is a complex interaction of mass transport within the graphite with chemi-sorption and reaction on accessible surfaces; experimental results from graphite to graphite are highly variable, and the description of the reaction is not yet completely consistent. A simple etch pit model relating surface area to burnoff has been proposed and shown to provide reasonable correlation with experimental data obtained from steam oxidation studies of nuclear grade H-327 graphite. Unaccounted differences between theory and experiment arise at burnoffs exceeding 3 to 5 percent. The model, while not complete nor comprehensive, is consistent with experimental observations of graphite oxidation by O 2 (air), CO 2 , or H 2 O, and could have some utility in safety analysis

  8. Noise-and delay-induced phase transitions of the dimer–monomer surface reaction model

    International Nuclear Information System (INIS)

    Zeng Chunhua; Wang Hua

    2012-01-01

    Highlights: ► We study the dimer–monomer surface reaction model. ► We show that noise induces first-order irreversible phase transition (IPT). ► Combination of noise and time-delayed feedback induce first- and second-order IPT. ► First- and second-order IPT is viewed as noise-and delay-induced phase transitions. - Abstract: The effects of noise and time-delayed feedback in the dimer–monomer (DM) surface reaction model are investigated. Applying small delay approximation, we construct a stochastic delayed differential equation and its Fokker–Planck equation to describe the state evolution of the DM reaction model. We show that the noise can only induce first-order irreversible phase transition (IPT) characteristic of the DM model, however the combination of the noise and time-delayed feedback can simultaneously induce first- and second-order IPT characteristics of the DM model. Therefore, it is shown that the well-known first- and second-order IPT characteristics of the DM model may be viewed as noise-and delay-induced phase transitions.

  9. Computational study of ethanol adsorption and reaction over rutile TiO2 (110) surfaces

    KAUST Repository

    Muir, J. N.

    2012-01-01

    Studies of the modes of adsorption and the associated changes in electronic structures of renewable organic compounds are needed in order to understand the fundamentals behind surface reactions of catalysts for future energies. Using planewave density functional theory (DFT) calculations, the adsorption of ethanol on perfect and O-defected TiO 2 rutile (110) surfaces was examined. On both surfaces the dissociative adsorption mode on five-fold coordinated Ti cations (Ti 4+ 5c) was found to be more favourable than the molecular adsorption mode. On the stoichiometric surface E ads was found to be equal to 0.85 eV for the ethoxide mode and equal to 0.76 eV for the molecular mode. These energies slightly increased when adsorption occurred on the Ti 4+ 5c closest to the O-defected site. However, both considerably increased when adsorption occurred at the removed bridging surface O; interacting with Ti 3+ cations. In this case the dissociative adsorption becomes strongly favoured (E ads = 1.28 eV for molecular adsorption and 2.27 eV for dissociative adsorption). Geometry and electronic structures of adsorbed ethanol were analysed in detail on the stoichiometric surface. Ethanol does not undergo major changes in its structure upon adsorption with its C-O bond rotating nearly freely on the surface. Bonding to surface Ti atoms is a σ type transfer from the O2p of the ethanol-ethoxide species. Both ethanol and ethoxide present potential hole traps on O lone pairs. Charge density and work function analyses also suggest charge transfer from the adsorbate to the surface, in which the dissociative adsorptions show a larger charge transfer than the molecular adsorption mode. This journal is © 2012 the Owner Societies.

  10. Computational study of ethanol adsorption and reaction over rutile TiO2 (110) surfaces.

    Science.gov (United States)

    Muir, J M R; Muir, J N; Choi, Y; Idriss, H

    2012-09-14

    Studies of the modes of adsorption and the associated changes in electronic structures of renewable organic compounds are needed in order to understand the fundamentals behind surface reactions of catalysts for future energies. Using planewave density functional theory (DFT) calculations, the adsorption of ethanol on perfect and O-defected TiO(2) rutile (110) surfaces was examined. On both surfaces the dissociative adsorption mode on five-fold coordinated Ti cations (Ti(4+)(5c)) was found to be more favourable than the molecular adsorption mode. On the stoichiometric surface E(ads) was found to be equal to 0.85 eV for the ethoxide mode and equal to 0.76 eV for the molecular mode. These energies slightly increased when adsorption occurred on the Ti(4+)(5c) closest to the O-defected site. However, both considerably increased when adsorption occurred at the removed bridging surface O; interacting with Ti(3+) cations. In this case the dissociative adsorption becomes strongly favoured (E(ads) = 1.28 eV for molecular adsorption and 2.27 eV for dissociative adsorption). Geometry and electronic structures of adsorbed ethanol were analysed in detail on the stoichiometric surface. Ethanol does not undergo major changes in its structure upon adsorption with its C-O bond rotating nearly freely on the surface. Bonding to surface Ti atoms is a σ type transfer from the O2p of the ethanol-ethoxide species. Both ethanol and ethoxide present potential hole traps on O lone pairs. Charge density and work function analyses also suggest charge transfer from the adsorbate to the surface, in which the dissociative adsorptions show a larger charge transfer than the molecular adsorption mode.

  11. Surface ECG and Fluoroscopy are Not Predictive of Right Ventricular Septal Lead Position Compared to Cardiac CT.

    Science.gov (United States)

    Rowe, Matthew K; Moore, Peter; Pratap, Jit; Coucher, John; Gould, Paul A; Kaye, Gerald C

    2017-05-01

    Controversy exists regarding the optimal lead position for chronic right ventricular (RV) pacing. Placing a lead at the RV septum relies upon fluoroscopy assisted by a surface 12-lead electrocardiogram (ECG). We compared the postimplant lead position determined by ECG-gated multidetector contrast-enhanced computed tomography (MDCT) with the position derived from the surface 12-lead ECG. Eighteen patients with permanent RV leads were prospectively enrolled. Leads were placed in the RV septum (RVS) in 10 and the RV apex (RVA) in eight using fluoroscopy with anteroposterior and left anterior oblique 30° views. All patients underwent MDCT imaging and paced ECG analysis. ECG criteria were: QRS duration; QRS axis; positive or negative net QRS amplitude in leads I, aVL, V1, and V6; presence of notching in the inferior leads; and transition point in precordial leads at or after V4. Of the 10 leads implanted in the RVS, computed tomography (CT) imaging revealed seven to be at the anterior RV wall, two at the anteroseptal junction, and one in the true septum. For the eight RVA leads, four were anterior, two septal, and two anteroseptal. All leads implanted in the RVS met at least one ECG criteria (median 3, range 1-6). However, no criteria were specific for septal position as judged by MDCT. Mean QRS duration was 160 ± 24 ms in the RVS group compared with 168 ± 14 ms for RVA pacing (P = 0.38). We conclude that the surface ECG is not sufficiently accurate to determine RV septal lead tip position compared to cardiac CT. © 2017 Wiley Periodicals, Inc.

  12. 16 CFR 1145.2 - Paint (and other similar surface-coating materials) containing lead; toys, children's articles...

    Science.gov (United States)

    2010-01-01

    ... 16 Commercial Practices 2 2010-01-01 2010-01-01 false Paint (and other similar surface-coating materials) containing lead; toys, children's articles, and articles of furniture bearing such paint (or... TO OTHER ACTS UNDER THE CONSUMER PRODUCT SAFETY ACT § 1145.2 Paint (and other similar surface-coating...

  13. Surface Treatment to Improve Corrosion Resistance in Lead-Alloy Coolants

    Energy Technology Data Exchange (ETDEWEB)

    Todd R. Allen; Kumar Sridharan; McLean T. Machut; Lizhen Tan

    2007-08-29

    One of the six proposed advanced reactor designs of the Generation IV Initiative, the Leadcooled Fast Reactor (LFR) possesses many characteristics that make it a desirable candidate for future nuclear energy production and responsible actinide management. These characteristics include favorable heat transfer, fluid dynamics, and neutronic performance compared to other candidate coolants. However, the use of a heavy liquid metal coolant presents a challenge for reactor designers in regards to reliable structural and fuel cladding materials in both a highly corrosive high temperature liquid metal and an intense radiation fieldi. Flow corrosion studies at the University of Wisconsin have examined the corrosion performance of candidate materials for application in the LFR concept as well as the viability of various surface treatments to improve the materials’ compatibility. To date this research has included several focus areas, which include the formulation of an understanding of corrosion mechanisms and the examination of the effects of chemical and mechanical surface modifications on the materials’ performance in liquid lead-bismuth by experimental testing in Los Alamos National Laboratory’s DELTA Loop, as well as comparison of experimental findings to numerical and physical models for long term corrosion prediction. This report will first review the literature and introduce the experiments and data that will be used to benchmark theoretical calculations. The experimental results will be followed by a brief review of the underlying theory and methodology for the physical and theoretical models. Finally, the results of theoretical calculations as well as experimentally obtained benchmarks and comparisons to the literature are presented.

  14. Self-cleaning and surface chemical reactions during hafnium dioxide atomic layer deposition on indium arsenide.

    Science.gov (United States)

    Timm, Rainer; Head, Ashley R; Yngman, Sofie; Knutsson, Johan V; Hjort, Martin; McKibbin, Sarah R; Troian, Andrea; Persson, Olof; Urpelainen, Samuli; Knudsen, Jan; Schnadt, Joachim; Mikkelsen, Anders

    2018-04-12

    Atomic layer deposition (ALD) enables the ultrathin high-quality oxide layers that are central to all modern metal-oxide-semiconductor circuits. Crucial to achieving superior device performance are the chemical reactions during the first deposition cycle, which could ultimately result in atomic-scale perfection of the semiconductor-oxide interface. Here, we directly observe the chemical reactions at the surface during the first cycle of hafnium dioxide deposition on indium arsenide under realistic synthesis conditions using photoelectron spectroscopy. We find that the widely used ligand exchange model of the ALD process for the removal of native oxide on the semiconductor and the simultaneous formation of the first hafnium dioxide layer must be significantly revised. Our study provides substantial evidence that the efficiency of the self-cleaning process and the quality of the resulting semiconductor-oxide interface can be controlled by the molecular adsorption process of the ALD precursors, rather than the subsequent oxide formation.

  15. Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride.

    Science.gov (United States)

    Raff, Jonathan D; Njegic, Bosiljka; Chang, Wayne L; Gordon, Mark S; Dabdub, Donald; Gerber, R Benny; Finlayson-Pitts, Barbara J

    2009-08-18

    Gaseous HCl generated from a variety of sources is ubiquitous in both outdoor and indoor air. Oxides of nitrogen (NO(y)) are also globally distributed, because NO formed in combustion processes is oxidized to NO(2), HNO(3), N(2)O(5) and a variety of other nitrogen oxides during transport. Deposition of HCl and NO(y) onto surfaces is commonly regarded as providing permanent removal mechanisms. However, we show here a new surface-mediated coupling of nitrogen oxide and halogen activation cycles in which uptake of gaseous NO(2) or N(2)O(5) on solid substrates generates adsorbed intermediates that react with HCl to generate gaseous nitrosyl chloride (ClNO) and nitryl chloride (ClNO(2)), respectively. These are potentially harmful gases that photolyze to form highly reactive chlorine atoms. The reactions are shown both experimentally and theoretically to be enhanced by water, a surprising result given the availability of competing hydrolysis reaction pathways. Airshed modeling incorporating HCl generated from sea salt shows that in coastal urban regions, this heterogeneous chemistry increases surface-level ozone, a criteria air pollutant, greenhouse gas and source of atmospheric oxidants. In addition, it may contribute to recently measured high levels of ClNO(2) in the polluted coastal marine boundary layer. This work also suggests the potential for chlorine atom chemistry to occur indoors where significant concentrations of oxides of nitrogen and HCl coexist.

  16. Surface reaction mechanisms during ozone and oxygen plasma assisted atomic layer deposition of aluminum oxide.

    Science.gov (United States)

    Rai, Vikrant R; Vandalon, Vincent; Agarwal, Sumit

    2010-09-07

    We have elucidated the reaction mechanism and the role of the reactive intermediates in the atomic layer deposition (ALD) of aluminum oxide from trimethyl aluminum in conjunction with O(3) and an O(2) plasma. In situ attenuated total reflection Fourier transform infrared spectroscopy data show that both -OH groups and carbonates are formed on the surface during the oxidation cycle. These carbonates, once formed on the surface, are stable to prolonged O(3) exposure in the same cycle. However, in the case of plasma-assisted ALD, the carbonates decompose upon prolonged O(2) plasma exposure via a series reaction kinetics of the type, A (CH(3)) --> B (carbonates) --> C (Al(2)O(3)). The ratio of -OH groups to carbonates on the surface strongly depends on the oxidizing agent, and also the duration of the oxidation cycle in plasma-assisted ALD. However, in both O(3) and O(2) plasma cycles, carbonates are a small fraction of the total number of reactive sites compared to the hydroxyl groups.

  17. Kinetic modeling for thermal dehydration of ferrous oxalate dihydrate polymorphs: a combined model for induction period-surface reaction-phase boundary reaction.

    Science.gov (United States)

    Ogasawara, Haruka; Koga, Nobuyoshi

    2014-04-03

    In this study, ferrous oxalate dihydrate polymorph particles, α- and β-phases, with square bipyramidal and quadratic prismatic shapes, respectively, were synthesized. Thermal dehydration of the samples was subjected to kinetic study as a typical reaction that indicates a significant induction period and a sigmoidal mass-loss behavior. On the basis of the formal kinetic analysis of the mass-loss traces recorded under isothermal, nonisothermal, and constant transformation rate conditions and the morphological observations of the surface textures of the partially reacted sample particles, a combined kinetic model for the induction period-surface reaction-phase boundary reaction was developed. The sigmoidal mass-loss behavior after the significant induction period under isothermal conditions was satisfactorily simulated by the combined kinetic model. The kinetic parameters for the component processes of induction period, surface reaction, and phase boundary reaction were separately determined from the kinetic simulation. The differences in the kinetic behaviors of the induction period and the phase boundary reaction between α- and β-phase samples were well described by the kinetic parameters. The applicability of the combined kinetic model to practical systems was demonstrated through characterizing the physicogeometrical kinetics of the thermal dehydration of ferrous oxalate dihydrate polymorphs.

  18. The Surface Reactions of Ethanol over UO2(100) Thin Film

    KAUST Repository

    Senanayake, Sanjaya D.

    2015-10-08

    The study of the reactions of oxygenates on well-defined oxide surfaces is important for the fundamental understanding of heterogeneous chemical pathways that are influenced by atomic geometry, electronic structure and chemical composition. In this work, an ordered uranium oxide thin film surface terminated in the (100) orientation is prepared on a LaAlO3 substrate and studied for its reactivity with a C-2 oxygenate, ethanol (CH3CH2OH). With the use of synchrotron X-ray photoelectron spectroscopy (XPS), we have probed the adsorption and desorption processes observed in the valence band, C1s, O1s and U4f to investigate the bonding mode, surface composition, electronic structure and probable chemical changes to the stoichiometric-UO2(100) [smooth-UO2(100)] and Ar+-sputtered UO2(100) [rough-UO2(100)] surfaces. Unlike UO2(111) single crystal and UO2 thin film, Ar-ion sputtering of this UO2(100) did not result in noticeable reduction of U cations. The ethanol molecule has C-C, C-H, C-O and O-H bonds, and readily donates the hydroxyl H while interacting strongly with the UO2 surfaces. Upon ethanol adsorption (saturation occurred at 0.5 ML), only ethoxy (CH3CH2O-) species is formed on smooth-UO2(100) whereas initially formed ethoxy species are partially oxidized to surface acetate (CH3COO-) on the Ar+-sputtered UO2(100) surface. All ethoxy and acetate species are removed from the surface between 600 and 700 K.

  19. Histopathological reaction over prosthesis surface covered with silicone and polyurethane foam implanted in rats.

    Science.gov (United States)

    Wagenführ-Júnior, Jorge; Ribas Filho, Jurandir Marcondes; Nascimento, Marcelo Mazza do; Ribas, Fernanda Marcondes; Wanka, Marcus Vinícius; Godoi, Andressa de Lima

    2012-12-01

    To evaluate whether polyurethane foam leads more intense foreign-body reaction than silicone foam. To compare the vascularization of the capsules surrounding the foam implants. To investigate if the capsule of polyurethane foam implanted has greater amount of collagen than that of silicone foam. Sixty-four young male Wistar rats were allocated into two groups: polyurethane foam and silicone foam. Subcutaneous discs were implanted into the dorsum of the animals in both groups. The capsules were assessed 28 days, two months, three months and six months postoperatively. Microscopic analysis with H&E stain was performed to evaluate the acute and chronic inflammatory process, foreign-body reaction and neovascularization. The analysis with picrosirius red was performed using the ImageProPlus software, to measure the number of vessels and collagen types I and III. There were no statistical differences between the two groups regarding the acute and chronic inflammatory processes. All rats from the polyurethane group, in all times, exhibited moderate or intense foreign-body reaction, with statistic significant difference (p=0.046) when compared with the silicone group, in which the reaction was either mild or nonexistent at two months. Vascular proliferation was significantly different between the groups at 28 days (p=0.0002), with the polyurethane group displaying greater neovascularization with H&E stain. Similar results were obtained with picrosirius red, which revealed in the polyurethane group a much greater number of vessels than in the silicone group (p=0.001). The collagen area was larger in the polyurethane group, significantly at 28 days (p=0.001) and at two months (p=0.030). Polyurethane foam elicited more intense foreign-body reaction when compared with silicone foam. The number of vessels was higher in the capsules of the polyurethane foam implants 28 days after the operation. The capsule of the polyurethane foam implants showed a greater amount of collagen

  20. Nickel, Lead and Zinc Contamination in the Surface Sediments of Agh Gel Wetland, Iran

    Directory of Open Access Journals (Sweden)

    Soheil Sobhan Ardakani

    2016-07-01

    Full Text Available Background & Aims of the Study: Due to the increased human activities around the Agh Gel wetland, this study aimed to measured accumulations of heavy metals (Ni, Pb and Zn in the surface sediment samples taken from this wetland. Materials & Methods: Samples were taken from 10 stations and exposed to bulk digestion and chemical partitioning. Finally, Ni, Pb and Zn concentrations were monitored with ICP-OES in the sediments. Also, geo-accumulation index, contamination factor and pollution load index were used to evaluate the magnitude of contaminants in the sediment profile. Results: The results showed, the average of metal concentration in samples (mg kg-1 wet weight were 34.20±3.58 for Ni, 25.37±2.52 for Pb and 127.20±15.21 for Zn, respectively. Therefore, the pattern of metal concentrations in sediment was determined as Zinc>Nickel >Lead. According to the mean I-geo values, sediments' qualities are classified as unpolluted category for Ni and Pb. Also, sediment's quality is classified as unpolluted to moderately polluted for Zn. The CF values for all elements are classified as moderate contamination. The PLI values indicated that metal pollution exists for all sampling stations. Conclusions: The obtained results indicated that the Agh Gel wetland has a potential to threaten by chemical pollutants such as agricultural effluent. So, in order to preserve the environment of the Agh Gel wetland from deterioration, monitoring of water and sediment qualities is recommended periodically.

  1. The Effectiveness of Surface Coatings on Preventing Interfacial Reaction During Ultrasonic Welding of Aluminum to Magnesium

    Science.gov (United States)

    Panteli, Alexandria; Robson, Joseph D.; Chen, Ying-Chun; Prangnell, Philip B.

    2013-12-01

    High power ultrasonic spot welding (USW) is a solid-state joining process that is advantageous for welding difficult dissimilar material couples, like magnesium to aluminum. USW is also a useful technique for testing methods of controlling interfacial reaction in welding as the interface is not greatly displaced by the process. However, the high strain rate deformation in USW has been found to accelerate intermetallic compound (IMC) formation and a thick Al12Mg17 and Al3Mg2 reaction layer forms after relatively short welding times. In this work, we have investigated the potential of two approaches for reducing the IMC reaction rate in dissimilar Al-Mg ultrasonic welds, both involving coatings on the Mg sheet surface to (i) separate the join line from the weld interface, using a 100- μm-thick Al cold spray coating, and (ii) provide a diffusion barrier layer, using a thin manganese physical vapor deposition (PVD) coating. Both methods were found to reduce the level of reaction and increase the failure energy of the welds, but their effectiveness was limited due to issues with coating attachment and survivability during the welding cycle. The effect of the coatings on the joint's interface microstructure, and the fracture behavior have been investigated in detail. Kinetic modeling has been used to show that the benefit of the cold spray coating can be attributed to the reaction rate reverting to that expected under static conditions. This reduces the IMC growth rate by over 50 pct because at the weld line, the high strain rate dynamic deformation in USW normally enhances diffusion through the IMC layer. In comparison, the thin PVD barrier coating was found to rapidly break up early in USW and become dispersed throughout the deformation layer reducing its effectiveness.

  2. Controllable Surface Reorganization Engineering on Cobalt Phosphide Nanowire Arrays for Efficient Alkaline Hydrogen Evolution Reaction.

    Science.gov (United States)

    Xu, Kun; Cheng, Han; Lv, Haifeng; Wang, Jingyu; Liu, Linqi; Liu, Si; Wu, Xiaojun; Chu, Wangsheng; Wu, Changzheng; Xie, Yi

    2018-01-01

    Developing highly efficient hydrogen evolution reaction (HER) catalysts in alkaline media is considered significant and valuable for water splitting. Herein, it is demonstrated that surface reorganization engineering by oxygen plasma engraving on electocatalysts successfully realizes a dramatically enhanced alkaline HER activity. Taking CoP nanowire arrays grown on carbon cloth (denoted as CoP NWs/CC) as an example, the oxygen plasma engraving can trigger moderate CoO x species formation on the surface of the CoP NWs/CC, which is visually verified by the X-ray absorption fine structure, high-resolution transmission electron microscopy, and energy-dispersive spectrometer (EDS) mapping. Benefiting from the moderate CoO x species formed on the surface, which can promote the water dissociation in alkaline HER, the surface reorganization of the CoP NWs/CC realizes almost fourfold enhanced alkaline HER activity and a 180 mV decreased overpotential at 100 mA cm -2 , compared with the pristine ones. More interestingly, this surface reorganization strategy by oxygen plasma engraving can also be effective to other electrocatalysts such as free-standing CoP, Co 4 N, O-CoSe 2 , and C-CoSe 2 nanowires, which verifies the universality of the strategy. This work thus opens up new avenues for designing alkaline HER electrocatalysts based on oxygen plasma engraving. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Induced Superaerophobicity onto a Non-superaerophobic Catalytic Surface for Enhanced Hydrogen Evolution Reaction.

    Science.gov (United States)

    Akbar, Kamran; Hussain, Sajjad; Truong, Linh; Roy, Sanjib Baran; Jeon, Jae Ho; Jerng, Sahng-Kyoon; Kim, Minsoo; Yi, Yeonjin; Jung, Jongwan; Chun, Seung-Hyun

    2017-12-20

    Despite tremendous progress in the development of novel electrocatalysts for hydrogen evolution reaction (HER), the accumulation of hydrogen gas bubbles produced on the catalyst surface has been rather poorly addressed. The bubbles block the surface of the electrode, thus resulting in poor performance even when excellent electrocatalysts are used. In this study, we show that vertically grown graphene nanohills (VGNHs) possess an excellent capability to quickly disengage the produced hydrogen gas bubbles from the electrode surface, and thus exhibit superaerophobic properties. To compensate for the poor electrolytic properties of graphene toward HER, the graphene surface was modified with WS 2 nanoparticles to accelerate the water-splitting process by using this hybrid catalyst (VGNHs-WS 2 ). For comparison purposes, WS 2 nanoparticles were also deposited on the flat graphene (FG) surface. Because of its superior superaerophobic properties, VGNHs-WS 2 outperformed FG-WS 2 in terms of both catalytic activity toward the HER and superaerophobicity. Furthermore, VGNHs-WS 2 exhibited a low onset potential (36 mV compared to 288 mV for FG-WS 2 ) and long-term stability in the HER over an extended period of 20 h. This study provides an efficient way to utilize highly conductive and superaerophobic VGNHs as support materials for intrinsic semiconductors, such as WS 2 , to simultaneously achieve superaerophobicity and high catalytic activity.

  4. Identifying the Active Surfaces of Electrochemically Tuned LiCoO2 for Oxygen Evolution Reaction

    International Nuclear Information System (INIS)

    Lu, Zhiyi; Chen, Guangxu; Li, Yanbin; Wang, Haotian; Xie, Jin

    2017-01-01

    Identification of active sites for catalytic processes has both fundamental and technological implications for rational design of future catalysts. Herein, we study the active surfaces of layered lithium cobalt oxide (LCO) for the oxygen evolution reaction (OER) using the enhancement effect of electrochemical delithiation (De-LCO). Our theoretical results indicate that the most stable (0001) surface has a very large overpotential for OER independent of lithium content. In contrast, edge sites such as the nonpolar (1120) and polar (0112) surfaces are predicted to be highly active and dependent on (de)lithiation. The effect of lithium extraction from LCO on the surfaces and their OER activities can be understood by the increase of Co 4+ sites relative to Co 3+ and by the shift of active oxygen 2p states. Experimentally, it is demonstrated that LCO nanosheets, which dominantly expose the (0001) surface show negligible OER enhancement upon delithiation. However, a noticeable increase in OER activity (~0.1 V in overpotential shift at 10 mA cm –2 ) is observed for the LCO nanoparticles, where the basal plane is greatly diminished to expose the edge sites, consistent with the theoretical simulations. In addition, we find that the OER activity of De-LCO nanosheets can be improved if we adopt an acid etching method on LCO to create more active edge sites, which in turn provides a strong evidence for the theoretical indication.

  5. Vinyl azides derived from allenes: thermolysis leading to multisubstituted 1,4-pyrazines and Mn(III)-catalyzed photochemical reaction leading to pyrroles.

    Science.gov (United States)

    Sajna, K V; Kumara Swamy, K C

    2012-10-05

    Thermolysis of phosphorus-based vinyl azides under solvent- and catalyst-free conditions furnished a new route for 1,4-pyrazines. A simple one-pot, Mn(III)-catalyzed photochemical route has been developed for multisubstituted pyrroles starting from allenes and 1,3-dicarbonyls via in situ-generated vinyl azides. The utility of new phosphorus-based pyrroles is also demonstrated in the Horner reaction. The structures of key products are unequivocally confirmed by X-ray crystallography.

  6. Unsteady flow of a Maxwell fluid over a stretching surface in presence of chemical reaction

    Directory of Open Access Journals (Sweden)

    Swati Mukhopadhyay

    2012-10-01

    Full Text Available An analysis is presented for unsteady two-dimensional flow of a Maxwell fluid over a stretching surface in presence of a first order constructive/destructive chemical reaction. Using suitable transformations, the governing partial differential equations are converted to ordinary one and are then solved numerically by shooting method. The flow fields and mass transfer are significantly influenced by the governing parameters. Fluid velocity initially decreases with increasing unsteadiness parameter and concentration decreases significantly due to unsteadiness. The effect of increasing values of the Maxwell parameter is to suppress the velocity field. But the concentration is enhanced with increasing Maxwell parameter.

  7. Kinetics studies of the F + HCl → HF + Cl reaction on an accurate potential energy surface

    Science.gov (United States)

    Lu, Dandan; Zhang, Ying; Li, Jun

    2018-02-01

    A full-dimensional electronic ground state potential energy surface for the hydrogen abstraction reaction F + HCl → HF + Cl is developed by using the permutation invariant polynomial neural network approach based on 6509 points computed at the level of CCSD(T)-F12a/AVTZ. Spin-orbit correction is also taken into account at the complete active space self-consistent field level. Theoretical thermal rate coefficients determined by the ring polymer molecular dynamics (RPMD) approach agree well with experiment, validating the accuracy of the PES. Kinetic isotope effect is also investigated.

  8. Catalytic effects of silver plasmonic nanoparticles on the redox reaction leading to ABTS˙+formation studied using UV-visible and Raman spectroscopy.

    Science.gov (United States)

    Garcia-Leis, A; Jancura, D; Antalik, M; Garcia-Ramos, J V; Sanchez-Cortes, S; Jurasekova, Z

    2016-09-29

    ABTS (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)) is a compound extensively employed to evaluate the free radical trapping capacity of antioxidant agents and complex mixtures such as biological fluids or foods. This evaluation is usually performed by using a colourimetric experiment, where preformed ABTS radical cation (ABTS˙ + ) molecules are reduced in the presence of an antioxidant causing an intensity decrease of the specific ABTS˙ + UV-visible absorption bands. In this work we report a strong effect of silver plasmonic nanoparticles (Ag NPs) on ABTS leading to the formation of ABTS˙ + . The reaction of ABTS with Ag NPs has been found to be dependent on the interfacial and plasmonic properties of NPs. Specifically, this reaction is pronounced in the presence of spherical nanoparticles prepared by the reduction of silver nitrate with hydroxylamine (AgH) and in the case of star-shaped silver nanoparticles (AgNS). On the other hand, spherical nanoparticles prepared by the reduction of silver nitrate with citrate apparently do not react with ABTS. Additionally, the formation of ABTS˙ + is investigated by surface-enhanced Raman scattering (SERS) and the assignment of the most intense vibrational bands of this compound is performed. The SERS technique enables us to detect this radical cation at very low concentrations of ABTS (∼2 μM). Altogether, these findings allow us to suggest the use of ABTS/Ag NPs-systems as reliable and easy going substrates to test the antioxidant capacity of various compounds, even at concentrations much lower than those usually used in the spectrophotometric assays. Moreover, we have suggested that ABTS could be employed as a suitable agent to investigate the interfacial and plasmonic properties of the metal nanoparticles and, thus, to characterize the nanoparticle metal systems employed for various purposes.

  9. Chemical Recognition of Active Oxygen Species on the Surface of Oxygen Evolution Reaction Electrocatalysts.

    Science.gov (United States)

    Yang, Chunzhen; Fontaine, Olivier; Tarascon, Jean-Marie; Grimaud, Alexis

    2017-07-17

    Owing to the transient nature of the intermediates formed during the oxygen evolution reaction (OER) on the surface of transition metal oxides, their nature remains largely elusive by the means of simple techniques. The use of chemical probes is proposed, which, owing to their specific affinities towards different oxygen species, unravel the role played by these species on the OER mechanism. For that, tetraalkylammonium (TAA) cations, previously known for their surfactant properties, are introduced, which interact with the active oxygen sites and modify the hydrogen bond network on the surface of OER catalysts. Combining chemical probes with isotopic and pH-dependent measurements, it is further demonstrated that the introduction of iron into amorphous Ni oxyhydroxide films used as model catalysts deeply modifies the proton exchange properties, and therefore the OER mechanism and activity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Reaction of ethane with deuterium over platinum(111) single-crystal surfaces

    International Nuclear Information System (INIS)

    Zaera, F.; Somorhai, G.A.

    1985-01-01

    Deuterium exchange and hydrogenolysis of ethane were studied over (111) platinum surfaces under atmospheric pressures and a temperature range of 475-625 K. Activation energies of 19 kcal/mol for exchange and 34 kcal/mol for hydrogenolysis were obtained. The exchange reaction rates displayed kinetic orders with respect to deuterium and ethane partial pressures of -0.55 and 1.2, respectively. The exchange production distribution was U-shaped, peaking at one and six deuterium atoms per ethane molecule, similar to results reported for other forms of platinum, e.g., supported, films, and foils. The pressure of ethylidyne moieties on the surface was inferred from low-energy electron diffraction and thermal desorption spectroscopy. A mechanism is proposed to explain the experimental results, in which ethylidyne constitutes an intermediate in one of two competitive pathways. 31 references, 9 figures, 3 tables

  11. The exchange reaction between hydrogen and deuterium. I. Importance of surface reactions in the steady-state mechanism

    International Nuclear Information System (INIS)

    Marteau, Chantal; Gaillard-Cusin, Francoise; James, H.

    1978-01-01

    Investigation of heterogeneous initiation process of gas phase linear chain reactions is carried out through the study of H 2 -D 2 exchange reaction. Experimental data under study concern mainly the stationary rate of HD formation and the prestationary proceeding. Steady-state method accounts for the first one of these data; it allows to clearly compare the wall process part to the part played by the homogeneous chain reaction towards HD formation. Activation energy of exchange elementary step between chemisorbed hydrogen (on silica) and gaseous deuterium has been evaluated: Esub(e1)=52+-1 Kcal/mole [fr

  12. Conformity of macroscopic behavior to local properties in the catalytic ammonia synthesis and oscillatory reactions on metal surfaces

    OpenAIRE

    Cholach, A. R.

    2016-01-01

    Unique catalytic potential of metal surfaces has encouraged a great number of basic and applied studies. The manuscript highlights the general regularities in a field on the grounds of strong interrelation between catalytic, kinetic and thermodynamic behaviour of the reaction system. The trials of the catalytic NH3 synthesis and the oscillatory NO+H2 reaction have revealed that the thermodynamics of the local structure determines the properties and multiplicity of the reaction intermediates e...

  13. X-ray photoelectron spectroscopy study of CO2 reaction with polycrystalline uranium surface

    International Nuclear Information System (INIS)

    Liu Kezhao; Yu Yong; Zhou Juesheng; Wu Sheng; Wang Xiaolin; Fu Yibei

    1999-10-01

    The adsorption of CO 2 on 'clean' depleted polycrystalline uranium metal surface has been studied by X-ray photoelectron spectroscopy (XPS) at 300 K. The 'clean' surface were prepared by Ar + ion sputtering under ultra-high vacuum (UHV) condition with a base pressure 6.7 x 10 -8 Pa. The result s shows that adsorption of CO 2 on 'clean' uranium metal took place in total dissociation, and leads to the formation of uranium dioxide, uranium carbides and free carbon. The total dissociation of CO 2 produced carbon, oxygen species, CO 2 2- and CO 3 2- species. The diffusion tendency of carbon was much stronger than that of oxygen, and led to form a carbide in oxide-metal interface while the oxygen remained on their surface as an oxide

  14. Derivatization reaction-based surface-enhanced Raman scattering (SERS) for detection of trace acetone.

    Science.gov (United States)

    Zheng, Ying; Chen, Zhuo; Zheng, Chengbin; Lee, Yong-Ill; Hou, Xiandeng; Wu, Li; Tian, Yunfei

    2016-08-01

    A facile method was developed for determination of trace volatile acetone by coupling a derivatization reaction to surface-enhanced Raman scattering (SERS). With iodide modified Ag nanoparticles (Ag IMNPs) as the SERS substrate, acetone without obvious Raman signal could be converted to SERS-sensitive species via a chemical derivatization reaction with 2,4-dinitrophenylhydrazine (2,4-DNPH). In addition, acetone can be effectively separated from liquid phase with a purge-sampling device and then any serious interference from sample matrices can be significantly reduced. The optimal conditions for the derivatization reaction and the SERS analysis were investigated in detail, and the selectivity and reproducibility of this method were also evaluated. Under the optimal conditions, the limit of detection (LOD) for acetone was 5mgL(-1) or 0.09mM (3σ). The relative standard deviation (RSD) for 80mgL(-1) acetone (n=9) was 1.7%. This method was successfully used for the determination of acetone in artificial urine and human urine samples with spiked recoveries ranging from 92% to 110%. The present method is convenient, sensitive, selective, reliable and suitable for analysis of trace acetone, and it could have a promising clinical application in early diabetes diagnosis. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. New Combinatorial Approach for the Investigation of Kinetics and Temperature Dependence of Surface Reactions in Thin Organic Films

    NARCIS (Netherlands)

    Shovsky, A.; Schönherr, Holger

    2005-01-01

    In this paper we present a new, simple, and reproducible method for the rapid determination of the temperature dependence of solution phase surface reactions of organic thin films on solid supports. Instead of estimating the extent of reaction for many separate samples for many different

  16. Experimental removal of wetland emergent vegetation leads to decreased methylmercury production in surface sediment

    Science.gov (United States)

    Windham-Myers, Lisamarie; Marvin-DiPasquale, Mark; Krabbenhoft, David P.; Agee, Jennifer L.; Cox, Marisa H.; Heredia-Middleton, Pilar; Coates, Carolyn; Kakouros, Evangelos

    2009-01-01

    We performed plant removal (devegetation) experiments across a suite of ecologically diverse wetland settings (tidal salt marshes, river floodplain, rotational rice fields, and freshwater wetlands with permanent or seasonal flooding) to determine the extent to which the presence (or absence) of actively growing plants influences the activity of the Hg(II)-methylating microbial community and the availability of Hg(II) to those microbes. Vegetated control plots were paired with neighboring devegetated plots in which photosynthetic input was terminated 4–8 months prior to measurements, through clipping aboveground biomass, severing belowground connections, and shading the sediment surface to prevent regrowth. Across all wetlands, devegetation decreased the activity of the Hg(II)-methylating microbial community (kmeth) by 38%, calculated MeHg production potential (MP) rates by 36%, and pore water acetate concentration by 78%. Decreases in MP were associated with decreases in microbial sulfate reduction in salt marsh settings. In freshwater agricultural wetlands, decreases in MP were related to indices of microbial iron reduction. Sediment MeHg concentrations were also significantly lower in devegetated than in vegetated plots in most wetland settings studied. Devegetation effects were correlated with live root density (percent volume) and were most profound in vegetated sites with higher initial pore water acetate concentrations. Densely rooted wetlands had the highest rates of microbial Hg(II)-methylation activity but often the lowest concentrations of bioavailable reactive Hg(II). We conclude that the exudation of labile organic carbon (e.g., acetate) by plants leads to enhanced microbial sulfate and iron reduction activity in the rhizosphere, which results in high rates of microbial Hg(II)-methyation and high MeHg concentrations in wetland sediment.

  17. Quantifying the contribution of airborne lead (Pb) to surface waters in northeastern Oklahoma

    Science.gov (United States)

    Li, J. J.; McDonald, J.; Curtis, H.

    2017-12-01

    The northeastern Oklahoma, home to a number of Native American Tribes, is part of the well-known Tri-State Mining District (TSMD). One hundred years of mining production in this area has left numerous, large chat piles on the surrounding environment, directly affecting the town of Picher and many other tribe communities. Byproducts of the mining, including lead (Pb)-contain dust have been transported to the atmosphere and seeped into groundwater, lakes, ponds and rivers. Due to this contamination, many children in the area have elevated levels of Pb in their bodies. Despite a substantial number of studies and efforts on the restoration of heavy metal contamination in this area (e.g. The Tar Creek Superfund Site, EPA), no studies have attempted to distinguish the contributions of different sources, particularly from the atmospheric deposition, of heavy metals to the aquatic environment. In this study, we analyzed the atmospheric deposition of Pb from 4 sites located close to the chat piles for the period of 2010 to 2016. Our preliminary analysis showed that atmospheric Pb has a strong seasonal pattern with two peak times in early spring and late fall, which largely correspond with the dry periods in the this area. Atmospheric concentrations of Pb monitored at these sites frequently exceeded 0.15 μg/m3, the National Ambient Air Quality Standards (NAAQS) standard for ambient air Pb, and was generally 10 times higher than atmospheric Pb monitored in Tulsa, OK, a major metropolitan area 150 km southwest of the monitoring sites. With the known Pb flux to the sediments of the water bodies, we estimated that the contribution of Pb from the atmospheric deposition to the surface waters is up to 25%, depending on the distance of the water bodies to concentrated distribution of the chat piles.

  18. Effect of surface functionalisation on the interaction of iron oxide nanoparticles with polymerase chain reaction.

    Science.gov (United States)

    Aysan, Ayse Beyza; Knejzlík, Zdeněk; Ulbrich, Pavel; Šoltys, Marek; Zadražil, Aleš; Štěpánek, František

    2017-05-01

    The combination of nanoparticles with the polymerase chain reaction (PCR) can have benefits such as easier sample handling or higher sensitivity, but also drawbacks such as loss of colloidal stability or inhibition of the PCR. The present work systematically investigates the interaction of magnetic iron oxide nanoparticles (MIONs) with the PCR in terms of colloidal stability and potential PCR inhibition due to interaction between the PCR components and the nanoparticle surface. Several types of MIONs with and without surface functionalisation by sodium citrate, dextran and 3-aminopropyl-triethoxysilane (APTES) were prepared and characterised by Transmission Electron Microscopy (TEM), dynamic light scattering (DLS) and Fourier Transform Infrared (FT-IR) spectroscopy. Colloidal stability in the presence of the PCR components was investigated both at room temperature and under PCR thermo-cycling. Dextran-stabilized MIONs show the best colloidal stability in the PCR mix at both room and elevated temperatures. Citrate- and APTES-stabilised as well as uncoated MIONs show a comparable PCR inhibition near the concentration 0.1mgml -1 while the inhibition of dextran stabilized MIONs became apparent near 0.5mgml -1 . It was demonstrated that the PCR could be effectively carried out even in the presence of elevated concentration of MIONs up to 2mgml -1 by choosing the right coating approach and supplementing the reaction mix by critical components, Taq DNA polymerase and Mg 2+ ions. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Controlled surface segregation leads to efficient coke-resistant nickel/platinum bimetallic catalysts for the dry reforming of methane

    KAUST Repository

    Li, Lidong

    2015-02-03

    Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core-shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. These catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure. The reform of reforming: A series of alumina-supported Ni/Pt bimetallic nanoparticles (NPs) with controlled surface composition and structure are prepared. Remarkable surface segregation for these bimetallic NPs is observed upon thermal treatment. These bimetallic NPs are active catalysts for CO2 reforming of CH4, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.

  20. Probing surface distributions of α clusters in 20Ne via α -transfer reaction

    Science.gov (United States)

    Fukui, Tokuro; Taniguchi, Yasutaka; Suhara, Tadahiro; Kanada-En'yo, Yoshiko; Ogata, Kazuyuki

    2016-03-01

    Background: Direct evidence of the α -cluster manifestation in bound states has not been obtained yet, although a number of experimental studies were carried out to extract the information of the clustering. In particular in conventional analyses of α -transfer reactions, there exist a few significant problems on reaction models, which are insufficient to qualitatively discuss the cluster structure. Purpose: We aim to verify the manifestation of the α -cluster structure from observables. As the first application, we plan to extract the spatial information of the cluster structure of the 20Ne nucleus in its ground state through the cross section of the α -transfer reaction 16O(6Li,d )20Ne. Methods: For the analysis of the transfer reaction, we work with the coupled-channel Born approximation (CCBA) approach, in which the breakup effect of 6Li is explicitly taken into account by means of the continuum-discretized coupled-channel method based on the three-body α +d +16O model. The two methods are adopted to calculate the overlap function between 20Ne and α +16O ; one is the microscopic cluster model (MCM) with the generator coordinate method, and the other is the phenomenological two-body potential model (PM). Results: We show that the CCBA calculation with the MCM wave function gives a significant improvement of the theoretical result on the angular distribution of the transfer cross section, which is consistent with the experimental data. Employing the PM, it is discussed which region of the cluster wave function is probed on the transfer cross section. Conclusions: It is found that the surface region of the cluster wave function is sensitive to the cross section. The present work is situated as the first step in obtaining important information to systematically investigate the cluster structure.

  1. Uptake of gaseous formaldehyde by soil surfaces: a combination of adsorption/desorption equilibrium and chemical reactions

    Directory of Open Access Journals (Sweden)

    G. Li

    2016-08-01

    Full Text Available Gaseous formaldehyde (HCHO is an important precursor of OH radicals and a key intermediate molecule in the oxidation of atmospheric volatile organic compounds (VOCs. Budget analyses reveal large discrepancies between modeled and observed HCHO concentrations in the atmosphere. Here, we investigate the interactions of gaseous HCHO with soil surfaces through coated-wall flow tube experiments applying atmospherically relevant HCHO concentrations of  ∼  10 to 40 ppbv. For the determination of uptake coefficients (γ, we provide a Matlab code to account for the diffusion correction under laminar flow conditions. Under dry conditions (relative humidity  =  0 %, an initial γ of (1.1 ± 0.05  ×  10−4 is determined, which gradually drops to (5.5 ± 0.4  ×  10−5 after 8 h experiments. Experiments under wet conditions show a smaller γ that drops faster over time until reaching a plateau. The drop of γ with increasing relative humidity as well as the drop over time can be explained by the adsorption theory in which high surface coverage leads to a reduced uptake rate. The fact that γ stabilizes at a non-zero plateau suggests the involvement of irreversible chemical reactions. Further back-flushing experiments show that two-thirds of the adsorbed HCHO can be re-emitted into the gas phase while the residual is retained by the soil. This partial reversibility confirms that HCHO uptake by soil is a complex process involving both adsorption/desorption and chemical reactions which must be considered in trace gas exchange (emission or deposition at the atmosphere–soil interface. Our results suggest that soil and soil-derived airborne particles can either act as a source or a sink for HCHO, depending on ambient conditions and HCHO concentrations.

  2. Uptake of gaseous formaldehyde by soil surfaces: a combination of adsorption/desorption equilibrium and chemical reactions

    Science.gov (United States)

    Li, Guo; Su, Hang; Li, Xin; Kuhn, Uwe; Meusel, Hannah; Hoffmann, Thorsten; Ammann, Markus; Pöschl, Ulrich; Shao, Min; Cheng, Yafang

    2016-08-01

    Gaseous formaldehyde (HCHO) is an important precursor of OH radicals and a key intermediate molecule in the oxidation of atmospheric volatile organic compounds (VOCs). Budget analyses reveal large discrepancies between modeled and observed HCHO concentrations in the atmosphere. Here, we investigate the interactions of gaseous HCHO with soil surfaces through coated-wall flow tube experiments applying atmospherically relevant HCHO concentrations of ˜ 10 to 40 ppbv. For the determination of uptake coefficients (γ), we provide a Matlab code to account for the diffusion correction under laminar flow conditions. Under dry conditions (relative humidity = 0 %), an initial γ of (1.1 ± 0.05) × 10-4 is determined, which gradually drops to (5.5 ± 0.4) × 10-5 after 8 h experiments. Experiments under wet conditions show a smaller γ that drops faster over time until reaching a plateau. The drop of γ with increasing relative humidity as well as the drop over time can be explained by the adsorption theory in which high surface coverage leads to a reduced uptake rate. The fact that γ stabilizes at a non-zero plateau suggests the involvement of irreversible chemical reactions. Further back-flushing experiments show that two-thirds of the adsorbed HCHO can be re-emitted into the gas phase while the residual is retained by the soil. This partial reversibility confirms that HCHO uptake by soil is a complex process involving both adsorption/desorption and chemical reactions which must be considered in trace gas exchange (emission or deposition) at the atmosphere-soil interface. Our results suggest that soil and soil-derived airborne particles can either act as a source or a sink for HCHO, depending on ambient conditions and HCHO concentrations.

  3. Surface-Induced Dissociation and Chemical Reactions of C2D4+ on Stainless Steel, Carbon (HOPG), and Two Different Diamond Surfaces

    Czech Academy of Sciences Publication Activity Database

    Feketeová, L.; Žabka, Ján; Zappa, F.; Grill, V.; Scheier, P.; Märk, T. D.; Herman, Zdeněk

    2009-01-01

    Roč. 20, č. 6 (2009), s. 927-938 ISSN 1044-0305 Institutional research plan: CEZ:AV0Z40400503 Keywords : surface-induced process * diamond surfaces * chemical reactions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.391, year: 2009

  4. The Effect of Leading-Edge Sweep and Surface Inclination on the Hypersonic Flow Field Over a Blunt Flat Plate

    Science.gov (United States)

    Creager, Marcus O.

    1959-01-01

    An investigation of the effects of variation of leading-edge sweep and surface inclination on the flow over blunt flat plates was conducted at Mach numbers of 4 and 5.7 at free-stream Reynolds numbers per inch of 6,600 and 20,000, respectively. Surface pressures were measured on a flat plate blunted by a semicylindrical leading edge over a range of sweep angles from 0 deg to 60 deg and a range of surface inclinations from -10 deg to +10 deg. The surface pressures were predicted within an average error of +/- 8 percent by a combination of blast-wave and boundary-layer theory extended herein to include effects of sweep and surface inclination. This combination applied equally well to similar data of other investigations. The local Reynolds number per inch was found to be lower than the free-stream Reynolds number per inch. The reduction in local Reynolds number was mitigated by increasing the sweep of the leading edge. Boundary-layer thickness and shock-wave shape were changed little by the sweep of the leading edge.

  5. Library of Antifouling Surfaces Derived From Natural Amino Acids by Click Reaction.

    Science.gov (United States)

    Xu, Chen; Hu, Xin; Wang, Jie; Zhang, Ye-Min; Liu, Xiao-Jiu; Xie, Bin-Bin; Yao, Chen; Li, Yi; Li, Xin-Song

    2015-08-12

    Biofouling is of great concern in numerous applications ranging from ophthalmological implants to catheters, and from bioseparation to biosensors. In this report, a general and facile strategy to combat surface fouling is developed by grafting of amino acids onto polymer substrates to form zwitterionic structure through amino groups induced epoxy ring opening click reaction. First of all, a library of poly(2-hydroxyethyl methacrylate-co-glycidyl methacrylate) hydrogels with zwitterionic surfaces were prepared, resulting in the formation of pairs of carboxyl anions and protonated secondary amino cations. The analysis of attenuated total reflectance Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy confirmed the successful immobilization of amino acids on the hydrogel surfaces. After that, the contact angle and equilibrium water content of the modified hydrogels showed that the hydrogels exhibited improved hydrophilicity compared with the parent hydrogel. Furthermore, the protein deposition was evaluated by bicinchoninic acid assay using bovine serum albumin (BSA) and lysozyme as models. The results indicated that the performance of the hydrogels was determined by the nature of incorporated amino acid: the hydrogels incorporated with neutral amino acids had nonspecific antiadsorption capability to both BSA and lysozyme; the hydrogels incorporated with charged amino acids showed antiadsorption behaviors against protein with same charge and enhanced adsorption to the protein with opposite charge; the optimal antiadsorption performance was observed on the hydrogels incorporated with polar amino acids with a hydroxyl residual. The improvement of antiprotein fouling of the neutral amino acids grafted hydrogels can be ascribed to the formation of zwitterionic surfaces. Finally, a couple of soft contact lenses grafted with amino acids were fabricated having improved antifouling property and hydrophilicity. The result demonstrated the success of

  6. Field and laboratory emission cell automation and control system for investigating surface chemistry reactions

    Science.gov (United States)

    Flemmer, Michael M.; Ham, Jason E.; Wells, J. R.

    2007-01-01

    A novel system [field and laboratory emission cell (FLEC) automation and control system] has been developed to deliver ozone to a surface utilizing the FLEC to simulate indoor surface chemistry. Ozone, humidity, and air flow rate to the surface were continuously monitored using an ultraviolet ozone monitor, humidity, and flow sensors. Data from these sensors were used as feedback for system control to maintain predetermined experimental parameters. The system was used to investigate the chemistry of ozone with α-terpineol on a vinyl surface over 72h. Keeping all other experimental parameters the same, volatile organic compound emissions from the vinyl tile with α-terpineol were collected from both zero and 100ppb(partsper109) ozone exposures. System stability profiles collected from sensor data indicated experimental parameters were maintained to within a few percent of initial settings. Ozone data from eight experiments at 100ppb (over 339h) provided a pooled standard deviation of 1.65ppb and a 95% tolerance of 3.3ppb. Humidity data from 17 experiments at 50% relative humidity (over 664h) provided a pooled standard deviation of 1.38% and a 95% tolerance of 2.77%. Data of the flow rate of air flowing through the FLEC from 14 experiments at 300ml/min (over 548h) provided a pooled standard deviation of 3.02ml/min and a 95% tolerance range of 6.03ml/min. Initial experimental results yielded long term emissions of ozone/α-terpineol reaction products, suggesting that surface chemistry could play an important role in indoor environments.

  7. Characterization of surface electrochemical reactions used in electrochemical atomic layer epitaxy and digital etching

    Science.gov (United States)

    Sorenson, Thomas Allen

    Surface analytical techniques have been used to characterize electrochemical reactions to be used in semiconductor processing technologies. Studies have been performed using UHV-EC methodology to determine conditions for the surface limited dissolution of CdTe(100). Electrochemical conditions were identified which resulted in the reduction of the top layer of tellurium atoms, leaving behind a cadmium enriched surface. Attempts to find an electrochemical potential for the oxidative dissolution of the cadmium surface were complicated by the simultaneous oxidation of the compound CdTe. In situ scanning tunneling microscopy has also been used to characterize the formation of tellurium atomic layers formed on Au(111) and Au(100) by underpotential deposition. On Au(100), the following sequence of surface structures was observed prior to bulk electrodeposition: a p(2x2), a (2x✓10), a (2x4), and a (✓2x✓5). The transitions between these structures was observed by STM and mechanisms for the phase transitions are presented. The results are correlated to UHV-EC studies of tellurium UPD on Au(100). On Au(111), the following sequence of structures was observeḑ: a (✓3 x✓3), a (✓7x✓13), and a (3x3). The (✓3x✓3) was shown to exist with a network of domain walls, forming long range triangular and diamond shaped superstructures. Conversion of the (✓3x✓3) to higher coverage structure resulted in roughening of the underlying Au surface and a mechanism is hypothesized to explain this transition. The STM results are also correlated to low energy electron diffraction (LEED) results obtained by UHV-EC studies. The surface structures formed by reductive UPD of the chalcogenide elements and Se on both Au(100) and Au(111) are compared. Both elements initially resulted in structures consisting of isolated atoms separated by distances close to the reported van der Waals diameter. Higher coverage structures resulted in interatomic chalcogenide bonding and the structures

  8. The influence of flow velocity on electrochemical reaction of metal surface

    Science.gov (United States)

    Li, Zhen; Zhang, Jiding

    2017-12-01

    In order to find out the effect of fluid flow velocity on electrochemical reaction, the electrochemical parameters of super 13Cr stainless steel in 3.5% NaCl aqueous solution were measured by a jet flow system at different flow velocities. The electrochemical characters such as open-circuit potential and polarization curve were monitored online using a three-electrode electrochemical system. The results show that the increase of wall shear stress caused by the high flow velocity leads to the rupture of passive films and the exposure of fresh metal in the corrosive media, which causes the increase of corrosion rate. Meanwhile, the corrosion rate shows a significant growth when the flow velocity is less than 0∼10.0 m/s. But it gradually decreases after reaching a maximum value.

  9. Reduction of the Electrode Overpotential of the Oxygen Evolution Reaction by Electrode Surface Modification

    Directory of Open Access Journals (Sweden)

    Cian-Tong Lu

    2017-01-01

    Full Text Available Metal–air batteries exhibit high potential for grid-scale energy storage because of their high theoretical energy density, their abundance in the earth’s crust, and their low cost. In these batteries, the oxygen evolution reaction (OER occurs on the air electrode during charging. This study proposes a method for improving the OER electrode performance. The method involves sequentially depositing a Ni underlayer, Sn whiskers, and a Ni protection layer on the metal mesh. Small and uniform gas bubbles form on the Ni/Sn/Ni mesh, leading to low overpotential and a decrease in the overall resistance of the OER electrode. The results of a simulated life cycle test indicate that the Ni/Sn/Ni mesh has a life cycle longer than 1,300 cycles when it is used as the OER electrode in 6 M KOH.

  10. Histopathology and immune histochemistry of red tattoo reactions. Interface dermatitis is the lead pathology, with increase in T-lymphocytes and Langerhans cells suggesting an allergic pathomechanism.

    Science.gov (United States)

    Høgsberg, T; Thomsen, B M; Serup, J

    2015-11-01

    The majority of tattoo reactions are affiliated to red pigmented areas and often suspected to be allergic in nature. A sizeable series of biopsies of such reactions has not previously been performed. The aim of this study was to type and grade epidermal and dermal changes in tattoo reactions to red/red nuances by microscopy and immunochemistry relevant for the assessment of a possible allergic pathomechanism. Skin biopsies were taken from red tattoo reactions, graded by conventional microscopy and stained for T and B-lymphocytes, Langerhans cells, macrophages and tumour necrosis factor (TNF)-α. The study included 19 biopsies from 19 patients. The culprit colours were red/pink (n = 15) and purple/bordeaux (n = 4). Interface dermatitis was clearly the lead pathology found in 78% of samples, overlapped with granulomatous (in 32%) and pseudolymphomatous reaction patterns (in 32%). Epidermal hyperkeratosis (in 89%) was common as was leakage of red pigment across the dermo-epidermal junction, with transepidermal elimination (in 28%). The dermal cellular infiltration was dominated by T-lymphocytes (in 100%), Langerhans cells (in 95%) and macrophages (in 100%). TNF-α was common. The predominant histological pattern of chronic tattoo reactions in red/red nuances is interface dermatitis. T-lymphocytes and Langerhans cells are increased suggesting an allergic pathomechanism. TNF-α may contribute to reactions. In many cases, overlapping reactive patterns were identified. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  11. Photogenerated carrier-induced reactions on uhv semiconductor surfaces. Technical progress report, December 15, 1989--December 14, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Osgood, R.M. Jr.

    1992-05-28

    The objective for this experimental work was to examine the reaction mechanisms, half-collision dynamics, and other optically induced chemical effects, that are operable on a well characterized single-crystal semiconductor surface. Of particular interest were reactions induced by charge transfer from the semiconductor surface including hot carrier and thermalized carrier processes. The primary technique to measure the desorbed fragment translational energies was time-of-flight mass-spectroscopy, used in conjunction with a pulsed tunable laser source. The work was carried out in ultrahigh vacuum, thus other surface spectroscopies such as temperature-programmed desorption, (TPD), (LEED), etc. were used as needed. In the project, the photoreactions of several halogen-containing molecules on GaAs(110) surfaces have been investigated. The studies have made the first observations of several new photochemical processes on uhv prepared surfaces including intermolecular charge transfer; desorption by thermal-carrier-induced reactions (including the measurement of coverage-dependent changes in the translational energies of the desorbed products); interferometric oscillation of photoinduced reactions; and self-quenching of thermal carrier reactions on surfaces.

  12. Unsteady MHD flow of an UCM fluid over a stretching surface with higher order chemical reaction

    Directory of Open Access Journals (Sweden)

    Sudhagar Palani

    2016-03-01

    Full Text Available The objective of this paper was to illustrate the frequent and wide occurrence of unsteady two dimensional MHD flow of an UCM fluid over a stretching surface in the presence of higher order chemical reaction in a diverse range of applications, both in nature and in technology. The governing partial differential equations are converted into ordinary differential equations by using similarity transformation. The ordinary differential equations were numerically solved by using shooting technique. The effects of different governing parameters on the flow field and mass transfer are shown in graphs and tables. The governing physical parameters significantly influence the flow field and mass transfer. Also, existing results in the literature are compared with the present study as a special case. In addition to practical applications in foams, suspensions, polymer solutions and melts, the present study also contributed to the existing literature.

  13. Surface Chemistry Dependence of Mechanochemical Reaction of Adsorbed Molecules-An Experimental Study on Tribopolymerization of α-Pinene on Metal, Metal Oxide, and Carbon Surfaces.

    Science.gov (United States)

    He, Xin; Kim, Seong H

    2018-02-20

    Mechanochemical reactions between adsorbate molecules sheared at tribological interfaces can induce association of adsorbed molecules, forming oligomeric and polymeric products often called tribopolymers). This study revealed the role or effect of surface chemistry of the solid substrate in mechanochemical polymerization reactions. As a model reactant, α-pinene was chosen because it was known to readily form tribopolymers at the sliding interface of stainless steel under vapor-phase lubrication conditions. Eight different substrate materials were tested-palladium, nickel, copper, stainless steel, gold, silicon oxide, aluminum oxide, and diamond-like carbon (DLC). All metal substrates and DLC were initially covered with surface oxide species formed naturally in air or during the oxidative sample cleaning. It was found that the tribopolymerization yield of α-pinene is much higher on the substrates that can chemisorb α-pinene, compared to the ones on which only physisorption occurs. From the load dependence of the tribopolymerization yield, it was found that the surfaces capable of chemisorption give a smaller critical activation volume for the mechanochemical reaction, compared to the ones capable of physisorption only. On the basis of these observations and infrared spectroscopy analyses of the adsorbed molecules and the produced polymers, it was concluded that the mechanochemical reaction mechanisms might be different between chemically reactive and inert surfaces and that the chemical reactivity of the substrate surface greatly influences the tribochemical polymerization reactions of adsorbed molecules.

  14. Numerical study of chemical reactions in a surface microdischarge tube with mist flow based on experiment

    International Nuclear Information System (INIS)

    Shibata, T; Nishiyama, H

    2014-01-01

    Recently, a water treatment method of spraying solution into a discharge region has been developed and shows high energy efficiency. In this study, a simulation model of a water treatment method using a surface microdischarge (SMD) tube with mist flow is proposed for further understanding the detailed chemical reactions. Our model has three phases (plasma, gas and liquid) and three simulation steps. The carrier gas is humid air including 2% or 3% water vapour. The chemical species diffusion characteristics in the SMD tube and the concentrations in a droplet are clarified in a wide pH interval. The simulation results show that the chemical species generated on the SMD tube inner wall are diffused to the central axis and dissolved into fine droplets. Especially, OH radicals dissolve into droplets a few mm away from the SMD tube wall because of acidification of the droplets. Furthermore, the hydrogen peroxide density, which is the most important indicator of a radical reaction in water, is influenced by the initial solution pH. This pH dependence results from ozone self-decomposition in water. (paper)

  15. Numerical study of chemical reactions in a surface microdischarge tube with mist flow based on experiment

    Science.gov (United States)

    Shibata, T.; Nishiyama, H.

    2014-03-01

    Recently, a water treatment method of spraying solution into a discharge region has been developed and shows high energy efficiency. In this study, a simulation model of a water treatment method using a surface microdischarge (SMD) tube with mist flow is proposed for further understanding the detailed chemical reactions. Our model has three phases (plasma, gas and liquid) and three simulation steps. The carrier gas is humid air including 2% or 3% water vapour. The chemical species diffusion characteristics in the SMD tube and the concentrations in a droplet are clarified in a wide pH interval. The simulation results show that the chemical species generated on the SMD tube inner wall are diffused to the central axis and dissolved into fine droplets. Especially, OH radicals dissolve into droplets a few mm away from the SMD tube wall because of acidification of the droplets. Furthermore, the hydrogen peroxide density, which is the most important indicator of a radical reaction in water, is influenced by the initial solution pH. This pH dependence results from ozone self-decomposition in water.

  16. Indirect glyphosate detection based on ninhydrin reaction and surface-enhanced Raman scattering spectroscopy

    Science.gov (United States)

    Xu, Meng-Lei; Gao, Yu; Li, Yali; Li, Xueliang; Zhang, Huanjie; Han, Xiao Xia; Zhao, Bing; Su, Liang

    2018-05-01

    Glyphosate is one of the most commonly-used and non-selective herbicides in agriculture, which may directly pollute the environment and threaten human health. A simple and effective approach to assessment of its damage to the natural environment is thus quite necessary. However, traditional chromatography-based detection methods usually suffer from complex pretreatment procedures. Herein, we propose a simple and sensitive method for the determination of glyphosate by combining ninhydrin reaction and surface-enhanced Raman scattering (SERS) spectroscopy. The product (purple color dye, PD) of the ninhydrin reaction is found to SERS-active and directly correlate with the glyphosate concentration. The limit of detection of the proposed method for glyphosate is as low as 1.43 × 10- 8 mol·L- 1 with a relatively wider linear concentration range (1.0 × 10- 7-1.0 × 10- 4 mol·L- 1), which demonstrates its great potential in rapid, highly sensitive concentration determination of glyphosate in practical applications for safety assessment of food and environment.

  17. Hydrogen-deuterium substitution in solid ethanol by surface reactions at low temperatures

    Science.gov (United States)

    Oba, Yasuhiro; Osaka, Kazuya; Chigai, Takeshi; Kouchi, Akira; Watanabe, Naoki

    2016-10-01

    Ethanol (CH3CH2OH) is one of the most abundant complex organic molecules in star-forming regions. Despite its detection in the gas phase only, ethanol is believed to be formed by low-temperature grain-surface reactions. Methanol, the simplest alcohol, has been a target for observational, experimental, and theoretical studies in view of its deuterium enrichment in the interstellar medium; however, the deuterium chemistry of ethanol has not yet been an area of focus. Recently, deuterated dimethyl ether, a structural isomer of ethanol, was found in star-forming regions, indicating that deuterated ethanol can also be present in those environments. In this study, we performed laboratory experiments on the deuterium fractionation of solid ethanol at low temperatures through a reaction with deuterium (D) atoms at 10 K. Hydrogen (H)-D substitution, which increases the deuteration level, was found to occur on the ethyl group but not on the hydroxyl group. In addition, when deuterated ethanol (e.g. CD3CD2OD) solid was exposed to H atoms at 10 K, D-H substitution that reduced the deuteration level occurred on the ethyl group. Based on the results, it is likely that deuterated ethanol is present even under H-atom-dominant conditions in the interstellar medium.

  18. Adsorption and reaction of CO and H2O on WC(0001) surface: A first-principles investigation

    Science.gov (United States)

    Tong, Yu-Jhe; Wu, Shiuan-Yau; Chen, Hsin-Tsung

    2018-01-01

    We have performed a spin-polarized density functional theory (DFT) study for understanding the detailed reaction mechanism of CO and H2O on WC (0001) surface. The adsorption properties and vibrational frequencies of H2O, OH, O, H, CO and CO2 on the WC (0001) surface were illustrated. These results are well in consistent with the experimental observations studied by temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS). Based on the adsorption results, potential energy profiles of H2O and OH dehydrogenation and HCO, COH, COOH, and CO2 formation on the WC (0001) surface were predicted. The calculation results demonstrated that the WC (0001) surface as Fe (110) surface exhibits significantly reaction activity toward the dehydrogenation of H2O and OH but less activity toward the formation of HCO, COH, COOH and CO2 compared to the Cu (111) and Pt (111) surfaces.

  19. Infrared thermoimages display of body surface temperature reaction in experimental cholecystitis

    Science.gov (United States)

    Zhang, Dong; Zhu, Yuan-Gen; Wang, Shu-You; Ma, Hui-Min; Ye, Yan-Yan; Fu, Wei-Xing; Hu, Wei-Guo

    2002-01-01

    AIM: To display the thermoimages of the body surface in experimental cholecystitis, to observe the body surface temperature reaction in visceral disorders, and to study if the theory of body surface-viscera correlation is true and the mechanism of temperature changes along the meridians. METHODS: By injecting bacteria suspension into the stricture bile duct and gallbladder, 21 rabbits were prepared as acute pyogenic cholangiocholecystitis models, with another 8 rabbits prepared by the same process except without injection of bacteria suspension as control. The body surface infrared thermoimages were continuously observed on the hair shaven rabbit skin with AGA-782 thermovision 24 h before, 1-11 d after and (2, 3 wk) 4 wk after the operation with a total of over 10 records of thermoimages. RESULTS: Twelve cases out of 21 rabbits with cholecystitis revealed bi-lateral longitudinal high temperature lines in its trunk; with negative findings in the control group. The high-temperature line appeared on d1-d2, first in the right trunk, after the preparation of the model, about 7 d after the model preparation, the lines appeared at the left side too, persisting for 4 wk. The hyper-temperature line revealed 1.1-2.7 °C higher than before the model preparation, 0.7-2.5 °C higher than the surrounding skin. The length of the high temperature line might reach a half length of the body trunk, or as long as the whole body itself. CONCLUSION: The appearance of the longitudinal high temperature lines at the lateral aspects of the trunk in the experimental group is directly bound up with the experimental animals pyogenic cholecystitis, with its running course quite similar to that of the Gallbladder Channel of Foot Shaoyang, but different to the zones of hyperalgesia and site of referred pain in cholecystitis. PMID:11925617

  20. Lead adsorption study on combustion derived γ-Fe2O3 surface

    Indian Academy of Sciences (India)

    2016-08-26

    AAS) and solution conductivity (SC). Reduction in the concentration and increase in conductance of eluent lead solution is observed. The potential use of solid adsorbents for the adsorption of heavy metal pollutants is envisaged ...

  1. Surface reactions of iron - enriched smectites: adsorption and transformation of hydroxy fatty acids and phenolic acids

    Science.gov (United States)

    Polubesova, Tamara; Olshansky, Yaniv; Eldad, Shay; Chefetz, Benny

    2014-05-01

    Iron-enriched smectites play an important role in adsorption and transformation of soil organic components. Soil organo-clay complexes, and in particular humin contain hydroxy fatty acids, which are derived from plant biopolymer cutin. Phenolic acids belong to another major group of organic acids detected in soil. They participate in various soil processes, and are of concern due to their allelopathic activity. We studied the reactivity of iron-enriched smectites (Fe(III)-montmorillonite and nontronite) toward both groups of acids. We used fatty acids- 9(10),16-dihydroxypalmitic acid (diHPA), isolated from curtin, and 9,10,16-trihydroxypalmitic acid (triHPA); the following phenolic acids were used: ferulic, p-coumaric, syringic, and vanillic. Adsorption of both groups of acids was measured. The FTIR spectra of fatty acid-mineral complexes indicated inner-sphere complexation of fatty acids with iron-enriched smectites (versus outer-sphere complexation with Ca(II)-montmorillonite). The LC-MS results demonstrated enhanced esterification of fatty acids on the iron-enriched smectite surfaces (as compared to Ca(II)-montmorillonite). This study suggests that fatty acids can be esterified on the iron-enriched smectite surfaces, which results in the formation of stable organo-mineral complexes. These complexes may serve as a model for the study of natural soil organo-clay complexes and humin. The reaction of phenolic acids with Fe(III)-montmorillonite demonstrated their oxidative transformation by the mineral surfaces, which was affected by molecular structure of acids. The following order of their transformation was obtained: ferulic >syringic >p-coumaric >vanillic. The LC-MS analysis demonstrated the presence of dimers, trimers, and tetramers of ferulic acid on the surface of Fe(III)-montmorillonite. Oxidation and transformation of ferulic acid were more intense on the surface of Fe(III)-montmorillonite as compared to Fe(III) in solution due to stronger complexation on

  2. Lead extraction from Cathode Ray Tube (CRT) funnel glass: Reaction mechanisms in thermal reduction with addition of carbon (C).

    Science.gov (United States)

    Lu, Xingwen; Ning, Xun-An; Chen, Da; Chuang, Kui-Hao; Shih, Kaimin; Wang, Fei

    2018-04-09

    This study quantitatively determined the extraction of lead from CRT funnel glass and examined the mechanisms of thermally reducing lead in the products of sintering Pb-glass with carbon in the pre-heated furnace. The experimentally derived results indicate that a 90.3 wt% lead extraction efficiency can be achieved with 20 wt% of C addition at 950 °C for 3 min under air. The formation of viscous semi-liquid glass blocked the oxygen supply between the interaction of C and Pb-glass, and was highly effective for the extraction of metallic Pb. A maximum of 87.3% lead recover was obtained with a C to Na 2 CO 3 ratio of 1/3 at 1200 °C. The decrease of C/Na 2 CO 3 ratio enhanced the metallic lead recovery by increasing the glass viscosity for effective sedimentation of metallic lead in the bottom. However, with the further increase of temperature and treatment time, re-vitrification of lead back to silicate-glass matrix was detected in both Pb-glass/C and Pb-glass/C/Na 2 CO 3 systems. The findings indicated that with proper controls, using C as an inexpensive reagent can effectively reduce treatment time and energy, which is crucial to a waste-to-resource technology for economically recovering lead from the waste CRT glass. Copyright © 2018 Elsevier Ltd. All rights reserved.

  3. Insight into the Role of Surface Wettability in Electrocatalytic Hydrogen Evolution Reactions Using Light-Sensitive Nanotubular TiO2 Supported Pt Electrodes

    Science.gov (United States)

    Meng, Chenhui; Wang, Bing; Gao, Ziyue; Liu, Zhaoyue; Zhang, Qianqian; Zhai, Jin

    2017-02-01

    Surface wettability is of importance for electrochemical reactions. Herein, its role in electrochemical hydrogen evolution reactions is investigated using light-sensitive nanotubular TiO2 supported Pt as hydrogen evolution electrodes (HEEs). The HEEs are fabricated by photocatalytic deposition of Pt particles on TiO2 nanotubes followed by hydrophobization with vaporized octadecyltrimethoxysilane (OTS) molecules. The surface wettability of HEEs is subsequently regulated in situ from hydrophobicity to hydrophilicity by photocatalytic decomposition of OTS molecules using ultraviolet light. It is found that hydrophilic HEEs demonstrate a larger electrochemical active area of Pt and a lower adhesion force to a gas bubble when compared with hydrophobic ones. The former allows more protons to react on the electrode surface at small overpotential so that a larger current is produced. The latter leads to a quick release of hydrogen gas bubbles from the electrode surface at large overpotential, which ensures the contact between catalysts and electrolyte. These two characteristics make hydrophilic HEEs generate a much high current density for HERs. Our results imply that the optimization of surface wettability is of significance for improving the electrocatalytic activity of HEEs.

  4. In situ Raman scattering study on a controllable plasmon-driven surface catalysis reaction on Ag nanoparticle arrays

    International Nuclear Information System (INIS)

    Dai, Z G; Xiao, X H; Zhang, Y P; Ren, F; Wu, W; Zhang, S F; Zhou, J; Jiang, C Z; Mei, F

    2012-01-01

    Control of the plasmon-driven chemical reaction for the transformation of 4-nitrobenzenethiol to p,p′-dimercaptoazobenzene by Ag nanoparticle arrays was studied. The Ag nanoparticle arrays were fabricated by means of nanosphere lithography. By changing the PS particle size, the localized surface plasmon resonance (LSPR) peaks of the Ag nanoparticle arrays can be tailored from 460 to 560 nm. The controlled reaction process was monitored by in situ surface-enhanced Raman scattering. The reaction can be dramatically influenced by varying the duration of laser exposure, Ag nanoparticle size, laser power and laser excitation wavelength. The maximum reaction speed was achieved when the LSPR wavelength of the Ag nanoparticle arrays matched the laser excitation wavelength. The experimental results reveal that the strong LSPR can effectively drive the transfer of the ‘hot’ electrons that decay from the plasmon to the reactants. The experimental results were confirmed by theoretical calculations. (paper)

  5. Neutron production in spallation reactions of 0.9 and 1.5 GeV protons on a thick lead target. Comparison between experimental data and Monte-Carlo simulations

    International Nuclear Information System (INIS)

    Krasa, A.; Krizek, F.; Wagner, V.; Kugler, A.; Henzl, V.; Henzlova, D.; Majerle, M.; Adam, J.; Caloun, P.; Bradnova, V.; Chultem, D.; Kalinnikov, V.G.; Krivopustov, M.I.; Solnyshkin, A.A.; Stegajlov, V.I.; Tsupko-Sitnikov, V.M.; Tumehndehlgehr, Ts.; Vasil'ev, S.I.

    2005-01-01

    This paper reports on two experiments performed at the Synchrophasotron/Nuclotron accelerator complex at JINR. Relativistic protons with energies 885 MeV and 1.5 GeV hit a massive cylindrical lead target. The spatial and energetic distributions of the neutron field produced by the spallation reactions were measured by the activation of Al, Au, Bi, Co, and Cu foils placed on the surface of the target and close to it. The yields of the radioactive nuclei produced by threshold reactions in these foils were determined by the analyses of their γ spectra. The comparison with Monte-Carlo based simulations was performed both with the LAHET+MCNP code and the MCNPX code

  6. Task-based lead exposures and work site characteristics of bridge surface preparation and painting contractors.

    Science.gov (United States)

    Virji, M Abbas; Woskie, Susan R; Pepper, Lewis D

    2009-02-01

    This study of bridge painters working for small contractors in Massachusetts investigated the causes of elevated blood lead levels and assessed their exposure to lead. Bridge work sites were evaluated for a 2-week period during which personal and area air samples and information on work site characteristics and lead abatement methods were gathered. Short-duration personal inhalable samples collected from 18 tasks had geometric means (GM) of 3 microg/m(3) to 7286 microg/m(3). Full-shift, time-weighted average (TWA) inhalable samples (>or=6 hours) collected from selected workers and work sites had GMs of 2 microg/m(3) to 15,704 microg/m(3); 80% of samples exceeded the permissible exposure limit (PEL) of 50 microg/m(3), on average by a factor of 30. Area inhalable samples collected from three locations ranged from 2 microg/m(3) to 40,866 microg/m(3) from inside the containment, 2 microg/m(3) to 471 microug/m(3) from a distance of 6 meters from the containment. Seventy nine percent of the area samples from inside the containment exceeded the PEL on average by a factor of 140. Through observations of work site characteristics, opportunities for improving work methods were identified, particularly the institution of engineering controls (which were only occasionally present) and improvement in the design and construction of the containment structure. The high levels of airborne lead exposures indicate a potential for serious exposure hazard for workers and environmental contamination, which can be mitigated through administrative and engineering controls. Although these data were collected over 10 years ago, a 2005 regulatory review by the Occupational Safety and Health Administration (OSHA) of its lead in construction standard reported that elevated lead exposures and blood lead levels, high occurrence of noncompliance with the lead standard, and nonimplementation of newer technology especially among small painting firms employing <10 workers are still widespread. As a

  7. Surface-induced reactions and dissociations of small acetone, acetonitrile and ethanol cluster ions: competitive chemical reactions, dissociation mechanisms and determination of dissociation energy

    Czech Academy of Sciences Publication Activity Database

    Mair, C.; Fedor, J.; Lezius, M.; Scheier, P.; Probst, M.; Herman, Zdeněk; Märk, T. D.

    2003-01-01

    Roč. 5, - (2003), s. 9.1-9.18 ISSN 1367-2630 R&D Projects: GA ČR GA203/00/0632 Grant - others:Czech-Austria Cooperation Programme in Science and Technology 2000-01 No. 6 Institutional research plan: CEZ:AV0Z4040901 Source of funding: O - operačné programy Keywords : physical chemistry * surface-induced reactions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.480, year: 2003

  8. Surface-active ionic liquids in micellar catalysis: impact of anion selection on reaction rates in nucleophilic substitutions.

    Science.gov (United States)

    Cognigni, Alice; Gaertner, Peter; Zirbs, Ronald; Peterlik, Herwig; Prochazka, Katharina; Schröder, Christian; Bica, Katharina

    2016-05-21

    A series of surface-active ionic liquids based on the 1-dodecyl-3-methylimidazolium cation and different anions such as halides and alkylsulfates was synthesized. The aggregation behavior of these ionic liquids in water was characterized by surface tension, conductivity measurements and UV-Vis spectroscopy in order to determine the critical micelle concentration (CMC) and to provide aggregation parameters. The determination of surface activity and aggregation properties of amphiphilic ionic liquids was accompanied by SAXS studies on selected surface-active ionic liquids. The application of these surface-active ionic liquids with different anions was tested in nucleophilic substitution reactions for the degradation of organophosphorus compounds. Kinetic studies via UV-Vis spectrophotometry showed a strong acceleration of the reaction in the micellar system compared to pure water. In addition, an influence of the anion was observed, resulting in a correlation between the anion binding to the micelle and the reaction rate constants, indicating that the careful choice of the surface-active ionic liquid can considerably affect the outcome of reactions.

  9. Surface Termination, Morphology and Bright Photoluminescence of Cesium Lead Halide Perovskite Nanocrystals

    NARCIS (Netherlands)

    ten Brinck, Stephanie; Infante, Ivan

    2016-01-01

    Colloidal cesium lead halide perovskite nanocrystals (CsPbX3 PNC, X=Cl, Br, I) exhibit important optoelectronic properties that make them amenable for a plethora of applications. The origin of these properties, even for as-synthesized and unpurified PNCs, is however largely unknown. Electronic

  10. Current Distribution over the Electrode Surface in a Lead-acid Cell during Discharge

    Czech Academy of Sciences Publication Activity Database

    Král, P.; Křivák, P.; Bača, P.; Calábek, M.; Micka, Karel

    2002-01-01

    Roč. 105, č. 1 (2002), s. 34-44 ISSN 0378-7753 R&D Projects: GA ČR GA102/98/1170 Institutional research plan: CEZ:AV0Z4040901 Keywords : grid design * current distribution * lead-acid cell Subject RIV: CG - Electrochemistry Impact factor: 1.777, year: 2002

  11. Electrodeposition of Pd based binary catalysts on Carbon paper via surface limited redox-replacement reaction for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Modibedi, RM

    2014-05-01

    Full Text Available attention as it is more abundant and also cheaper than Pt. In this presentation, Electrochemical Atomic Layer Deposition (ECALD) was used in the preparation of binary ORR catalysts. The binary nanoclusters were synthesised via surface-limited redox-replacement...

  12. Investigation Into Accessible Surface Vinyl Concentrations of Nonstoichiometric PDMS Microspheres from Hydrosilylation Reactions and Their Further Crosslinking Reactions

    DEFF Research Database (Denmark)

    Ma, Baoguang; Hansen, Jens Henrik; Hvilsted, Søren

    2015-01-01

    titration method, which is based on efficiently and covalently bonding mono-functional hydride to vinyl, is employed to determine surface vinyl concentration. The titration method exhibits good reproducibility in detection, thereby underlining its potential applicability as a general titration method...

  13. Reaction kinetics of metal deposition via surface limited red-ox replacement of underpotentially deposited metal monolayers

    International Nuclear Information System (INIS)

    Gokcen, Dincer; Bae, Sang-Eun; Brankovic, Stanko R.

    2011-01-01

    The study of the kinetics of metal deposition via surface limited red-ox replacement of underpotentially deposited metal monolayers is presented. The model system was Pt submonolayer deposition on Au(1 1 1) via red-ox replacement of Pb and Cu UPD monolayers on Au(1 1 1). The kinetics of a single replacement reaction was studied using the formalism of the comprehensive analytical model developed to fit the open circuit potential transients from deposition experiments. The practical reaction kinetics parameters like reaction half life, reaction order and reaction rate constant are determined and discussed with their relevance to design and control of deposition experiments. The effects of transport limitation and the role of the anions/electrolyte on deposition kinetics are investigated and their significance to design of effective deposition process is discussed.

  14. Process optimization of batch biosorption of lead using Lactobacillius bulgaricus in an aqueous phase system using response surface methodology.

    Science.gov (United States)

    Sedighi, Mehdi; Ghasemi, Mostafa; Hassan, Sedky H A; Daud, Wan Ramli Wan; Ismail, Manal; Abdallah, Elgorban

    2012-05-01

    Response surface methodology (RSM) based on central composite rotatable design was used to investigate the effects of operating variable, mainly, pH, weight of biomass, and initial lead ion concentration on the lead adsorption capacity at ambient temperature using dried cells of Lactobacillius bulgaricus. Using RSM, quadratic polynomial equation was obtained for predicting the percent of lead ion removal. Analysis of variance showed that the effects of pH and weight of dried biomass were concluded to be the key factors influencing the capacity of lead ion removal. At pH lower than 2 (high acidic condition) and in alkaline condition, there is no significant biosorption. The optimum percent of lead ion removal was found at pH of 6.78, biomass concentration of 6.58 g/l and initial lead concentration 36.22 ppm. In this condition, percent of lead ion removal was 86.21%. This study showed RSM effectiveness for modeling of biosorption process.

  15. Applications of computer simulation, nuclear reactions and elastic scattering to surface analysis of materials

    Directory of Open Access Journals (Sweden)

    Pacheco de Carvalho, J. A.

    2008-08-01

    Full Text Available This article involves computer simulation and surface analysis by nuclear techniques, which are non-destructive. Both the “energy method of analysis” for nuclear reactions and elastic scattering are used. Energy spectra are computer simulated and compared with experimental data, giving target composition and concentration profile information. The method is successfully applied to thick flat targets of graphite, quartz and sapphire and targets containing thin films of aluminium oxide. Depth profiles of 12C and 16O nuclei are determined using (d,p and (d,α deuteron induced reactions. Rutherford and resonance elastic scattering of (4He+ ions are also used.

    Este artículo trata de simulación por ordenador y del análisis de superficies mediante técnicas nucleares, que son no destructivas. Se usa el “método de análisis en energia” para reacciones nucleares, así como el de difusión elástica. Se simulan en ordenador espectros en energía que se comparan com datos experimentales, de lo que resulta la obención de información sobre la composición y los perfiles de concentración de la muestra. Este método se aplica con éxito em muestras espesas y planas de grafito, cuarzo y zafiro y muestras conteniendo películas finas de óxido de aluminio. Se calculan perfiles en profundidad de núcleos de 12C y de 16O a través de reacciones (d,p y (d,α inducidas por deuterones. Se utiliza también la difusión elástica de iones (4He+, tanto a Rutherford como resonante.

  16. Reversible redox reaction and water configuration on a positively charged platinum surface: first principles molecular dynamics simulation.

    Science.gov (United States)

    Ikeshoji, Tamio; Otani, Minoru; Hamada, Ikutaro; Okamoto, Yasuharu

    2011-12-07

    The water dissociation reaction and water molecule configuration on a positively charged platinum (111) surface were investigated by means of first principles molecular dynamics under periodic boundary conditions. Water molecules on the Pt surface were mostly in the O-down orientation but some H-down structures were also found. OH(-) ion, generated by removing H from H(2)O in the bulk region, moved to the Pt surface, on which a positive charge is induced, by a Grotthuss-like proton-relay mechanism and adsorbed on it as OH(Pt). Hydrogen atom exchange between OH(Pt) and a near-by water molecule frequently occurred on the Pt surface and had a low activation energy of the same order as room temperature energy. When a positive charge (7 μC cm(-2)) was added to the Pt surface, H(3)O(+) and OH(Pt) were generated from 2H(2)O on the Pt. This may be coupled with an electron transfer to the Pt electrode [2H(2)O → H(3)O(+) + OH(Pt) + e(-)]. The opposite reaction was also observed on the same charged surface during a simulation of duration about 10 ps; it is a reversible redox reaction. When further positive charge (14 μC cm(-2)) was added, the reaction shifted to the right hand side completely. Thus, this one-electron transfer reaction, which is a part of the oxygen electrode reaction in fuel cells and water electrolysis, was confirmed to be a low activation energy process.

  17. Surface modification of TiO2 nanoparticles via photocataliticaly induced reaction: Influence of functionality of silane coupling agent

    International Nuclear Information System (INIS)

    Tomovska, Radmila; Daniloska, Vesna; Asua, Jose M.

    2013-01-01

    Highlights: ► TiO 2 nanoparticles were modified by photocatalytic induced surface reaction. ► TiO 2 nanoparticles were subjects of modification and catalysts for the reaction. ► No cleavage of Si-C bond in silane coupling agent 3-triethoxysilyl propyl isocianate. ► High influence of functional group in silane on the Si-C cleavage was determined. ► Different electronegativity of the functionalities in the silane determines reaction way. - Abstract: In the present work the surface modification of TiO 2 nanoparticles by photocatalyticaly induced reaction with silane coupling agent 3-triethoxysilyl propyl isocianate (PIC) has been presented. It was demonstrated establishing of covalent Ti-O-Si bond between the nanoparticles and the PIC molecule. In comparison with previous results, it was demonstrated the high influence of the functional group from the silane coupling agent on the reaction course during surface functionalziation of TiO 2 nanoparticles. Depending on the amount and type (electronegativity of the end-functionalities) of the silane compound, high control of the surface characteristics of TiO 2 nanoparticles could be achieved.

  18. Spectroscopic evidence for ternary surface complexes in the lead(II)-malonic acid-hematite system

    Science.gov (United States)

    Lenhart, J.J.; Bargar, J.R.; Davis, J.A.

    2001-01-01

    Using extended X-ray absorption fine structure (EXAFS) and attenuated total reflectance Fourier-transform infrared (ATR-FTIR) measurements, we examined the sorption of Pb(II) to hematite in the presence of malonic acid. Pb LIII-edge EXAFS measurements performed in the presence of malonate indicate the presence of both Fe and C neighbors, suggesting that a major fraction of surface-bound malonate is bonded to adsorbed Pb(II). In the absence of Pb(II), ATR-FTIR measurements of sorbed malonate suggest the formation of more than one malonate surface complex. The dissimilarity of the IR spectrum of malonate sorbed on hematite to those for aqueous malonate suggest at least one of the sorbed malonate species is directly coordinated to surface Fe atoms in an inner-sphere mode. In the presence of Pb, little change is seen in the IR spectrum for sorbed malonate, indicating that geometry of malonate as it coordinates to sorbed Pb(II) adions is similar to the geometry of malonate as it coordinates to Fe in the hematite surface. Fits of the raw EXAFS spectra collected from pH 4 to pH 8 result in average Pb-C distances of 2.98 to 3.14 A??, suggesting the presence of both four- and six-membered Pb-malonate rings. The IR results are consistent with this interpretation. Thus, our results suggest that malonate binds to sorbed Pb(II) adions, forming ternary metal-bridging surface complexes. ?? 2001 Academic Press.

  19. Surface reactivity of Ge[111] for organic functionalization by means of a radical-initiated reaction: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Rubio-Pereda, Pamela, E-mail: rubio.pereda@gmail.com [Centro de Investigación Científica y de Educación Superior de Ensenada 3918, Código Postal 22860, Ensenada, Baja California (Mexico); Takeuchi, Noboru, E-mail: takeuchi@cnyn.unam.mx [Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Apartado Postal 14, Código Postal 22800, Ensenada, Baja California (Mexico)

    2016-08-30

    Highlights: • The surface reactivity of the Ge [111] surface is studied with DFT for the attachment of organic molecules by means of a radical-initiated reaction. • A hydrogen vacancy in the hydrogen terminated Ge [111] surface exhibits an accumulation of charge and electron pairing. • These characteristics make the hydrogen vacancy less reactive for the attachment of unsaturated organic molecules. • The adsorption of acetylene is probable to occur while the adsorption of ethylene and styrene is substantially less probable to occur. • The hydrogen terminated Ge [111] surface is found to be less reactive than its two-dimensional analogue, the hydrogen-terminated germanene. - Abstract: The study of interfacial chemistry at semiconductor surfaces has become an important area of research. Functionalities such as molecular recognition, biocompatibility of surfaces, and molecular computing, could be achieved by the combinations of organic chemistry with the semiconductor technology. One way to accomplish this goal is by means of organic functionalization of semiconductor surfaces such as the bulk-terminated germanium surfaces, more specifically the Ge[111]. In this work, we theoretically study, by applying density functional theory, the surface reactivity of the bulk-terminated Ge[111] surface for organic functionalization by means of a radical-initiated reaction of unsaturated molecules such as acetylene, ethylene and styrene with a hydrogen vacancy on a previously hydrogen-terminated Ge[111] surface. Results derived from this work are compared with those obtained in our previous calculations on the germanene surface, following the same chemical route. Our calculations show an accumulation of electronic charge at the H-vacancy having as a result electron pairing due to strong lattice-electron coupling and therefore a diminished surface reactivity. Calculation of the transition states for acetylene and ethylene indicates that the surface reactivity of the

  20. Surface reactivity of Ge[111] for organic functionalization by means of a radical-initiated reaction: A DFT study

    International Nuclear Information System (INIS)

    Rubio-Pereda, Pamela; Takeuchi, Noboru

    2016-01-01

    Highlights: • The surface reactivity of the Ge [111] surface is studied with DFT for the attachment of organic molecules by means of a radical-initiated reaction. • A hydrogen vacancy in the hydrogen terminated Ge [111] surface exhibits an accumulation of charge and electron pairing. • These characteristics make the hydrogen vacancy less reactive for the attachment of unsaturated organic molecules. • The adsorption of acetylene is probable to occur while the adsorption of ethylene and styrene is substantially less probable to occur. • The hydrogen terminated Ge [111] surface is found to be less reactive than its two-dimensional analogue, the hydrogen-terminated germanene. - Abstract: The study of interfacial chemistry at semiconductor surfaces has become an important area of research. Functionalities such as molecular recognition, biocompatibility of surfaces, and molecular computing, could be achieved by the combinations of organic chemistry with the semiconductor technology. One way to accomplish this goal is by means of organic functionalization of semiconductor surfaces such as the bulk-terminated germanium surfaces, more specifically the Ge[111]. In this work, we theoretically study, by applying density functional theory, the surface reactivity of the bulk-terminated Ge[111] surface for organic functionalization by means of a radical-initiated reaction of unsaturated molecules such as acetylene, ethylene and styrene with a hydrogen vacancy on a previously hydrogen-terminated Ge[111] surface. Results derived from this work are compared with those obtained in our previous calculations on the germanene surface, following the same chemical route. Our calculations show an accumulation of electronic charge at the H-vacancy having as a result electron pairing due to strong lattice-electron coupling and therefore a diminished surface reactivity. Calculation of the transition states for acetylene and ethylene indicates that the surface reactivity of the

  1. Lead-silicate glass surface sputtered by an argon cluster ion beam investigated by XPS

    Czech Academy of Sciences Publication Activity Database

    Zemek, Josef; Jiříček, Petr; Houdková, Jana; Jurek, Karel; Gedeon, O.

    2017-01-01

    Roč. 469, Aug (2017), s. 1-6 ISSN 0022-3093 R&D Projects: GA MŠk LM2015088; GA ČR(CZ) GA15-12580S Institutional support: RVO:68378271 Keywords : lead-silicate glass * XPS * BO * NBO * Argon duster ion beam sputtering * X-ray irradiation Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.124, year: 2016

  2. Quasiclassical trajectory study of the Cl +CH4 reaction dynamics on a quadratic configuration interaction with single and double excitation interpolated potential energy surface

    Science.gov (United States)

    Castillo, J. F.; Aoiz, F. J.; Bañares, L.

    2006-09-01

    An ab initio interpolated potential energy surface (PES) for the Cl +CH4 reactive system has been constructed using the interpolation method of Collins and co-workers [J. Chem. Phys. 102, 5647 (1995); 108, 8302 (1998); 111, 816 (1999); Theor. Chem. Acc. 108, 313 (2002)]. The ab initio calculations have been performed using quadratic configuration interaction with single and double excitation theory to build the PES. A simple scaling all correlation technique has been used to obtain a PES which yields a barrier height and reaction energy in good agreement with high level ab initio calculations and experimental measurements. Using these interpolated PESs, a detailed quasiclassical trajectory study of integral and differential cross sections, product rovibrational populations, and internal energy distributions has been carried out for the Cl +CH4 and Cl +CD4 reactions, and the theoretical results have been compared with the available experimental data. It has been shown that the calculated total reaction cross sections versus collision energy for the Cl +CH4 and Cl +CD4 reactions is very sensitive to the barrier height. Besides, due to the zero-point energy (ZPE) leakage of the CH4 molecule to the reaction coordinate in the quasiclassical trajectory (QCT) calculations, the reaction threshold falls below the barrier height of the PES. The ZPE leakage leads to CH3 and HCl coproducts with internal energy below its corresponding ZPEs. We have shown that a Gaussian binning (GB) analysis of the trajectories yields excitation functions in somehow better agreement with the experimental determinations. The HCl(v'=0) and DCl(v'=0) rotational distributions are as well very sensitive to the ZPE problem. The GB correction narrows and shifts the rotational distributions to lower values of the rotational quantum numbers. However, the present QCT rotational distributions are still hotter than the experimental distributions. In both reactions the angular distributions shift from

  3. Arsenic, cadmium, lead, and mercury in surface soils, Pueblo, Colorado: Implications for population health risk

    Science.gov (United States)

    Diawara, D.M.; Litt, J.S.; Unis, D.; Alfonso, N.; Martinez, L.A.; Crock, J.G.; Smith, D.B.; Carsella, J.

    2006-01-01

    Decades of intensive industrial and agricultural practices as well as rapid urbanization have left communities like Pueblo, Colorado facing potential health threats from pollution of its soils, air, water and food supply. To address such concerns about environmental contamination, we conducted an urban geochemical study of the city of Pueblo to offer insights into the potential chemical hazards in soil and inform priorities for future health studies and population interventions aimed at reducing exposures to inorganic substances. The current study characterizes the environmental landscape of Pueblo in terms of heavy metals, and relates this to population distributions. Soil was sampled within the city along transects and analyzed for arsenic (As), cadmium (Cd), mercury (Hg) and lead (Pb). We also profiled Pueblo's communities in terms of their socioeconomic status and demographics. ArcGIS 9.0 was used to perform exploratory spatial data analysis and generate community profiles and prediction maps. The topsoil in Pueblo contains more As, Cd, Hg and Pb than national soil averages, although average Hg content in Pueblo was within reported baseline ranges. The highest levels of As concentrations ranged between 56.6 and 66.5 ppm. Lead concentrations exceeded 300 ppm in several of Pueblo's residential communities. Elevated levels of lead are concentrated in low-income Hispanic and African-American communities. Areas of excessively high Cd concentration exist around Pueblo, including low income and minority communities, raising additional health and environmental justice concerns. Although the distribution patterns vary by element and may reflect both industrial and non-industrial sources, the study confirms that there is environmental contamination around Pueblo and underscores the need for a comprehensive public health approach to address environmental threats in urban communities. ?? Springer 2006.

  4. Arsenic, cadmium, lead, and mercury in surface soils, Pueblo, Colorado: implications for population health risk.

    Science.gov (United States)

    Diawara, Moussa M; Litt, Jill S; Unis, Dave; Alfonso, Nicholas; Martinez, Leeanne; Crock, James G; Smith, David B; Carsella, James

    2006-08-01

    Decades of intensive industrial and agricultural practices as well as rapid urbanization have left communities like Pueblo, Colorado facing potential health threats from pollution of its soils, air, water and food supply. To address such concerns about environmental contamination, we conducted an urban geochemical study of the city of Pueblo to offer insights into the potential chemical hazards in soil and inform priorities for future health studies and population interventions aimed at reducing exposures to inorganic substances. The current study characterizes the environmental landscape of Pueblo in terms of heavy metals, and relates this to population distributions. Soil was sampled within the city along transects and analyzed for arsenic (As), cadmium (Cd), mercury (Hg) and lead (Pb). We also profiled Pueblo's communities in terms of their socioeconomic status and demographics. ArcGIS 9.0 was used to perform exploratory spatial data analysis and generate community profiles and prediction maps. The topsoil in Pueblo contains more As, Cd, Hg and Pb than national soil averages, although average Hg content in Pueblo was within reported baseline ranges. The highest levels of As concentrations ranged between 56.6 and 66.5 ppm. Lead concentrations exceeded 300 ppm in several of Pueblo's residential communities. Elevated levels of lead are concentrated in low-income Hispanic and African-American communities. Areas of excessively high Cd concentration exist around Pueblo, including low income and minority communities, raising additional health and environmental justice concerns. Although the distribution patterns vary by element and may reflect both industrial and non-industrial sources, the study confirms that there is environmental contamination around Pueblo and underscores the need for a comprehensive public health approach to address environmental threats in urban communities.

  5. Optical and surface morphological properties of triethylamine passivated lead sulphide nanoparticles

    International Nuclear Information System (INIS)

    Navaneethan, M.; Nisha, K.D.; Ponnusamy, S.; Muthamizhchelvan, C.

    2009-01-01

    The triethylamine capped lead sulphide (PbS) nanoparticles were successfully synthesized by simple wet chemical method. The synthesized product has been characterized by powder X-ray diffraction (XRD), UV-vis spectrophotometry, FTIR spectroscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM) and photoluminescence studies. The size of the PbS nanoparticles was determined from AFM, TEM, XRD and from these studies it is found that the size of the particles of the order of 10-15 nm. Significant 'blue shift' from bulk material was observed on the PbS nanoparticles using UV-vis and photoluminescence spectrum.

  6. Surface decoration through electrostatic interaction leading to enhanced reactivity: Low temperature synthesis of nanostructured chromium borides (CrB and CrB2)

    International Nuclear Information System (INIS)

    Menaka,; Kumar, Bharat; Kumar, Sandeep; Ganguli, A.K.

    2013-01-01

    The present study describes a novel low temperature route at ambient pressure for the synthesis of nanocrystalline chromium borides (CrB and CrB 2 ) without using any flux or additives. The favorable and intimate mixing of nanoparticles of chromium acetate (Cr source) and boron forms an active chromium–boron precursor which decomposes at much lower temperature (400 °C) to form CrB (which is ∼1000 °C less than the known ambient pressure synthesis). The chromium acetate nanoparticles (∼5 nm) decorate the larger boron particles (150–200 nm) due to electrostatic interactions resulting from opposing surface charges of boron (zeta potential:+48.101 mV) and chromium acetate (zeta potential:−4.021 mV) in ethanolic medium and is evident in the TEM micrographs. The above method leads to the formation of pure CrB film like structure at 400 °C and nanospheres (40–60 nm) at 600 °C. Also, chromium diboride (CrB 2 ) nanoparticles (25 nm) could be obtained at 1000 °C. - Graphical abstract: Variation of surface charge of reactants, precursor and the products, chromium borides (CrB and CrB 2 ). Highlights: ► Novel borothermal reduction process for synthesis of chromium boride. ► Significant lowering of reaction temperature to obtain nanocrystalline chromium boride. ► Enhanced reactivity due to appropriate surface interactions

  7. Fusability and survivability in reactions leading to heavy nuclei in the vicinity of the N = 126 shell

    International Nuclear Information System (INIS)

    Sagajdak, R.N.

    2008-01-01

    The production of heavy nuclei from Rn to Th around the N = 126 neutron shell in complete fusion reactions of nuclei has been considered in a systematic way in the framework of the conventional barrier-passing fusion model coupled with the Standard Statistical Model (SSM). Available data on the excitation functions for fusion and production of evaporation residues obtained in very asymmetric combinations are described with these models rather well. In the interaction of massive projectiles with heavy target nuclei quasi-fission effects appear in the entrance reaction channel. The quantity of the fusion probability introduced empirically has been used to reproduce excitation functions with the same SSM parameters (fission barriers) as those obtained in the analysis of very asymmetric combinations. A lack of stabilization against fission around N = 126 for Th nuclei was earlier explained with a reduced collective contribution to the level density in spherical nuclei. However, the present analysis shows severe inhibition for fusion, i.e., the drop in production cross sections of Th nuclei in the vicinity of N = 126 is mainly caused by entrance channel effects. The macroscopic component of fission barriers for nuclei involved in a deexcitation cascade has been derived and compared with the theoretical model predictions and available data

  8. Unraveling surface and bulk trap states in lead halide perovskite solar cells using impedance spectroscopy

    Science.gov (United States)

    Han, Changfeng; Wang, Kai; Zhu, Xixiang; Yu, Haomiao; Sun, Xiaojuan; Yang, Qin; Hu, Bin

    2018-03-01

    Organic-inorganic hybrid perovskites (OIHPs) have been widely recognized as an excellent candidate for next-generation photovoltaic materials because of their highly efficient power conversion. Acquiring a complete understanding of trap states and dielectric properties in OIHP-based solar cells at the steady state is highly desirable in order to further explore and improve their optoelectronic functionalities and properties. We report CH3NH3PbI3-x Cl x -based planar solar cells with a power conversion efficiency (PCE) of 15.8%. The illumination intensity dependence of the current density-voltage (J-V) revealed the presence of trap-assisted recombination at low fluences. Non-destructive ac impedance spectroscopy (ac-IS) was applied to characterize the device at the steady state. The capacitance-voltage (C-V) spectra exhibited some distinct variations at a wide range of ac modulation frequencies with and without photo-excitations. Since the frequency-dependent chemical capacitance ({{C}μ }) is concerned with the surface and bulk related density of states (DOS) in CH3NH3PbI3-x Cl x , we verified this by fitting the corresponding DOS by a Gaussian distribution function. We ascertained that the electronic sub-gap trap states present in the solution processed CH3NH3PbI3-x Cl x and their distribution differs from the surface to the bulk. In fact, we demonstrated that both surfaces that were adjacent to the electron and hole transport layers featured analogous DOS. Despite this, photo- and bias-induced giant dielectric responses (i.e. both real and imaginary parts) were detected. A remarkable reduction of {{C}μ } at higher frequencies (i.e. more than 100 kHz) was ascribed to the effect of dielectric loss in CH3NH3PbI3-x Cl x .

  9. Optimization of Lead Removal via Napier Grass in Synthetic Brackish Water using Response Surface Model

    Science.gov (United States)

    Hongsawat, P.; Suttiarporn, P.; Wutsanthia, K.; Kongsiri, G.

    2018-03-01

    The efficiency of the lead (Pb) phytoremediation by Napier grass was studied on the plant’s growth and plant’s tolerance on the Pb toxicity in synthetic brackish water. It was found that the plant was high tolerance to high level of Pb concentration (10 mg/l) in synthetic brackish water. Which revealed on the possibilities of plant’s growth under the presence of Pb contaminated condition. According to the Pb removal efficiency, the highest one (88.63±4.9%) was found at 10 ppm Pb concentration, 0.3 g/l NaCl concentration during the period 45 day. However, this study investigated the optimum condition for lead (Pb) removal from synthetic brackish water using phytoremediation treatment with Napier grass through a Box-Behnken Design. Three operational variables, i.e. Pb concentration (1, 5.5, 10 mg/l), NaCl (0.1, 0.3, 0.5 g/l) and period time (7, 26, 45 day), were determined. The results were provided evidence that the highest Pb removal efficiency (93.56%) from synthetic brackish water via Napier grass was Pb and NaCl concentration at 10 mg/l and 0.5 g/l during 45 day.

  10. Final Report: Molecular Basis for Microbial Adhesion and Geochemical Surface Reactions: A Study Across Scales

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, David Adams [The University of Alabama

    2013-06-27

    Computational chemistry was used to help provide a molecular level description of the interactions of Gram-negative microbial membranes with subsurface materials. The goal is to develop a better understanding of the molecular processes involved in microbial metal binding, microbial attachment to mineral surfaces, and, eventually, oxidation/reduction reactions (electron transfer) that can occur at these surfaces and are mediated by the bacterial exterior surface. The project focused on the interaction of the outer microbial membrane, which is dominated by an exterior lipopolysaccharide (LPS) portion, of Pseudomonas aeruginosa with the mineral goethite and with solvated ions in the environment. This was originally a collaborative project with T.P. Straatsma and B. Lowery of the Pacific Northwest National Laboratory. The University of Alabama effort used electronic structure calculations to predict the molecular behavior of ions in solution and the behavior of the sugars which form a critical part of the LPS. The interactions of the sugars with metal ions are expected to dominate much of the microscopic structure and transport phenomena in the LPS. This work, in combination with the molecular dynamics simulations of Straatsma and the experimental electrochemistry and microscopy measurements of Lowry, both at PNNL, is providing new insights into the detailed molecular behavior of these membranes in geochemical environments. The effort at The University of Alabama has three components: solvation energies and structures of ions in solution, prediction of the acidity of the critical groups in the sugars in the LPS, and binding of metal ions to the sugar anions. An important aspect of the structure of the LPS membrane as well as ion transport in the LPS is the ability of the sugar side groups such as the carboxylic acids and the phosphates to bind positively charged ions. We are studying the acidity of the acidic side groups in order to better understand the ability of

  11. Efficient and Adaptive Methods for Computing Accurate Potential Surfaces for Quantum Nuclear Effects: Applications to Hydrogen-Transfer Reactions.

    Science.gov (United States)

    DeGregorio, Nicole; Iyengar, Srinivasan S

    2018-01-09

    We present two sampling measures to gauge critical regions of potential energy surfaces. These sampling measures employ (a) the instantaneous quantum wavepacket density, an approximation to the (b) potential surface, its (c) gradients, and (d) a Shannon information theory based expression that estimates the local entropy associated with the quantum wavepacket. These four criteria together enable a directed sampling of potential surfaces that appears to correctly describe the local oscillation frequencies, or the local Nyquist frequency, of a potential surface. The sampling functions are then utilized to derive a tessellation scheme that discretizes the multidimensional space to enable efficient sampling of potential surfaces. The sampled potential surface is then combined with four different interpolation procedures, namely, (a) local Hermite curve interpolation, (b) low-pass filtered Lagrange interpolation, (c) the monomial symmetrization approximation (MSA) developed by Bowman and co-workers, and (d) a modified Shepard algorithm. The sampling procedure and the fitting schemes are used to compute (a) potential surfaces in highly anharmonic hydrogen-bonded systems and (b) study hydrogen-transfer reactions in biogenic volatile organic compounds (isoprene) where the transferring hydrogen atom is found to demonstrate critical quantum nuclear effects. In the case of isoprene, the algorithm discussed here is used to derive multidimensional potential surfaces along a hydrogen-transfer reaction path to gauge the effect of quantum-nuclear degrees of freedom on the hydrogen-transfer process. Based on the decreased computational effort, facilitated by the optimal sampling of the potential surfaces through the use of sampling functions discussed here, and the accuracy of the associated potential surfaces, we believe the method will find great utility in the study of quantum nuclear dynamics problems, of which application to hydrogen-transfer reactions and hydrogen

  12. Polysiloxane surface modified with bipyrazolic tripodal receptor for quantitative lead adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Radi, Smaail, E-mail: radi_smaail@yahoo.fr [Laboratoire de Chimie Organique, Macromoleculaire et Produits Naturels, Equipe de Chimie Bio-organique et Macromoleculaire, Unite Associee au CNRST URAC 25, Departement de Chimie, Faculte des Sciences, Universite Med I, BP 524, 60 000 Oujda (Morocco); Tighadouini, Said; Toubi, Yahya [Laboratoire de Chimie Organique, Macromoleculaire et Produits Naturels, Equipe de Chimie Bio-organique et Macromoleculaire, Unite Associee au CNRST URAC 25, Departement de Chimie, Faculte des Sciences, Universite Med I, BP 524, 60 000 Oujda (Morocco); Bacquet, Maryse [Universite des Sciences et Technologies de Lille, UMET: Unite Materiaux et Transformations UMR8207, Equipe Ingenierie des Systemes Polymeres, Batiment C6 salle 119-59655 Villeneuve d' Ascq (France)

    2011-01-15

    A new silica gel compound modified N,N-bis(3,5-dimethylpyrazol-1-ylmethyl) amine (SiN{sub 2}Pz) was synthesized and characterized by elemental analysis, FT-IR, {sup 13}C NMR of the solid state, nitrogen adsorption-desorption isotherm, BET surface area and BJH pore sizes. The new surface exhibits good chemical and thermal stability determined by thermogravimetry curves (TGA). The effect of pH and stirring time on the adsorption of Pb(II) were studied. The process of metal retention was followed by batch method and the optimum pH value for the quantitative adsorption of this toxic metal ion was 7. At this pH value, the new functionalized polysiloxane presents further improvements and shows higher affinity (123 mg of Pb{sup 2+}/g of silica) for the effective adsorption of Pb(II) compared to others described sorbents. The extracted amounts of Pb(II) were determined by atomic absorption measurements.

  13. Two leading modes of the interannual variability in South American surface air temperature during austral winter

    Science.gov (United States)

    Li, Yanjie; Li, Jianping; Kucharski, Fred; Feng, Jin; Zhao, Sen; Zheng, Jiayu

    2017-11-01

    The first two empirical orthogonal function (EOF) modes of the surface air temperature (SAT) interannual variability in the South American (SA) continent have been revealed in several previous studies. This presentation focuses on winter season and furtherly investigates the detailed advection and cloud-radiation processes and teleconnections from tropical sea surface temperature anomalies (SSTA) combining statistical analysis with Rossby wave dynamics and modelling experiments. The EOF1, featured with the anomalous center in the central part, is related to the tropical eastern Pacific SSTA, which may impact on the SA SAT variability through the Walker circulation and a regional Hadley cell. The anomalous center is largely attributed to low-level advection transported by the Hadley cell. The EOF2, as a fluctuation between anomalies in the southeast Brazil and the southern tip, is related to the SSTA surrounding the Maritime Continent, which may generate a barotropic wave train propagating to the SA continent. This wave train can strengthen high latitude westerly flow transporting warm advection to the southern tip, and generate southeast anomalous flow transporting cold advection to the southeast Brazil. Meanwhile, the cloud-radiation processes are also involved to enhance the advection-induced SAT anomalies in both areas.

  14. Transition process leading to microbubble emission boiling on horizontal circular heated surface in subcooled pool

    Science.gov (United States)

    Ueno, Ichiro; Ando, Jun; Horiuchi, Kazuna; Saiki, Takahito; Kaneko, Toshihiro

    2016-11-01

    Microbubble emission boiling (MEB) produces a higher heat flux than critical heat flux (CHF) and therefore has been investigated in terms of its heat transfer characteristics as well as the conditions under which MEB occurs. Its physical mechanism, however, is not yet clearly understood. We carried out a series of experiments to examine boiling on horizontal circular heated surfaces of 5 mm and of 10 mm in diameter, in a subcooled pool, paying close attention to the transition process to MEB. High-speed observation results show that, in the MEB regime, the growth, condensation, and collapse of the vapor bubbles occur within a very short time. In addition, a number of fine bubbles are emitted from the collapse of the vapor bubbles. By tracking these tiny bubbles, we clearly visualize that the collapse of the vapor bubbles drives the liquid near the bubbles towards the heated surface, such that the convection field around the vapor bubbles under MEB significantly differs from that under nucleate boiling. Moreover, the axial temperature gradient in a heated block (quasi-heat flux) indicates a clear difference between nucleate boiling and MEB. A combination of quasi-heat flux and the measurement of the behavior of the vapor bubbles allows us to discuss the transition to MEB. This work was financially supported by the 45th Research Grant in Natural Sciences from The Mitsubishi Foundation (2014 - 2015), and by Research Grant for Boiler and Pressurized Vessels from The Japan Boiler Association (2016).

  15. Surface air concentration and deposition of lead-210 in French Guiana: two years of continuous monitoring

    International Nuclear Information System (INIS)

    Melieres, Marie-Antoinette; Pourchet, Michel; Richard, Sandrine

    2003-01-01

    To make up for the lack of data on 210 Pb aerosol deposition in tropical regions and to use this radionuclide as an aerosol tracer,a monitoring station was run for two years at Petit-Saut, French Guiana. Lead-210 concentration in air at ground level was monitored continuously together with atmospheric total deposition. The air concentration has a mean value of 0.23±0.02 mBq m -3 during both wet and dry seasons, and it is only weakly affected by the precipitation mechanism. This result was unexpected in a wet tropical region, with a high precipitation rate. In contrast, deposition clearly correlates with precipitation for low/moderate rainfall ( -2 y -1 . This provides a procedure fo estimating this mean flux at other sites in French Guiana

  16. Bone reactions adjacent to titanium implants with different surface characteristics subjected to static load. A study in the dog (II)

    DEFF Research Database (Denmark)

    Gotfredsen, K; Berglundh, T; Lindhe, J

    2001-01-01

    The purpose of the present study was to compare bone reactions adjacent to titanium implants with either a titanium plasma-sprayed (TPS) or a machined surface subjected to lateral static loading induced by an expansion force. In 3 labrador dogs, the 2nd, 3rd and 4th mandibular premolars were...

  17. Measurements and Evaluation of Nuclear Reaction Cross Sections Leading to Various Practical Applications in Science and Technology

    Energy Technology Data Exchange (ETDEWEB)

    Khandaker, Mayeen Uddin; Lee, Young Ouk; Cho, Young Sik

    2008-07-15

    This report contains the measurements and evaluation of production cross sections of some medically and technologically important radionuclides over the energy range 1-40 MeV by using a conventional stacked-foil activation technique combined with high purity germanium (HPGe) -ray spectrometry. The irradiations were done by using the external beam line of the MC-50 cyclotron at the Korea Institute of Radiological and Medical Sciences (KIRAMS). The standard cross sections for monitor reactions were taken from IAEA web site. Integral yields for the investigated radionuclides were deduced using the measured cross-sections. Reported data were compared with the available literature data, theoretical calculations by the codes TALYS and ALICE-IPPE, and a good overall agreement among them was found.

  18. A Radial Basis Function (RBF)-Finite Difference (FD) Method for Diffusion and Reaction-Diffusion Equations on Surfaces.

    Science.gov (United States)

    Shankar, Varun; Wright, Grady B; Kirby, Robert M; Fogelson, Aaron L

    2016-06-01

    In this paper, we present a method based on Radial Basis Function (RBF)-generated Finite Differences (FD) for numerically solving diffusion and reaction-diffusion equations (PDEs) on closed surfaces embedded in ℝ d . Our method uses a method-of-lines formulation, in which surface derivatives that appear in the PDEs are approximated locally using RBF interpolation. The method requires only scattered nodes representing the surface and normal vectors at those scattered nodes. All computations use only extrinsic coordinates, thereby avoiding coordinate distortions and singularities. We also present an optimization procedure that allows for the stabilization of the discrete differential operators generated by our RBF-FD method by selecting shape parameters for each stencil that correspond to a global target condition number. We show the convergence of our method on two surfaces for different stencil sizes, and present applications to nonlinear PDEs simulated both on implicit/parametric surfaces and more general surfaces represented by point clouds.

  19. Design of a multi-enzyme reaction on an electrode surface for an L-glutamate biofuel anode.

    Science.gov (United States)

    Sakamoto, Hiroaki; Komatsu, Tomohiro; Yamasaki, Koji; Satomura, Takenori; Suye, Shin-Ichiro

    2017-02-01

    To design and construct a novel bio-anode electrode based on the oxidation of glutamic acid to produce 2-oxoglutarate, generating two electrons from NADH. Efficient enzyme reaction and electron transfer were observed owing to immobilization of the two enzymes using a mixed self-assembled monolayer. The ratio of the immobilized enzymes was an important factor affecting the efficiency of the system; thus, we quantified the amounts of immobilized enzyme using a quartz crystal microbalance to further evaluate the electrochemical reaction. The electrochemical reaction proceeded efficiently when approximately equimolar amounts of the enzyme were on the electrode. The largest oxidation peak current increase (171 nA) was observed under these conditions. Efficient multi-enzyme reaction on the electrode surface has been achieved which is applicable for biofuel cell application.

  20. Generalized Temporal Acceleration Scheme for Kinetic Monte Carlo Simulations of Surface Catalytic Processes by Scaling the Rates of Fast Reactions.

    Science.gov (United States)

    Dybeck, Eric C; Plaisance, Craig P; Neurock, Matthew

    2017-04-11

    A novel algorithm is presented that achieves temporal acceleration during kinetic Monte Carlo (KMC) simulations of surface catalytic processes. This algorithm allows for the direct simulation of reaction networks containing kinetic processes occurring on vastly disparate time scales which computationally overburden standard KMC methods. Previously developed methods for temporal acceleration in KMC were designed for specific systems and often require a priori information from the user such as identifying the fast and slow processes. In the approach presented herein, quasi-equilibrated processes are identified automatically based on previous executions of the forward and reverse reactions. Temporal acceleration is achieved by automatically scaling the intrinsic rate constants of the quasi-equilibrated processes, bringing their rates closer to the time scales of the slow kinetically relevant nonequilibrated processes. All reactions are still simulated directly, although with modified rate constants. Abrupt changes in the underlying dynamics of the reaction network are identified during the simulation, and the reaction rate constants are rescaled accordingly. The algorithm was utilized here to model the Fischer-Tropsch synthesis reaction over ruthenium nanoparticles. This reaction network has multiple time-scale-disparate processes which would be intractable to simulate without the aid of temporal acceleration. The accelerated simulations are found to give reaction rates and selectivities indistinguishable from those calculated by an equivalent mean-field kinetic model. The computational savings of the algorithm can span many orders of magnitude in realistic systems, and the computational cost is not limited by the magnitude of the time scale disparity in the system processes. Furthermore, the algorithm has been designed in a generic fashion and can easily be applied to other surface catalytic processes of interest.

  1. Assessing the speciation pattern of lead and zinc in surface water collected from Abegede creek, Ijora and Lagos

    International Nuclear Information System (INIS)

    Adeniyi, A.A.; Okedeyi, O.O.

    2004-01-01

    A two stage sequential extraction procedure for the speciation of zinc and lead has been applied to surface water randomly collected from three sites in Abegede Creek, Ijora and Lagos. The determination of the labile and non-labile metals species was carried out by flame atomic absorption spectrophotometry (FAAS). The mean values of non-labile zinc and lead concentrations from the three sites, A, B and Care 0.54 minus plus 0.25 mg/l; 0.55 plus minus 0.26 mg/l;1.13 plus 0.76 mg/l; respectively for zinc and 0.13 plus minus 0.09 mg/l; 0.17 plus minus 0.07 mg/l;0.42 plus minus 0.23 mg/l respectively for lead. These are higher than for the labile species in the three sites;0.14 plus minus 0.07 mg/l; 0.21 plus minus 0.22 mg/l; 0.73 plus minus 0.82 mg/l, respectively for zinc and ND; 0.02 plus minus 0.04 mg/l; 0.16 plus minus 0.22 mg/l, respectively for lead. The statistical analysis of variance of the distribution of zinc and lead in the three sites were estimated at 95% confidence level. The values of metal and obtained were compared with Nigeria's background values for some rivers and the World Health Organization limits for drinking water respectively and found to be generally higher especially for lead levels. The probable sources of zinc and lead in the Creek are from natural and point sources, although there could be non-point source contributions from urban run-offs and vehicular exhaust. (author)

  2. Selection of optimal recording sites for limited lead body surface potential mapping: A sequential selection based approach

    Directory of Open Access Journals (Sweden)

    McCullagh Paul J

    2006-02-01

    Full Text Available Abstract Background In this study we propose the development of a new algorithm for selecting optimal recording sites for limited lead body surface potential mapping. The proposed algorithm differs from previously reported methods in that it is based upon a simple and intuitive data driven technique that does not make any presumptions about deterministic characteristics of the data. It uses a forward selection based search technique to find the best combination of electrocardiographic leads. Methods The study was conducted using a dataset consisting of body surface potential maps (BSPM recorded from 116 subjects which included 59 normals and 57 subjects exhibiting evidence of old Myocardial Infarction (MI. The performance of the algorithm was evaluated using spatial RMS voltage error and correlation coefficient to compare original and reconstructed map frames. Results In all, three configurations of the algorithm were evaluated and it was concluded that there was little difference in the performance of the various configurations. In addition to observing the performance of the selection algorithm, several lead subsets of 32 electrodes as chosen by the various configurations of the algorithm were evaluated. The rationale for choosing this number of recording sites was to allow comparison with a previous study that used a different algorithm, where 32 leads were deemed to provide an acceptable level of reconstruction performance. Conclusion It was observed that although the lead configurations suggested in this study were not identical to that suggested in the previous work, the systems did bear similar characteristics in that recording sites were chosen with greatest density in the precordial region.

  3. Laser Induced Reaction for Prebond Surface Preparation of Aluminum Alloys.;Stage 2

    National Research Council Canada - National Science Library

    Rotel, M

    1993-01-01

    ...) using a room temperature cured modified epoxy adhesive(2). Surface treatment of the Al adherend by excimer laser causes the removal of weak surface boundary layers, oxidation and morphological changes of the surface...

  4. Surface air concentration and deposition of lead-210 in French Guiana: two years of continuous monitoring

    Energy Technology Data Exchange (ETDEWEB)

    Melieres, Marie-Antoinette E-mail: melieres@glaciog.ujf-grenoble.fr; Pourchet, Michel; Richard, Sandrine

    2003-07-01

    To make up for the lack of data on {sup 210}Pb aerosol deposition in tropical regions and to use this radionuclide as an aerosol tracer,a monitoring station was run for two years at Petit-Saut, French Guiana. Lead-210 concentration in air at ground level was monitored continuously together with atmospheric total deposition. The air concentration has a mean value of 0.23{+-}0.02 mBq m{sup -3} during both wet and dry seasons, and it is only weakly affected by the precipitation mechanism. This result was unexpected in a wet tropical region, with a high precipitation rate. In contrast, deposition clearly correlates with precipitation for low/moderate rainfall (<15 cm per 15-day), while this correlation is masked by strong fluctuations at high rainfall. The estimated mean annual deposition over the last ten years is 163{+-}75 Bq m{sup -2} y{sup -1}. This provides a procedure fo estimating this mean flux at other sites in French Guiana.

  5. Isomerization Reaction Surfaces: Quantum Mechanical Studies of Triplet C2H2, Singlet AlHO and Singlet C2H2O

    National Research Council Canada - National Science Library

    Vacek, George

    1995-01-01

    High-level ab initio molecular electronic structure theory has been utilized to investigate specific isomerization reaction surfaces including the triplet acetylene and vinylidene potential energy (PE...

  6. An accurate potential energy surface for the F + H2 → HF + H reaction by the coupled-cluster method.

    Science.gov (United States)

    Chen, Jun; Sun, Zhigang; Zhang, Dong H

    2015-01-14

    A three dimensional potential energy surface for the F + H2 → HF + H reaction has been computed by the spin unrestricted coupled cluster method with singles, doubles, triples, and perturbative quadruples [UCCSDT(2)Q] using the augmented correlation-consistent polarised valence quadruple zeta basis set for the fluorine atom and the correlation-consistent polarised valence quadruple zeta basis set for the hydrogen atom. All the calculations are based on the restricted open-shell Hartree-Fock orbitals, together with the frozen core approximations, and the UCCSD(T)/complete basis set (CBS) correction term was included. The global potential energy surface was calculated by fitting the sampled ab initio points without any scaling factor for the correlation energy part using a neutral network function method. Extensive dynamics calculations have been carried out on the potential energy surface. The reaction rate constants, integral cross sections, product rotational states distribution, and forward and backward scattering as a function of collision energy of the F + HD → HF + D, F + HD → DF + H, and F + H2 reaction, were calculated by the time-independent quantum dynamics scattering theory using the new surface. The satisfactory agreement with the reported experimental observations previously demonstrates the accuracy of the new potential energy surface.

  7. Surface hydrophobicity and acidity effect on alumina catalyst in catalytic methanol dehydration reaction.

    Science.gov (United States)

    Osman, Ahmed I; Abu-Dahrieh, Jehad K; Rooney, David W; Thompson, Jillian; Halawy, Samih A; Mohamed, Mohamed A

    2017-12-01

    Methanol to dimethyl ether (MTD) is considered one of the main routes for the production of clean bio-fuel. The effect of copper loading on the catalytic performance of different phases of alumina that formed by calcination at two different temperatures was examined for the dehydration of methanol to dimethyl ether (DME). A range of Cu loadings of (1, 2, 4, 6, 10 and 15% Cu wt/wt) on Al 2 O 3 calcined at 350 and 550 °C were prepared and characterized by TGA, XRD, BET, NH 3 -TPD, TEM, H 2 -TPR, SEM, EDX, XPS and DRIFT-Pyridine techniques. The prepared catalysts were used in a fixed bed reactor under reaction conditions in which the temperature ranged from 180-300 °C with weight hourly space velocity (WHSV) = 12.1 h -1 . It was observed that all catalysts calcined at 550 °C (γ-Al 2 O 3 support phase) exhibited higher activity than those calcined at 350 °C (γ-AlOOH), and this is due to the phase support change. Furthermore, the optimum Cu loading was found to be 6% Cu/γ-Al 2 O 3 with this catalyst also showing a high degree of stability under steady state conditions and this is attributed to the enhancement in surface acidity and hydrophobicity. The addition of copper to the support improved the catalyst properties and activity. For all the copper modified catalysts, the optimum catalyst with high degree of activity and stability was 6% copper loaded on gamma alumina. © 2017 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

  8. Comparison of alpha decay and alpha transfer reactions in the lead region. [R matrix theory, absolute alpha widths, cross sections, 93 MeV

    Energy Technology Data Exchange (ETDEWEB)

    DeVries, R.M.

    1978-01-01

    Data were taken for five transitions in the lead region allowing a quantitative comparison with corresponding alpha-decay data via R-matrix theory using the same target + alpha nuclear potential. Good agreement between the absolute reduced widths determined from the two sets of data suggests that in transfer reactions, as in alpha decay, an alpha particle in its ground state is transferred in a one-step process. In a separate analysis, elastic and total reaction cross sections for the systems ..cap alpha.. + /sup 208/Pb, /sup 209/Bi were analyzed to obtain a limited set of potentials which, in turn, were used to calculate absolute alpha widths. Existing shell model calculations give ..gamma../sub ..cap alpha..//sup 2/ values three orders of magnitude smaller.

  9. Surface modification and multiple exciton generation studies of lead(II) sulfide nanoparticles

    Science.gov (United States)

    Zemke, Jennifer M.

    2011-12-01

    Solar energy is a green alternative to fossil fuels but solar technologies to date have been plagued by low conversion efficiencies and high input costs making solar power inaccessible to much of the developing world. Semiconductor nanoparticles (NPs) may provide a route to efficient, economical solar devices through a phenomenon called multiple exciton generation (MEG). Through MEG, semiconductor NPs use a high-energy input photon to create more than one exciton (electron-hole pair) per photon absorbed, thereby exhibiting large photoconversion efficiencies. While MEG has been studied in many NP systems, and we understand some of the factors that affect MEG, a rigorous analysis of the NP-ligand interface with respect to MEG is missing. This dissertation describes how the NP ligand shell directly affects MEG and subsequent charge carrier recombination. Chapter I describes the motivation for studying MEG with respect to NP surface chemistry. Chapter II provides an in-depth overview of the transient absorption experiment used to measure MEG in the NP samples. Chapter III highlights the effect of oleic acid and sodium 2, 3-dimercaptopropane sulfonate on MEG in PbS NPs. The differences in carrier recombination were accounted for by two differences between these ligands: the coordinating atom and/or the secondary structure of the ligand. Because of these hypotheses, experiments were designed to elucidate the origin of these effects by controlling the NP ligand shell. Chapter IV details a viable synthetic route to thiol and amine-capped PbS NPs using sodium 3-mercaptopropane sulfonate as an intermediate ligand. With the versatile ligand exchange described in Chapter IV, the MEG yield and carrier recombination was investigated for ligands with varying headgroups but the same secondary structure. The correlation of ligand donor atom to MEG is outlined in Chapter V. Finally, Chapter VI discusses the conclusions and future outlook of the research reported in this dissertation

  10. The coupling effect of gas-phase chemistry and surface reactions on oxygen permeation and fuel conversion in ITM reactors

    KAUST Repository

    Hong, Jongsup

    2015-08-01

    © 2015 Elsevier B.V. The effect of the coupling between heterogeneous catalytic reactions supported by an ion transport membrane (ITM) and gas-phase chemistry on fuel conversion and oxygen permeation in ITM reactors is examined. In ITM reactors, thermochemical reactions take place in the gas-phase and on the membrane surface, both of which interact with oxygen permeation. However, this coupling between gas-phase and surface chemistry has not been examined in detail. In this study, a parametric analysis using numerical simulations is conducted to investigate this coupling and its impact on fuel conversion and oxygen permeation rates. A thermochemical model that incorporates heterogeneous chemistry on the membrane surface and detailed chemical kinetics in the gas-phase is used. Results show that fuel conversion and oxygen permeation are strongly influenced by the simultaneous action of both chemistries. It is shown that the coupling somewhat suppresses the gas-phase kinetics and reduces fuel conversion, both attributed to extensive thermal energy transfer towards the membrane which conducts it to the air side and radiates to the reactor walls. The reaction pathway and products, in the form of syngas and C2 hydrocarbons, are also affected. In addition, the operating regimes of ITM reactors in which heterogeneous- or/and homogeneous-phase reactions predominantly contribute to fuel conversion and oxygen permeation are elucidated.

  11. Reaction of Br2 with adsorbed CO on Pt, studied by the surface interrogation mode of scanning electrochemical microscopy.

    Science.gov (United States)

    Wang, Qian; Rodríguez-López, Joaquín; Bard, Allen J

    2009-12-02

    Scanning electrochemical microscopy surface interrogation (SI-SECM) in the cyclic voltammetry mode was successfully used to detect and quantify adsorbed CO on a Pt electrode by reaction with electrogenerated Br(2). The two-electrode setup used in this new technique allowed the production of Br(2) on an interrogator tip, which reported a transient positive feedback above a Pt substrate at open circuit as an indication of the reactivity of this halogen with CO((ads)). Br(-) and CO(2) are shown to be the main products of the reaction (in the absence of O(2)), which may involve the formation of bromophosgene as a hydrolyzable intermediate. Under saturation conditions, CO((ads)) was reproducibly quantified at the polycrystalline Pt surface with theta(CO) approximately = 0.5. The reaction is shown to be blocked by the action of pre-adsorbed cyanide, which demonstrates the surface character of the process. The formation of CO(2) as an end product was further tested in a bulk experiment: addition of Pt black to a mixture of Br(2) in 0.5 M H(2)SO(4) through which CO was bubbled gave a precipitate of BaCO(3) in a saturated solution of Ba(OH)(2). The use of SI-SECM allowed access to a reaction that would otherwise be difficult to prove through conventional electrochemistry on a single electrode.

  12. Organometallic Bonding in an Ullmann-Type On-Surface Chemical Reaction Studied by High-Resolution Atomic Force Microscopy.

    Science.gov (United States)

    Kawai, Shigeki; Sadeghi, Ali; Okamoto, Toshihiro; Mitsui, Chikahiko; Pawlak, Rémy; Meier, Tobias; Takeya, Jun; Goedecker, Stefan; Meyer, Ernst

    2016-10-01

    The on-surface Ullmann-type chemical reaction synthesizes polymers by linking carbons of adjacent molecules on solid surfaces. Although an organometallic compound is recently identified as the reaction intermediate, little is known about the detailed structure of the bonded organometallic species and its influence on the molecule and the reaction. Herein atomic force microscopy at low temperature is used to study the reaction with 3,9-diiododinaphtho[2,3-b:2',3'-d]thiophene (I-DNT-VW), which is polymerized on Ag(111) in vacuum. Thermally sublimated I-DNT-VW picks up a Ag surface atom, forming a CAg bond at one end after removing an iodine. The CAg bond is usually short-lived, and a CAgC organometallic bond immediately forms with an adjacent molecule. The existence of the bonded Ag atoms strongly affects the bending angle and adsorption height of the molecular unit. Density functional theory calculations reveal the bending mechanism, which reveals that charge from the terminus of the molecule is transferred via the Ag atom into the organometallic bond and strengths the local adsorption to the substrate. Such deformations vanish when the Ag atoms are removed by annealing and CC bonds are established. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Charge exchange, surface-induced dissociation and reactions of doubly charged molecular ions SF42+ upon impact on a stainless steel surface: A comparison with surface-induced dissociation of singly charged SF4+ molecular ions

    Czech Academy of Sciences Publication Activity Database

    Feketeová, L.; Grill, V.; Zappa, F.; Endstrasser, N.; Rasul, B.; Herman, Zdeněk; Scheier, P.; Märk, T. D.

    2008-01-01

    Roč. 276, č. 1 (2008), s. 37-42 ISSN 1387-3806 Institutional research plan: CEZ:AV0Z40400503 Keywords : doubly charged ion * surface-induced dissociations * surface-induced reaction * charge exchange Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.445, year: 2008

  14. Boson states in the reaction π-p → π-π-π+p with leading π+ meson at 25 GeV/c

    International Nuclear Information System (INIS)

    Antipov, Yu.M.; Baud, R.

    1975-01-01

    The reaction π - + p → p + π - + π - + π + at 25 GeV/c was studied in the mass region M sub(3π) >>= 1.8 GeV with leading π + in the final state. The mass spectrum of π 1 π - -system evidently shows peaks rho deg, f, g deg resonances and an enhancement in S'-region. It is shown that the g deg and π - mesons are mainly in A4 state J sub(P) = 3 + S-wave g degπ - like A1(sup(rhoπ)) and A3(sup(fπ))

  15. Conjugate Heat Transfer Study at Interior Surface of NGV Leading Edge with Combined Shower Head and Impingement Cooling

    Directory of Open Access Journals (Sweden)

    Arun Kumar Pujari

    2014-01-01

    Full Text Available A computational study on conjugate heat transfer is carried out to present the behavior of nondimensional temperature and heat transfer coefficient of a Nozzle Guide Vane (NGV leading edge. Reynolds number of both mainstream flow and coolant impinging jets are varied. The NGV has five rows of film cooling holes arranged in shower head manner and four rows of impingement holes arranged in staggered manner. The results are presented by considering materials of different thermal conductivity. The results show that the mainstream flow affects the temperature distribution on the interior side of the vane leading edge for high conductivity material whereas it has negligible effects for low conductivity material. The effect of changing blowing ratio on internal heat transfer coefficient and internal surface temperature is also presented.

  16. Kinetic modeling and determination of reaction constants of Alzheimer's beta-amyloid fibril extension and dissociation using surface plasmon resonance.

    Science.gov (United States)

    Hasegawa, Kazuhiro; Ono, Kenjiro; Yamada, Masahito; Naiki, Hironobu

    2002-11-19

    To establish the kinetic model of the extension and dissociation of beta-amyloid fibrils (f(A)beta) in vitro, we analyzed these reactions using a surface plasmon resonance (SPR) biosensor. Sonicated f(A)beta were immobilized on the surface of the SPR sensor chip as seeds. The SPR signal increased linearly as a function of time after amyloid beta-peptides (Abeta) were injected into the f(A)beta-immobilized chips. The extension of f(A)beta was confirmed by atomic force microscopy. When flow cells were washed with running buffer, the SPR signal decreased with time after the extension reaction. The curve fitting resolved the dissociation reaction into the fast exponential and slow linear decay phases. Kinetic analysis of the effect of Abeta/f(A)beta concentrations on the reaction rate indicated that both the extension reaction and the slow linear phase of the dissociation were consistent with a first-order kinetic model; i.e., the extension/dissociation reactions proceed via consecutive association/dissociation of Abeta onto/from the end of existing fibrils. On the basis of this model, the critical monomer concentration ([M](e)) and the equilibrium association constant (K) were calculated, for the first time, to be 20 nM and 5 x 10(7) M(-1), respectively. Alternatively, [M](e) was directly measured as 200 nM, which may represent the equilibrium between the extension reaction and the fast phase of the dissociation. The SPR biosensor is a useful quantitative tool for the kinetic and thermodynamic study of the molecular mechanisms of f9A)beta formation in vitro.

  17. Oxygen 18 concentration profile measurements near the surface by 18O(p,α)15N resonance reaction

    International Nuclear Information System (INIS)

    Amsel, G.; David, D.

    1975-01-01

    The method of spectrum reduction in nuclear reaction microanalysis does not allow to obtain depth resolutions better than the order of 2000A. Resolutions of the order of 200A may be obtained by using the narrow resonance technique, when applied to thin films. The latter technique was extended to thick targets, with deep concentration profiles presenting a sharp gradient near the surface. This method is presented and illustrated by the study of 18 O profiles in oxygen diffusion measurements in growing ZrO 2 , using the 629keV resonance of the reaction 18 O(p,α) 15 N [fr

  18. Pencil lead scratches on steel surfaces as a substrate for LIBS analysis of dissolved salts in liquids

    Energy Technology Data Exchange (ETDEWEB)

    Jijon, D; Costa, C, E-mail: judijival@hotmail.com [Departamento de Fisica, Escuela Politecnica Nacional, Ladron de Guevara E11-256, Apartado 17-12-866, Quito (Ecuador)

    2011-01-01

    A new substrate for the quantitative analysis of salts dissolved in liquids with Laser-induced Breakdown Spectroscopy (LIBS) is introduced for the first time. A steel surface scratched with HB pencil lead is introduced as a very efficient and sensitive substrate for quantitative analysis of dissolved salts in liquids. In this work we demonstrate the analytical quality of this system with the analysis of the crystalline deposits formed by the dried aqueous solutions of salts. We focused on analytical parameters such as sensitivity and linearity for the salt cations in each case. Four salts were studied (Sr(NO{sub 3}){sub 2}, LiSO{sub 4}, RbCl and BaCl), at nine different concentrations each. To improve linearity and lower the overall error in the calibration curves, we introduce a novel outlier removal method that takes into account the homogeneity of the dry deposits on the analytical surface.

  19. Directed surfaces structures and interfaces for enhanced electrocatalyst activity, selectivity, and stability for energy conversion reactions

    Energy Technology Data Exchange (ETDEWEB)

    Jaramillo, Thomas F. [Stanford Univ., CA (United States). Dept. of Chemical Engineering. Shriram Center

    2016-04-20

    In this project, we have employed a systematic approach to develop active, selective, and stable catalyst materials for important electrochemical reactions involving energy conversion. In particular, we have focused our attention on developing active catalyst materials for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). HER: We have synthesized and investigated several highly active and acid stable non-precious metal HER catalysts, including: [Mo3S13]2- nanoclusters (Nature Chemistry, 2014) and molybdenum phosphosulfide (MoP|S) (Angewandte Chemie, 2014). We have also aimed to engineer these catalyst formulations in a membrane electrode assembly (MEA) for fundamental studies of water electrolysis at high current densities, approximately 1 A/cm2 (ChemSusChem, 2015). We furthermore investigated transition metal phosphide (TMP) catalysts for HER by a combined experimental–theoretical approach (Energy & Environmental Science, 2015). By synthesizing different TMPs and comparing experimentally determined HER activities with the hydrogen adsorption free energies, ΔGH, calculated by density functional theory, we showed that the TMPs follow a volcano relationship for the HER. Using our combined experimental–theoretical model, we predicted that the mixed metal TMP, Fe0.5Co0.5P, should have a near-optimal ΔGH. We synthesized several mixtures of Co and Fe phosphides alloys and confirmed that Fe0.5Co0.5P exhibits the highest HER activity of the investigated TMPs (Energy & Environmental Science, 2015). The understanding gained as to how to improve catalytic activity for the HER, particularly for non-precious metal materials, is important to DOE targets for sustainable H2 production. OER: We have developed a SrIrO3/IrOx catalyst for acidic conditions (submitted, 2016). The Sr

  20. Growth, surface treatment and characterization of polycrystalline lead iodide thick films prepared using close space deposition technique

    International Nuclear Information System (INIS)

    Zhu, Xinghua; Sun, Hui; Yang, Dingyu; Zheng, Xiaolin

    2012-01-01

    Lead iodide (PbI 2 ) polycrystalline thick films were fabricated on glass substrates with a conductive indium–tin-oxide layer using a close space deposition technique. The morphology of the as-deposited PbI 2 films is typically and highly oriented polycrystalline structure, made up of microcrystal platelets upright on the substrate plane. Two techniques including the surface mechanical cutting and after-growth cadmium telluride coating were employed to improve the films′ surface properties. It was shown that both of the film surface treatment methods markedly decreased the dark current of PbI 2 films. The photo-to-dark current ratio of about 2.05 under 241 Am γ-ray source with activity of 2.78 μCi irradiation was obtained from the film treated using both surface cutting and after-growth CdTe coating. Charge transport characteristics of these films were measured and the hole mobility 7.7×10 −2 –1.67×10 −1 cm 2 /V s was estimated.

  1. AES study of the reaction between a thin Fe-film and β-SiC (100) surface

    International Nuclear Information System (INIS)

    Mizokawa, Yusuke; Nakanishi, Shigemitsu; Miyase, Sunao

    1989-01-01

    The solid state reaction between thin Fe-films and β-SiC(100) in UHV has been studied using AES. Even at room temperature, the reaction between the thin Fe-film and SiC occurred and formed Fe-silicide and graphite with a minor product of Fe-carbide (Fe 3 C). The reaction proceeded with an increase of Fe-coverage to some extent. With annealing of 15 A-Fe-film/SiC below 540degC, the Fe-silicide formation was accelerated, but because the amount of available Fe was small, the dissolved carbon atoms were forced to form not the Fe-carbide but the graphite phase. Above 640degC, the Fe-silicide started to decompose and the carbon atoms diffused to the surface and formed surface graphite layers. With annealing at 1080degC, the free-Si segregats at the surface and formed Si-Si bonds, as well as the Si-C bonds consuming the surface graphite phase. (author)

  2. Site-selective reversible Diels-Alder reaction between a biphenylene-based polyarene and a semiconductor surface.

    Science.gov (United States)

    Godlewski, Szymon; Engelund, Mads; Peña, Diego; Zuzak, Rafał; Kawai, Hiroyo; Kolmer, Marek; Caeiro, Jorge; Guitián, Enrique; Vollhardt, K Peter C; Sánchez-Portal, Daniel; Szymonski, Marek; Pérez, Dolores

    2018-04-12

    Understanding the mechanisms involved in the covalent attachment of organic molecules to surfaces is a major challenge for nanotechnology and surface science. On the basis of classical organic chemistry mechanistic considerations, key issues such as selectivity and reactivity of the organic adsorbates could be rationalized and exploited for the design of molecular-scale circuits and devices. Here we use tris(benzocyclobutadieno)triphenylene, a singular Y-shaped hydrocarbon containing antiaromatic cyclobutadienoid rings, as a molecular probe to study the reaction of polycyclic conjugated molecules with atomic scale moieties, dangling-bond (DB) dimers on a hydrogen-passivated Ge(001):H surface. By combining molecular design, synthesis, scanning tunneling microscopy and spectroscopy (STM/STS) and computational modeling, we show that the attachment involves a concerted [4+2] cycloaddition reaction that is completely site-selective and fully reversible. This selectivity, governed by the bond alternation induced by the presence of the cyclobutadienoid rings, allows for the control of the orientation of the molecules with respect to the surface DB-patterning. We also demonstrate that by judicious modification of the electronic levels of the polycyclic benzenoid through substituents, the reaction barrier height can be modified. Finally, we show that after deliberate tip-induced covalent bond cleavage, adsorbed molecules can be used to fine tune the electronic states of the DB dimer. This power to engineer deliberately the bonding configuration and electronic properties opens new perspectives for creating prototypical nanoscale circuitry.

  3. Single Electron Transfer-Promoted Photochemical Reactions of Secondary N-Trimethylsilylmethyl-N-benzylamines Leading to Aminomethylation of Fullerene C60.

    Science.gov (United States)

    Lim, Suk Hyun; Jeong, Ho Cheol; Sohn, Youngku; Kim, Young-Il; Cho, Dae Won; Woo, Hee-Jae; Shin, Ik-Soo; Yoon, Ung Chan; Mariano, Patrick S

    2016-03-18

    Photoreactions between C60 and secondary N-trimethylsilylmethyl-N-benzylamines were explored to evaluate the feasibility of a new method for secondary aminomethylation of electron acceptors. The results show that photoreactions of C60 with these secondary amines in 10% EtOH-toluene occur to form aminomethyl-1,2-dihydrofullerenes predominantly through a pathway involving single electron transfer (SET)-promoted formation of secondary aminium radicals followed by preferential loss of the α-trimethylsilyl group. The aminomethyl radicals formed in this manner then couple with C60 or C60(•-) to form radical or anion precursors of the aminomethyl-1,2-dihydrofullerenes. In contrast to thermal and photochemical strategies developed previously, the new SET photochemical approach using α-trimethylsilyl-substituted secondary amines is both mild and efficient, and as a result, it should be useful in broadening the library of substituted fullerenes. Moreover, the results should have an impact on the design of SET-promoted C-C bond forming reactions. Specifically, introduction of an α-trimethylsilyl group leads to a change in the chemoselectivity of SET-promoted reactions of secondary amines with acceptors that typically favor aminium radical N-H deprotonation, leading to N-C bond formation. Finally, symmetric and unsymmetric fulleropyrrolidines are also generated in yields that are highly dependent on the electronic properties of arene ring substituents in amines, irradiation time, and solvent.

  4. Probing adsorption phenomena on a single crystal Pt-alloy surface under oxygen reduction reaction conditions

    DEFF Research Database (Denmark)

    Bondarenko, Alexander S.; Stephens, Ifan E.L.; Bech, Lone

    2012-01-01

    The adsorption dynamics of *OH and *O species at Pt(111) and Cu/Pt(111) near-surface alloy (NSA) surfaces in oxygen-free and O2-saturated 0.1M HClO4 was investigated. Subsurface Cu modifies the electronic structure at the Pt(111) surface resulting in weaker bonding to adsorbates like *OH, *H or *...

  5. Quantum dynamical study of the O(1D)+HCl reaction employing three electronic state potential energy surfaces

    Science.gov (United States)

    Yang, Huan; Han, Ke-Li; Nanbu, Shinkoh; Nakamura, Hiroki; Balint-Kurti, Gabriel G.; Zhang, Hong; Smith, Sean C.; Hankel, Marlies

    2008-01-01

    Quantum dynamical calculations are reported for the title reaction, for both product arrangement channels and using potential energy surfaces corresponding to the three electronic states, 1A'1, 2A'1, and 1A″1, which correlate with both reactants and products. The calculations have been performed for J =0 using the time-dependent real wavepacket approach by Gray and Balint-Kurti [J. Chem. Phys. 108, 950 (1998)]. Reaction probabilities for both product arrangement channels on all three potential energy surfaces are presented for total energies between 0.1 and 1.1eV. Product vibrational state distributions at two total energies, 0.522 and 0.722eV, are also presented for both channels and all three electronic states. Product rotational quantum state distributions are presented for both product arrangement channels and all three electronic states for the first six product vibrational states.

  6. Bone reactions adjacent to titanium implants with different surface characteristics subjected to static load. A study in the dog (II)

    DEFF Research Database (Denmark)

    Gotfredsen, K; Berglundh, T; Lindhe, J

    2001-01-01

    extracted bilaterally. 12 weeks later, 2 implants with a TPS surface were placed in one side and 2 implants with a machined surface were placed in the contralateral side. Twelve weeks after implant installation, crowns, connected in pairs with orthodontic expansion screws, were fitted to the implants......The purpose of the present study was to compare bone reactions adjacent to titanium implants with either a titanium plasma-sprayed (TPS) or a machined surface subjected to lateral static loading induced by an expansion force. In 3 labrador dogs, the 2nd, 3rd and 4th mandibular premolars were...... and histometric examination. A higher marginal bone level was observed around implants with a TPS surface compared to machined implants. Furthermore, the values describing the amount of bone-to-implant contact at the bone/implant interface as well as the density of the peri-implant bone were lower at the machined...

  7. Quantal Study of the Exchange Reaction for N + N2 using an ab initio Potential Energy Surface

    Science.gov (United States)

    Wang, Dunyou; Stallcop, James R.; Huo, Winifred M.; Dateo, Christopher E.; Schwenke, David W.; Partridge, Harry; Kwak, Dochan (Technical Monitor)

    2002-01-01

    The N + N2 exchange rate is calculated using a time-dependent quantum dynamics method on a newly determined ab initio potential energy surface (PES) for the ground A" state. This ab initio PES shows a double barrier feature in the interaction region with the barrier height at 47.2 kcal/mol, and a shallow well between these two barriers, with the minimum at 43.7 kcal/mol. A quantum dynamics wave packet calculation has been carried out using the fitted PES to compute the cumulative reaction probability for the exchange reaction of N + N2(J=O). The J - K shift method is then employed to obtain the rate constant for this reaction. The calculated rate constant is compared with experimental data and a recent quasi-classical calculation using a LEPS PES. Significant differences are found between the present and quasiclassical results. The present rate calculation is the first accurate 3D quantal dynamics study for N + N2 reaction system and the ab initio PES reported here is the first such surface for N3.

  8. C-13 isotopic studies of the surface catalysed reactions of methane

    International Nuclear Information System (INIS)

    Long, M.A.; He, S.J.X.; Adebajo, M.

    1997-01-01

    The ability of methane to methylate aromatic compounds, which are considered to be models for coal, is being studied. Related to this reaction, but at higher temperatures, is the direct formation of benzene from methane in the presence of these catalysts. Controversy exists in the literature on the former reaction, and 13 C isotope studies are being used to resolve the question. The interest in this reaction arises because the utilisation of methane, in the form of natural gas, in place of hydrogen for direct coal liquefaction would have major economic advantage. For this reason Isotope studies in this area have contributed significantly to an understanding of the methylation reactions. The paper describes experiments utilising methane 13 C, which show that methylation of aromatics such as naphthalene by the methane 13 C is catalysed by microporous, Cu-exchanged SAPO-5, at elevated pressures (6.8 MPa) and temperatures around 400 degree C. The mass spectrometric analysis and n.m.r. study of the isotopic composition of the products of the methylation reaction demonstrate unequivocally that methane provides the additional carbon atom for the methylated products. Thermodynamic calculations predict that the reaction is favourable at high methane pressures under these experimental conditions. The mechanism as suggested by the isotope study is discussed. The catalysts which show activity for the activation of methane for direct methylation of organic compounds, such as naphthalene, toluene, phenol and pyrene, are substituted aluminophosphate molecular sieves, EIAPO-5 (where El=Pb, Cu, Ni and Si) and a number of metal substituted zeolites. Our earlier tritium studies had shown that these catalysts will activate alkanes, at least as far as isotope hydrogen exchange reactions are concerned

  9. Computational studies of atmospherically-relevant chemical reactions in water clusters and on liquid water and ice surfaces.

    Science.gov (United States)

    Gerber, R Benny; Varner, Mychel E; Hammerich, Audrey D; Riikonen, Sampsa; Murdachaew, Garold; Shemesh, Dorit; Finlayson-Pitts, Barbara J

    2015-02-17

    CONSPECTUS: Reactions on water and ice surfaces and in other aqueous media are ubiquitous in the atmosphere, but the microscopic mechanisms of most of these processes are as yet unknown. This Account examines recent progress in atomistic simulations of such reactions and the insights provided into mechanisms and interpretation of experiments. Illustrative examples are discussed. The main computational approaches employed are classical trajectory simulations using interaction potentials derived from quantum chemical methods. This comprises both ab initio molecular dynamics (AIMD) and semiempirical molecular dynamics (SEMD), the latter referring to semiempirical quantum chemical methods. Presented examples are as follows: (i) Reaction of the (NO(+))(NO3(-)) ion pair with a water cluster to produce the atmospherically important HONO and HNO3. The simulations show that a cluster with four water molecules describes the reaction. This provides a hydrogen-bonding network supporting the transition state. The reaction is triggered by thermal structural fluctuations, and ultrafast changes in atomic partial charges play a key role. This is an example where a reaction in a small cluster can provide a model for a corresponding bulk process. The results support the proposed mechanism for production of HONO by hydrolysis of NO2 (N2O4). (ii) The reactions of gaseous HCl with N2O4 and N2O5 on liquid water surfaces. Ionization of HCl at the water/air interface is followed by nucleophilic attack of Cl(-) on N2O4 or N2O5. Both reactions proceed by an SN2 mechanism. The products are ClNO and ClNO2, precursors of atmospheric atomic chlorine. Because this mechanism cannot result from a cluster too small for HCl ionization, an extended water film model was simulated. The results explain ClNO formation experiments. Predicted ClNO2 formation is less efficient. (iii) Ionization of acids at ice surfaces. No ionization is found on ideal crystalline surfaces, but the process is efficient on

  10. Surface Oxidation of AuNi Heterodimers to Achieve High Activities toward Hydrogen/Oxygen Evolution and Oxygen Reduction Reactions.

    Science.gov (United States)

    Ni, Bing; He, Peng; Liao, Wenxin; Chen, Shuangming; Gu, Lin; Gong, Yue; Wang, Kai; Zhuang, Jing; Song, Li; Zhou, Gang; Wang, Xun

    2018-04-01

    Although much attention has been paid to the exploration of highly active electrocatalysts, especially catalysts for hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), the development of multifunctional catalysts remains a challenge. Here, we utilize AuNi heterodimers as the starting materials to achieve high activities toward HER, OER and ORR. The HER and ORR activities in an alkali environment are similar to those of Pt catalysts, and the OER activity is very high and better than that of commercial IrO 2 . Both the experimental and calculated results suggest that the surface oxidation under oxidative conditions is the main reason for the different activities. The NiO/Ni interface which exists in the as-synthesized heterodimers contributes to high HER activity, the Ni(OH) 2 -Ni-Au interface and the surface Ni(OH) 2 obtained in electrochemical conditons gives rise to promising ORR and OER activities, respectively. As a comparison, a Au@Ni core-shell structure is also synthesized and examined. The core-shell structure shows lower activities for HER and OER than the heterodimers, and reduces O 2 selectively to H 2 O 2 . The work here allows for the development of a method to design multifunctional catalysts via the partial oxidation of a metal surface to create different active centers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. A Chemical-Adsorption Strategy to Enhance the Reaction Kinetics of Lithium-Rich Layered Cathodes via Double-Shell Surface Modification.

    Science.gov (United States)

    Guo, Lichao; Li, Jiajun; Cao, Tingting; Wang, Huayu; Zhao, Naiqin; He, Fang; Shi, Chunsheng; He, Chunnian; Liu, Enzuo

    2016-09-21

    Sluggish surface reaction kinetics hinders the power density of Li-ion battery. Thus, various surface modification techniques have been applied to enhance the electronic/ionic transfer kinetics. However, it is challenging to obtain a continuous and uniform surface modification layer on the prime particles with structure integration at the interface. Instead of classic physical-adsorption/deposition techniques, we propose a novel chemical-adsorption strategy to synthesize double-shell modified lithium-rich layered cathodes with enhanced mass transfer kinetics. On the basis of experimental measurement and first-principles calculation, MoO2S2 ions are proved to joint the layered phase via chemical bonding. Specifically, the Mo-O or Mo-S bonds can flexibly rotate to bond with the cations in the layered phase, leading to the good compatibility between the thiomolybdate adsorption layer and layered cathode. Followed by annealing treatment, the lithium-excess-spinel inner shell forms under the thiomolybdate adsorption layer and functions as favorable pathways for lithium and electron. Meanwhile, the nanothick MoO3-x(SO4)x outer shell protects the transition metal from dissolution and restrains electrolyte decomposition. The double-shell modified sample delivers an enhanced discharge capacity almost twice as much as that of the unmodified one at 1 A g(-1) after 100 cycles, demonstrating the superiority of the surface modification based on chemical adsorption.

  12. Insight into chemoselectivity of nitroarene hydrogenation: A DFT-D3 study of nitroarene adsorption on metal surfaces under the realistic reaction conditions

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lidong [Key Laboratory for Advanced Materials, Center for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237 (China); Cao, Xiao-Ming, E-mail: xmcao@ecust.edu.cn [Key Laboratory for Advanced Materials, Center for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237 (China); Hu, P., E-mail: p.hu@qub.ac.uk [Key Laboratory for Advanced Materials, Center for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237 (China); School of Chemistry and Chemical Engineering, The Queen’s University of Belfast, Belfast, BT9 5AG (United Kingdom)

    2017-01-15

    Highlights: • Comparing the chemical bonding strengths between different functional groups of nitroarenes and metal surfaces. • Obtaining the variation trends of adsorption configurations of nitrobenzene and 4-nitrostyrene against their coverage. • Identifying the coverage of nitroarene and hydrogen on Pt(111) and Au(111) under the realistic hydrogenation condition. • Proposing Gibbs free adsorption energy per surface area as a descriptor to roughly evaluate the hydrogenation selectivity. - Abstract: The adsorption of nitrobenzene and 4-nitrostyrene on the Pt(111) and the Au(111) surfaces under the general reaction condition of nitroarene catalytic hydrogenation is investigated utilizing periodic density functional theory calculations with the Grimme’s empirical three-body dispersion correction to understand the influence of adsorption configurations on chemoselectivity of nitroarene compound hydrogenation. It is found that at the low coverage both nitrobenzene and 4-nitrostyrene tend to adsorb paralleling to the Pt(111) and the Au(111) surfaces. Based on the crystal orbital Hamilton population analysis, it is found that the chemical bonding between nitro group and Pt(111) surface is weak. The adsorption configurations of nitrobenzene and 4-nitrostyrene are determined by the chemisorption strength of phenyl group and vinyl group. Under the reaction condition, the 1/9 ML nitrobenzene and 4/9 ML hydrogen atom can be coadsorbed while the 1/6 ML 4-nitrostyrene and 1/3 ML hydrogen atom can be coadsorbed on Pt(111). With the increase of the coverage, nitrobenzene still remains its paralleled adsorption configuration while the adsorption configuration of 4-nitrostyrene is switched to the tilted adsorption configuration through vinyl group without the chemisorption of phenyl and nitro group on Pt(111). In addition, the competitive adsorption with hydrogen will not change the adsorption configuration of nitrobenzene and 4-nitrostyrene under the reaction condition

  13. Response surface modeling of lead (׀׀) removal by graphene oxide-Fe3O4 nanocomposite using central composite design.

    Science.gov (United States)

    Khazaei, Mohammad; Nasseri, Simin; Ganjali, Mohammad Reza; Khoobi, Mehdi; Nabizadeh, Ramin; Mahvi, Amir Hossein; Nazmara, Shahrokh; Gholibegloo, Elham

    2016-01-01

    Magnetic graphene oxide (Fe3O4@SiO2-GO) nanocomposite was fabricated through a facile process and its application as an excellent adsorbent for lead (II) removal was also demonstrated by applying response surface methodology (RSM). Fe3O4@SiO2-GO nanocomposite was synthesized and characterized properly. The effects of four independent variables, initial pH of solution (3.5-8.5), nanocomposite dosage (1-60 mg L(-1)), contact time (2-30 min), and initial lead (II) ion concentration (0.5-5 mg L(-1)) on the lead (II) removal efficiency were investigated and the process was optimized using RSM. Using central composite design (CCD), 44 experiments were carried out and the process response was modeled using a quadratic equation as function of the variables. The optimum values of the variables were found to be 6.9, 30.5 mg L(-1), 16 min, and 2.49 mg L(-1) for pH, adsorbent dosage, contact time, and lead (II) initial concentration, respectively. The amount of adsorbed lead (II) after 16 min was recorded as high as 505.81 mg g(-1) for 90 mg L(-1) initial lead (II) ion concentration. The Sips isotherm was found to provide a good fit with the adsorption data (KS = 256 L mg(-1), nS = 0.57, qm = 598.4 mg g(-1), and R(2) = 0.984). The mean free energy Eads was 9.901 kJ/mol which confirmed the chemisorption mechanism. The kinetic study determined an appropriate compliance of experimental data with the double exponential kinetic model (R(2) = 0.982). Quadratic and reduced models were examined to correlate the variables with the removal efficiency of Fe3O4@SiO2-GO. According to the analysis of variance, the most influential factors were identified as pH and contact time. At the optimum condition, the adsorption yield was achieved up to nearly 100 %.

  14. Solar Atmosphere to Earth's Surface: Long Lead Time dB/dt Predictions with the Space Weather Modeling Framework

    Science.gov (United States)

    Welling, D. T.; Manchester, W.; Savani, N.; Sokolov, I.; van der Holst, B.; Jin, M.; Toth, G.; Liemohn, M. W.; Gombosi, T. I.

    2017-12-01

    The future of space weather prediction depends on the community's ability to predict L1 values from observations of the solar atmosphere, which can yield hours of lead time. While both empirical and physics-based L1 forecast methods exist, it is not yet known if this nascent capability can translate to skilled dB/dt forecasts at the Earth's surface. This paper shows results for the first forecast-quality, solar-atmosphere-to-Earth's-surface dB/dt predictions. Two methods are used to predict solar wind and IMF conditions at L1 for several real-world coronal mass ejection events. The first method is an empirical and observationally based system to estimate the plasma characteristics. The magnetic field predictions are based on the Bz4Cast system which assumes that the CME has a cylindrical flux rope geometry locally around Earth's trajectory. The remaining plasma parameters of density, temperature and velocity are estimated from white-light coronagraphs via a variety of triangulation methods and forward based modelling. The second is a first-principles-based approach that combines the Eruptive Event Generator using Gibson-Low configuration (EEGGL) model with the Alfven Wave Solar Model (AWSoM). EEGGL specifies parameters for the Gibson-Low flux rope such that it erupts, driving a CME in the coronal model that reproduces coronagraph observations and propagates to 1AU. The resulting solar wind predictions are used to drive the operational Space Weather Modeling Framework (SWMF) for geospace. Following the configuration used by NOAA's Space Weather Prediction Center, this setup couples the BATS-R-US global magnetohydromagnetic model to the Rice Convection Model (RCM) ring current model and a height-integrated ionosphere electrodynamics model. The long lead time predictions of dB/dt are compared to model results that are driven by L1 solar wind observations. Both are compared to real-world observations from surface magnetometers at a variety of geomagnetic latitudes

  15. Transition State Theory for solvated reactions beyond recrossing-free dividing surfaces

    OpenAIRE

    Revuelta, F.; Bartsch, Thomas; Garcia-Muller, P. L.; Hernandez, Rigoberto; Benito, R. M.; Borondo, F.

    2016-01-01

    The accuracy of rate constants calculated using transition state theory depends crucially on the correct identification of a recrossing--free dividing surface. We show here that it is possible to define such optimal dividing surface in systems with non--Markovian friction. However, a more direct approach to rate calculation is based on invariant manifolds and avoids the use of a dividing surface altogether, Using that method we obtain an explicit expression for the rate of crossing an anharmo...

  16. Origin of Power Laws for Reactions at Metal Surfaces Mediated by Hot Electrons

    DEFF Research Database (Denmark)

    Olsen, Thomas; Schiøtz, Jakob

    2009-01-01

    density functional theory and the delta self-consistent field method. With a simplifying assumption, the power law becomes exact and we obtain a simple physical interpretation of the exponent n, which represents the number of adsorbate vibrational states participating in the reaction....... of such experiments is the emergence of a power law dependence of the reaction yield on the laser fluence Y similar to F-n. We propose a model of multiple inelastic scattering by hot electrons which reproduces this power law and the observed exponents of several experiments. All parameters are calculated within...

  17. Possible scenarios for SiS formation in the interstellar medium: Electronic structure calculations of the potential energy surfaces for the reactions of the SiH radical with atomic sulphur and S2

    Science.gov (United States)

    Rosi, Marzio; Mancini, Luca; Skouteris, Dimitrios; Ceccarelli, Cecilia; Faginas Lago, Noelia; Podio, Linda; Codella, Claudio; Lefloch, Bertrand; Balucani, Nadia

    2018-03-01

    In this Letter we report on the first characterization of the reactions SiH + S and SiH + S2 by means of electronic structure calculations of the stationary points along the reactive potential energy surfaces. According to our calculations, both reactions are barrierless and can lead to the formation of SiS (a species observed in interstellar objects) for which there are no convincing formation routes in current astrochemical models. Furthermore, we have verified that SiS2 cannot be considered an interstellar reservoir of sulphur because it is easily attacked by the abundant H atoms.

  18. Lead-chalcogenide mid-infrared vertical external cavity surface emitting lasers with improved threshold: Theory and experiment

    Science.gov (United States)

    Fill, Matthias; Debernardi, Pierluigi; Felder, Ferdinand; Zogg, Hans

    2013-11-01

    Mid-infrared Vertical External Cavity Surface Emitting Lasers (VECSEL) based on narrow gap lead-chalcogenide (IV-VI) semiconductors exhibit strongly reduced threshold powers if the active layers are structured laterally for improved optical confinement. This is predicted by 3-d optical calculations; they show that lateral optical confinement is needed to counteract the anti-guiding features of IV-VIs due to their negative temperature dependence of the refractive index. An experimental proof is performed with PbSe quantum well based VECSEL grown on a Si-substrate by molecular beam epitaxy and emitting around 3.3 μm. With proper mesa-etching, the threshold intensity is about 8-times reduced.

  19. Lead-chalcogenide mid-infrared vertical external cavity surface emitting lasers with improved threshold: Theory and experiment

    Energy Technology Data Exchange (ETDEWEB)

    Fill, Matthias [ETH Zurich, Laser Spectroscopy and Sensing Lab, 8093 Zurich (Switzerland); Phocone AG, 8005 Zurich (Switzerland); Debernardi, Pierluigi [IEIIT-CNR, Torino 10129 (Italy); Felder, Ferdinand [Phocone AG, 8005 Zurich (Switzerland); Zogg, Hans [ETH Zurich (Switzerland)

    2013-11-11

    Mid-infrared Vertical External Cavity Surface Emitting Lasers (VECSEL) based on narrow gap lead-chalcogenide (IV-VI) semiconductors exhibit strongly reduced threshold powers if the active layers are structured laterally for improved optical confinement. This is predicted by 3-d optical calculations; they show that lateral optical confinement is needed to counteract the anti-guiding features of IV-VIs due to their negative temperature dependence of the refractive index. An experimental proof is performed with PbSe quantum well based VECSEL grown on a Si-substrate by molecular beam epitaxy and emitting around 3.3 μm. With proper mesa-etching, the threshold intensity is about 8-times reduced.

  20. Formation of HCN + in Heterogeneous Reactions of N 2 + and N + with Surface Hydrocarbons

    Czech Academy of Sciences Publication Activity Database

    Harnish, M.; Keim, A.; Scheier, P.; Herman, Zdeněk

    2013-01-01

    Roč. 117, č. 39 (2013), s. 9653-9660 ISSN 1089-5639 Institutional support: RVO:61388955 Keywords : SLOW POLYATOMIC IONS * CHEMICAL-REACTIONS * ROOM-TEMPERATURE Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.775, year: 2013

  1. A constrained reduced-dimensionality search algorithm to follow chemical reactions on potential energy surfaces

    Science.gov (United States)

    Lankau, Timm; Yu, Chin-Hui

    2013-06-01

    A constrained reduced-dimensionality algorithm can be used to efficiently locate transition states and products in reactions involving conformational changes. The search path (SP) is constructed stepwise from linear combinations of a small set of manually chosen internal coordinates, namely the predictors. The majority of the internal coordinates, the correctors, are optimized at every step of the SP to minimize the total energy of the system so that the path becomes a minimum energy path connecting products and transition states with the reactants. Problems arise when the set of predictors needs to include weak coordinates, for example, dihedral angles, as well as strong ones such as bond distances. Two principal constraining methods for the weak coordinates are proposed to mend this situation: static and dynamic constraints. Dynamic constraints are automatically activated and revoked depending on the state of the weak coordinates among the predictors, while static ones require preset control factors and act permanently. All these methods enable the successful application (4 reactions are presented involving cyclohexane, alanine dipeptide, trimethylsulfonium chloride, and azafulvene) of the reduced dimensionality method to reactions where the reaction path covers large conformational changes in addition to the formation/breaking of chemical bonds. Dynamic constraints are found to be the most efficient method as they require neither additional information about the geometry of the transition state nor fine tuning of control parameters.

  2. Ab Initio and DFT Potential Energy Surfaces for Cyanuric Chloride Reactions

    National Research Council Canada - National Science Library

    Pai, Sharmila

    1998-01-01

    ... on the potential energy surface were calculated using the 6-31G and 6-311 +Gbasis sets. DFT(B3LYP) geometry optimizations and zero-point corrections for critical points on the potential energy surface were calculated with the 6-31G, 6-311...

  3. In situ spectroscopy of ligand exchange reactions at the surface of colloidal gold and silver nanoparticles

    International Nuclear Information System (INIS)

    Dinkel, Rebecca; Peukert, Wolfgang; Braunschweig, Björn

    2017-01-01

    Gold and silver nanoparticles with their tunable optical and electronic properties are of great interest for a wide range of applications. Often the ligands at the surface of the nanoparticles have to be exchanged in a second step after particle formation in order to obtain a desired surface functionalization. For many techniques, this process is not accessible in situ . In this review, we present second-harmonic scattering (SHS) as an inherently surface sensitive and label-free optical technique to probe the ligand exchange at the surface of colloidal gold and silver nanoparticles in situ and in real time. First, a brief introduction to SHS and basic features of the SHS of nanoparticles are given. After that, we demonstrate how the SHS intensity decrease can be correlated to the thiol coverage which allows for the determination of the Gibbs free energy of adsorption and the surface coverage. (topical review)

  4. Evaluation of the cross-sections of threshold reactions leading to the production of long-lived radionuclides during irradiation of steels by thermonuclear spectrum neutrons

    International Nuclear Information System (INIS)

    Blokhin, A.I.; Buleeva, N.N.; Manokhin, V.N.; Mikhajlyukova, M.V.; Nasyrova, S.M.; Skripova, M.V.

    2002-01-01

    The present paper analyses and evaluates the cross-sections of threshold reactions leading to the production of long-lived radionuclides during the irradiation, by thermonuclear spectrum neutrons, of steels containing V, Ti, Cr, Fe and Ni. On the basis of empirical systematics. a new evaluation of the (n,2n), (n,p), (n,np), (n,α) and (n,nα) excitation functions is made for all isotopes of V, Ti, Cr, Fe and Ni and for intermediate isotopes produced in the chain from irradiated isotopes up to production of the long-lived radionuclides 39 Ar, 42 Ar, 41 Ca, 53 Mn, 60 Fe, 60 Co, 59 Ni and 63 Ni. A comparison is made with the experimental and other evaluated data. (author)

  5. Evaluation of the cross-sections of threshold reactions leading to the production of long-lived radionuclides during irradiation of steels by thermonuclear spectrum neutrons

    CERN Document Server

    Blokhin, A I; Manokhin, V N; Mikhajlyukova, M V; Nasyrova, S M; Skripova, M V

    2001-01-01

    The present paper analyses and evaluates the cross-sections of threshold reactions leading to the production of long-lived radionuclides during the irradiation, by thermonuclear spectrum neutrons, of steels containing V, Ti, Cr, Fe and Ni. On the basis of empirical systematics. a new evaluation of the (n,2n), (n,p), (n,np), (n,alpha) and (n,n alpha) excitation functions is made for all isotopes of V, Ti, Cr, Fe and Ni and for intermediate isotopes produced in the chain from irradiated isotopes up to production of the long-lived radionuclides sup 3 sup 9 Ar, sup 4 sup 2 Ar, sup 4 sup 1 Ca, sup 5 sup 3 Mn, sup 6 sup 0 Fe, sup 6 sup 0 Co, sup 5 sup 9 Ni and sup 6 sup 3 Ni. A comparison is made with the experimental and other evaluated data.

  6. Measurement of activation reaction rate distribution on a mercury target with a lead-reflector and light-water-moderator for high energy proton bombardment using AGS accelerator

    International Nuclear Information System (INIS)

    Kasugai, Yoshimi; Takada, Hiroshi; Meigo, Shin-ichiro

    2001-02-01

    Characteristic of spallation neutrons driven by GeV protons from a mercury target with a lead-reflector and light-water-moderator was studied experimentally using the Alternating Gradient Synchrotron (AGS) facility of Brookhaven National Laboratory in a framework of the ASTE (AGS Spallation Target Experiment) collaboration. Several reaction rates along with the mercury target were measured with the activation method at incident proton energies of 1.94, 12 and 24 GeV. Indium, niobium, aluminum, cobalt, nickel and bismuth were used as activation detectors to cover the threshold energy of between 0.33 and 40.9 MeV. This report summarizes the experimental procedure with all the measured data. (author)

  7. Polar Organic Compounds in Surface Waters Collected Near Lead-Zinc Mine and Milling Operations in Missouri

    Science.gov (United States)

    Rostad, C. E.; Schmitt, C. J.; Schumacher, J. G.; Leiker, T. J.

    2007-12-01

    Surface-water samples were collected near a lead mine and mill tailings about 70 miles southwest of St. Louis, Missouri, during the summer of 2006. The purpose of this sampling was to determine if polar organic compounds were present that could be a cause of documented negative impacts to biota downstream. Water samples contained relatively high concentrations of dissolved organic carbon for surface waters (greater than 20 mg/L), but were colorless, which precluded naturally occurring aquatic humic or fulvic acids. Previous analysis indicated that samples were devoid of pesticides and acid/base/neutral extractable semi-volatile organic compounds, such as polycyclic aromatic hydrocarbons. After isolation by three different types of solid phase extraction, samples were analyzed by electrospray ionization/mass spectrometry. Polar organic compounds commonly used in the milling process, such as alkyl xanthates, were not found; however, xanthate degradation products were detected. Most of the polar organic compounds identified contained sulfonate groups, which are characteristic of some of the reagents used in the milling process. Sulfonate compounds may have low sorption onto soil or sediments and be mobile in the aqueous environment.

  8. "Turn-on" fluorescence detection of lead ions based on accelerated leaching of gold nanoparticles on the surface of graphene.

    Science.gov (United States)

    Fu, Xiuli; Lou, Tingting; Chen, Zhaopeng; Lin, Meng; Feng, Weiwei; Chen, Lingxin

    2012-02-01

    A novel platform for effective "turn-on" fluorescence sensing of lead ions (Pb(2+)) in aqueous solution was developed based on gold nanoparticle (AuNP)-functionalized graphene. The AuNP-functionalized graphene exhibited minimal background fluorescence because of the extraordinarily high quenching ability of AuNPs. Interestingly, the AuNP-functionalized graphene underwent fluorescence restoration as well as significant enhancement upon adding Pb(2+), which was attributed to the fact that Pb(2+) could accelerate the leaching rate of the AuNPs on graphene surfaces in the presence of both thiosulfate (S(2)O(3)(2-)) and 2-mercaptoethanol (2-ME). Consequently, this could be utilized as the basis for selective detection of Pb(2+). With the optimum conditions chosen, the relative fluorescence intensity showed good linearity versus logarithm concentration of Pb(2+) in the range of 50-1000 nM (R = 0.9982), and a detection limit of 10 nM. High selectivity over common coexistent metal ions was also demonstrated. The practical application had been carried out for determination of Pb(2+) in tap water and mineral water samples. The Pb(2+)-specific "turn-on" fluorescence sensor, based on Pb(2+) accelerated leaching of AuNPs on the surface of graphene, provided new opportunities for highly sensitive and selective Pb(2+) detection in aqueous media.

  9. In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts.

    Science.gov (United States)

    Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A

    2016-10-24

    The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Quantification of Hydrogen Concentrations in Surface and Interface Layers and Bulk Materials through Depth Profiling with Nuclear Reaction Analysis.

    Science.gov (United States)

    Wilde, Markus; Ohno, Satoshi; Ogura, Shohei; Fukutani, Katsuyuki; Matsuzaki, Hiroyuki

    2016-03-29

    Nuclear reaction analysis (NRA) via the resonant (1)H((15)N,αγ)(12)C reaction is a highly effective method of depth profiling that quantitatively and non-destructively reveals the hydrogen density distribution at surfaces, at interfaces, and in the volume of solid materials with high depth resolution. The technique applies a (15)N ion beam of 6.385 MeV provided by an electrostatic accelerator and specifically detects the (1)H isotope in depths up to about 2 μm from the target surface. Surface H coverages are measured with a sensitivity in the order of ~10(13) cm(-2) (~1% of a typical atomic monolayer density) and H volume concentrations with a detection limit of ~10(18) cm(-3) (~100 at. ppm). The near-surface depth resolution is 2-5 nm for surface-normal (15)N ion incidence onto the target and can be enhanced to values below 1 nm for very flat targets by adopting a surface-grazing incidence geometry. The method is versatile and readily applied to any high vacuum compatible homogeneous material with a smooth surface (no pores). Electrically conductive targets usually tolerate the ion beam irradiation with negligible degradation. Hydrogen quantitation and correct depth analysis require knowledge of the elementary composition (besides hydrogen) and mass density of the target material. Especially in combination with ultra-high vacuum methods for in-situ target preparation and characterization, (1)H((15)N,αγ)(12)C NRA is ideally suited for hydrogen analysis at atomically controlled surfaces and nanostructured interfaces. We exemplarily demonstrate here the application of (15)N NRA at the MALT Tandem accelerator facility of the University of Tokyo to (1) quantitatively measure the surface coverage and the bulk concentration of hydrogen in the near-surface region of a H2 exposed Pd(110) single crystal, and (2) to determine the depth location and layer density of hydrogen near the interfaces of thin SiO2 films on Si(100).

  11. Dynamics of surface-migration: Electron-induced reaction of 1,2-dihaloethanes on Si(100)

    Science.gov (United States)

    Huang, Kai; MacLean, Oliver; Guo, Si Yue; McNab, Iain R.; Ning, Zhanyu; Wang, Chen-Guang; Ji, Wei; Polanyi, John C.

    2016-10-01

    Scanning Tunneling Microscopy was used to investigate the electron-induced reaction of 1,2-dibromoethane (DBE) and 1,2-dichloroethane (DCE) on Si(100).We observed a long-lived physisorbed molecular state of DBE at 75 K and of DCE at 110 K. As a result we were able to characterize by experiment and also by ab initio theory the dynamics of ethylene production in the electron-induced surface-reaction of these physisorbed species. For both DBE and DCE the ethylene product was observed to migrate across the surface. In the case of DBE the recoil of the ethylene favored the silicon rows, migrating by an average distance of 22 Å, and up to 100 Å. Trajectory calculations were performed for this electron-induced reaction, using an 'Impulsive Two-State' model involving an anionic excited state and a neutral ground-potential. The model agreed with experiment in reproducing both migration and desorption of the ethylene product. The computed migration exhibited a 'ballistic' launch and subsequent 'bounces', thereby accounting for the observed long-range migratory dynamics.

  12. Metal enrichment and lead isotope analysis for source apportionment in the urban dust and rural surface soil.

    Science.gov (United States)

    Yu, Yang; Li, Yingxia; Li, Ben; Shen, Zhenyao; Stenstrom, Michael K

    2016-09-01

    To understand the metal accumulation in the environment and identify its sources, 29 different metal contents and lead (Pb) isotope ratios were determined for 40 urban dust samples, 36 surface soil samples, and one river sediment sample collected in the municipality of Beijing, China. Results showed that cadmium, copper (Cu), mercury, Pb, antimony (Sb), and zinc demonstrated to be the typical urban contaminants and mostly influenced by the adjacent human activities with higher content to background ratios and SD values. Among the 29 metal elements investigated, Cu and Sb were found to be the most distinct elements that were highly affected by the developing level and congestion status of the cities with much higher contents in dust in more developed and congested cities. There was a relatively wider range of Pb isotope ratios of country surface soil than those of urban dust. The results of source identification based on Pb isotope ratios showed that coal combustion was the first largest Pb source and vehicle exhaust was the second largest source. The sum of them accounted for 74.6% mass proportion of overall Pb pollution on average. The surface soil sample collected at an iron mine had the highest (204)Pb/(206)Pb, (207)Pb/(206)Pb, and (208)Pb/(206)Pb ratios indicating ore had much higher ratios than other sources. The fine particle subsamples had higher (204)Pb/(206)Pb, (207)Pb/(206)Pb, and (208)Pb/(206)Pb ratios than the coarse particle subsamples indicating more anthropogenic sources of coal combustion and vehicle exhaust for fine particles and more background influence for coarse particles. These results help with pinpointing the major Pb sources and applying suitable measures for the target sources. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Transition state theory for solvated reactions beyond recrossing-free dividing surfaces.

    Science.gov (United States)

    Revuelta, F; Bartsch, Thomas; Garcia-Muller, P L; Hernandez, Rigoberto; Benito, R M; Borondo, F

    2016-06-01

    The accuracy of rate constants calculated using transition state theory depends crucially on the correct identification of a recrossing-free dividing surface. We show here that it is possible to define such optimal dividing surface in systems with non-Markovian friction. However, a more direct approach to rate calculation is based on invariant manifolds and avoids the use of a dividing surface altogether, Using that method we obtain an explicit expression for the rate of crossing an anharmonic potential barrier. The excellent performance of our method is illustrated with an application to a realistic model for LiNC⇌LiCN isomerization.

  14. Final Report: The Impact of Carbonate on Surface Protonation, Electron Transfer and Crystallization Reactions in Iron Oxide Nanoparticles and Colloids

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, David Adams [The University of Alabama

    2013-07-02

    This project addresses key issues of importance in the geochemical behavior of iron oxides and in the geochemical cycling of carbon and iron. For Fe, we are specifically studying the influence of carbonate on electron transfer reactions, solid phase transformations, and the binding of carbonate to reactive sites on the edges of particles. The emphasis on carbonate arises because it is widely present in the natural environment, is known to bind strongly to oxide surfaces, is reactive on the time scales of interest, and has a speciation driven by acid-base reactions. The geochemical behavior of carbonate strongly influences global climate change and CO{sub 2} sequestration technologies. Our goal is to answer key questions with regards to specific site binding, electron transfer reactions, and crystallization reactions of iron oxides that impact both the geochemical cycling of iron and CO{sub 2} species. Our work is focused on the molecular level description of carbonate chemistry in solution including the prediction of isotope fractionation factors. We have also done work on critical atmospheric species.

  15. Diagnostics for the Analysis of Surface Chemistry Effects on Composite Energetic Material Reactions

    Science.gov (United States)

    2015-10-30

    LIMITATION OF ABSTRACT 15. NUMBER OF PAGES 5d. PROJECT NUMBER 5e. TASK NUMBER 5f. WORK UNIT NUMBER 5c. PROGRAM ELEMENT NUMBER 5b. GRANT NUMBER 5a...integration time) and a NETZSCH STA 449 Jupiter that will allow for consistency and efficiency with its automatic 20 sample changer. (2) Together these...Purchase of the NETZSCH STA 449 Jupiter (DSC-TGA) to resolve reaction kinetics under equilibrium conditions. Images of this instrumentation are included in

  16. Reduction of the Electrode Overpotential of the Oxygen Evolution Reaction by Electrode Surface Modification

    OpenAIRE

    Lu, Cian-Tong; Chiu, Yen-Wen; Li, Mei-Jing; Hsueh, Kan-Lin; Hung, Ju-Shei

    2017-01-01

    Metal–air batteries exhibit high potential for grid-scale energy storage because of their high theoretical energy density, their abundance in the earth’s crust, and their low cost. In these batteries, the oxygen evolution reaction (OER) occurs on the air electrode during charging. This study proposes a method for improving the OER electrode performance. The method involves sequentially depositing a Ni underlayer, Sn whiskers, and a Ni protection layer on the metal mesh. Small and uniform gas ...

  17. Characterisation and surface reactions of iron oxides and fluorapatite in aqueous suspensions

    OpenAIRE

    Jarlbring, Mathias

    2004-01-01

    The final objective of this study is to produce chemical models of flotation- like systems, including oxidation products of magnetite (maghemite and hematite) together with apatite. This is started by investigating the acid base properties, surface complexation and surface characteristics of the systems hematite-H+ and maghemite-H+ (paper I), fluorapatite-OH- (paper II) and a mixed system of maghemite-fluorapatite-OH- (paper III). Synthetic minerals were prepared and characterised with BET, S...

  18. Surface functionalization of graphite and carbon nanotubes by vacuum-ultraviolet photochemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Girard-Lauriault, Pierre-Luc, E-mail: pierre-luc.girard-lauriault@mcgill.ca [BAM Bundesanstalt fuer Materialforschung und - pruefung, D-12203 Berlin (Germany); Department of Chemical Engineering, McGill University, Montreal, H3A 2B2 (Canada); Illgen, Rene [BAM Bundesanstalt fuer Materialforschung und - pruefung, D-12203 Berlin (Germany); Ruiz, Juan-Carlos; Wertheimer, Michael R. [Groupe de Physique et Technologie des Couches Minces (GCM), Department of Engineering Physics, Ecole Polytechnique, Montreal, QC, H3C3A7 (Canada); Unger, Wolfgang E.S. [BAM Bundesanstalt fuer Materialforschung und - pruefung, D-12203 Berlin (Germany)

    2012-09-01

    Highlights: Black-Right-Pointing-Pointer Graphite and CNT surfaces were functionalized by VUV photochemistry in NH{sub 3} or O{sub 2}. Black-Right-Pointing-Pointer Significant amounts of N and O were incorporated at the materials surface. Black-Right-Pointing-Pointer Primary amine and hydroxyl groups were successfully incorporated at the surface. Black-Right-Pointing-Pointer NEXAFS permitted to assess the conservation of the aromatic structure. - Abstract: Graphite and multiwall carbon nanotube surfaces were functionalized by vacuum-ultraviolet induced photochemistry in NH{sub 3} or O{sub 2}, in order to introduce amino- (NH{sub 2}) or hydroxyl (OH) functionalities, respectively. Modified surfaces were characterized by X-ray photoelectron spectroscopy (XPS), which showed significant incorporation of nitrogen (N) and oxygen (O) at the materials' surface. While high-resolution XP spectra did not yield much specific information about the incorporated functional groups, chemical derivatization with 4-trifluoromethyl benzaldehyde and trifluoroacetic anhydride accompanied by XPS enabled quantification of NH{sub 2} and OH groups, respectively. Using near edge X-ray absorption fine structure spectroscopy, we assessed the conservation of the aromatic structure following functionalization treatments.

  19. Magnetohydrodynamic flow of a Casson fluid over an exponentially inclined permeable stretching surface with thermal radiation and chemical reaction

    Directory of Open Access Journals (Sweden)

    P. Bala Anki Reddy

    2016-06-01

    Full Text Available This article investigates the theoretical study of the steady two-dimensional MHD convective boundary layer flow of a Casson fluid over an exponentially inclined permeable stretching surface in the presence of thermal radiation and chemical reaction. The stretching velocity, wall temperature and wall concentration are assumed to vary according to specific exponential form. Velocity slip, thermal slip, solutal slip, thermal radiation, chemical reaction and suction/blowing are taken into account. The proposed model considers both assisting and opposing buoyant flows. The non-linear partial differential equations of the governing flow are converted into a system of coupled non-linear ordinary differential equations by using the similarity transformations, which are then solved numerically by shooting method with fourth order Runge–Kutta scheme. The numerical solutions for pertinent parameters on the dimensionless velocity, temperature, concentration, skin friction coefficient, the heat transfer coefficient and the Sherwood number are illustrated in tabular form and are discussed graphically.

  20. The NO-carbon reaction: the influence of potassium and CO on reactivity and populations of oxygen surface complexes

    Energy Technology Data Exchange (ETDEWEB)

    Diana Lopez; Joseph Calo [Brown University, Providence, RI (United States). Division of Engineering

    2007-08-15

    Results on the effects of a metal catalyst and the role of CO as a reducing agent are reported for a resin char and a Wyodak coal char, as well as demineralized samples of the latter. The effect of an active metal catalyst, such as potassium in the current work, is to significantly increase the reactivity both by increasing the number of reaction sites via the catalyst dispersion and reducing the activation energy and by increasing CO{sub 2} production. The latter is a beneficial result because it means that less carbon is consumed per molecule of NO reduced. Additional CO in the gas phase 'catalyzes' NO reduction via the creation of more labile surface complexes and facilitation of desorption of other oxygen complexes. This effect decreases with an increasing temperature and disappears by about 1123 K. The activation energy of this reaction is comparable to that induced by the metal catalyst. 21 refs., 9 figs., 2 tabs.

  1. Hydrogen adsorption and hydrogen evolution reaction on a polycrystalline Pt electrode studied by surface-enhanced infrared absorption spectroscopy

    International Nuclear Information System (INIS)

    Kunimatsu, Keiji; Senzaki, Takahiro; Samjeske, Gabor; Tsushima, Minoru; Osawa, Masatoshi

    2007-01-01

    Hydrogen evolution reaction (HER) on a polycrystalline Pt electrode has been investigated in Ar-purged acids by surface-enhanced infrared absorption spectroscopy and electrochemical kinetic analysis (Tafel plot). A vibrational mode characteristic to H atom adsorbed at atop sites (terminal H) was observed at 2080-2095 cm -1 . This band appears at 0.1 V (RHE) and grows at more negative potentials in parallel to the increase in hydrogen evolution current. Good signal-to-noise ratio of the spectra enabled us to establish the quantitative relation between the band intensity (equivalently, coverage) of terminal H and the kinetics of HER, from which we conclude that terminal H atom is the reaction intermediate in HER and the recombination of two terminal H atoms is the rate-determining step. The quantitative analysis of the infrared data also revealed that the adsorption of terminal H follows the Frumkin isotherm with repulsive interaction

  2. Modeling the photochemical transformation of nitrobenzene under conditions relevant to sunlit surface waters: Reaction pathways and formation of intermediates.

    Science.gov (United States)

    Vione, Davide; De Laurentiis, Elisa; Berto, Silvia; Minero, Claudio; Hatipoglu, Arzu; Cinar, Zekiye

    2016-02-01

    Nitrobenzene (NB) would undergo photodegradation in sunlit surface waters, mainly by direct photolysis and triplet-sensitized oxidation, with a secondary role of the *OH reaction. Its photochemical half-life time would range from a few days to a couple of months under fair-weather summertime irradiation, depending on water chemistry and depth. NB phototransformation gives phenol and the three nitrophenol isomers, in different yields depending on the considered pathway. The minor *OH role in degradation would make NB unsuitable as *OH probe in irradiated natural water samples, but the selectivity towards *OH could be increased by monitoring the formation of phenol from NB+*OH. The relevant reaction would proceed through ipso-addition of *OH on the carbon atom bearing the nitro-group, forming a pre-reactive complex that would evolve into a transition state (and then into a radical addition intermediate) with very low activation energy barrier. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Modeling convection-diffusion-reaction systems for microfluidic molecular communications with surface-based receivers in Internet of Bio-Nano Things.

    Science.gov (United States)

    Kuscu, Murat; Akan, Ozgur B

    2018-01-01

    We consider a microfluidic molecular communication (MC) system, where the concentration-encoded molecular messages are transported via fluid flow-induced convection and diffusion, and detected by a surface-based MC receiver with ligand receptors placed at the bottom of the microfluidic channel. The overall system is a convection-diffusion-reaction system that can only be solved by numerical methods, e.g., finite element analysis (FEA). However, analytical models are key for the information and communication technology (ICT), as they enable an optimisation framework to develop advanced communication techniques, such as optimum detection methods and reliable transmission schemes. In this direction, we develop an analytical model to approximate the expected time course of bound receptor concentration, i.e., the received signal used to decode the transmitted messages. The model obviates the need for computationally expensive numerical methods by capturing the nonlinearities caused by laminar flow resulting in parabolic velocity profile, and finite number of ligand receptors leading to receiver saturation. The model also captures the effects of reactive surface depletion layer resulting from the mass transport limitations and moving reaction boundary originated from the passage of finite-duration molecular concentration pulse over the receiver surface. Based on the proposed model, we derive closed form analytical expressions that approximate the received pulse width, pulse delay and pulse amplitude, which can be used to optimize the system from an ICT perspective. We evaluate the accuracy of the proposed model by comparing model-based analytical results to the numerical results obtained by solving the exact system model with COMSOL Multiphysics.

  4. Assessment of lead, cadmium, and zinc contamination of roadside soils, surface films, and vegetables in Kampala City, Uganda

    International Nuclear Information System (INIS)

    Nabulo, Grace; Oryem-Origa, Hannington; Diamond, Miriam

    2006-01-01

    The relationship between traffic density and trace metal concentrations in roadside soils, surface films, and a selected vegetable weed, Amaranthus dubius Mart. Ex Thell., was determined in 11 farming sites along major highways around Kampala City in Uganda. Surface soil, atmospherically deposited surface films on windows, and leaves of Amaranthus dubius were sampled at known distances from the roads and analyzed for lead (Pb), zinc (Zn), and cadmium (Cd) using flame atomic absorption spectrophotometry. Atmospherically deposited trace metal particulates were sampled using window glass as an inert, passive collector. Total trace metal concentrations in soils ranged from 30.0±2.3 to 64.6±11.7 mg/kg Pb, 78.4±18.4 to 265.6±63.2 mg/kg Zn, and 0.8±0.13 to 1.40±0.16 mg/kg Cd. Total trace metal levels in soil decreased rapidly with distance from the road. Total Pb decreased with distance up to 30 m from the road, where it reached a background soil concentration of 28 mg/kg dry weight. The study found background values of 50 and 1.4 mg/kg for Zn and Cd in roadside soils, respectively. Similarly, Pb concentration in Amaranthus dubius leaves decreased with increasing distance from the road edge. The dominant pathway for Pb contamination was from atmospheric deposition, which was consistent with Pb concentrations in surface films. The mean Pb concentrations in leaves of roadside crops were higher than those in their respective roots, with the highest leaf-to-root ratio observed in the Brassica oleraceae acephala group. The lowest Pb and Zn concentrations were found in the fruit compared to the leaves of the same crops. Leaves of roadside vegetables were therefore considered a potential source of heavy metal contamination to farmers and consumers in urban areas. It is recommended that leafy vegetables should be grown 30 m from roads in high-traffic, urban areas

  5. Potassium-promoted synthesis of surface formate and reactions of formic acid on Co{10 overline10}

    Science.gov (United States)

    Toomes, R. L.; King, D. A.

    1996-03-01

    A detailed study is presented, using reflection-absorption IR spectroscopy (RAIRS) and thermal desportion spectroscopy (TDS), of the synthesis of surface formate from CO, O 2 and H 2 and of the structure and the reactions of HCOOH with K predosed Co{10 overline10}. The surface formate is readily synthesised at 300 K by exposing a hydrogen and K mixed adlayer to 0.75 L O 2, and then to 2.5 L CO. Using 13C 16O, 18O 2 and D 2 a range of isotopically labelled formates were synthesised. These are used to help identify possible reaction mechanisms: it is shown that one atom from O 2 and one CO molecule contribute to the formation of each surface formate species. The isotopic species also aid in assigning multiple bands observed in the C-H (and C-D) stretching regions of the IR spectra. The adsorption of HCOOH onto multilayer K on Co{10 overline10} at 160 K produces formate, bridge-bound via the O atoms to K, with multiple orientations of the formate ion in a solid formate film. At a K coverage of 0.5 ML, however, the formate is not tilted from the surface normal within the molecular plane. At high HCOOH exposures, undissociated HCOOH is adsorbed, with its molecular plane close to the surface normal. Above 250 K on first layer K HCOOH is desorbed and the formate decomposes to CO, H 2 and atomic O. On the multilayer, a tetradendate oxalate species is formed at ˜ 450 K, and carbonate is formed above 500 K; both decompose to CO and O as the temperature is raised to 660 K.

  6. Real-time monitoring of the progress of polymerization reactions directly on surfaces at open atmosphere by ambient mass spectrometry.

    Science.gov (United States)

    Nørgaard, Asger W; Vaz, Boniek G; Lauritsen, Frants R; Eberlin, Marcos N

    2010-12-15

    The progress of an on-surface polymerization process involving alkyl and perfluoroalkyl silanes and siloxanes was monitored in real-time via easy ambient sonic spray ionization mass spectrometry (EASI-MS). When sprayed on surfaces, the organosilicon compounds present in commercially available nanofilm products (NFPs) react by condensation to form a polymeric coating. A NFP for coating of floor materials (NFP-1) and a second NFP for coating tiles and ceramics (NFP-2) were applied to glass, filter paper or cotton surfaces and the progress of the polymerization was monitored by slowly scanning the surface. Via EASI(+)-MS monitoring, significant changes in the composition of hydrolysates and condensates of 1H,1H,2H,2H-perfluorooctyl triisopropoxysilane (NFP-1) and hexadecyl triethoxysilane (NFP-2) were observed over time. The abundances of the hydrolyzed species decreased compared with those of the non-hydrolysed species for both NFP-1 and NFP-2 and the heavier oligomers became relatively more abundant over a period of 15-20 min. A similar tendency favouring the heavier oligomers was observed via EASI(-)-MS. This work illustrates the potential of ambient mass spectrometry for the direct monitoring of polymerization reactions on surfaces. Copyright © 2010 John Wiley & Sons, Ltd.

  7. Reaction paths of alane dissociation on the Si(0 0 1) surface

    Science.gov (United States)

    Smith, Richard; Bowler, David R.

    2018-03-01

    Building on our earlier study, we examine the kinetic barriers to decomposition of alane, AlH3, on the Si(0 0 1) surface, using the nudged elastic band approach within density functional theory. We find that the initial decomposition to AlH with two H atoms on the surface proceeds without a significant barrier. There are several pathways available to lose the final hydrogen, though these present barriers of up to 1 eV. Incorporation is more challenging, with the initial structures less stable in several cases than the starting structures, just as was found for phosphorus. We identify a stable route for Al incorporation following selective surface hydrogen desorption (e.g. by scanning tunneling microscope tip). The overall process parallels PH3, and indicates that atomically precise acceptor doping should be possible.

  8. Radiation-induced reactions in D, L-α-alanine adsorbed in solid surfaces

    International Nuclear Information System (INIS)

    Aguilar, E; Negrón-Mendoza, A.; Camargo, C.

    2013-01-01

    The aim of this work is to study the behavior under irradiation of D, L and D-L α-alanine adsorbed in solid surfaces, as possible phase in the chemical evolution that may have occurred on the primitive Earth or in extraterrestrial environments and to evaluate the contribution of solids (a clay mineral) as shields for the adsorbed amino acids against a external energy source. The results show that α-alanine is adsorbed in the surfaces as function of pH and its yield of decomposition in mineral suspension is lower than the system without the solid surface. These results show the importance of nuclear techniques in these types of studies. (author)

  9. Permutation invariant potential energy surfaces for polyatomic reactions using atomistic neural networks

    International Nuclear Information System (INIS)

    Kolb, Brian; Zhao, Bin; Guo, Hua; Li, Jun; Jiang, Bin

    2016-01-01

    The applicability and accuracy of the Behler-Parrinello atomistic neural network method for fitting reactive potential energy surfaces is critically examined in three systems, H + H 2 → H 2 + H, H + H 2 O → H 2 + OH, and H + CH 4 → H 2 + CH 3 . A pragmatic Monte Carlo method is proposed to make efficient choice of the atom-centered mapping functions. The accuracy of the potential energy surfaces is not only tested by fitting errors but also validated by direct comparison in dynamically important regions and by quantum scattering calculations. Our results suggest this method is both accurate and efficient in representing multidimensional potential energy surfaces even when dissociation continua are involved.

  10. Investigation of silicate surface chemistry and reaction mechanisms associated with mass transport in geologic media

    International Nuclear Information System (INIS)

    White, A.F.; Perry, D.L.

    1982-01-01

    The concentration and rate of transport of radionuclides through geologic media can be strongly influenced by the extent of sorption on aquifer surfaces. Over time intervals relevant to such transport processes, rock and mineral surfaces cannot be considered as inert, unreactive substrates but rather as groundwater/solidphase interfaces which are commonly in a state of natural or artificially induced disequilibrium. The goal of the present research is to define experimentally the type of water/rock interactions that will influence surface chemistry and hence sorption characteristics and capacities of natural aquifers. As wide a range of silicate minerals as possible was selected for study to represent rock-forming minerals in basalt, tuff, and granite. The minerals include K-feldspar, plagioclase feldspar, olivine, hornblende, biotite, and volcanic glass

  11. [The reaction of human surface and inside body temperature to extreme hypothermia].

    Science.gov (United States)

    Panchenko, O A; Onishchenko, V O; Liakh, Iu Ie

    2011-01-01

    The dynamics of changes in the parameters of the surface and core body temperature under the systematic impact of ultra-low temperature is described in this article. As a source of ultra-low temperature was used (Cryo Therapy Chamber) Zimmer Medizin Systeme firm Zimmer Electromedizin (Germany) (-110 degrees C). Surface and internal body temperature was measured by infrared thermometer immediately before visiting cryochamber and immediately after exiting. In the study conducted 47,464 measurements of body temperature. It was established that the internal temperature of the human body under the influence of ultra-low temperatures in the proposed mode of exposure remains constant, and the surface temperature of the body reduces by an average of 11.57 degrees C. The time frame stabilization of adaptive processes of thermoregulation under the systematic impact of ultra-low temperature was defined in the study.

  12. Feasibility Study of Venus Surface Cooling Using Chemical Reactions with the Atmosphere

    Science.gov (United States)

    Evans, Christopher

    2013-01-01

    A literature search and theoretical analysis were conducted to investigate the feasibility of cooling a craft on Venus through chemical reformation of materials from the atmosphere. The core concept was to take carbon dioxide (CO2) from the Venus atmosphere and chemically reform it into simpler compounds such as carbon, oxygen, and carbon monoxide. This process is endothermic, taking energy from the surroundings to produce a cooling effect. A literature search was performed to document possible routes for achieving the desired reactions. Analyses indicated that on Venus, this concept could theoretically be used to produce cooling, but would not perform as well as a conventional heat pump. For environments other than Venus, the low theoretical performance limits general applicability of this concept, however this approach to cooling may be useful in niche applications. Analysis indicated that environments with particular atmospheric compositions and temperatures could allow a similar cooling system to operate with very good performance. This approach to cooling may also be useful where the products of reaction are also desirable, or for missions where design simplicity is valued. Conceptual designs for Venus cooling systems were developed using a modified concept, in which an expendable reactant supply would be used to promote more energetically favorable reactions with the ambient CO2, providing cooling for a more limited duration. This approach does not have the same performance issues, but the use of expendable supplies increases the mass requirements and limits the operating lifetime. This paper summarizes the findings of the literature search and corresponding analyses of the various cooling options.

  13. A numerical model for chemical reaction on slag layer surface and slag layer behavior in entrained-flow gasifier

    Directory of Open Access Journals (Sweden)

    Liu Sheng

    2013-01-01

    Full Text Available The paper concerns with slag layer accumulation, chemical reaction on slag layer surface, and slag layer flow, heat and mass transfer on the wall of entrained-flow coal gasifier. A slag layer model is developed to simulate slag layer behaviors in the coal gasifier. This 3-D model can predict temperature, slag particle disposition rate, disposition particle composition, and syngas distribution in the gasifier hearth. The model is used to evaluate the effects of O2/coal ratio on slag layer behaviors.

  14. Core-shell Si/Cu nanocomposites synthesized by self-limiting surface reaction as anodes for lithium ion batteries

    Science.gov (United States)

    Xu, Kaiqi; Zhang, Zhizhen; Su, Wei; Huang, Xuejie

    Core-shell Si/Cu nanocomposites were synthesized via a flexible self-limiting surface reaction without extra reductant for the first time. The nano Si was uniformly coated with Cu nanoparticles with a diameter of 5-10nm, which can enhance the electronic conductivity of the nanocomposites and buffer the huge volume change during charge/discharge owing to its high ductility. Benefited from the unique structure, the Si/Cu nanocomposites exhibited a good electrochemical performance as anodes for lithium ion batteries, which exhibited a capacity retention of 656mAh/g after 50 cycles and a coulombic efficiency of more than 99%.

  15. Evidence for surface chemical reactions between gold and BiCaSrCuO

    International Nuclear Information System (INIS)

    Hwu, Y.; Lozzi, L.; La Rosa, S.; Onellion, M.

    1991-01-01

    We explored the reactivity of gold on cleaved 2212 BiCaSrCuO by synchrotron-radiation photoemission spectroscopy. We found no evidence for reactivity when the substrate was at room temperature, similar to what has been reported for very low temperatures (20 K). At intermediate temperatures (100 K), however, clear evidence was found of a chemical reaction with formation of a localized nonmetallic phase. These findings have potentially important implications for the manufacturing of devices based on BiCaSrCuO

  16. Combinatorial Density Functional Theory-Based Screening of Surface Alloys for the Oxygen Reduction Reaction

    DEFF Research Database (Denmark)

    Greeley, Jeffrey Philip; Nørskov, Jens Kehlet

    2009-01-01

    for the ORR but, with few exceptions, they are found to be thermodynamically unstable in the acidic environments typical of low-temperature fuel cells. The results suggest that, absent other thermodynamic or kinetic mechanisms to stabilize the alloys, surface alloys are unlikely to serve as useful ORR......, potential-dependent computational tests of the stability of these alloys in aqueous, acidic environments are presented. These activity and stability criteria are applied to a database of DFT calculations on nearly 750 binary transition metal surface alloys; of these, many are predicted to be active...

  17. Heterogeneous chemical reaction of chlorine nitrate and water on sulfuric-acid surfaces at room temperature

    Science.gov (United States)

    Rossi, Michel J.; Malhotra, Ripudaman; Golden, David M.

    1987-01-01

    The use of H2SO4 as a catalyst for aerosol production of chlorine compounds in the chemistry of the antarctic stratosphere was investigated in laboratory trials. The experiments involved the gas surface collision rate of a molecule on a given surface during its residence time in a Knudsen cell in molecular flow conditions. Chlorine nitrate gas was made to flow through a chamber exposed to a container holding a 95.6 pct H2SO4 solution. Gas leaving the cell was scanned with a mass spectrometer. A sticking coefficient of 0.00032 was found for the chlorine nitrate, a value five times that previously reported.

  18. Temperature dependent halogen activation by N2O5 reactions on halide-doped ice surfaces

    Directory of Open Access Journals (Sweden)

    J. A. Thornton

    2012-06-01

    Full Text Available We examined the reaction of N2O5 on frozen halide salt solutions as a function of temperature and composition using a coated wall flow tube technique coupled to a chemical ionization mass spectrometer (CIMS. The molar yield of photo-labile halogen compounds was near unity for almost all conditions studied, with the observed reaction products being nitryl chloride (ClNO2 and/or molecular bromine (Br2. The relative yield of ClNO2 and Br2 depended on the ratio of bromide to chloride ions in the solutions used to form the ice. At a bromide to chloride ion molar ratio greater than 1/30 in the starting solution, Br2 was the dominant product otherwise ClNO2 was primarily produced on these near pH-neutral brines. We demonstrate that the competition between chlorine and bromine activation is a function of the ice/brine temperature presumably due to the preferential precipitation of NaCl hydrates from the brine below 250 K. Our results provide new experimental confirmation that the chemical environment of the brine layer changes with temperature and that these changes can directly affect multiphase chemistry. These findings have implications for modeling air-snow-ice interactions in polar regions and likely in polluted mid-latitude regions during winter as well.

  19. Temperature dependent halogen activation by N2O5 reactions on halide-doped ice surfaces

    Science.gov (United States)

    Lopez-Hilfiker, F. D.; Constantin, K.; Kercher, J. P.; Thornton, J. A.

    2012-06-01

    We examined the reaction of N2O5 on frozen halide salt solutions as a function of temperature and composition using a coated wall flow tube technique coupled to a chemical ionization mass spectrometer (CIMS). The molar yield of photo-labile halogen compounds was near unity for almost all conditions studied, with the observed reaction products being nitryl chloride (ClNO2) and/or molecular bromine (Br2). The relative yield of ClNO2 and Br2 depended on the ratio of bromide to chloride ions in the solutions used to form the ice. At a bromide to chloride ion molar ratio greater than 1/30 in the starting solution, Br2 was the dominant product otherwise ClNO2 was primarily produced on these near pH-neutral brines. We demonstrate that the competition between chlorine and bromine activation is a function of the ice/brine temperature presumably due to the preferential precipitation of NaCl hydrates from the brine below 250 K. Our results provide new experimental confirmation that the chemical environment of the brine layer changes with temperature and that these changes can directly affect multiphase chemistry. These findings have implications for modeling air-snow-ice interactions in polar regions and likely in polluted mid-latitude regions during winter as well.

  20. High-resolution mass spectrometry for the analysis of interfacial kinetics of organic surface reactions

    NARCIS (Netherlands)

    Sen, Rickdeb

    2017-01-01

    In this thesis, XPS and DART–HRMS have been used in close conjugation to supplement each other, since the latter is a relatively new addition to surface chemist’s repertoire that – after development – needed a firm comparison to build up a reputation of its own. The strength of our approach has

  1. Reaction of Tri-methylaluminum on Si (001) Surface for Initial Aluminum Oxide Thin-Film Growth

    International Nuclear Information System (INIS)

    Kim, Dae Hee; Kim, Dae Hyun; Jeong, Yong Chan; Seo, Hwa Il; Kim, Yeong Cheol

    2010-01-01

    We studied the reaction of tri-methylaluminum (TMA) on hydroxyl (OH)-terminated Si (001) surfaces for the initial growth of aluminum oxide thin-films using density functional theory. TMA was adsorbed on the oxygen atom of OH due to the oxygen atom's lone pair electrons. The adsorbed TMA reacted with the hydrogen atom of OH to produce a di-methylaluminum group (DMA) and methane with an energy barrier of 0.50 eV. Low energy barriers in the range of 0 - 0.11 eV were required for DMA migration to the inter-dimer, intra-dimer, and inter-row sites on the surface. A unimethylaluminum group (UMA) was generated at each site with low energy barriers in the range of 0.21 - 0.25 eV. Among the three sites, the inter-dimer site was the most probable for UMA formation

  2. Incorporating an Inert Polymer into the Interlayer Passivates Surface Defects in Methylammonium Lead Halide Perovskite Solar Cells.

    Science.gov (United States)

    Bi, Shiqing; Zhang, Xuning; Qin, Liang; Wang, Rong; Zhou, Jiyu; Leng, Xuanye; Qiu, Xiaohui; Zhang, Yuan; Zhou, Huiqiong; Tang, Zhiyong

    2017-10-17

    The hysteresis effect and instability are important concerns in hybrid perovskite photovoltaic devices that hold great promise in energy conversion applications. In this study, we show that the power conversion efficiency (PCE), hysteresis, and device lifetime can be simultaneously improved for methylammoniumlead halide (CH 3 NH 3 PbI 3-x Cl x ) solar cells after incorporating poly(methyl methacrylate) (PMMA) into the PC 61 BM electron extraction layer (EEL). By choosing appropriate molecular weights of PMMA, we obtain a 30 % enhancement of PCE along with effectively lowered hysteresis and device degradation, adopting inverted planar device structure. Through the combinatorial study using Kelvin probe force microscopy, diode mobility measurements, and irradiation-dependent solar cell characterization, we attribute the enhanced device parameters (fill factor and open circuit voltage) to the surface passivation of CH 3 NH 3 PbI 3-x Cl x , leading to mitigating charge trapping at the cathode interface and resultant Shockley-Read-Hall charge recombination. Beneficially, modified by inert PMMA, CH 3 NH 3 PbI 3-x Cl x solar cells display a pronounced retardation in performance degradation, resulting from improved film quality in the PC 61 BM layer incorporating PMMA which increases the protection for underneath perovskite films. This work enables a versatile and effective interface approach to deal with essential concerns for solution-processed perovskite solar cells by air-stable and widely accessible materials. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Using Monoclonal Antibody to Determine Lead Ions with a Localized Surface Plasmon Resonance Fiber-optic Biosensor

    Directory of Open Access Journals (Sweden)

    Mon-Fu Chung

    2008-01-01

    Full Text Available A novel reflection-based localized surface plasmon resonance (LSPR fiber-optic probe has been developed to determine the heavy metal lead ion concentration. Monoclonal antibody as the detecting probe containing massive amino groups to capture Pb(II-chelate complexes was immobilized onto gold nanoparticle-modified optical fiber (NMAuOF. The optimal immobilizing conditions of monoclonal antibody on to the NMAuOF are 189 μg/mL in pH7.4 PBS for 2 h at 25°C. The absorbability of the functionalized NMAuOF sensor increases to 12.2 % upon changing the Pb(II-EDTA level from 10 to 100 ppb with a detection limit of 0.27 ppb. The sensor retains 92.7 % of its original activity and gives reproducible results after storage in 5% D-( -Trehalose dehydrate solution at 4°C for 35 days. In conclusion, the monoclonal antibody-functionalized NMAuOF sensor shows a promising result for determining the concentration of Pb(II with high sensitivity.

  4. Adsorption and reaction of trace gas-phase organic compounds on atmospheric water film surfaces: a critical review.

    Science.gov (United States)

    Donaldson, D J; Valsaraj, Kalliat T

    2010-02-01

    The air-water interface in atmospheric water films of aerosols and hydrometeors (fog, mist, ice, rain, and snow) presents an important surface for the adsorption and reaction of many organic trace gases and gaseous reactive oxidants (hydroxyl radical (OH(.)), ozone (O(3)), singlet oxygen (O(2)((1)Delta(g))), nitrate radicals (NO(3)(.)), and peroxy radicals (RO(2)(.)). Knowledge of the air-water interface partition constant of hydrophobic organic species is necessary for elucidating the significance of the interface in atmospheric fate and transport. Various methods of assessing both experimental and theoretical values of the thermodynamic partition constant and adsorption isotherm are described in this review. Further, the reactivity of trace gases with gas-phase oxidants (ozone and singlet oxygen) at the interface is summarized. Oxidation products are likely to be more water-soluble and precursors for secondary organic aerosols in hydrometeors. Estimation of characteristic times shows that heterogeneous photooxidation in water films can compete effectively with homogeneous gas-phase reactions for molecules in the atmosphere. This provides further support to the existing thesis that reactions of organic compounds at the air-water interface should be considered in gas-phase tropospheric chemistry.

  5. Probing the rate-determining region of the potential energy surface for a prototypical ion-molecule reaction.

    Science.gov (United States)

    Xie, Changjian; Liu, Xinguo; Sweeny, Brendan C; Miller, Thomas M; Ard, Shaun G; Shuman, Nicholas S; Viggiano, Albert A; Guo, Hua

    2018-03-13

    We report a joint experimental-theoretical study of the F -  + HCl → HF + Cl - reaction kinetics. The experimental measurement of the rate coefficient at several temperatures was made using the selected ion flow tube method. Theoretical rate coefficients are calculated using the quasi-classical trajectory method on a newly developed global potential energy surface, obtained by fitting a large number of high-level ab initio points with augmentation of long-range electrostatic terms. In addition to good agreement between experiment and theory, analyses suggest that the ion-molecule reaction rate is significantly affected by shorter-range interactions, in addition to the traditionally recognized ion-dipole and ion-induced dipole terms. Furthermore, the statistical nature of the reaction is assessed by comparing the measured and calculated HF product vibrational state distributions to that predicted by the phase space theory.This article is part of the theme issue 'Modern theoretical chemistry'. © 2018 The Author(s).

  6. Optimization of Maillard reaction with ribose for enhancing anti-allergy effect of fish protein hydrolysates using response surface methodology.

    Science.gov (United States)

    Yang, Sung-Yong; Kim, Se-Wook; Kim, Yoonsook; Lee, Sang-Hoon; Jeon, Hyeonjin; Lee, Kwang-Won

    2015-06-01

    Halibut is served on sushi and as sliced raw fish fillets. We investigated the optimal conditions of the Maillard reaction (MR) with ribose using response surface methodology to reduce the allergenicity of its protein. A 3-factored and 5-leveled central composite design was used, where the independent variables were substrate (ribose) concentration (X1, %), reaction time (X2, min), and pH (X3), while the dependent variables were browning index (Y1, absorbance at 420nm), DPPH scavenging (Y2, EC50 mg/mL), FRAP (Y3, mM FeSO4/mg extract) and β-hexosaminidase release (Y4, %). The optimal conditions were obtained as follows: X1, 28.36%; X2, 38.09min; X3, 8.26. Maillard reaction products of fish protein hydrolysate (MFPH) reduced the amount of nitric oxide synthesis compared to the untreated FPH, and had a significant anti-allergy effect on β-hexosaminidase and histamine release, compared with that of the FPH control. We concluded that MFPH, which had better antioxidant and anti-allergy activities than untreated FPH, can be used as an improved dietary source. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Chemical reaction effect on MHD free convective surface over a moving vertical plate through porous medium

    Directory of Open Access Journals (Sweden)

    R.S. Tripathy

    2015-09-01

    Full Text Available An attempt has been made to study the heat and mass transfer effect in a boundary layer flow of an electrically conducting viscous fluid subject to transverse magnetic field past over a moving vertical plate through porous medium in the presence of heat source and chemical reaction. The governing non-linear partial differential equations have been transformed into a two-point boundary value problem using similarity variables and then solved numerically by fourth order Runge–Kutta fourth order method with shooting technique. Graphical results are discussed for non-dimensional velocity, temperature and concentration profiles while numerical values of the skin friction, Nusselt number and Sherwood number are presented in tabular form for various values of parameters controlling the flow system.

  8. Surface Induced Dissociations and Reactions of Acetonitrile Monomer, Dimer and Trimer Ions

    Czech Academy of Sciences Publication Activity Database

    Mair, C.; Herman, Zdeněk; Fedor, J.; Lezius, M.; Märk, T. D.

    2003-01-01

    Roč. 118, č. 3 (2003), s. 1479-1486 ISSN 0021-9606 R&D Projects: GA ČR GA203/00/0632 Grant - others:Cooperation PST(AT) 2000-06 Institutional research plan: CEZ:AV0Z4040901 Keywords : surface-induced * acetonitrile monomer * trimer ions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.950, year: 2003

  9. Photocatalytic Reaction of Gas-Phase Naphthalene on Paint- and Sunscreen-Coated Surfaces

    OpenAIRE

    Ashley, Nicholas A.; McBride, Noelle; Krumholt, Jason; Baker, Breeana; Valsaraj, Kalliat T.

    2012-01-01

    The uses of metal oxide nanoparticles in modern paint and sunscreen formulations are widespread. Through materials characterization and kinetic experiments, it is demonstrated that fresh surface coatings of paint and sunscreen photocatalytically degrade gaseous naphthalene. The primary metal oxides are TiO2 in the form of the rutile phase in paint and as anatase in sunscreen formulations. Other metal oxides present are Al2O3 and ZnO. Several organic fillers that are photochemically active are...

  10. Sulfur dioxide reactions on ice surfaces: Implications for dry deposition to snow

    Science.gov (United States)

    Martha H. Conklin; Richard A. Sommerfeld; S. Kay Laird; John E. Villinski

    1993-01-01

    Controlled exposure of ice to a reactive gas, SO2, demonstrated the importance of the chemical composition of the ice surface on the accumulation of acidity in snow. In a series of bench-scale continuous-flow column experiments run at four temperatures (-1, -8, -30 and -60°C), SO2 was shown to dissolve and to react with other species in the ice-air interfacial region...

  11. Numerical study of the influence of surface reaction probabilities on reactive species in an rf atmospheric pressure plasma containing humidity

    Science.gov (United States)

    Schröter, Sandra; Gibson, Andrew R.; Kushner, Mark J.; Gans, Timo; O’Connell, Deborah

    2018-01-01

    The quantification and control of reactive species (RS) in atmospheric pressure plasmas (APPs) is of great interest for their technological applications, in particular in biomedicine. Of key importance in simulating the densities of these species are fundamental data on their production and destruction. In particular, data concerning particle-surface reaction probabilities in APPs are scarce, with most of these probabilities measured in low-pressure systems. In this work, the role of surface reaction probabilities, γ, of reactive neutral species (H, O and OH) on neutral particle densities in a He–H2O radio-frequency micro APP jet (COST-μ APPJ) are investigated using a global model. It is found that the choice of γ, particularly for low-mass species having large diffusivities, such as H, can change computed species densities significantly. The importance of γ even at elevated pressures offers potential for tailoring the RS composition of atmospheric pressure microplasmas by choosing different wall materials or plasma geometries.

  12. Field emission techniques for studying surface reactions: applying them to NO-H2 interaction with Pd tips.

    Science.gov (United States)

    Visart de Bocarmé, T; Kruse, Norbert

    2011-05-01

    The adsorption of NO and its reaction with H(2) over Pd tips were investigated by means of field ion microscopy (FIM) and pulsed field desorption mass spectrometry (PFDMS) in the 10(-3)Pa pressure range and at sample temperatures between 400 and 600K. By varying the H(2) partial pressure while keeping the other control parameters constant, the NO+H(2) reaction over Pd crystallites is shown to exhibit a strong hysteresis effect. The hysteresis region narrows with increase in temperature and the H(2) pressures delimiting this hysteresis decrease as well. Abrupt transformations of the micrographs are observed by FIM from bright to dark patterns and vice versa. These transformations define the hysteresis region. The collected data allow establishing a novel kinetic phase diagram of the NO+H(2)/Pd system within the range of temperatures and pressures indicated. The observed features are correlated with a local chemical analysis by means of field pulses. NO(+) seems to be the dominating imaging species under all conditions. At high relative H(2) pressures (the "hydrogen-side"), H atoms seem to diffuse subsurface. This process is blocked at lower H(2) pressure (the "NO-side") due to NO(ad) and O(ad) accumulation on the surface. Probe-hole measurements with field pulses indicate that the Pd surface undergoes oxidation as revealed by the occurrence of PdO(2)(+) species in the mass spectra. Copyright © 2010 Elsevier B.V. All rights reserved.

  13. Investigation of the rates of surface and bulk ROS-generating reactions using indigo dye as an indicator

    Science.gov (United States)

    Anderson, Carly; Clark, Douglas; Graves, David

    2014-10-01

    We present evidence for the existence of two distinct processes that contribute to the generation of reactive oxygen and nitrogen species (RONS) in liquids exposed to cold atmospheric plasma (CAP) in air. At the plasma-liquid interface, there exists a fast surface reaction zone where RONS from the gas phase interact with species in the liquid. RONS can also be produced by ``slow'' chemical reactions in the bulk liquid, even long after plasma exposure. To separate the effects of these processes, we used indigo dye as an indicator of ROS production; specifically generation of hydroxyl radical. The rate of indigo decolorization while in direct contact with CAP is compared with the expected rate of hydroxyl radical generation at the liquid surface. When added to aqueous solutions after CAP exposure, indigo dye reacts on a time scale consistent with the production of peroxynitrous acid, ONOOH, which is known to decompose to hydroxyl radical below a pH of 6.8. In this study, the CAP used was a air corona discharge plasma run in a positive streamer mode.

  14. Surface patterning with natural and synthetic polymers via an inverse electron demand Diels-Alder reaction employing microcontact chemistry.

    Science.gov (United States)

    Roling, Oliver; Mardyukov, Artur; Lamping, Sebastian; Vonhören, Benjamin; Rinnen, Stefan; Arlinghaus, Heinrich F; Studer, Armido; Ravoo, Bart Jan

    2014-10-21

    Bioorthogonal ligation methods are the focus of current research due to their versatile applications in biotechnology and materials science for post-functionalization and immobilization of biomolecules. Recently, inverse electron demand Diels-Alder (iEDDA) reactions employing 1,2,4,5-tetrazines as electron deficient dienes emerged as powerful tools in this field. We adapted iEDDA in microcontact chemistry (μCC) in order to create enhanced surface functions. μCC is a straightforward soft-lithography technique which enables fast and large area patterning with high pattern resolutions. In this work, tetrazine functionalized surfaces were reacted with carbohydrates conjugated with norbornene or cyclooctyne acting as strained electron rich dienophiles employing μCC. It was possible to create monofunctional as well as bifunctional substrates which were specifically addressable by proteins. Furthermore we structured glass supported alkene terminated self-assembled monolayers with a tetrazine conjugated atom transfer radical polymerization (ATRP) initiator enabling surface grafted polymerizations of poly(methylacrylate) brushes. The success of the surface initiated iEDDA via μCC as well as the functionalization with natural and synthetic polymers was verified via fluorescence and optical microscopy, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), atomic force microscopy (AFM) and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR).

  15. Surface analysis of topmost layer of epitaxial layered oxide thin film: Application to delafossite oxide for oxygen evolution reaction

    Science.gov (United States)

    Toyoda, Kenji; Adachi, Hideaki; Miyata, Nobuhiro; Hinogami, Reiko; Orikasa, Yuki; Uchimoto, Yoshiharu

    2018-02-01

    Delafossite oxides (ABO2) have a layered structure with alternating layers of A and B elements, the topmost layer of which appears to determine their performance, such as the oxygen evolution reaction (OER) activity. In this study, we investigated the topmost layer of single-domain (0 0 1)-oriented AgCoO2 epitaxial thin film for potential use as an OER catalyst. The thin film was confirmed to possess OER activity at a level comparable to the catalyst in powder form. Atomic scattering spectroscopy revealed the topmost layer to be composed of CoO6 octahedra. In situ X-ray absorption spectroscopy showed that the oxidation of Co at the surface did not change under different potentials, which suggests that there is no valence fluctuation of Co in the stable CoO6 octahedral structure. However, the oxidation number of Co at the surface was lower than that in the bulk. Our density functional theoretical calculations also showed the Co atoms at the surface to have a slightly higher electron occupancy than those in the bulk, and suggests that the unoccupied t2g states of Co at the surface have an influence on OER activity.

  16. Hydrogen Evolution Reaction Property in Alkaline Solution of Molybdenum Disulfide Modified by Surface Anchor of Nickel–Phosphorus Coating

    Directory of Open Access Journals (Sweden)

    Jun He

    2017-06-01

    Full Text Available Molybdenum disulfide (MoS2 is unfavorable for practical application in the hydrogen evolution reaction (HER process due to its inert basal surface, inferior conductivity, and limited amount of active edge sites. For the purpose of enhancing the HER performance of this catalyst, the HER activity of its basal surface should be increased. Herein, three types of nickel-phosphorus (Ni–P coatings—namely, low phosphorus (LP, medium phosphorus (MP and high phosphorus (HP —were anchored onto the surfaces of MoS2 nanoparticles via an electroless plating process; thus, three Ni–P/MoS2 composites (Ni–LP/MoS2, Ni–MP/MoS2, and Ni–HP/MoS2 were fabricated. Crystal structures, morphologies, chemical components, and HER performances of each in an alkaline solution were characterized. Both Ni–LP/MoS2 and Ni–MP/MoS2 showed a crystal nature, while the amorphous feature for Ni–HP/MoS2 was validated. The three Ni–P/MoS2 composites exhibited a higher HER activity than the pure MoS2. The HER performance of the Ni–MP/MoS2 composite was more outstanding than those of other two composites, which could be attributed to the presence of metastable nickel phosphides, and the excellent conductivity of Ni–MP coating anchored on the basal surface of MoS2.

  17. Kinetics of electrochemically controlled surface reactions on bulk and thin film metals studied with Fourier transform impedance spectroscopy and surface plasmon resonance techniques

    Science.gov (United States)

    Assiongbon, Kankoe A.

    2005-07-01

    In the work presented in this thesis, the surface sensitive electrochemical techniques of cyclic voltametry (CV), potential step (PS) and Fourier transform impedance spectroscopy (FT-EIS), as well as the optical technique of surface plasmon resonance (SPR), were used to probe a wide variety of surface processes at various metal/liquid interface. Three polycrystalline metals (Au, Ta and Cu) and a Cr-coated gold film were used for these studies in different aqueous environments. A combination of CV with FT-EIS and PS was used to investigate electronic and structural proprieties of a modified bulk electrode of Au. This experimental system involved under potential deposition (UPD) of Bi3+ on Au in a supporting aqueous electrolyte containing ClO-4 . UPD range of Bi3+ was determined, and adsorption kinetics of Bi3+ in the presence of coadsorbing anion, ClO-4 were quantified. Potentiodynamic growth of oxide films of Ta in the following electrolytes NaNO3, NaNO3 + 5wt% H2O2, NaOH and NaOH + 5wt% H2O2 had been investigated. The oxide films were grown in the range -0.1 → +0.4V (high electric field) at a scan rate of 10 mV/s. Time resolved A.C. impedance spectroscopy measurements in the frequency range (0.1--20 KHz) were performed to characterize the surface reactions of oxide formation. The results are interpreted in terms of charge conductivity O2- through the oxide film, and disintegration of H2O2 into OH-. In a high pH medium (pH 12), dissociation of H2O2 was catalytically enhanced. This led to destabilization of the electrogenerated tantalum oxide surface film in the form of a soluble hexatantalate species. In contrast with the electrolytes, NaNO3, NaNO3 + 5wt% H2O2, NaOH, where only the oxide growth was observed, the A.C. impedance spectroscopy measurements in NaOH + 5wt% H 2O2 showed competition between oxide formation and its removal. These results are relevant for chemical slurry design in chemical mechanical polishing (CMP) of Ta. Further investigations were

  18. Correlation of Growth and Surface Properties of Poly(\\(p\\-xylylenes to  Reaction Conditions

    Directory of Open Access Journals (Sweden)

    Andreas Reichel

    2015-05-01

    Full Text Available Parylene, a non-critical, non-toxic layer material, which is not only a candidate for low-\\(K\\ dielectrics, but also well suited for long-term applications in the human body, has been deposited by (plasma-enhanced chemical vapor deposition of the monomeric species. To that end, a specially-designed reactor exhibiting a cracker tube at its entrance, which serves as the upstream control, and a cooling trap in front of the downstream control has been applied. The process of polymerization has been traced and is explained by evaporating the dimeric species followed by dissociation in the cracker at elevated temperatures and, eventually, to the coating of the polymeric film in terms of thermodynamics. Alternatively, the process of dissociation has been accomplished applying a microwave plasma. In both cases, the monomerization is controlled by mass spectrometry. The window for surface polymerization could be clearly defined in terms of a factor of dilution by an inert gas for the chemical vapor deposition (CVD case and in the case of plasma-enhanced chemical vapor deposition (PECVD, additionally by the power density. The characterization of the layer parameters has been carried out by several analytical tools: scanning electron microscopy and atomic force microscopy to determine the surface roughness and density and depth of voids in the film, which influence the layer capacitance and deteriorate the breakdown voltage, a bulk property. The main issue is the conduct against liquids between the two borders' hydrophilic and hydrophobic conduct, but also the super-hydrophobic character, which is the condition for the Lotus effect. The surface tension has been evaluated by contact angle measurements. Fourier-transform infrared spectroscopy has proven the conservation of all of the functional groups during polymerization.

  19. Reaction probability of molecular deuterium with a disordered InSb (110) surface

    International Nuclear Information System (INIS)

    Wolf, B.; Zehe, A.

    1987-01-01

    A detailed experimental analysis of the interaction of molecular deuterium with sputter-damaged InSb surfaces by the aid of SIMS is given. The sticking probability of D 2 and its transformation to a chemisorbed state resulting in InD + signals in SIMS measurements can be determined by adsorption experimens both with and without a hot tungsten filament. The calculated sticking probability of D 2 = 2 x 10 -4 is at least three orders of magnitude higher than the known-value for a cleavage plane of InSb

  20. Transition state determination of enzyme reaction on free energy surface: Application to chorismate mutase

    Science.gov (United States)

    Higashi, Masahiro; Hayashi, Shigehiko; Kato, Shigeki

    2007-04-01

    The transition state on the free energy surface for Claisen rearrangement of chorismate in Bacillus subtilis chorismate mutase is calculated with a method based on a linear response theory. The calculated activation free energy is 16.9 kcal/mol, which is in good agreement with the experimental one. The catalytic ability of the enzyme is examined by comparing the activation barrier with that in aqueous solution and found to be mainly attributed to the conformational restriction of the substrate. We also calculate the kinetic isotope effects, which are in accord with the experimental estimates.

  1. Nanostructured silver for applications in surface enhanced Raman spectroscopy and photoelectrochemical reactions

    Science.gov (United States)

    Clayton, Daniel A.

    Initial work focused on characterizing silver and its surface enhanced Raman spectroscopy (SERS) capabilities. Silver nanowires were chosen as an ideal material and scanning confocal microscopy studies were performed to identify hot spots. The silver nanowires were found to exhibit fluorescence blinking that was attributed to small silver clusters undergoing rapid interchange from Ag0 to Ag2O. Control of this blinking was accomplished through the removal of oxygen and through electrochemical control of the system. SERS was also recorded from these nanowires. Deconvolution of the SERS signal from the fluorescence was accomplished either by increasing the SERS analyte concentration or increasing the total number of "hot spots" in the focus volume. Silver applications were studied by performing a SERS study of Rhodamine 6G (R6G) and Poly(3-hexylthiophene-2,5-diyl) (P3HT). A Tollens' silver substrate was utilized as the SERS substrate and similar blinking effects were found to arise. P3HT was cast from 4 different solvents:dichloromethane, chlorobenzene, THF, and toluene. The solvent effects were studied, with kinking of the polymer noted in the non-chlorinated solvents. Single molecule studies in conjunction with polarization control indicated that the P3HT formed in an overlapping manner with only partial charge transfer within the molecule. Finally silvers interactions with TiO2 were studied. Micron scale single crystal anatase TiO2 was synthesized by using HF in a hydrothermal process forming a truncated bipyramidal structure consisting of [101] and [001] faces. Fluorine was present in small amounts on the surface of the TiO2 as confirmed by x-ray photoelectron spectroscopy (XPS). An annealing process was used to remove the fluorine. Nitrogen doping was attempted, but was not found to occur in significant amounts. Visible light sensitivity was noted in annealed samples but did not occur in the bulk as demonstrated through photoelectrochemical measurements. Silver

  2. Development of a chemical kinetic measurement apparatus and the determination of the reaction rate constants for lithium-lead/water interaction

    International Nuclear Information System (INIS)

    Biney, P.O.

    1993-04-01

    An experimental set-up for accurate measurement of hydrogen generation rate in Lithium-Lead (Li 17 Pb 83 ) Steam or water interactions has been designed. The most important features of the design include a pneumatic actuated quick opening and closing high temperature all stainless steel valve used to control the reaction time and the placement of most measuring devices below a water line to minimize leakage of the hydrogen collected. A PC based data acquisition and control system provides remote process sequencing, acquisition and control of all major components of the set-up. Initial tests indicate that the first design objective of maintaining leakproof gas collection chamber has been achieved. Initial pressure tests indicated that the pressure drop over a time span of 30 minutes was within the tolerance of the pressure transducer used to measure the pressure (within 0.690 kPa) at a nominal system pressure of 685 kPa. The experimental system hardware, data acquisition and control programs and data analysis program have been completed, tested and are currently functional

  3. Palladium-Catalyzed Reductive Coupling Reaction of Terminal Alkynes with Aryl Iodides Utilizing Hafnocene Difluoride as a Hafnium Hydride Precursor Leading to trans-Alkenes.

    Science.gov (United States)

    Takahashi, Keita; Ogiwara, Yohei; Sakai, Norio

    2018-01-26

    Herein, we describe a reductive cross-coupling of alkynes and aryl iodides by using a novel catalytic system composed of a catalytic amount of palladium dichloride and a promoter precursor, hafnocene difluoride (Cp 2 HfF 2 , Cp=cyclopentadienyl anion), in the presence of a mild reducing reagent, a hydrosilane, leading to a one-pot preparation of trans-alkenes. In this process, a series of coupling reactions efficiently proceeds through the following three steps: (i) an initial formation of hafnocene hydride from hafnocene difluoride and the hydrosilane, (ii) a subsequent hydrohafnation toward alkynes, and (iii) a final transmetalation of the alkenyl hafnium species to a palladium complex. This reductive coupling could be chemoselectively applied to the preparation of trans-alkenes with various functional groups, such as an alkyl group, a halogen, an ester, a nitro group, a heterocycle, a boronic ester, and an internal alkyne. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Unraveling the Role of Transport, Electrocatalysis, and Surface Science in the Solid Oxide Fuel Cell Cathode Oxygen Reduction Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Gopalan, Srikanth [Boston Univ., MA (United States)

    2017-04-06

    This final report for project FE0009656 covers the period from 10/01/2012 to 09/30/2015 and covers research accomplishments on the effects of carbon dioxide on the surface composition and structure of cathode materials for solid oxide fuel cells (SOFCs), specifically La1-xSrxFeyCo1- yO3-δ (LSCF). Epitaxially deposited thin films of LSCF on various single-crystal substrates have revealed the selective segregation of strontium to the surface thereby resulting in a surface enrichment of strontium. The near surface compositional profile in the films have been measured using total x-ray fluorescence (TXRF), and show that the kinetics of strontium segregation are higher at higher partial pressures of carbon dioxide. Once the strontium segregates to the surface, it leads to the formation of precipitates of SrO which convert to SrCO3 in the presence of even modest concentrations of carbon dioxide in the atmosphere. This has important implications for the performance of SOFCs which is discussed in this report. These experimental observations have also been verified by Density Functional Theory calculations (DFT) which predict the conditions under which SrO and SrCO3 can occur in LSCF. Furthermore, a few cathode compositions which have received attention in the literature as alternatives to LSCF cathodes have been studied in this work and shown to be thermodynamically unstable under the operating conditions of the SOFCs.

  5. Surface structure-dependent pyrite oxidation in relatively dry and moist air: Implications for the reaction mechanism and sulfur evolution

    Science.gov (United States)

    Zhu, Jianxi; Xian, Haiyang; Lin, Xiaoju; Tang, Hongmei; Du, Runxiang; Yang, Yiping; Zhu, Runliang; Liang, Xiaoliang; Wei, Jingming; Teng, H. Henry; He, Hongping

    2018-05-01

    Pyrite oxidation not only is environmentally significant in the formation of acid mine (or acid rock) drainage and oxidative acidification of lacustrine sediment but also is a critical stage in geochemical sulfur evolution. The oxidation process is always controlled by the reactivity of pyrite, which in turn is controlled by its surface structure. In this study, the oxidation behavior of naturally existing {1 0 0}, {1 1 1}, and {2 1 0} facets of pyrite was investigated using a comprehensive approach combining X-ray photoelectron spectroscopy, diffuse reflectance Fourier transform infrared spectroscopy, and time-of-flight secondary-ion mass spectrometry with periodic density functional theoretical (DFT) calculations. The experimental results show that (i) the initial oxidation rates of both pyrite {1 1 1} and {2 1 0} are much greater than that of pyrite {1 0 0}; (ii) the initial oxidation rate of pyrite {2 1 0} is greater than that of pyrite {1 1 1} in low relative humidity, which is reversed in high relative humidity; and (iii) inner sphere oxygen-bearing sulfur species are originally generated from surface reactions and then converted to outer sphere species. The facet dependent rate law can be expressed as: r{hkl} =k{hkl}haP0.5(t + 1) - 0.5 , where r{hkl} is the orientation dependent reaction rate, k{hkl} is the orientation dependent rate constant, h is the relative humidity, P is the oxygen partial pressure, and t is the oxidation time in seconds. {1 1 1} is the most sensitive facet for pyrite oxidation. Combined with DFT theoretical investigations, water catalyzed electron transfer is speculated as the rate-limiting step. These findings disclose the structure-reactivity dependence of pyrite, which not only presents new insight into the mechanism of pyrite oxidation but also provides fundamental data to evaluate sulfur speciation evolution, suggesting that the surface structure sensitivity should be considered to estimate the reactivity at the mineral

  6. Controlling successive ionic layer absorption and reaction cycles to optimize silver nanoparticle-induced localized surface plasmon resonance effects on the paper strip

    Science.gov (United States)

    Lee, Jae-Chul; Kim, Wansun; Park, Hun-Kuk; Choi, Samjin

    2017-03-01

    This study investigates why a silver nanoparticle (SNP)-induced surface-enhanced Raman scattering (SERS) paper chip fabricated at low successive ionic layer absorption and reaction (SILAR) cycles leads to a high SERS enhancement factor (7 × 108) with an inferior nanostructure and without generating a hot spot effect. The multi-layered structure of SNPs on cellulose fibers, verified by magnified scanning electron microscopy (SEM) and analyzed by a computational simulation method, was hypothesized as the reason. The pattern of simulated local electric field distribution with respect to the number of SILAR cycles showed good agreement with the experimental Raman intensity, regardless of the wavelength of the excitation laser sources. The simulated enhancement factor at the 785-nm excitation laser source (2.8 × 109) was 2.5 times greater than the experimental enhancement factor (1.1 × 109). A 532-nm excitation laser source exhibited the highest maximum local electric field intensity (1.9 × 1011), particularly at the interparticle gap called a hot spot. The short wavelength led to a strong electric field intensity caused by strong electromagnetic coupling arising from the SNP-induced local surface plasmon resonance (LSPR) effects through high excitation energy. These findings suggest that our paper-based SILAR-fabricated SNP-induced LSPR model is valid for understanding SNP-induced LSPR effects.

  7. Decreased blood hepatitis B surface antibody levels linked to e-waste lead exposure in preschool children

    International Nuclear Information System (INIS)

    Xu, Xijin; Chen, Xiaojuan; Zhang, Jian; Guo, Pi; Fu, Tingzao; Dai, Yifeng; Lin, Stanley L.; Huo, Xia

    2015-01-01

    Highlights: • Secondary exploratory analyses displayed a correlation of blood Pb to HBsAb levels. • Generalized linear mixed models were used to analyze two-phase data. • Children from an e-waste area had higher blood Pb levels and lower HBsAb titers. • Nearly 50% of Pb-exposed children fail to develop sufficient HBV immunity. • Different vaccination strategies are required for in e-waste areas. - Abstract: Lead (Pb) is a widespread environmental contaminant that can profoundly affect the immune system in vaccinated children. To explore the association between blood Pb and HBsAb levels in children chronically exposed to Pb, we measured hepatitis B surface antibody (HBsAb) titers, to reflect the immune response in the children of Guiyu, an electronic and electrical waste (e-waste) recycling area well known for environmental Pb contamination. We performed secondary exploratory analyses of blood Pb levels and plasma HBsAb titers in samples, taken in two phases between 2011 and 2012, from 590 children from Guiyu (exposed group) and Haojiang (reference group). Children living in the exposed area had higher blood Pb levels and lower HBsAb titers compared with children from the reference area. At each phase, generalized linear mixed models (GLMMs) showed that HBsAb titers were significantly negatively associated with child blood Pb levels. This work shows that a decreased immune response to hepatitis B vaccine and immune system might have potential harm to children with chronic Pb exposure. Importantly, nearly 50% of chronically exposed children failed to develop sufficient immunity to hepatitis in response to vaccination. Thus different vaccination strategies are needed for children living under conditions of chronic Pb exposure

  8. Decreased blood hepatitis B surface antibody levels linked to e-waste lead exposure in preschool children

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Xijin [Laboratory of Environmental Medicine and Developmental Toxicology, and Guangdong Provincial Key Laboratory of Infectious Diseases, Shantou University Medical College, Shantou 515041, Guangdong (China); Department of Cell Biology and Genetics, Shantou University Medical College, Shantou 515041, Guangdong (China); Chen, Xiaojuan; Zhang, Jian [Laboratory of Environmental Medicine and Developmental Toxicology, and Guangdong Provincial Key Laboratory of Infectious Diseases, Shantou University Medical College, Shantou 515041, Guangdong (China); Guo, Pi [Department of Public Health, Shantou University Medical College, Shantou 515041, Guangdong (China); Fu, Tingzao; Dai, Yifeng [Laboratory of Environmental Medicine and Developmental Toxicology, and Guangdong Provincial Key Laboratory of Infectious Diseases, Shantou University Medical College, Shantou 515041, Guangdong (China); Lin, Stanley L. [Department of Pathophysiology and Key Immunopathology Laboratory of Guangdong Province, Shantou University Medical College, Shantou 515041, Guangdong (China); Huo, Xia, E-mail: xhuo@stu.edu.cn [Laboratory of Environmental Medicine and Developmental Toxicology, and Guangdong Provincial Key Laboratory of Infectious Diseases, Shantou University Medical College, Shantou 515041, Guangdong (China)

    2015-11-15

    Highlights: • Secondary exploratory analyses displayed a correlation of blood Pb to HBsAb levels. • Generalized linear mixed models were used to analyze two-phase data. • Children from an e-waste area had higher blood Pb levels and lower HBsAb titers. • Nearly 50% of Pb-exposed children fail to develop sufficient HBV immunity. • Different vaccination strategies are required for in e-waste areas. - Abstract: Lead (Pb) is a widespread environmental contaminant that can profoundly affect the immune system in vaccinated children. To explore the association between blood Pb and HBsAb levels in children chronically exposed to Pb, we measured hepatitis B surface antibody (HBsAb) titers, to reflect the immune response in the children of Guiyu, an electronic and electrical waste (e-waste) recycling area well known for environmental Pb contamination. We performed secondary exploratory analyses of blood Pb levels and plasma HBsAb titers in samples, taken in two phases between 2011 and 2012, from 590 children from Guiyu (exposed group) and Haojiang (reference group). Children living in the exposed area had higher blood Pb levels and lower HBsAb titers compared with children from the reference area. At each phase, generalized linear mixed models (GLMMs) showed that HBsAb titers were significantly negatively associated with child blood Pb levels. This work shows that a decreased immune response to hepatitis B vaccine and immune system might have potential harm to children with chronic Pb exposure. Importantly, nearly 50% of chronically exposed children failed to develop sufficient immunity to hepatitis in response to vaccination. Thus different vaccination strategies are needed for children living under conditions of chronic Pb exposure.

  9. Diagnosing the leading mode of interdecadal covariability between the Indian Ocean sea surface temperature and summer precipitation in southern China

    Science.gov (United States)

    Liu, Jingpeng; Ren, Hong-Li; Li, Weijing; Zuo, Jinqing

    2018-03-01

    Precipitation in southern China during boreal summer (June to August) shows a substantial interdecadal variability on the timescale longer than 8 years. In this study, based on the analysis of singular value decomposition, we diagnose the leading mode of interdecadal covariability between the observational precipitation in southern China and the sea surface temperature (SST) in the Indian Ocean. Results indicate that there exist a remarkable southern China zonal dipole (SCZD) pattern of interdecadal variability of summer precipitation and an interdecadal Indian Ocean basin mode (ID-IOBM) of SST. It is found that the SCZD is evidently covaried with the ID-IOBM, which may induce anomalous inter-hemispheric vertical circulation and atmospheric Kelvin waves. During the warm phase of the ID-IOBM, an enhanced lower-level convergence and upper-level divergence exist over the tropical Indian Ocean, which is a typical Gill-Matsuno-type response to the SST warming. Meanwhile, the accompanied upper-level outflow anomalies further converge over the Indo-China peninsula, resulting in a lower-level anticyclone that contributes to reduction of the eastward moisture transport from the Bay of Bengal to the west part of southern China. In addition, the Kelvin wave-like pattern, as a response of the warm ID-IOBM phase, further induces the lower-level anticyclonic anomaly over the South China Sea-Philippines. Such an anticyclonic circulation is favorable for more water vapor transport from the East China Sea into the east part of southern China. Therefore, the joint effects of the anomalous inter-hemispheric vertical circulation and the Kelvin wave-like pattern associated with the ID-IOBM may eventually play a key role in generating the SCZD pattern.

  10. Transtendon rotator-cuff repair of partial-thickness articular surface tears can lead to medial rotator-cuff failure

    Directory of Open Access Journals (Sweden)

    Woods TC

    2014-06-01

    Full Text Available Tom C Woods,4 Michael J Carroll,1 Atiba A Nelson,2 Kristie D More,2 Randa Berdusco,1 Stephen Sohmer,3 Richard S Boorman,1,2 Ian KY Lo1,21Department of Surgery, 2Sport Medicine Centre, University of Calgary, Calgary, AB, Canada; 3Department of Orthopaedics, University of British Columbia, Vancouver, 4St Joseph's Hospital, Comox, BC, CanadaPurpose: The purpose of this study was to evaluate clinical and anatomic outcomes of patients following transtendon rotator-cuff repair of partial articular supraspinatus tendon avulsion (PASTA lesions.Patients and methods: Patients in the senior author's practice who had isolated PASTA lesions treated by transtendon rotator-cuff repair were included (n=8 and retrospectively reviewed. All patients were evaluated preoperatively and at a mean of 21.2 months (±9.7 months postoperatively using standardized clinical evaluation (physical exam, American Shoulder and Elbow Surgeons, and Simple Shoulder Test. All patients underwent postoperative imaging with a magnetic resonance imaging arthrogram.Results: There was a significant improvement in American Shoulder and Elbow Surgeons (42.7±17.5 to 86.9±25.2 and Simple Shoulder Test (4.6±3.2 to 10.1±3.8 scores from pre- to postoperative, respectively. Postoperative imaging demonstrated full-thickness medial cuff tearing in seven patients, and one patient with a persistent partial articular surface defect.Conclusion: Transtendon repair of PASTA lesions may lead to improvements in clinical outcome. However, postoperative imaging demonstrated a high incidence of full-thickness rotator-cuff defects following repair.Keywords: rotator cuff, PASTA lesion, transtendon repair

  11. The multichannel n-propyl + O2 reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism

    Science.gov (United States)

    Bartlett, Marcus A.; Liang, Tao; Pu, Liang; Schaefer, Henry F.; Allen, Wesley D.

    2018-03-01

    The n-propyl + O2 reaction is an important model of chain branching reactions in larger combustion systems. In this work, focal point analyses (FPAs) extrapolating to the ab initio limit were performed on the n-propyl + O2 system based on explicit quantum chemical computations with electron correlation treatments through coupled cluster single, double, triple, and perturbative quadruple excitations [CCSDT(Q)] and basis sets up to cc-pV5Z. All reaction species and transition states were fully optimized at the rigorous CCSD(T)/cc-pVTZ level of theory, revealing some substantial differences in comparison to the density functional theory geometries existing in the literature. A mixed Hessian methodology was implemented and benchmarked that essentially makes the computations of CCSD(T)/cc-pVTZ vibrational frequencies feasible and thus provides critical improvements to zero-point vibrational energies for the n-propyl + O2 system. Two key stationary points, n-propylperoxy radical (MIN1) and its concerted elimination transition state (TS1), were located 32.7 kcal mol-1 and 2.4 kcal mol-1 below the reactants, respectively. Two competitive β-hydrogen transfer transition states (TS2 and TS2') were found separated by only 0.16 kcal mol-1, a fact unrecognized in the current combustion literature. Incorporating TS2' in master equation (ME) kinetic models might reduce the large discrepancy of 2.5 kcal mol-1 between FPA and ME barrier heights for TS2. TS2 exhibits an anomalously large diagonal Born-Oppenheimer correction (ΔDBOC = 1.71 kcal mol-1), which is indicative of a nearby surface crossing and possible nonadiabatic reaction dynamics. The first systematic conformational search of three hydroperoxypropyl (QOOH) intermediates was completed, uncovering a total of 32 rotamers lying within 1.6 kcal mol-1 of their respective lowest-energy minima. Our definitive energetics for stationary points on the n-propyl + O2 potential energy surface provide key benchmarks for future studies

  12. Electrochemically Driven Surface-Confined Acid/Base Reaction for an Ultrafast H(+) Supercapacitor.

    Science.gov (United States)

    Gan, Shiyu; Zhong, Lijie; Gao, Lifang; Han, Dongxue; Niu, Li

    2016-02-10

    We discovered an organic weak acid, 3,4,9,10-perylene tetracarboxylic acid (PTCA), confined on the electrode surface, revealing a reversible and ultrafast protonation/deprotonation non-Faradaic process but exhibiting analogous voltammetric peaks (capacitive peaks). A further synthesized PTCA-graphene supramolecular nanocomplex discloses a wide voltage window (1.2 V) and ultrahigh specific capacitance up to 143 F g(-1) at an ultrafast charge-discharge density of 1000 A g(-1) (at least 1 order of magnitude faster than present speeds). The capacitance retention maintained at 73% after 5000 cycles. This unique capacitive voltammetric behavior suggests a new type of charge-storage modes, which may offer a way for overcoming the present difficulties of supercapacitors.

  13. Modification of the glass surface induced by redox reactions and internal diffusion processes

    DEFF Research Database (Denmark)

    Smedskjær, Morten Mattrup; Deubener, Joachim; Yue, Yuanzheng

    In this paper we report a novel way to modify the glass surface in favor of some physical performances. The main step is to perform iso-thermal treatments on the selected silicate glasses containing transition metal at temperatures near the glass transition temperature for various durations under...... different gases. As a result, we have observed a striking phenomenon, i.e., the outward diffusion of divalent cations occurs not only under an oxidizing atmosphere of heat-treatment, but also under nitrogen, even under reducing atmospheres like H2/N2 (10/90). The extent of the cationic diffusion depends...... on temperature and duration of heat-treatments. The mechanism of the diffusion depends on the type of the gases used for the heat-treatments. In this paper we propose several possible models describing mechanisms of the cationic diffusion, and hence, of the formation of the nano-layer. We also report the effect...

  14. Activation of noble metals on metal-carbide surfaces: novel catalysts for CO oxidation, desulfurization and hydrogenation reactions.

    Science.gov (United States)

    Rodriguez, José A; Illas, Francesc

    2012-01-14

    This perspective article focuses on the physical and chemical properties of highly active catalysts for CO oxidation, desulfurization and hydrogenation reactions generated by depositing noble metals on metal-carbide surfaces. To rationalize structure-reactivity relationships for these novel catalysts, well-defined systems are required. High-resolution photoemission, scanning tunneling microscopy (STM) and first-principles periodic density-functional (DF) calculations have been used to study the interaction of metals of Groups 9, 10 and 11 with MC(001) (M = Ti, Zr, V, Mo) surfaces. DF calculations give adsorption energies that range from 2 eV (Cu, Ag, Au) to 6 eV (Co, Rh, Ir). STM images show that Au, Cu, Ni and Pt grow on the carbide substrates forming two-dimensional islands at very low coverage, and three-dimensional islands at medium and large coverages. In many systems, the results of DF calculations point to the preferential formation of admetal-C bonds with significant electronic perturbations in the admetal. TiC(001) and ZrC(001) transfer some electron density to the admetals facilitating bonding of the adatom with electron-acceptor molecules (CO, O(2), C(2)H(4), SO(2), thiophene, etc.). For example, the Cu/TiC(001) and Au/TiC(001) systems are able to cleave both S-O bonds of SO(2) at a temperature as low as 150 K, displaying a reactivity much larger than that of TiC(001) or extended surfaces of bulk copper and gold. At temperatures below 200 K, Au/TiC is able to dissociate O(2) and perform the 2CO + O(2)→ 2CO(2) reaction. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(001) or Au(111), a Au/TiC(001) surface displays an activity for the hydrodesulfurization of thiophene higher than that of conventional Ni/MoS(x) catalysts. In general, the Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces. Thus, metal carbides are excellent supports for enhancing the chemical

  15. Multi-resistive reduced graphene oxide diode with reversible surface electrochemical reaction induced carrier control.

    Science.gov (United States)

    Seo, Hyungtak; Ahn, Seungbae; Kim, Jinseo; Lee, Young-Ahn; Chung, Koo-Hyun; Jeon, Ki-Joon

    2014-07-10

    The extended application of graphene-based electronic devices requires a bandgap opening in order to realize the targeted device functionality. Since the bandgap tuning of pristine graphene is limited to 360 meV, the chemical modification of graphene is considered essential to achieve a large bandgap opening at the expense of electrical properties degradation. Reduced graphene oxide (RGO) has attracted significant interest for fabricating graphene-based semiconductors since it has several advantages over other forms of chemically modified graphene; such as tunable bandgap opening, decent electrical properties, and easy synthesis. Because of the reduced bonding nature of RGO, the role of metastable oxygen in the RGO matrix is recently highlighted and it may offer emerging ionic devices. In this study, we show that multi-resistivity RGO/n-Si diodes can be obtained by controlling the RGO thickness at a nanometer scale. This is made possible by (1) a metastable lattice-oxygen drift within bulk RGO and (2) electrochemical ambient hydroxyl (OH) formation at the RGO surface. The effect demonstrated in a p-RGO/n-Si heterojunction diode is equivalent to electrochemically driven reversible electronic manipulation and therefore provides an important basis for the application of O bistability in RGO for chemical sensors and electrocatalysis.

  16. Application of atomic mutations included in nuclear reactions, 40Ar(γ, p)39Cl(β decay)39Ar, to surface study

    International Nuclear Information System (INIS)

    Ohkuma, Juzo

    1987-01-01

    It has been found that the nuclear transformation processes which are initiated by photonuclear reactions can be used for studying the adsorption and chemical reactions taking place on solid surfaces. Chemically reactive 39 Cl was produced by irradiating 40 Ar with high-energy bremsstrahlung, and its blow was directed onto several material surfaces. The amount of chlorine adsorption was ascertained by detecting its radioactivity. Desorption without heating the adsorber samples inevitably occurred owing to the nuclear decay of 39 Cl. The adsorption and desorption rates were compared for several elements. A fast growth of oxide islands on sample surfaces was observed during the adsorption-desorption process. (author)

  17. Monitoring the inorganic chemical reaction by surface-enhanced Raman spectroscopy: A case of Fe³⁺ to Fe²⁺ conversion.

    Science.gov (United States)

    Qin, Suhua; Meng, Juan; Tang, Xianghu; Yang, Liangbao

    2016-01-01

    Monitoring the process of organic chemical reactions to study the kinetics by surface-enhanced Raman spectroscopy (SERS) is currently of immense interest. However, monitoring the inorganic chemical reaction is still an extremely difficulty for researchers. This study exactly focused on the monitor of inorganic chemical reaction. Capillary coated with silver nanoparticles was introduced, which was an efficient platform for monitoring reactions with SERS due to the advantages of sensitivity and excellent reproducibility. The photoreduction of [Fe(phen)3](3+) to [Fe(phen)3](2+) was used as model reaction to demonstrated the feasibility of SERS monitoring inorganic chemical reaction by involving in metal-organic complexes. Moreover, the preliminary implementation demonstrated that the kinetics of photoreduction can be real-time monitored by in situ using the SERS technique on a single constructed capillary, which may be useful for the practical application of SERS technique. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. A neural network potential energy surface for the F + CH4reaction including multiple channels based on coupled cluster theory.

    Science.gov (United States)

    Chen, Jun; Xu, Xin; Liu, Shu; Zhang, Dong H

    2018-03-22

    We report here a new global and full dimensional potential energy surface (PES) for the F + CH4 reaction. This PES was constructed by using neural networks (NN) fitting to about 99 000 ab initio energies computed at the UCCSD(T)-F12a/aug-cc-pVTZ level of theory, and the correction terms considering the influence of a larger basis set as well as spin-orbit couplings were further implemented with a hierarchial scheme. This PES, covering both the abstraction and substitution channels, has an overall fitting error of 8.24 meV in total, and 4.87 meV for energies within 2.5 eV using a segmented NN fitting method, and is more accurate than the previous PESs.

  19. The effect of surface modification by reduced graphene oxide on the electrocatalytic activity of nickel towards the hydrogen evolution reaction.

    Science.gov (United States)

    Chanda, Debabrata; Hnát, Jaromír; Dobrota, Ana S; Pašti, Igor A; Paidar, Martin; Bouzek, Karel

    2015-10-28

    To find cheap, efficient and durable hydrogen evolution reaction catalysts is one of the major challenges when developing an alkaline water electrolysis system. In this paper we describe an electrochemically reduced graphene oxide (RGO)-modified Ni electrode, which could be used as a pre-eminent candidate for such a system. The experimentally determined characteristics of this electrode showing superior electrocatalytic activity were complemented by density functional theory calculations. Thermodynamic considerations led to the conclusion that H atoms, formed upon H2O discharge on Ni, spill onto the RGO, which serves as an H adatom acceptor, enabling continuous cleaning of Ni-active sites and an alternative pathway for H2 production. This mode of action is rendered by the unique reactivity of RGO, which arises due to the presence of O surface groups within the graphene structure. The significant electrocatalytic activity and life time (>35 days) of the RGO towards the HER under conditions of alkaline water electrolysis are demonstrated.

  20. MHD Convective Flow of Jeffrey Fluid Due to a Curved Stretching Surface with Homogeneous-Heterogeneous Reactions.

    Directory of Open Access Journals (Sweden)

    Maria Imtiaz

    Full Text Available This paper looks at the flow of Jeffrey fluid due to a curved stretching sheet. Effect of homogeneous-heterogeneous reactions is considered. An electrically conducting fluid in the presence of applied magnetic field is considered. Convective boundary conditions model the heat transfer analysis. Transformation method reduces the governing nonlinear partial differential equations into the ordinary differential equations. Convergence of the obtained series solutions is explicitly discussed. Characteristics of sundry parameters on the velocity, temperature and concentration profiles are analyzed by plotting graphs. Computations for pressure, skin friction coefficient and surface heat transfer rate are presented and examined. It is noted that fluid velocity and temperature through curvature parameter are enhanced. Increasing values of Biot number correspond to the enhancement in temperature and Nusselt number.

  1. Growth, reaction and nanowire formation of Fe on the ZnS(1 0 0) surface.

    Science.gov (United States)

    Man, Ka Lun; Pavlovska, Anastassia; Bauer, Ernst; Locatelli, Andrea; Menteş, Tevfik O; Niño, Miguel A; Wong, George K L; Sou, Iam Keong; Altman, Michael S

    2014-08-06

    The growth and reaction of Fe on a ZnS(1 0 0) substrate are studied in situ and with high lateral resolution using low energy electron microscopy (LEEM), micro low energy electron diffraction ( μLEED), x-ray photoemission electron microscopy (XPEEM), microprobe x-ray photoelectron spectroscopy ( μXPS) and x-ray magnetic circular dichroism PEEM (XMCDPEEM) for complementary structural, chemical, and magnetic characterization. Initially, a two-dimensional (Fe, Zn)S reaction layer forms with thickness that depends on growth temperature. Further growth results in the formation of a variety of three-dimensional crystals, most of them strongly elongated in the form of 'nanowires' of two distinct types, labeled as A and B. Type A nanowires are oriented near the ZnS[1 1 0] direction and are composed of Fe. Type B nanowires are oriented predominantly along directions a few degrees off the ZnS[0 0 1] direction and are identified as Greigite (Fe3S4). Both types of nanowires are magnetic with Curie temperatures above 450 °C. The understanding of the reactive growth mechanism in this system that is provided by these investigations may help to develop growth methods for other elemental and transition metal chalcogenide nanostructures on ZnS and possibly on other II-VI semiconductor surfaces.

  2. Histopathology and immune histochemistry of red tattoo reactions. Interface dermatitis is the lead pathology, with increase in T-lymphocytes and Langerhans cells suggesting an allergic pathomechanism

    DEFF Research Database (Denmark)

    Høgsberg, T; Thomsen, B M; Serup, J

    2015-01-01

    BACKGROUND: The majority of tattoo reactions are affiliated to red pigmented areas and often suspected to be allergic in nature. A sizeable series of biopsies of such reactions has not previously been performed. The aim of this study was to type and grade epidermal and dermal changes in tattoo...... reactions to red/red nuances by microscopy and immunochemistry relevant for the assessment of a possible allergic pathomechanism. METHODS: Skin biopsies were taken from red tattoo reactions, graded by conventional microscopy and stained for T and B-lymphocytes, Langerhans cells, macrophages and tumour......-α was common. CONCLUSION: The predominant histological pattern of chronic tattoo reactions in red/red nuances is interface dermatitis. T-lymphocytes and Langerhans cells are increased suggesting an allergic pathomechanism. TNF-α may contribute to reactions. In many cases, overlapping reactive patterns were...

  3. Stabilization of silver nanoparticles in nonanoic acid: A temperature activated conformation reaction observed with surface enhanced Raman spectroscopy

    International Nuclear Information System (INIS)

    Henneke, Dale E.; Malyavanatham, Gokul; Kovar, Desiderio; O'Brien, D.T.; Becker, M.F.; Nichols, William T.; Keto, J.W.

    2003-01-01

    Silver nanoparticles were synthesized by ultraviolet (λ=248 nm) laser ablation of an aerosol of micron-sized source particles entrained in nitrogen. As a result of thermionic electron emission and photoionization, nanoparticles produced in this manner were highly charged. The resulting aerosol was primarily composed of nanometer sized particles. The charged nanoparticles were deflected by an electric field that was perpendicular to the aerosol flow. Deflected nanoparticles were deposited directly into n-nonanoic acid flowing along the negative collection electrode. Suspensions of nanoparticles collected in this manner were dark gray in color and were found to be flocculated. When the suspensions were heated to temperatures above 75 deg. C, a color change from gray to clear was observed. Ultraviolet/visible extinction spectroscopy was performed on each suspension following annealing at different temperatures and times. By modeling the absorption decrease as a first order reaction, a good fit for the data was found. Analysis by dynamic light scattering (DLS) showed that the initial mean flocculent size of the gray suspensions was 602 nm. DLS analysis of the suspensions taken at different annealing intervals showed that the flocculent size decreased, but maintained a narrow size distribution until the size shrank below the instrument resolution limit. The reduction in flocculent size coincided with the observed color change, and an irreversible transition to a deflocculated primary nanoparticle suspension is observed. Surface enhanced Raman scattering is used to confirm that the reaction results from a change in the orientation of the nonanoic molecule on the surface of the nanoparticle

  4. Anion-π Catalysis of Enolate Chemistry: Rigidified Leonard Turns as a General Motif to Run Reactions on Aromatic Surfaces.

    Science.gov (United States)

    Cotelle, Yoann; Benz, Sebastian; Avestro, Alyssa-Jennifer; Ward, Thomas R; Sakai, Naomi; Matile, Stefan

    2016-03-18

    To integrate anion-π, cation-π, and ion pair-π interactions in catalysis, the fundamental challenge is to run reactions reliably on aromatic surfaces. Addressing a specific question concerning enolate addition to nitroolefins, this study elaborates on Leonard turns to tackle this problem in a general manner. Increasingly refined turns are constructed to position malonate half thioesters as close as possible on π-acidic surfaces. The resulting preorganization of reactive intermediates is shown to support the disfavored addition to enolate acceptors to an absolutely unexpected extent. This decisive impact on anion-π catalysis increases with the rigidity of the turns. The new, rigidified Leonard turns are most effective with weak anion-π interactions, whereas stronger interactions do not require such ideal substrate positioning to operate well. The stunning simplicity of the motif and its surprisingly strong relevance for function should render the introduced approach generally useful. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Surface tectonics of nanoporous networks of melamine-capped molecular building blocks formed through interface Schiff-base reactions.

    Science.gov (United States)

    Liu, Xuan-He; Wang, Dong; Wan, Li-Jun

    2013-10-01

    Control over the assembly of molecules on a surface is of great importance for the fabrication of molecule-based miniature devices. Melamine (MA) and molecules with terminal MA units are promising candidates for supramolecular interfacial packing patterning, owing to their multiple hydrogen-bonding sites. Herein, we report the formation of self-assembled structures of MA-capped molecules through a simple on-surface synthetic route. MA terminal groups were successfully fabricated onto rigid molecular cores with 2-fold and 3-fold symmetry through interfacial Schiff-base reactions between MA and aldehyde groups. Sub-molecular scanning tunneling microscopy (STM) imaging of the resultant adlayer revealed the formation of nanoporous networks. Detailed structural analysis indicated that strong hydrogen-bonding interactions between the MA groups persistently drove the formation of nanoporous networks. Herein, we demonstrate that functional groups with strong hydrogen-bond-formation ability are promising building blocks for the guided assembly of nanoporous networks and other hierarchical 2D assemblies. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Understanding Gender Differences in Children's Risk Taking and Injury: A Comparison of Mothers' and Fathers' Reactions to Sons and Daughters Misbehaving in Ways that Lead to Injury

    Science.gov (United States)

    Morrongiello, Barbara A.; Zdzieborski, Daniel; Normand, Jackie

    2010-01-01

    This study compared reactions of mothers and fathers to the risk taking behavior of sons and daughters. Mother-father pairs (N = 52) imagined their 2-year-old boy or girl behaving in risky ways in common home situations that could, and did, result in injury. Emotional and parenting reactions to the behaviors were assessed before and after injury.…

  7. Characterization of a microwave absorbent prepared by coprecipitation reaction of iron oxide on the surface of graphite nanosheet

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Yongqing, E-mail: ylqqyyq@yahoo.cn [Department of Applied Chemistry, School of Science, Northwestern Polytechnical University, Xi' an 710072 (China); Qi, Shuhua [Department of Applied Chemistry, School of Science, Northwestern Polytechnical University, Xi' an 710072 (China); Wang, Jianning [Personnel Department, Ningxia University, Yinchuan 710021 (China)

    2012-12-01

    Highlights: Black-Right-Pointing-Pointer NanoG was prepared by ultrasonication of EG. Black-Right-Pointing-Pointer Fe{sub 3}O{sub 4} was precipitated on the NanoG's surface. Black-Right-Pointing-Pointer The structure was characterized by SEM, XRD, EDS and FTIR. Black-Right-Pointing-Pointer Properties such as thermal stability, conductivity and microwave absorbing were measured. - Abstract: Fe{sub 3}O{sub 4} was precipitated on the surface of graphite nanosheet (NanoG) to produce a microwave absorbing material Fe{sub 3}O{sub 4}/NanoG. The structure was characterized by scanning electron microscopy, energy dispersive spectroscopy, Fourier transform infrared spectroscopy and X-ray diffraction. Results show that under basic conditions, FeCl{sub 3}{center_dot}6H{sub 2}O and FeSO{sub 4}{center_dot}7H{sub 2}O can be used in a coprecipitation reaction to obtain Fe{sub 3}O{sub 4} nanoparticles, which are bound to and well distributed on the NanoG surface. Thermogravimetric analysis shows that the thermal stability of Fe{sub 3}O{sub 4}/NanoG is good. According to the four-point-probe test, with the increasing mass ratios of Fe{sub 3}O{sub 4} to NanoG, the conductivities of Fe{sub 3}O{sub 4}/NanoG decrease. Measurement of electromagnetic parameters shows that Fe{sub 3}O{sub 4}/NanoG has better microwave absorbing properties than Fe{sub 3}O{sub 4} and NanoG.

  8. Impacts of anions on the oxygen reduction reaction kinetics on platinum and palladium surfaces in alkaline solutions.

    Science.gov (United States)

    Zhu, Shangqian; Hu, Xiaomeng; Shao, Minhua

    2017-03-15

    The fundamental understanding of the impacts induced by anions on oxygen reduction reaction (ORR) in alkaline media is of great importance in the design of more advanced catalysts for alkaline fuel cells (AFC). In this study, the specific adsorption of F - , Cl - , ClO 4 - , CO 3 2- , SO 4 2- , and citrate anions on Pt/C and Pd/C catalysts, and their impacts on the ORR kinetics in alkaline solutions were systematically studied. It was found that F - , Cl - and ClO 4 - did not specifically adsorb on Pt or Pd surfaces and had no poisoning effect on ORR. CO 3 2- and SO 4 2- had significant effects on Pt/C and lowered the activity even at a very low concentration. On the other hand, their impacts on Pd/C were negligible. Self-dissociation of citrate anions was found to occur on both Pt/C and Pd/C in the H adsorption/desorption and double layer regions. For the first time, surface enhanced infrared absorption spectroscopy (SEIRAS) with the attenuated total reflection (ATR) technique was used to investigate the self-dissociation of citrate on Pt and Pd thin film electrodes. The breaking of carboxylic groups and the carbon backbone was proposed as a possible dissociation pathway for citrate. The adsorbed species have a negligible effect on ORR activity on Pt/C as they are removed by oxidation before 0.75 V. In contrast, their oxidation on Pd/C surfaces is not completed until 0.91 V, which causes a lower ORR activity observed in rotating disk electrode measurements. The findings in this paper emphasize the importance of specific adsorption of anions and double-layer interfacial effects on the ORR activity measurement in alkaline solutions.

  9. Ab initio R1 mechanism of photostimulated oxygen isotope exchange reaction on a defect TiO2 surface: The case of terminal oxygen atom exchange

    Science.gov (United States)

    Kevorkyants, Ruslan; Sboev, Mikhail. N.; Chizhov, Yuri V.

    2017-05-01

    Based on density functional theory we propose R1 mechanism of photostimulated oxygen isotope exchange (POIEx) reaction between 16O18O and terminal oxygen atom of a defect TiO2 surface, which is modeled by amorphous Ti8O16 nanocluster in excited S1 electronic state. The proposed mechanism involves four adsorption intermediates and five transition states. The computed activation energy of the POIEx equals 0.24 eV. The computed g-tensors of the predicted ozonide O3- chemisorption species match well EPR data on O2 adsorption on UV-irradiated nanocrystalline TiO2. This match serves a mean of justification of the proposed R1 mechanism of the POIEx reaction. In addition, it is found that the proposed R1 POIEx reaction's mechanism differs from R1 mechanism of thermo-assisted OIEx reaction on a surface of supported vanadium oxide catalyst VOx/TiO2 reported earlier.

  10. Comparison of home lead dust reduction techniques on hard surfaces: the New Jersey assessment of cleaning techniques trial.

    OpenAIRE

    Rich, David Q; Rhoads, George G; Yiin, Lih-Ming; Zhang, Junfeng; Bai, Zhipeng; Adgate, John L; Ashley, Peter J; Lioy, Paul J

    2002-01-01

    High efficiency particulate air filter (HEPA) vacuums, which collect particles > 0.3 micro m, and trisodium phosphate (TSP), a detergent claimed to selectively remove lead, have been included in the HUD Guidelines for the Evaluation and Control of Lead Based Paint Hazards in Housing without systematic validation of their effectiveness. At the time the study was initiated, both HEPA vacuums and TSP were relatively expensive, they were not readily found in urban retail centers, and there were e...

  11. Right Bundle Branch Block-Like Pattern During Ventricular Pacing: A Surface Electrocardiographic Mapping Technique to Locate the Ventricular Lead.

    Science.gov (United States)

    Almehairi, Mohammed; Enriquez, Andres; Redfearn, Damian; Michael, Kevin; Abdollah, Hoshiar; Alfagih, Ahmed; Nolan, Robert; Baranchuk, Adrian; Simpson, Christopher S

    2015-08-01

    In patients with paced rhythm, a right bundle branch block (RBBB)-like pattern may suggest inadvertent left ventricular (LV) lead placement. However, in most cases, the lead is indeed in the right ventricle as intended. We performed a retrospective analysis of postimplantation electrocardiograms (ECGs) for the period 2000-2013 to determine the prevalence of a RBBB-like pattern. A 12-lead ECG was recorded in the standard position and with displacement of leads V1-V2 to the fifth and sixth intercostal spaces (ICSs), assessing the ability of this manoeuvre to unmask a concealed LBBB-like pattern. Patients with true LV pacing, both endocardial and epicardial, were used as controls (n = 10). A total of 943 patients were analyzed. The prevalence of RBBB-like pattern was 8.1% (n = 77), and 26 patients were included in the study. Displacement of leads V1-V2 to the fifth ICS resulted in transition to a LBBB-like pattern with a QS wave in V1 in 14 of 26 patients (sensitivity, 53%; specificity, 100%), whereas displacement to the sixth ICS resulted in a QS pattern in all patients (sensitivity and specificity, 100%). In all patients in the control group, the ECG depicted a RBBB configuration with leads V1-V2 in the standard position, as well as at the fifth and sixth ICSs. In patients with paced rhythm and a RBBB-like pattern on the 12-lead ECG, displacement of leads V1-V2 to the sixth ICS accurately identifies the presence of true right ventricular pacing. Copyright © 2015 Canadian Cardiovascular Society. Published by Elsevier Inc. All rights reserved.

  12. Energy disposal and thermal rate constants for the OH + HBr and OH + DBr reactions: quasiclassical trajectory calculations on an accurate potential energy surface.

    Science.gov (United States)

    de Oliveira-Filho, Antonio G S; Ornellas, Fernando R; Bowman, Joel M

    2014-12-26

    We report reaction cross sections, energy disposal, and rate constants for the OH + HBr → Br + H2O and OH + DBr → Br + HDO reactions from quasiclassical trajectory calculations using an ab initio potential energy surface [ de Oliveira-Filho , A. G. S. ; Ornellas , F. R. ; Bowman , J. M. J. Phys. Chem. Lett. 2014 , 5 , 706 - 712 ]. Comparison with available experiments are made and generally show good agreement.

  13. Impact of surface ocean conditions and aerosol provenance on the dissolution of aerosol manganese, cobalt, nickel and lead in seawater

    OpenAIRE

    Fishwick, MP; Ussher, SJ; Sedwick, PN; Lohan, MC; Worsfold, PJ; Buck, KN; Church, TM

    2018-01-01

    © 2017. Atmospheric deposition is an important pathway by which bioactive trace metals are delivered to the surface ocean. The proportions of total aerosol trace metals that dissolve in seawater, and thus become available to biota, are not well constrained and are therefore a key uncertainty when estimating atmospheric fluxes of these elements to surface waters. The aim of this study was to elucidate the main physico-chemical controls on the dissolution of the bioactive trace metals manganese...

  14. Role of graphene on the surface chemical reactions of BiPO4-rGO with low OH-related defects.

    Science.gov (United States)

    Gao, Erping; Wang, Wenzhong

    2013-11-21

    Graphene has been widely introduced into photocatalysis to enhance photocatalytic performance due to its unique physical and chemical properties. However, the effect of graphene on the surface chemical reactions of photocatalysis has not been clearly researched, which is important for photocatalysis because photocatalytic reactions ultimately occur on the catalyst surface. Herein, a two-step solution-phase reaction has been designed to synthesize quasi-core-shell structured BiPO4-rGO cuboids and the role of graphene on the surface chemical reactions was investigated in detail. It was found that the introduced graphene modified the process and the mechanism of the surface chemical reactions. The change mainly originates from the interaction between graphene and the adsorbed O2 molecule. Due to the electron transfer from graphene to adsorbed O2, graphene could tune the interfacial charge transport and efficiently activate molecular oxygen to form O2˙(-) anions as the major oxidation species instead of ˙OH. In addition, the two-step synthesis approach could efficiently suppress the formation of OH-related defects in the lattice. As a result, the BiPO4-rGO composite exhibited superior photocatalytic activity to BiPO4 and P25, about 4.3 times that of BiPO4 and 6.9 times that of P25.

  15. Evaluation of two lead-based paint removal and waste stabilization technology combinations on typical exterior surfaces.

    Science.gov (United States)

    Daniels, A E; Kominsky, J R; Clark, P J

    2001-10-12

    A study was conducted to demonstrate the effectiveness of a wet abrasive blasting technology to remove lead-based paint from exterior wood siding and brick substrates as well as to evaluate the effectiveness of two waste stabilization technologies to stabilize the resulting blast media (coal slag and mineral sand) paint debris thereby reducing the leachable lead content. The lead-based paint removal technology effectiveness was determined by the use of an X-ray fluorescence (XRF) spectrum analyzer (L- and K-shell). The effectiveness of the technologies to stabilize the debris was evaluated through the toxicity characteristic leaching procedure (TCLP). Wet abrasive blasting effectively removed the lead-based paint coating from both the wood and brick substrates to below the US Department of Housing and Urban Development Guideline (1mg/cm(2)) with no minimal or no damage to the underlying substrates (Pstabilization technologies consistently stabilized the resultant paint debris to achieve a leachable lead content below the RCRA regulatory threshold of <5 mg/l.

  16. Effect of partial slip and chemical reaction on convection of a viscoelastic fluid over a stretching surface with Cattaneo-Christov heat flux model

    Science.gov (United States)

    Eswaramoorthi, S.; Bhuvaneswari, M.; Sivasankaran, S.; Niranjan, H.; Rajan, S.

    2017-11-01

    This article explores the effect of homogeneous-heterogeneous chemical reaction and partial slipon convective flow of a viscoelastic fluid with Cattaneo-Christov heat flux modelin the presence of suction/injection and convective boundary condition. The governing system of non-linear partial differential equations arereformed into ordinary differential equations with the help of similarity variables and then they are solved using homotopy analysis method. It is found that the surface heat transfer rate enhances on increasing the thermal relaxation time parameter and the surface mass transfer rate improved by increasing the slip parameter and homogeneous chemical reaction parameter.

  17. Thermal Rate Coefficients and Kinetic Isotope Effects for the Reaction OH + CH4 → H2O + CH3 on an ab Initio-Based Potential Energy Surface.

    Science.gov (United States)

    Li, Jun; Guo, Hua

    2018-03-15

    Thermal rate coefficients for the title reaction and its various isotopologues are computed using a tunneling-corrected transition-state theory on a global potential energy surface recently developed by fitting a large number of high-level ab initio points. The calculated rate coefficients are found to agree well with the measured ones in a wide temperature range, validating the accuracy of the potential energy surface. Strong non-Arrhenius effects are found at low temperatures. In addition, the calculations reproduced the primary and secondary kinetic isotope effects. These results confirm the strong influence of tunneling to this heavy-light-heavy hydrogen abstraction reaction.

  18. Thermal decomposition of a molecular material {N(n-C4H94[FeIIFeIII(C2O43]}∞ leading to ferrite: A reaction kinetics study

    Directory of Open Access Journals (Sweden)

    Bhattacharjee Ashis

    2013-01-01

    Full Text Available A multi-step thermal decomposition of a molecular precursor, {N(n-C4H94[FeIIFeIII(C2O43}∞ has been studied using non-isothermal thermogravimetry (TG measurements in the temperature range 300 to ~800 K at multiple heating rates (5, 10 and 20 K min-1. The thermal decomposition of the oxalate-based complex proceeds stepwise through a series of intermediate reactions. Two different isoconversional methods, namely, improved iterative method and model-free method are employed to evaluate the kinetic parameters: activation energy and rate of reaction, and the most probable reaction mechanism of thermal decomposition is also determined. The different reaction pathways leading to different steps in the TG profile have also been explored which are supplemented by earlier experimental observations of the present authors.

  19. The R-wave deflection interval in lead V3 combining with R-wave amplitude index in lead V1: a new surface ECG algorithm for distinguishing left from right ventricular outflow tract tachycardia origin in patients with transitional lead at V3.

    Science.gov (United States)

    Cheng, Zhongwei; Cheng, Kang'an; Deng, Hua; Chen, Taibo; Gao, Peng; Zhu, Kongbo; Fang, Quan

    2013-09-30

    To distinguish left ventricular outflow tract (LVOT) from right ventricular outflow tract (RVOT) origin in idiopathic premature ventricular contractions or ventricular tachycardia (PVCs/VT) patients with transitional lead at V3 is still a challenge. We sought to develop a new electrocardiography (ECG) algorithm for distinguishing LVOT from RVOT origin in patients with idiopathic outflow tract PVCs/VT with precordial transitional lead at V3. We analyzed the surface ECG characteristics in a retrospective cohort of idiopathic PVCs/VT patients with transitional lead at V3 who underwent successful radiofrequency catheter ablation and developed a new surface ECG algorithm, then validated it in a prospective cohort. A total of 82 consecutive patients (47 ± 17 years, 39% male) underwent radiofrequency catheter ablation of idiopathic outflow tract PVCs/VT between January 2006 and August 2010. Among them, 31 patients (38%) with transitional lead at V3 constituted the retrospective cohort. Based on the areas under the receiver operating characteristic curves, R-wave deflection interval in lead V3>80 ms and R-wave amplitude index in lead V1>0.30 were selected to develop the new surface ECG algorithm. It correctly identified the origin sites of eleven from 12 patients in the prospective cohort, yielding the accuracy of 91.7%. We presented a new simple surface ECG algorithm, R-wave deflection interval in lead V3>80 ms combining with R-wave amplitude index in lead V1>0.30 which can reliably distinguish LVOT from RVOT origin in idiopathic outflow tract PVCs/VT in patients with transitional lead at V3. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

  20. Parameterization of N2O5 Reaction Probabilities on the Surface of Particles Containing Ammonium, Sulfate, and Nitrate

    Science.gov (United States)

    A comprehensive parameterization was developed for the heterogeneous reaction probability (γ) of N2O5 as a function of temperature, relative humidity, particle composition, and phase state, for use in advanced air quality models. The reaction probabilities o...

  1. Molecular dynamics simulation of sodium aluminosilicate glass structures and glass surface-water reactions using the reactive force field (ReaxFF)

    Science.gov (United States)

    Dongol, R.; Wang, L.; Cormack, A. N.; Sundaram, S. K.

    2018-05-01

    Reactive potentials are increasingly used to study the properties of glasses and glass water reactions in a reactive molecular dynamics (MD) framework. In this study, we have simulated a ternary sodium aluminosilicate glass and investigated the initial stages of the glass surface-water reactions at 300 K using reactive force field (ReaxFF). On comparison of the simulated glass structures generated using ReaxFF and classical Buckingham potentials, our results show that the atomic density profiles calculated for the surface glass structures indicate a bond-angle distribution dependency. The atomic density profiles also show higher concentrations of non-bridging oxygens (NBOs) and sodium ions at the glass surface. Additionally, we present our results of formation of silanol species and the diffusion of water molecules at the glass surface using ReaxFF.

  2. Degradation of Reactive Yellow X-RG by O3/Fenton system: response surface approach, reaction mechanism, and degradation pathway.

    Science.gov (United States)

    Shen, Yongjun; Xu, Qihui; Liang, Jun; Xu, Wei

    2016-11-01

    O 3 /Fenton for the treatment of effluent containing Reactive Yellow X-RG is investigated. The response surface methodology is applied to study the main and interactive effects of the parameters. With the initial dye concentration being controlled at 300 mg L -1 , the optimized conditions for wastewater treatment are 3.68, 29.19 and 18.49 mg min -1 for initial pH, mole ratio of [H 2 O 2 ]/[Fe 2+ ] and ozone dosage, respectively. The regression quadratic model well describing the degradation efficiency of O 3 /Fenton process is developed and validated by the analysis of variances, respectively. In addition, a possible pathway for Reactive Yellow X-RG degradation is proposed by detecting the temporal evolution of intermediates in the solution, with the use of some techniques including ultraviolet spectrophotometric method (UV-Vis), Fourier transform infrared spectroscopy (FT-IR) and gas chromatography-mass spectrometry (GC/MS). Meanwhile, every reaction step is given to explain the degradation mechanisms.

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

    Science.gov (United States)

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

    2013-06-07

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

  4. A novel one-pot de-blocking and conjugation reaction step leads to process intensification in the manufacture of PEGylated insulin IN-105.

    Science.gov (United States)

    Hazra, Partha; Chatterjee, Amarnath; Shabandri, Qais; Adhikary, Laxmi; Dave, Nitesh; Buddha, Madhavan

    2012-10-01

    Bio-catalytic in vitro multistep reactions can be combined in a single step in one pot by optimizing multistep reactions under identical reaction condition. Using this analogy, the process of making PEGylated insulin, IN-105, was simplified. Instead of taking the purified active insulin bulk powder as the starting material for the conjugation step, an insulin process intermediate, partially purified insulin ester, was taken as starting material. Process intensification (PI) was established by performing a novel de-blocking (de-esterification) of the partially purified insulin ester and conjugation at B-29 Lys residue of B chain with a short-chain methoxy polyethylene glycol (mPEG) in a single-pot reactor. The chromatographic profile at the end of the reaction was found similar irrespective of whether both the reactions were performed sequentially or simultaneously. The conjugated product of interest, IN-105 (conjugation at LysB(29)), was purified from the heterogeneous mixture of conjugated products. The new manufacturing process was deduced to be more simplified and economical in making the insulin conjugates as several downstream purification steps could be circumvented. The physicochemical characteristics of IN-105 manufactured through this economic process was found to be indifferent from the product formed through the traditional process where the conjugation starting material was purified from bulk insulin.

  5. Enzymatic acidolysis of triolein with palmitic and caprylic acids: Optimization of reaction parameters by response surface methodology

    Directory of Open Access Journals (Sweden)

    Keskin, H.

    2012-09-01

    Full Text Available An acidolysis reaction of triolein with caprylic and palmitic acids was performed using immobilized sn-1,3 specific lipase from Mucor miehei to produce a reduced calorie spreadable structured lipid (SL. Response surface methodology was applied to model and optimize the reaction conditions using a four-factor five-level central composite rotatable design. The selected factors were time (10-24 h, enzyme load (10-25 wt%, substrate mole ratio (Triolein:Caprylic acid:Palmitic acid, (1:1:1-1:2.5:2.5 and temperature (45-60 °C. The produced SLs were compared to fat extracts of commercial margarine in terms of melting profile and solid fat content (SFC. SL with a melting peak of 42 °C and SFC of 40.69% at 0 °C was very similar to soft margarines. The caloric value of this SL was determined as 37.74 kJ/g, theoretically. The optimum reaction conditions were found as reaction time 14 h; substrate mole ratio 1:2.1:2.1; temperature 58 °C; and enzyme load 15 wt%. Under optimum conditions, the product contained 29.68% COC, 25.47% POC, and 3.80% POP.

    La reacción de acidolísis de la trioleina con los ácidos caprílico y palmítico se realizó utilizando lipasa inmovilizada Mucor miehei, específica de sn-1, 3, para producir una grasa de untar baja en calorías compuesta de lípidos estructurados (SL. La metodología de superficie de respuesta se aplica para modelar y optimizar las condiciones de reacción utilizando un factor-cuatro y nivel-cinco de diseño central compuesto. Los factores seleccionados fueron el tiempo (10-24 h, la carga de enzima (10-25% en peso, la relación molar de sustratos (Trioleína:Ácido Caprílico:Ácido Palmítico, (1:1:1-1:2.5:2.5 y la temperatura (45-60 °C. Los SLs producidos se compararon con extractos de grasa de margarina comercial en términos de perfil de fusión y contenido de grasa sólida (SFC. El SL con un pico de fusión a 42 °C y SFC de 40,69% a 0 °C era muy similar a las

  6. Mechanism of ({sup 14}N, {sup 12}B) reactions at intermediate energy leading to large spin-polarization of {sup 12}B

    Energy Technology Data Exchange (ETDEWEB)

    Mitsuoka, Shin-ichi [Osaka Univ., Ibaraki (Japan). Research Center for Nuclear Physics; Shimoda, Tadashi; Miyatake, Hiroari [and others

    1996-05-01

    To study mechanisms of the ({sup 14}N, {sup 12}B) reactions at intermediate energies, double differential cross section and nuclear spin-polarization of the {sup 12}B projectile-like fragments have been measured as a function of longitudinal momentum in the angular range of 0deg - 9deg. Large spin-polarization of the reaction products {sup 12}B has been observed in the {sup 9}Be({sup 14}N, {sup 12}B) reaction at 39.3 MeV/u. The momentum distributions at forward angles exhibit characteristic features which can not be understood by the current projectile fragmentation picture. It is shown that by assuming the existence of direct two-proton transfer process in addition to the fragmentation process, both the cross section and polarization of {sup 12}B fragments are successfully explained. The target and incident energy dependence of the momentum distribution are also explained reasonably. (author)

  7. Conjugate Heat Transfer Study at Interior Surface of NGV Leading Edge with Combined Shower Head and Impingement Cooling

    OpenAIRE

    Arun Kumar Pujari; B. V. S. S. S. Prasad; N. Sitaram

    2014-01-01

    A computational study on conjugate heat transfer is carried out to present the behavior of nondimensional temperature and heat transfer coefficient of a Nozzle Guide Vane (NGV) leading edge. Reynolds number of both mainstream flow and coolant impinging jets are varied. The NGV has five rows of film cooling holes arranged in shower head manner and four rows of impingement holes arranged in staggered manner. The results are presented by considering materials of different thermal conductivity. T...

  8. Critical Intermediate Structure That Directs the Crystalline Texture and Surface Morphology of Organo-Lead Trihalide Perovskite.

    Science.gov (United States)

    Chia, Hao-Chung; Sheu, Hwo-Shuenn; Hsiao, Yu-Yun; Li, Shao-Sian; Lan, Yi-Kang; Lin, Chung-Yao; Chang, Je-Wei; Kuo, Yen-Chien; Chen, Chia-Hao; Weng, Shih-Chang; Su, Chun-Jen; Su, An-Chung; Chen, Chun-Wei; Jeng, U-Ser

    2017-10-25

    We have identified an often observed yet unresolved intermediate structure in a popular processing with dimethylformamide solutions of lead chloride and methylammonium iodide for perovskite solar cells. With subsecond time-resolved grazing-incidence X-ray scattering and X-ray photoemission spectroscopy, supplemental with ab initio calculation, the resolved intermediate structure (CH 3 NH 3 ) 2 PbI 2 Cl 2 ·CH 3 NH 3 I features two-dimensional (2D) perovskite bilayers of zigzagged lead-halide octahedra and sandwiched CH 3 NH 3 I layers. Such intermediate structure reveals a hidden correlation between the intermediate phase and the composition of the processing solution. Most importantly, the 2D perovskite lattice of the intermediate phase is largely crystallographically aligned with the [110] planes of the three-dimensional perovskite cubic phase; consequently, with sublimation of Cl ions from the organo-lead octahedral terminal corners in prolonged annealing, the zigzagged octahedral layers of the intermediate phase can merge with the intercalated methylammonium iodide layers for templated growth of perovskite crystals. Regulated by annealing temperature and the activation energies of the intermediate and perovskite, deduced from analysis of temperature-dependent structural kinetics, the intermediate phase is found to selectively mature first and then melt along the layering direction for epitaxial conversion into perovskite crystals. The unveiled epitaxial conversion under growth kinetics controls might be general for solution-processed and intermediate-templated perovskite formation.

  9. Electrochemical Oxidation of Resorcinol in Aqueous Medium Using Boron-Doped Diamond Anode: Reaction Kinetics and Process Optimization with Response Surface Methodology.

    Science.gov (United States)

    Körbahti, Bahadır K; Demirbüken, Pelin

    2017-01-01

    Electrochemical oxidation of resorcinol in aqueous medium using boron-doped diamond anode (BDD) was investigated in a batch electrochemical reactor in the presence of Na 2 SO 4 supporting electrolyte. The effect of process parameters such as resorcinol concentration (100-500 g/L), current density (2-10 mA/cm 2 ), Na 2 SO 4 concentration (0-20 g/L), and reaction temperature (25-45°C) was analyzed on electrochemical oxidation using response surface methodology (RSM). The optimum operating conditions were determined as 300 mg/L resorcinol concentration, 8 mA/cm 2 current density, 12 g/L Na 2 SO 4 concentration, and 34°C reaction temperature. One hundred percent of resorcinol removal and 89% COD removal were obtained in 120 min reaction time at response surface optimized conditions. These results confirmed that the electrochemical mineralization of resorcinol was successfully accomplished using BDD anode depending on the process conditions, however the formation of intermediates and by-products were further oxidized at much lower rate. The reaction kinetics were evaluated at optimum conditions and the reaction order of electrochemical oxidation of resorcinol in aqueous medium using BDD anode was determined as 1 based on COD concentration with the activation energy of 5.32 kJ/mol that was supported a diffusion-controlled reaction.

  10. Dose-volume histogram and dose-surface histogram analysis for skin reactions to carbon ion radiotherapy for bone and soft tissue sarcoma.

    Science.gov (United States)

    Yanagi, Takeshi; Kamada, Tadashi; Tsuji, Hiroshi; Imai, Reiko; Serizawa, Itsuko; Tsujii, Hirohiko

    2010-04-01

    To evaluate the usefulness of the dose-volume histogram (DVH) and dose-surface histogram (DSH) as clinically relevant and available parameters that helped to identify bone and soft tissue sarcoma patients at risk of developing late skin reactions, including ulceration, when treated with carbon ion radiotherapy. Thirty-five patients with bone and soft tissue sarcoma treated with carbon ion beams were studied. The clinical skin reactions were evaluated. Some pretreatment variables were compared with the grade of late skin reactions. Average DVH and DSH were established in accordance with the grading of the skin reactions. Prescribed dose, the difference in depths between the skin surface and the proximal extent of the tumor, and some DVH/DSH parameters were correlated with late skin reaction (> or = grade 3) according to univariate analysis. Furthermore, the area irradiated with over 60 GyE (S(60)>20 cm(2)) on DSH was the most important factor by multivariate analysis. The area irradiated with over 60 GyE (S(60)>20 cm(2)) on DSH was found to be a parameter for use as a predictor of late skin reactions. Copyright 2009 Elsevier Ireland Ltd. All rights reserved.

  11. Electrochemical Oxidation of Resorcinol in Aqueous Medium Using Boron-Doped Diamond Anode: Reaction Kinetics and Process Optimization with Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    Bahadır K. Körbahti

    2017-10-01

    Full Text Available Electrochemical oxidation of resorcinol in aqueous medium using boron-doped diamond anode (BDD was investigated in a batch electrochemical reactor in the presence of Na2SO4 supporting electrolyte. The effect of process parameters such as resorcinol concentration (100–500 g/L, current density (2–10 mA/cm2, Na2SO4 concentration (0–20 g/L, and reaction temperature (25–45°C was analyzed on electrochemical oxidation using response surface methodology (RSM. The optimum operating conditions were determined as 300 mg/L resorcinol concentration, 8 mA/cm2 current density, 12 g/L Na2SO4 concentration, and 34°C reaction temperature. One hundred percent of resorcinol removal and 89% COD removal were obtained in 120 min reaction time at response surface optimized conditions. These results confirmed that the electrochemical mineralization of resorcinol was successfully accomplished using BDD anode depending on the process conditions, however the formation of intermediates and by-products were further oxidized at much lower rate. The reaction kinetics were evaluated at optimum conditions and the reaction order of electrochemical oxidation of resorcinol in aqueous medium using BDD anode was determined as 1 based on COD concentration with the activation energy of 5.32 kJ/mol that was supported a diffusion-controlled reaction.

  12. Evaporation residue cross sections and average neutron multiplicities in the /sup 64/Ni+/sup 92/Zr and /sup 12/C+/sup 144/Sm reactions leading to /sup 156/Er

    Energy Technology Data Exchange (ETDEWEB)

    Janssens, R.V.F.; Holzmann, R.; Henning, W.; Khoo, T.L.; Lesko, K.T.; Stephans, G.S.F.; Radford, D.C.; Van den Berg, A.M.; Kuehn, W.; Ronningen, R.M.

    1986-11-27

    Evaporation residue cross sections and neutron multiplicity distributions have been measured for the /sup 12/C+/sup 144/Sm and /sup 64/Ni+/sup 92/Zr reactions leading to the same compound nucleous /sup 156/Er. Statistical model calculations can account for the data in the /sup 12/C-induced reaction. In contrast, the inhibition of neutron emission with respect to statistical model predictions seen in /sup 64/Ni+/sup 92/Zr cannot be explained even with the inclusion of the broad angular momentum distributions required to describe the fusion cross section data.

  13. Doomed reservoirs in Kansas, USA? Climate change and groundwater mining on the Great Plains lead to unsustainable surface water storage

    Science.gov (United States)

    Brikowski, T. H.

    2008-06-01

    SummaryStreamflow declines on the Great Plains of the US are causing many Federal reservoirs to become profoundly inefficient, and will eventually drive them into unsustainability as negative annual reservoir water budgets become more common. The streamflow declines are historically related to groundwater mining, but since the mid-1980s correlate increasingly with climate. This study highlights that progression toward unsustainability, and shows that future climate change will continue streamflow declines at historical rates, with severe consequences for surface water supply. An object lesson is Optima Lake in the Oklahoma Panhandle, where streamflows have declined 99% since the 1960s and the reservoir has never been more than 5% full. Water balances for the four westernmost Federal reservoirs in Kansas (Cedar Bluff, Keith Sebelius, Webster and Kirwin) show similar tendencies. For these four, reservoir inflow has declined by 92%, 73%, 81% and 64% respectively since the 1950s. Since 1990 total evaporated volumes relative to total inflows amounted to 68%, 83%, 24% and 44% respectively. Predictions of streamflow and reservoir performance based on climate change models indicate 70% chance of steady decline after 2007, with a ˜50% chance of failure (releases by gravity flow impossible) of Cedar Bluff Reservoir between 2007 and 2050. Paradoxically, a 30% chance of storage increase prior 2020 is indicated, followed by steady declines through 2100. Within 95% confidence the models predict >50% decline in surface water resources between 2007 and 2050. Ultimately, surface storage of water resources may prove unsustainable in this region, forcing conversion to subsurface storage.

  14. Effect of surface reactions on steel, Al2O3 and Si3N4counterparts on their tribological performance with polytetrafluoroethylene filled composites

    NARCIS (Netherlands)

    Shen, J.T.; Top, M.; Ivashenko, O.; Rudolf, P.; Pei, Yutao T.; De Hosson, J.Th.M.

    2015-01-01

    The influence of surface reactions on the tribo-performance of steel, Al2O3 and Si3N4 balls sliding against polytetrafluoroethylene/SiO2/epoxy composites was investigated. Al2O3 ball were found to exhibit the best tribo-performance, namely a low coefficient of friction and the lowest wear rates of

  15. Activation of electrophilicity of stable Y-delocalized carbamate cations in intramolecular aromatic substitution reaction: evidence for formation of diprotonated carbamates leading to generation of isocyanates.

    Science.gov (United States)

    Kurouchi, Hiroaki; Kawamoto, Kyoko; Sugimoto, Hiromichi; Nakamura, Satoshi; Otani, Yuko; Ohwada, Tomohiko

    2012-10-19

    Although cations with three heteroatoms, such as monoprotonated guanidine and urea, are stabilized by Y-shaped conjugation and such Y-conjugated cations are sufficiently basic to be further protonated (or protosolvated) to dications in strongly acid media, only O-monoprotonated species have been detected in the case of carbamates even in magic acid. We found that the trifluoromethanesulfonic acid-catalyzed cyclization of arylethylcarbamates proceeds to afford dihydroisoquinolones in high yield. In strong acids, methyl carbamates are fully O-monoprotonated, and these monocations do not undergo cyclization even under heating. But, as the acidity of the reaction medium is further increased, the cyclization reaction of methyl phenethylcarbamates starts to proceed as a first-order reaction, with a linear relationship between rate and acidity. The sign and magnitude of the entropy of activation ΔS(‡) were found to be similar to those of other A(Ac)1 reactions. These results strongly support the idea that further protonation of the O-protonated carbamates is involved in the cyclization, but the concentration of the dications is very low and suggests that the rate-determining step is dissociation of methanol from the diprotonated carbamate to generate protonated isocyanate, which reacts with the aromatic ring. Therefore, O-protonated carbamates are weak bases in sharp contrast to other Y-shaped monocations.

  16. Concave pit-containing scaffold surfaces improve stem cell-derived osteoblast performance and lead to significant bone tissue formation.

    Directory of Open Access Journals (Sweden)

    Antonio Graziano

    2007-06-01

    Full Text Available Scaffold surface features are thought to be important regulators of stem cell performance and endurance in tissue engineering applications, but details about these fundamental aspects of stem cell biology remain largely unclear.In the present study, smooth clinical-grade lactide-coglyolic acid 85:15 (PLGA scaffolds were carved as membranes and treated with NMP (N-metil-pyrrolidone to create controlled subtractive pits or microcavities. Scanning electron and confocal microscopy revealed that the NMP-treated membranes contained: (i large microcavities of 80-120 microm in diameter and 40-100 microm in depth, which we termed primary; and (ii smaller microcavities of 10-20 microm in diameter and 3-10 microm in depth located within the primary cavities, which we termed secondary. We asked whether a microcavity-rich scaffold had distinct bone-forming capabilities compared to a smooth one. To do so, mesenchymal stem cells derived from human dental pulp were seeded onto the two types of scaffold and monitored over time for cytoarchitectural characteristics, differentiation status and production of important factors, including bone morphogenetic protein-2 (BMP-2 and vascular endothelial growth factor (VEGF. We found that the microcavity-rich scaffold enhanced cell adhesion: the cells created intimate contact with secondary microcavities and were polarized. These cytological responses were not seen with the smooth-surface scaffold. Moreover, cells on the microcavity-rich scaffold released larger amounts of BMP-2 and VEGF into the culture medium and expressed higher alkaline phosphatase activity. When this type of scaffold was transplanted into rats, superior bone formation was elicited compared to cells seeded on the smooth scaffold.In conclusion, surface microcavities appear to support a more vigorous osteogenic response of stem cells and should be used in the design of therapeutic substrates to improve bone repair and bioengineering applications in the

  17. Dye surface coating enables visible light activation of TiO2 nanoparticles leading to degradation of neighboring biological structures.

    Science.gov (United States)

    Blatnik, Jay; Luebke, Lanette; Simonet, Stephanie; Nelson, Megan; Price, Race; Leek, Rachael; Zeng, Leyong; Wu, Aiguo; Brown, Eric

    2012-02-01

    Biologically and chemically modified nanoparticles are gaining much attention as a new tool in cancer detection and treatment. Herein, we demonstrate that an alizarin red S (ARS) dye coating on TiO2 nanoparticles enables visible light activation of the nanoparticles leading to degradation of neighboring biological structures through localized production of reactive oxygen species. Successful coating of nanoparticles with dye is demonstrated through sedimentation, spectrophotometry, and gel electrophoresis techniques. Using gel electrophoresis, we demonstrate that visible light activation of dye-TiO2 nanoparticles leads to degradation of plasmid DNA in vitro. Alterations in integrity and distribution of nuclear membrane associated proteins were detected via fluorescence confocal microscopy in HeLa cells exposed to perinuclear localized ARS-TiO2 nanoparticles that were photoactivated with visible light. This study expands upon previous studies that indicated dye coatings on TiO2 nanoparticles can serve to enhance imaging, by clearly showing that dye coatings on TiO2 nanoparticles can also enhance the photoreactivity of TiO2 nanoparticles by allowing visible light activation. The findings of our study suggest a therapeutic application of dye-coated TiO2 nanoparticles in cancer research; however, at the same time they may reveal limitations on the use of dye assisted visualization of TiO2 nanoparticles in live-cell imaging.

  18. Efficient Computational Research Protocol to Survey Free Energy Surface for Solution Chemical Reaction in the QM/MM Framework: The FEG-ER Methodology and Its Application to Isomerization Reaction of Glycine in Aqueous Solution.

    Science.gov (United States)

    Takenaka, Norio; Kitamura, Yukichi; Nagaoka, Masataka

    2016-03-03

    In solution chemical reaction, we often need to consider a multidimensional free energy (FE) surface (FES) which is analogous to a Born-Oppenheimer potential energy surface. To survey the FES, an efficient computational research protocol is proposed within the QM/MM framework; (i) we first obtain some stable states (or transition states) involved by optimizing their structures on the FES, in a stepwise fashion, finally using the free energy gradient (FEG) method, and then (ii) we directly obtain the FE differences among any arbitrary states on the FES, efficiently by employing the QM/MM method with energy representation (ER), i.e., the QM/MM-ER method. To validate the calculation accuracy and efficiency, we applied the above FEG-ER methodology to a typical isomerization reaction of glycine in aqueous solution, and reproduced quite satisfactorily the experimental value of the reaction FE. Further, it was found that the structural relaxation of the solute in the QM/MM force field is not negligible to estimate correctly the FES. We believe that the present research protocol should become prevailing as one computational strategy and will play promising and important roles in solution chemistry toward solution reaction ergodography.

  19. Preferential adsorption and surface precipitation of lead(II) ions onto anatase in artificially contaminated Dixie clay.

    Science.gov (United States)

    Suzuki, Tasuma; Okita, Miyu; Kakoyama, Satoshi; Niinae, Masakazu; Nakata, Hideki; Fujii, Hiroshi; Tasaka, Yukio

    2017-09-15

    During TEM-EDS (transmission electron microscopy coupled with an X-ray energy dispersive spectrometer) analysis of Dixie clay artificially contaminated with Pb(II), we observed that Pb(II) was preferentially adsorbed and precipitated on the surface of TiO 2 . To deepen the understanding of the mechanism and importance of this phenomenon, batch sorption experiments, XANES (X-ray absorption near edge spectroscopy) analysis, and sequential extraction analysis were performed. The TiO 2 in Dixie clay was found to be anatase, and anatase showed a higher Pb(II) sorption propensity than rutile, α-FeOOH, and one of two MnO 2 investigated in this study. Our experimental results indicated that the Pb precipitates preferentially formed on the surface of anatase was Pb(II) hydroxide or Pb(II) oxide. Additionally, sequential extraction analysis showed that at least 32% and 42% of Pb(II) was sorbed onto anatase in the Dixie clay contaminated with a Pb content of 736mg Pb/kg and 1,958mg Pb/kg, respectively. These results demonstrated that in addition to Fe and Mn oxides that are well-known metal oxides that serve as sinks for Pb(II) in the soil environment, TiO 2 is also a metal oxide that controls the behavior and fate of Pb(II) in soils. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. An improved potential energy surface and multi-temperature quasiclassical trajectory calculations of N2 + N2 dissociation reactions.

    Science.gov (United States)

    Bender, Jason D; Valentini, Paolo; Nompelis, Ioannis; Paukku, Yuliya; Varga, Zoltan; Truhlar, Donald G; Schwartzentruber, Thomas; Candler, Graham V

    2015-08-07

    Accurate modeling of high-temperature hypersonic flows in the atmosphere requires consideration of collision-induced dissociation of molecular species and energy transfer between the translational and internal modes of the gas molecules. Here, we describe a study of the N2 + N2⟶N2 + 2N and N2 + N2⟶4N nitrogen dissociation reactions using the quasiclassical trajectory (QCT) method. The simulations used a new potential energy surface for the N4 system; the surface is an improved version of one that was presented previously. In the QCT calculations, initial conditions were determined based on a two-temperature model that approximately separates the translational-rotational temperature from the vibrational temperature of the N2 diatoms. Five values from 8000 K to 30,000 K were considered for each of the two temperatures. Over 2.4 × 10(9) trajectories were calculated. We present results for ensemble-averaged dissociation rate constants as functions of the translational-rotational temperature T and the vibrational temperature T(v). The rate constant depends more strongly on T when T(v) is low, and it depends more strongly on T(v) when T is low. Quasibound reactant states contribute significantly to the rate constants, as do exchange processes at higher temperatures. We discuss two sets of runs in detail: an equilibrium test set in which T = T(v) and a nonequilibrium test set in which T(v) energy and a minor loss of rotational energy. In the nonequilibrium test set, as T(v) decreases while T is fixed, higher-j molecules contribute more significantly to the dissociation rate, dissociating trajectories tend to result in a greater rotational energy loss, and the dissociation probability's dependence on v weakens. In this way, as T(v) decreases, rotational energy appears to compensate for the decline in average vibrational energy in promoting dissociation. In both the equilibrium and nonequilibrium test sets, in every case, the average total internal energy loss in the

  1. Surface partitioning studies of N-methylcarbamate-treated post-harvest crops using SFE-HPLC-postcolumn reaction-fluorescence.

    Science.gov (United States)

    Stuart, I A; Ansell, R O; MacLachlan, J; Bather, P A

    1999-03-01

    The partitioning characteristics of selected carbamate insecticides (carbaryl, aldicarb, bendiocarb and pirimicarb) on five fruit and vegetable types were investigated. Post-harvest samples were surface-saturated with a methanolic-aqueous mixed carbamate spiking solution for a number of time periods. Samples were taken at 3, 7, 10 and 14 d, and extracted using supercritical CO2 at pressure = 300 atm modified with 10% dimethyl sulfoxide. Extracts were analysed by HPLC-postcolumn reaction-fluorescence detection at lambda ex = 330 nm and lambda em = 450 nm for N-methylcarbamates and at lambda ex = 315 nm and lambda em = 380 nm for pirimicarb. The relative partitioning of each insecticide between sample skin and flesh was investigated. This included the determination of both half-life and normalised matrix metabolic rate studies with respect to each carbamate. Multilinear regression (MLR) was applied to a number of insecticide and matrix-based variables to develop regression models for carbamate partitioning for each matrix type studied. Experimentally derived carbamate half-lives ranged from 3.6 d (carbaryl in pear flesh) to 8.0 d (bendiocarb in banana skin). Determinations of normalised metabolic rates were based on calculating the time period from the point of sampling through to the point where carbamate concentration was reduced to 5% of its initial value. These values ranged from 16.2 d (bendiocarb in potato skin) to 34.7 d (bendiocarb in banana skin). Although no practicable MLR partitioning models were obtained, it was found that the models created indicated that carbamate solubility in water (and hence log P) and the number of days in contact with the spiking solution were the most important parameters in model construction.

  2. Balancing the Hydrogen Evolution Reaction, Surface Energetics, and Stability of Metallic MoS2 Nanosheets via Covalent Functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Link, Elisa M [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Benson, Eric E [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Zhang, Hanyu [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Nanayakkara, Sanjini U [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Bronstein, Noah [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Blackburn, Jeffrey L [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Schuman, Samuel [Formerly NREL; Ferrere, Suzanne [Formerly NREL

    2017-12-27

    We modify the fundamental electronic properties of metallic (1T phase) nanosheets of molybdenum disulfide (MoS2) through covalent chemical functionalization, and thereby directly influence the kinetics of the hydrogen evolution reaction (HER), surface energetics, and stability. Chemically exfoliated, metallic MoS2 nanosheets are functionalized with organic phenyl rings containing electron donating or withdrawing groups. We find that MoS2 functionalized with the most electron donating functional group (p-(CH3CH2)2NPh-MoS2) is the most efficient catalyst for HER in this series, with initial activity that is slightly worse compared to the pristine metallic phase of MoS2. The p-(CH3CH2)2NPh-MoS2 is more stable than unfunctionalized metallic MoS2 and outperforms unfunctionalized metallic MoS2 for continuous H2 evolution within 10 min under the same conditions. With regards to the entire studied series, the overpotential and Tafel slope for catalytic HER are both directly correlated with the electron donating strength of the functional group. The results are consistent with a mechanism involving ground-state electron donation or withdrawal to/from the MoS2 nanosheets, which modifies the electron transfer kinetics and catalytic activity of the MoS2 nanosheet. The functional groups preserve the metallic nature of the MoS2 nanosheets, inhibiting conversion to the thermodynamically stable semiconducting state (2H) when mildly annealed in a nitrogen atmosphere. We propose that the electron density and, therefore, reactivity of the MoS2 nanosheets are controlled by the attached functional groups. Functionalizing nanosheets of MoS2 and other transition metal dichalcogenides provides a synthetic chemical route for controlling the electronic properties and stability within the traditionally thermally unstable metallic state.

  3. Single-Tube Reaction Using Perfluorocarbons: A Prerequisite Step Leading to the Whole-Slide In Situ Technique on Histopathological Slides.

    Directory of Open Access Journals (Sweden)

    Yi-Chang Chen

    Full Text Available Developing a robust, novel method for performing multiple reactions in a single tube is not only time- and cost-saving but also critical for future high-throughput whole-slide in situ techniques on diseased tissues. In this study, we introduce the use of perfluorocarbons and compound-coated magnetic particles to create pseudochambers in a single tube, allowing different reactions to be performed in different phases. Perfluorocarbons also serve as cell lysis buffer and polymerase chain reaction (PCR buffer owing to their highly penetrating, repellent and emulsifiable properties. Using this method, nucleic acids can be isolated and purified from various sample types and sizes, followed by PCR, real-time PCR, or multiplex PCR in the same tube. No incubation or enzyme digesting time is needed and the risk of cross-contamination is reduced. Tests can be performed in microemulsions (water-in-oil droplets containing sequence-specific captures and probes for further high-throughput detection. We present a simple, quick, and robust procedure as a prerequisite step to future high-throughput in situ techniques.

  4. Study of cadmium, lead and tin distribution in surface marine sediment samples from Ria de Arousa (NW of Spain)

    Energy Technology Data Exchange (ETDEWEB)

    Barciela-Alonso, M.C.; Pazos-Capeans, P.; Regueira-Miguens, M.E.; Bermejo-Barrera, A.; Bermejo-Barrera, P

    2004-10-25

    In this work a study of the Cd, Pb and Sn content in marine surface sediment from the Ria de Arousa has been realised. For this, 21 sediment samples were taken in triplicate, lyophilised and sieved, and the fraction <63 {mu}m was taken for analysis. The samples were prepared in a form of slurries and analysed by electrothermal atomic absorption spectrometry. The concentration ranges obtained were 90-990 {mu}g kg{sup -1} Cd, 26.5-91.3 {mu}g g{sup -1} Pb and 5.0-20.8 {mu}g g{sup -1} Sn. The highest concentrations of these metals are in the inner part of the Ria, near to the port and urban nucleus such as Vilagarcia or Rianxo, and decrease toward the mouth of the Ria.

  5. Barley yellow dwarf virus Infection Leads to Higher Chemical Defense Signals and Lower Electrophysiological Reactions in Susceptible Compared to Tolerant Barley Genotypes

    Science.gov (United States)

    Paulmann, Maria K.; Kunert, Grit; Zimmermann, Matthias R.; Theis, Nina; Ludwig, Anatoli; Meichsner, Doreen; Oelmüller, Ralf; Gershenzon, Jonathan; Habekuss, Antje; Ordon, Frank; Furch, Alexandra C. U.; Will, Torsten

    2018-01-01

    Barley yellow dwarf virus (BYDV) is a phloem limited virus that is persistently transmitted by aphids. Due to huge yield losses in agriculture, the virus is of high economic relevance. Since the control of the virus itself is not possible, tolerant barley genotypes are considered as the most effective approach to avoid yield losses. Although several genes and quantitative trait loci are known and used in barley breeding for virus tolerance, little is known about molecular and physiological backgrounds of this trait. Therefore, we compared the anatomy and early defense responses of a virus susceptible to those of a virus-tolerant cultivar. One of the very early defense responses is the transmission of electrophysiological reactions. Electrophysiological reactions to BYDV infection might differ between susceptible and tolerant cultivars, since BYDV causes disintegration of sieve elements in susceptible cultivars. The structure of vascular bundles, xylem vessels and sieve elements was examined using microscopy. All three were significantly decreased in size in infected susceptible plants where the virus causes disintegration of sieve elements. This could be associated with an uncontrolled ion exchange between the sieve-element lumen and apoplast. Further, a reduced electrophysiological isolation would negatively affect the propagation of electrophysiological reactions. To test the influence of BYDV infection on electrophysiological reactions, electropotential waves (EPWs) induced by leaf-tip burning were recorded using aphids as bioelectrodes. EPWs in infected susceptible plants disappeared already after 10 cm in contrast to those in healthy susceptible or infected tolerant or healthy tolerant plants. Another early plant defense reaction is an increase in reactive oxygen species (ROS). Using a fluorescent dye, we found a significant increase in ROS content in infected susceptible plants but not in infected tolerant plants. Similar results were found for the

  6. Barley yellow dwarf virus Infection Leads to Higher Chemical Defense Signals and Lower Electrophysiological Reactions in Susceptible Compared to Tolerant Barley Genotypes

    Directory of Open Access Journals (Sweden)

    Maria K. Paulmann

    2018-03-01

    Full Text Available Barley yellow dwarf virus (BYDV is a phloem limited virus that is persistently transmitted by aphids. Due to huge yield losses in agriculture, the virus is of high economic relevance. Since the control of the virus itself is not possible, tolerant barley genotypes are considered as the most effective approach to avoid yield losses. Although several genes and quantitative trait loci are known and used in barley breeding for virus tolerance, little is known about molecular and physiological backgrounds of this trait. Therefore, we compared the anatomy and early defense responses of a virus susceptible to those of a virus-tolerant cultivar. One of the very early defense responses is the transmission of electrophysiological reactions. Electrophysiological reactions to BYDV infection might differ between susceptible and tolerant cultivars, since BYDV causes disintegration of sieve elements in susceptible cultivars. The structure of vascular bundles, xylem vessels and sieve elements was examined using microscopy. All three were significantly decreased in size in infected susceptible plants where the virus causes disintegration of sieve elements. This could be associated with an uncontrolled ion exchange between the sieve-element lumen and apoplast. Further, a reduced electrophysiological isolation would negatively affect the propagation of electrophysiological reactions. To test the influence of BYDV infection on electrophysiological reactions, electropotential waves (EPWs induced by leaf-tip burning were recorded using aphids as bioelectrodes. EPWs in infected susceptible plants disappeared already after 10 cm in contrast to those in healthy susceptible or infected tolerant or healthy tolerant plants. Another early plant defense reaction is an increase in reactive oxygen species (ROS. Using a fluorescent dye, we found a significant increase in ROS content in infected susceptible plants but not in infected tolerant plants. Similar results were found

  7. Low-Speed Investigation of Upper-Surface Leading-Edge Blowing on a High-Speed Civil Transport Configuration

    Science.gov (United States)

    Banks, Daniel W.; Laflin, Brenda E. Gile; Kemmerly, Guy T.; Campbell, Bryan A.

    1999-01-01

    The paper identifies speed, agility, human interface, generation of sensitivity information, task decomposition, and data transmission (including storage) as important attributes for a computer environment to have in order to support engineering design effectively. It is argued that when examined in terms of these attributes the presently available environment can be shown to be inadequate. A radical improvement is needed, and it may be achieved by combining new methods that have recently emerged from multidisciplinary design optimisation (MDO) with massively parallel processing computer technology. The caveat is that, for successful use of that technology in engineering computing, new paradigms for computing will have to be developed - specifically, innovative algorithms that are intrinsically parallel so that their performance scales up linearly with the number of processors. It may be speculated that the idea of simulating a complex behaviour by interaction of a large number of very simple models may be an inspiration for the above algorithms; the cellular automata are an example. Because of the long lead time needed to develop and mature new paradigms, development should begin now, even though the widespread availability of massively parallel processing is still a few years away.

  8. Mechanisms and energetics of surface reactions at the copper-water interface. A critical literature review with implications for the debate on corrosion of copper in anoxic water

    Energy Technology Data Exchange (ETDEWEB)

    Johansson, Adam Johannes; Brinck, Tore [Applied Physical Chemistry, KTH Royal Inst. of Technology, Stockholm (Sweden)

    2012-06-15

    In order to make a critical analysis of the discussion of corrosion of copper in pure anoxic water it is necessary to understand the chemical reactivity at the copper-water interface. Even though the most fundamental issue, i.e. the nature and existence of a hypothetical product that is thermodynamically stable, is still under debate, it is clear that if anoxic corrosion really exists, it must be initiated through oxidative surface reactions at the copper-water interface. This report presents a survey of the peer reviewed literature on the reactivity of copper surfaces in water. Reactions discussed involve molecular adsorption of water, dissociation of the OH-bonds in adsorbed water molecules and hydroxyl groups, the disproportionation/synproportionation equilibrium between hydroxyl groups/hydroxide ions, water molecules and atomic oxygen, the surface diffusion of adsorbed species, and the formation of hydrogen gas (molecular hydrogen). Experimental, as well as theoretical (quantum chemical) studies are reviewed. It is concluded that a limited amount of hydrogen gas (H{sub 2}) should be formed as the result of dissociative water adsorption at certain copper surfaces. Quantitative estimates of the amounts of H2 that could form at the copper-water interface are made. Assuming that the water-cleavage/hydrogen-formation reaction proceeds on an ideal [110] or [100] surface until a hydroxyl monolayer (ML) is reached, the amount of H{sub 2} formed is {approx} 2.4 ng cm{sup -2} copper surface. Based on the literature cited, this is most likely possible, thermodynamically as well as kinetically. Although not proven, it is not unlikely that the reaction can proceed until an oxide ML is formed, which would give 4.8 ng cm{sup -2}. If the formation of an oxide ML is thermodynamically feasible the surface will probably react further, since Cu{sub 2}O(s) is known to activate and cleave the water molecule when it adsorbs at the Cu{sub 2}O(s) surface. Assuming the formation of a

  9. Photoluminescence and self-assembly of cesium lead halide perovskite nanocrystals: Effects of chain length of organic amines and reaction temperature

    International Nuclear Information System (INIS)

    Yuan, Yi; Liu, Zheming; Liu, Zhenyang; Peng, Lan; Li, Yongjie; Tang, Aiwei

    2017-01-01

    Highlights: • CsPbBr 3 perovskite nanocrystals have been synthesized in the presence of organic amines with different hydrocarbon length. • The photoluminescence of the CsPbBr 3 nanocrystals is affected by the varying the carbon length of the organic amines. • The lower reaction temperature and hydrocarbon chain length of the organic ligands play a significant role in the self-assembly of CsPbBr 3 nanocrystals. - Abstract: All-inorganic halide perovskites have become one of the most prospective materials for lightening and display technology due to their color-tunable and narrow-band emission. Herein, we have systematically studied the effects of organic amines with different hydrocarbon chain length on the optical properties and morphology as well as the crystal structure of colloidal CsPbBr 3 nanocrystals (NCs), which were synthesized in the presence of oleic acid (OA) and organic amines by using a simple hot-injection approach. The hydrocarbon chain length has shown an independent correlation to the morphology and crystal structure of the as-obtained CsPbBr 3 NCs at 160 °C, but their optical properties can be affected to some extent. The photoluminescence quantum yields (PLQYs) of the CsPbBr 3 NCs synthesized in the presence of organic amines with long carbon chain length are generally in the range of 55–80% for different reaction time, but the PLQYs of less than 20% are obtained for the products synthesized in the presence of octylamine (OTAm) with short carbon chain length. The effects of the reaction temperature on the optical properties, size and crystal structure of the CsPbBr 3 NCs synthesized in the presence of cetylamine (CTAm) are studied. Interestingly, some nanoplates also appear in these CsPbBr 3 NCs obtained at relatively low temperatures (120 and 140 °C), which have a strong tendency to self-assemble into face-to-face nanostructures. Such a similar self-assembly behavior is also observed in the product synthesized in the presence of

  10. Photoluminescence and self-assembly of cesium lead halide perovskite nanocrystals: Effects of chain length of organic amines and reaction temperature

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Yi; Liu, Zheming; Liu, Zhenyang; Peng, Lan; Li, Yongjie; Tang, Aiwei, E-mail: awtang@bjtu.edu.cn

    2017-05-31

    Highlights: • CsPbBr{sub 3} perovskite nanocrystals have been synthesized in the presence of organic amines with different hydrocarbon length. • The photoluminescence of the CsPbBr{sub 3} nanocrystals is affected by the varying the carbon length of the organic amines. • The lower reaction temperature and hydrocarbon chain length of the organic ligands play a significant role in the self-assembly of CsPbBr{sub 3} nanocrystals. - Abstract: All-inorganic halide perovskites have become one of the most prospective materials for lightening and display technology due to their color-tunable and narrow-band emission. Herein, we have systematically studied the effects of organic amines with different hydrocarbon chain length on the optical properties and morphology as well as the crystal structure of colloidal CsPbBr{sub 3} nanocrystals (NCs), which were synthesized in the presence of oleic acid (OA) and organic amines by using a simple hot-injection approach. The hydrocarbon chain length has shown an independent correlation to the morphology and crystal structure of the as-obtained CsPbBr{sub 3} NCs at 160 °C, but their optical properties can be affected to some extent. The photoluminescence quantum yields (PLQYs) of the CsPbBr{sub 3} NCs synthesized in the presence of organic amines with long carbon chain length are generally in the range of 55–80% for different reaction time, but the PLQYs of less than 20% are obtained for the products synthesized in the presence of octylamine (OTAm) with short carbon chain length. The effects of the reaction temperature on the optical properties, size and crystal structure of the CsPbBr{sub 3} NCs synthesized in the presence of cetylamine (CTAm) are studied. Interestingly, some nanoplates also appear in these CsPbBr{sub 3} NCs obtained at relatively low temperatures (120 and 140 °C), which have a strong tendency to self-assemble into face-to-face nanostructures. Such a similar self-assembly behavior is also observed in the

  11. Wet chemical functionalization of III-V semiconductor surfaces: alkylation of gallium arsenide and gallium nitride by a Grignard reaction sequence.

    Science.gov (United States)

    Peczonczyk, Sabrina L; Mukherjee, Jhindan; Carim, Azhar I; Maldonado, Stephen

    2012-03-13

    Crystalline gallium arsenide (GaAs) (111)A and gallium nitride (GaN) (0001) surfaces have been functionalized with alkyl groups via a sequential wet chemical chlorine activation, Grignard reaction process. For GaAs(111)A, etching in HCl in diethyl ether effected both oxide removal and surface-bound Cl. X-ray photoelectron (XP) spectra demonstrated selective surface chlorination after exposure to 2 M HCl in diethyl ether for freshly etched GaAs(111)A but not GaAs(111)B surfaces. GaN(0001) surfaces exposed to PCl(5) in chlorobenzene showed reproducible XP spectroscopic evidence for Cl-termination. The Cl-activated GaAs(111)A and GaN(0001) surfaces were both reactive toward alkyl Grignard reagents, with pronounced decreases in detectable Cl signal as measured by XP spectroscopy. Sessile contact angle measurements between water and GaAs(111)A interfaces after various levels of treatment showed that GaAs(111)A surfaces became significantly more hydrophobic following reaction with C(n)H(2n-1)MgCl (n = 1, 2, 4, 8, 14, 18). High-resolution As 3d XP spectra taken at various times during prolonged direct exposure to ambient lab air indicated that the resistance of GaAs(111)A to surface oxidation was greatly enhanced after reaction with Grignard reagents. GaAs(111)A surfaces terminated with C(18)H(37) groups were also used in Schottky heterojunctions with Hg. These heterojunctions exhibited better stability over repeated cycling than heterojunctions based on GaAs(111)A modified with C(18)H(37)S groups. Raman spectra were separately collected that suggested electronic passivation by surficial Ga-C bonds at GaAs(111)A. Specifically, GaAs(111)A surfaces reacted with alkyl Grignard reagents exhibited Raman signatures comparable to those of samples treated with 10% Na(2)S in tert-butanol. For GaN(0001), high-resolution C 1s spectra exhibited the characteristic low binding energy shoulder demonstrative of surface Ga-C bonds following reaction with CH(3)MgCl. In addition, 4

  12. LEADING WITH LEADING INDICATORS

    International Nuclear Information System (INIS)

    PREVETTE, S.S.

    2005-01-01

    This paper documents Fluor Hanford's use of Leading Indicators, management leadership, and statistical methodology in order to improve safe performance of work. By applying these methods, Fluor Hanford achieved a significant reduction in injury rates in 2003 and 2004, and the improvement continues today. The integration of data, leadership, and teamwork pays off with improved safety performance and credibility with the customer. The use of Statistical Process Control, Pareto Charts, and Systems Thinking and their effect on management decisions and employee involvement are discussed. Included are practical examples of choosing leading indicators. A statistically based color coded dashboard presentation system methodology is provided. These tools, management theories and methods, coupled with involved leadership and employee efforts, directly led to significant improvements in worker safety and health, and environmental protection and restoration at one of the nation's largest nuclear cleanup sites

  13. Atypical McMurry Cross-Coupling Reactions Leading to a New Series of Potent Antiproliferative Co