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Sample records for oxygen adsorption sites

  1. A first-principles study of oxygen adsorption on Ir(111) surface

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Hengjiao, E-mail: gaohengjiao@163.com; Xiong, Yuqing, E-mail: xiongyq@hotmail.com; Liu, Xiaoli, E-mail: shantianzi@126.com; Zhao, Dongcai, E-mail: zhaodongc@163.com; Feng, Yudong, E-mail: yudong_feng@sina.com; Wang, Lanxi, E-mail: wanglanxi@live.com; Wang, Jinxiao, E-mail: coldwind716@gmail.com

    2016-12-15

    Highlights: • Adsorption of oxygen on Ir(111) surface was studied by density functional theory. • The most stable adsorption site was determined by adsorption energy calculation. • Adsorption of oxygen at bridge and top site on Ir surface was the most stable ones. • Interaction of O 2p and Ir 5d orbits is relatively strong and formed hybridization. - Abstract: In order to understand deposition mechanism of iridium thin film by atomic layer deposition, the adsorption of oxygen on Ir(111) surface was studied by use of density functional theory and a periodical slab model. By calculating the adsorption energy and structure of oxygen at four adsorption sites (top, bridge, fcc-hollow and hcp-hollow) on Ir(111) surface, the most stable adsorption site was determined. On this basis, the banding mechanism of O and Ir atoms was studied by density of states of oxygen and iridium atoms. Oxygen adsorbed at hcp(parallel) site on Ir(111) surface was the most stable one according to the adsorption energy calculation results. Orbital charge analysis indicate that charge transferred from 5p and 5d orbit to 2p orbit of adsorbed O atoms, and 6s orbit of iridium atoms. Meanwhile, density of state study indicated that adsorption of oxygen on Ir(111) surface is mainly due to the interaction between 2p orbit of O atoms and 5d orbit of iridium atoms.

  2. Weakly-bound adsorption states and low-temperature adsorption kinetiks of oxygen on tungsten (100) and (110) faces

    International Nuclear Information System (INIS)

    Zhukov, V.V.; Osovskij, V.D.; Ptushnikov, Yu.G.; Sukretnyj, V.G.; Chujkov, B.A.

    1986-01-01

    A molecular beam technique with an effusion source operating at T=200 K is used to study the adsorption interaction of oxygen with W(100) and (110) faces in the range of the simple temperatures from 5 to 340 K. Three weakly-bound adsorption states of oxygen are detected corresponding to adsorption in the second, third and forth monolayer. These states are characterized by adsorption energies of 0.13, 0.08 and 0.07 eV and desorption temperatures of 45, 27 and 25 K, respectively. The kinetics of filling of these states is almost similar for both faces, whereas the adsorption kinetics in the first monolayer is essentially different. A dissociative nature of adsorption at T >or approx. 5 K and a jump migration mechanism of the admolecules in the precursor state to the stationary adsorption sites are suggested

  3. Oxygen adsorption on Pt(110)-(1x2): new high-coverage structures

    DEFF Research Database (Denmark)

    Helveg, Stig; Lorensen, Henrik Qvist; Horch, Sebastian

    1999-01-01

    From an interplay between scanning tunneling microscopy (STM) experiments and density functional theory (DFT) calculations, a comprehensive picture is obtained for oxygen adsorption on the Pt(110)-(1 x 2) surface, from single isolated oxygen atoms chemisorbed in FCC sites along the platinum ridges...... adsorption and platinum lattice distortions. (C) 1999 Elsevier Science B.V. All rights reserved....

  4. Atomic hydrogen and oxygen adsorptions in single-walled zigzag silicon nanotubes

    International Nuclear Information System (INIS)

    Chen, Haoliang; Ray, Asok K.

    2013-01-01

    Ab initio calculations have been performed to study the electronic and geometric structure properties of zigzag silicon nanotubes. Full geometry and spin optimizations have been performed without any symmetry constraints with an all electron 3-21G* basis set and the B3LYP hybrid functional. The largest zigzag SiNT studied here, (12, 0), has a binding energy per atom of 3.584 eV. Atomic hydrogen and oxygen adsorptions on (9, 0) and (10, 0) nanotubes have also been studied by optimizing the distances of the adatoms from both inside and outside the tube. The adatom is initially placed in four adsorption sites-parallel bridge (PB), zigzag bridge (ZB), hollow, and on-top site. The on-top site is the most preferred site for hydrogen atom adsorbed on (9, 0), with an adsorption energy of 3.0 eV and an optimized distance of 1.49 Å from the adatom to the nearest silicon atom. For oxygen adsorption on (9, 0), the most preferred site is the ZB site, with an adsorption energy of 5.987 eV and an optimized distance of 1.72 Å. For atomic hydrogen adsorption on (10, 0), the most preferred site is also the on-top site with an adsorption energy of 3.174 eV and an optimized distance of 1.49 Å. For adsorption of atomic oxygen on (10, 0), the most preferred site is PB site, with an adsorption energy of 6.306 eV and an optimized distance of 1.71 Å. The HOMO–LUMO gaps of (9, 0) after adsorptions of hydrogen and oxygen atoms decrease while the HOMO–LUMO gaps of (10, 0) increase after adsorption of hydrogen and oxygen

  5. Oxygen adsorption on the Al0.25Ga0.75N (0001) surface: A first-principles study

    Science.gov (United States)

    Fu, Jiaqi; Song, Tielei; Liang, Xixia; Zhao, Guojun

    2018-04-01

    To understand the interaction mechanism for the oxygen adsorption on AlGaN surface, herein, we built the possible models of oxygen adsorption on Al0.25Ga0.75N (0001) surface. For different oxygen coverage, three kinds of adsorption site are considered. Then the favorable adsorption sites are characterized by first principles calculation for (2 × 2) supercell of Al0.25Ga0.75N (0001) surface. On basis of the optimal adsorption structures, our calculated results show that all the adsorption processes are exothermic, indicating that the (0001) surface orientation is active towards the adsorption of oxygen. The doping of Al is advantage to the adsorption of O atom. Additionally, the adsorption energy decreases with reducing the oxygen coverage, and the relationship between them is approximately linear. Owing to the oxygen adsorption, the surface states in the fundamental band gap are significant reduced with respect to the free Al0.25Ga0.75N (0001) surface. Moreover, the optical properties on different oxygen coverage are also discussed.

  6. Oxygen adsorption on the Al9Co2(001) surface: first-principles and STM study

    International Nuclear Information System (INIS)

    Villaseca, S Alarcón; Loli, L N Serkovic; Ledieu, J; Fournée, V; Dubois, J-M; Gaudry, É; Gille, P

    2013-01-01

    Atomic oxygen adsorption on a pure aluminum terminated Al 9 Co 2 (001) surface is studied by first-principle calculations coupled with STM measurements. Relative adsorption energies of oxygen atoms have been calculated on different surface sites along with the associated STM images. The local electronic structure of the most favourable adsorption site is described. The preferential adsorption site is identified as a ‘bridge’ type site between the cluster entities exposed at the (001) surface termination. The Al–O bonding between the adsorbate and the substrate presents a covalent character, with s–p hybridization occurring between the states of the adsorbed oxygen atom and the aluminum atoms of the surface. The simulated STM image of the preferential adsorption site is in agreement with experimental observations. This work shows that oxygen adsorption generates important atomic relaxations of the topmost surface layer and that sub-surface cobalt atoms strongly influence the values of the adsorption energies. The calculated Al–O distances are in agreement with those reported in Al 2 O and Al 2 O 3 oxides and for oxygen adsorption on Al(111). (paper)

  7. Activated carbon oxygen content influence on water and surfactant adsorption.

    Science.gov (United States)

    Pendleton, Phillip; Wu, Sophie Hua; Badalyan, Alexander

    2002-02-15

    This research investigates the adsorption properties of three activated carbons (AC) derived from coconut, coal, and wood origin. Each carbon demonstrates different levels of resistance to 2 M NaOH treatment. The coconut AC offers the greatest and wood AC the least resistance. The influence of base treatment is mapped in terms of its effects on specific surface area, micropore volume, water adsorption, and dodecanoic acid adsorption from both water and 2 M NaOH solution. A linear relationship exists between the number of water molecules adsorbed at the B-point of the water adsorption isotherm and the oxygen content determined from elemental analysis. Surfactant adsorption isotherms from water and 2 M NaOH indicate that the AC oxygen content effects a greater dependence on affinity for surfactant than specific surface area and micropore volume. We show a linear relationship between the plateau amount of surfactant adsorbed and the AC oxygen content in both water and NaOH phases. The higher the AC oxygen content, the lower the amount of surfactant adsorbed. In contrast, no obvious relationship could be drawn between the surfactant amount adsorbed and the surface area.

  8. Site competition on metal surfaces: an electron spectroscopic study of sequential adsorption on W(110)

    International Nuclear Information System (INIS)

    Steinkilberg, M.; Menzel, D.

    1977-01-01

    Using UPS and XPS, the sequential adsorption of hydrogen + carbon monoxide, and of hydrogen + oxygen, on W(110) has been studied at room temperature. Adsorption of CO on a H-covered surface is rapid and leads to total displacement of hydrogen. The resulting CO layer however, is different from that formed on the clean surface under identical conditions, in that it consists of a higher percentage of virgin CO, while considerably more β-CO forms on the clean surface. Oxygen does not adsorb on a H-covered surface, nor displace hydrogen. It is concluded that hydrogen most probably occupies the same sites utilized by dissociative adsorption of CO and oxygen, while virgin CO can also occupy different sites; its adsorption can thus lead to interactional weakening of the H-surface bond. (Auth.)

  9. Electron stimulated desorption study of oxygen adsorption on tungsten

    International Nuclear Information System (INIS)

    Prince, R.H.; Floyd, G.R.

    1978-01-01

    The adsorption of oxygen on a polycrystalline tungsten surface at approximately 800 K has been studied by means of electron stimulated desorption (ESD). Although precision gas dosing was not employed, the initial sticking probability for dissociative adsorption appears to be essentially unity, while the variation with coverage suggests that a high degree of order exists and that precursor state kinetics are significant. A most noticeable and reproducible discontinuity in ESD parameters occurs at a fractional coverage theta approximately 0.8 (exposure approximately 1.4 X 10 15 molecules/cm 2 incident) which is interpreted as an order-disorder transition within a single (β 1 ) chemisorption state, and results in an increase in the ionic desorption cross-section by a factor of approximately 1.26. A discussion of the adsorption kinetics and the disorder transition is given in terms of current models of dissociative adsoption which include the effects of nearest neighbour lateral interactions. (Auth.)

  10. First principles study of dissolved oxygen water adsorption on Fe (001 surfaces

    Directory of Open Access Journals (Sweden)

    Dong ZHANG

    2018-02-01

    Full Text Available In order to study the mechanism of dissolved oxygen content on the surface corrosion behavior of Fe-based heat transfer, the first principle is used to study the adsorption of O2 monomolecular, H2O monolayer and dissolved oxygen system on Fe-based heat transfer surface. The GGA/PBE approximation is used to calculate the adsorption energy, state density and population change during the adsorption process. Calculations prove that when the dissolved oxygen is adsorbed on the Fe-based surface, the water molecule tends to adsorb at the top sites, and the oxygen molecule tends to adsorb at Griffiths. When the H2O molecule adsorbs and interacts on the Fe (001 surface, the charge distribution of the interfacial double electric layer changes to cause the Fe atoms to lose electrons, resulting in the change of the surface potential. When the O2 molecule adsorbs on the Fe (001 crystal surfaces, the electrons on the Fe (001 surface are lost and the surface potential increases. O2 molecule and the surface of the Fe atoms are prone to electron transfer, in which O atom's 2p orbit for the adsorption of O2 molecule on Fe (001 crystal surface play a major role. With the increase of the proportion of O2 molecule in the dissolved oxygen water, the absolute value of the adsorption energy increases, and the interaction of the Fe-based heat transfer surface is stronger. This study explores the influence law of different dissolved oxygen on the Fe base heat exchange surface corrosion, and the base metal corrosion mechanism for experimental study provides a theoretical reference.

  11. Coverage-dependent adsorption thermodynamics of oxygen on ZnO(0001)

    Energy Technology Data Exchange (ETDEWEB)

    Li, Ming; Seebauer, Edmund G., E-mail: eseebaue@illinois.edu

    2017-03-01

    Highlights: • Adsorption enthalpy and entropy of oxygen on Zn-term ZnO(0001) were measured by photoreflectance. • These parameters are large in magnitude and vary nonmonotonically with coverage. • Many kinds of sites, chemical species and reconstructions contribute to this behavior. • Entropic and enthalpic contributions to the free energy are comparable near room temperature. - Abstract: The equilibrium behavior of oxygen adsorbed on metal oxide surfaces such as ZnO(0001) often affects their behavior in applications such as gas sensing. The present work attempts to bridge this distinct gap to applications from an alternate perspective by employing the optical technique of photoreflectance (PR) to measure the enthalpy ΔH{sub ads} and entropy ΔS{sub ads} of oxygen adsorption as a function of coverage on Zn-terminated ZnO(0001). The large and strongly coverage-dependent parameters, stemming from a multiplicity of sites, chemical species and reconstructions, lead to a nonmonotonic coverage variation in both ΔH{sub ads} and ΔS{sub ads}. The entropic contribution to the free energy is comparable to the enthalpic contribution even near room temperature, so that temperature effects on oxygen adsorption may be uncommonly large.

  12. Modulating Protein Adsorption on Oxygen Plasma Modified Polysiloxane Surfaces

    International Nuclear Information System (INIS)

    Marletta, G.

    2006-01-01

    In the present paper we report the study on the adsorption behaviour of three model globular proteins, Human Serum Albumin, Lactoferrin and Egg Chicken Lysozyme onto both unmodified surfaces of a silicon-based polymer and the corresponding plasma treated surfaces. In particular, thin films of hydrophobic polysiloxane (about 90 degree of static water contact angle, WCA) were converted by oxygen plasma treatment at reduced pressure into very hydrophilic phases of SiOx (WCA less than 5 degree). The kinetics of protein adsorption processes were investigated by QCM-D technique, while the chemical structure and topography of the protein adlayer have been studied by Angular resolved-XPS and AFM respectively. It turned out that Albumin and Lysozyme exhibited the opposite preferential adsorption respectively onto the hydrophobic and hydrophilic surfaces, while Lactoferrin did not exhibit significant differences. The observed protein behaviour are discussed both in terms of surface-dependent parameters, including surface free energy and chemical structure, and in terms of protein-dependent parameters, including charge as well as the average molecular orientation in the adlayers. Finally, some examples of differential adsorption behaviour of the investigated proteins are reported onto nanopatterned polysiloxane surfaces consisting of hydrophobic nanopores surrounded by hydrophilic (plasma-treated) matrix and the reverse

  13. Effects of hydration and oxygen vacancy on CO2 adsorption and activation on beta-Ga2O3(100).

    Science.gov (United States)

    Pan, Yun-xiang; Liu, Chang-jun; Mei, Donghai; Ge, Qingfeng

    2010-04-20

    The effects of hydration and oxygen vacancy on CO(2) adsorption on the beta-Ga(2)O(3)(100) surface have been studied using density functional theory slab calculations. Adsorbed CO(2) is activated on the dry perfect beta-Ga(2)O(3)(100) surface, resulting in a carbonate species. This adsorption is slightly endothermic, with an adsorption energy of 0.07 eV. Water is preferably adsorbed molecularly on the dry perfect beta-Ga(2)O(3)(100) surface with an adsorption energy of -0.56 eV, producing a hydrated perfect beta-Ga(2)O(3)(100) surface. Adsorption of CO(2) on the hydrated surface as a carbonate species is also endothermic, with an adsorption energy of 0.14 eV, indicating a slightly repulsive interaction when H(2)O and CO(2) are coadsorbed. The carbonate species on the hydrated perfect surface can be protonated by the coadsorbed H(2)O to a bicarbonate species, making the CO(2) adsorption exothermic, with an adsorption energy of -0.13 eV. The effect of defects on CO(2) adsorption and activation has been examined by creating an oxygen vacancy on the dry beta-Ga(2)O(3)(100) surface. The formation of an oxygen vacancy is endothermic, by 0.34 eV, with respect to a free O(2) molecule in the gas phase. Presence of the oxygen vacancy promoted the adsorption and activation of CO(2). In the most stable CO(2) adsorption configuration on the dry defective beta-Ga(2)O(3)(100) surface with an oxygen vacancy, one of the oxygen atoms of the adsorbed CO(2) occupies the oxygen vacancy site, and the CO(2) adsorption energy is -0.31 eV. Water favors dissociative adsorption at the oxygen vacancy site on the defective surface. This process is spontaneous, with a reaction energy of -0.62 eV. These results indicate that, when water and CO(2) are present in the adsorption system simultaneously, water will compete with CO(2) for the oxygen vacancy sites and impact CO(2) adsorption and conversion negatively.

  14. [Adsorption of heavy metals on the surface of birnessite relationship with its Mn average oxidation state and adsorption sites].

    Science.gov (United States)

    Wang, Yan; Tan, Wen-Feng; Feng, Xiong-Han; Qiu, Guo-Hong; Liu, Fan

    2011-10-01

    Adsorption characteristics of mineral surface for heavy metal ions are largely determined by the type and amount of surface adsorption sites. However, the effects of substructure variance in manganese oxide on the adsorption sites and adsorption characteristics remain unclear. Adsorption experiments and powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) were combined to examine the adsorption characteristics of Pb2+, Cu2+, Zn2+ and Cd2+ sequestration by birnessites with different Mn average oxidation state (AOS), and the Mn AOS dependent adsorption sites and adsorption characteristics. The results show that the maximum adsorption capacity of Pb2+, Cu2+, Zn2+ and Cd2+ increased with increasing birnessite Mn AOS. The adsorption capacity followed the order of Pb2+ > Cu2+ > Zn2+ > Cd2+. The observations suggest that there exist two sites on the surface of birnessite, i. e., high-binding-energy site (HBE site) and low-binding-energy site (LBE site). With the increase of Mn AOS for birnessites, the amount of HBE sites for heavy metal ions adsorption remarkably increased. On the other hand, variation in the amount of LBE sites was insignificant. The amount of LBE sites is much more than those of HBE sites on the surface of birnessite with low Mn AOS. Nevertheless, both amounts on the surface of birnessite with high Mn AOS are very close to each other. Therefore, the heavy metal ions adsorption capacity on birnessite is largely determined by the amount of HBE sites. On birnessite surface, adsorption of Cu2+, Zn2+, and Cd2+ mostly occurred at HBE sites. In comparison with Zn2+ and Cd2+, more Cu2+ adsorbed on the LBW sites. Pb2+ adsorption maybe occupy at both LBE sites and HBE sites simultaneously.

  15. Adsorption of oxygen on low-index surfaces of the TiAl{sub 3} alloy

    Energy Technology Data Exchange (ETDEWEB)

    Latyshev, A. M.; Bakulin, A. V.; Kulkova, S. E., E-mail: kulkova@ms.tsc.ru [National Research Tomsk State University (Russian Federation); Hu, Q. M.; Yang, R. [Chinese Academy of Sciences, Shenyang National Laboratory for Materials Science, Institute of Metal Research (China)

    2016-12-15

    Method of the projector augmented waves in the plane-wave basis within the generalized-gradient approximation for the exchange-correlation functional has been used to study oxygen adsorption on (001), (100), and (110) low-index surfaces of the TiAl{sub 3} alloy. It has been established that the sites that are most energetically preferred for the adsorption of oxygen are hollow (H) positions on the (001) surface and bridge (B) positions on the (110) and (100) surfaces. Structural and electronic factors that define their energy preference have been discussed. Changes in the atomic and electronic structure of subsurface layers that occur as the oxygen concentration increases to three monolayers have been analyzed. It has been shown that the formation of chemical bonds of oxygen with both components of the alloy leads to the appearance of states that are split-off from the bottoms of their valence bands, which is accompanied by the formation of a forbidden gap at the Fermi level and by a weakening of the Ti–Al metallic bonds in the alloy. On the Al-terminated (001) and (110) surfaces, the oxidation of aluminum dominates over that of titanium. On the whole, the binding energy of oxygen on the low-index surfaces with a mixed termination is higher than that at the aluminum-terminated surface. The calculation of the diffusion of oxygen in the TiAl{sub 3} alloy has shown that the lowest barriers correspond to the diffusion between tetrahedral positions in the (001) plane; the diffusion of oxygen in the [001] direction occurs through octahedral and tetrahedral positions. An increase in the concentration of aluminum in the alloy favors a reduction in the height of the energy barriers as compared to the corresponding barriers in the γ-TiAl alloy.

  16. Adsorption of ionizable organic contaminants on multi-walled carbon nanotubes with different oxygen contents

    International Nuclear Information System (INIS)

    Li Xiaona; Zhao Huimin; Quan Xie; Chen Shuo; Zhang Yaobin; Yu Hongtao

    2011-01-01

    Multi-walled carbon nanotubes (MWNTs), which are considered to be promising candidates for the adsorption of toxic organics, are released into aqueous environment with their increasing production and application. In this study, the adsorption behaviors of five structurally related ionizable organic contaminants namely perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorooctanesulfonamide (PFOSA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-n-nonylphenol (4-NP) onto MWNTs with different oxygen contents (3.84-22.85%) were investigated. The adsorption kinetics was investigated and simulated with pseudo-second-order model. The adsorption isotherms were found to be fitted with Freundlich model and influenced by both the properties of organic chemicals and the oxygen contents of MWNTs. As adsorption capacity decreases dramatically with the increasing of oxygen contents, the MWNTs with the lowest oxygen contents possess the highest adsorption capacity among four MWNTs. For the MWNTs with the oxygen contents of 3.84%, the adsorption affinity related with hydrophobic interaction and π-electron polarizability decreased in the order of 4-NP > PFOSA > PFOS > 2,4-D > PFOA. Furthermore, the adsorption characters of five contaminants were affected by solution pH and solute pK a considering electrostatic repulse force and hydrogen bonding, which showed the adsorption of MWNTs with lower oxygen content is much sensitive to solution chemistry.

  17. Adsorption of atomic oxygen on PdAg/Pd(111) surface alloys and coadsorption of CO

    Energy Technology Data Exchange (ETDEWEB)

    Farkas, Arnold P. [Institute of Surface Chemistry and Catalysis, Ulm University, D-89069 Ulm (Germany); Reaction Kinetics Research Group, University of Szeged, Chemical Research Center of the Hungarian Academy of Sciences, H-6720 Szeged (Hungary); Bansmann, Joachim; Diemant, Thomas; Behm, R. Juergen [Institute of Surface Chemistry and Catalysis, Ulm University, D-89069 Ulm (Germany)

    2011-07-01

    The interaction of dissociated oxygen with structurally well-defined PdAg/Pd(111) surface alloys and the coadsorption of CO was studied by high resolution electron energy loss spectroscopy (HREELS) and temperature-programmed desorption (TPD). After oxygen saturation of the non-modified Pd(111) surface at RT, we observed the formation of a prominent peak in the HREEL spectra at 60 meV corresponding to the perpendicular vibration of oxygen atoms adsorbed in threefold hollow sites. Deposition of small Ag amounts does not change the signal intensity of this peak; it decreases only above 20% Ag. Beyond this Ag content, the peak intensity steeply declines and disappears at around 55-60% Ag. CO coadsorption on the oxygen pre-covered surfaces at 120 K leads to the formation of additional features in HREELS. For a surface alloy with 29% Ag, three loss features due to CO adsorption in on-top, bridge, and threefold-hollow sites can be discriminated already after the lowest CO exposure. Annealing of the co-adsorbed layer to 200 K triggers a decrease of the oxygen concentration due to CO{sub 2} formation. These findings are corroborated by TPD spectra of the CO desorption and CO{sub 2} production.

  18. Effect of Humid Aging on the Oxygen Adsorption in SnO₂ Gas Sensors.

    Science.gov (United States)

    Suematsu, Koichi; Ma, Nan; Watanabe, Ken; Yuasa, Masayoshi; Kida, Tetsuya; Shimanoe, Kengo

    2018-01-16

    To investigate the effect of aging at 580 °C in wet air (humid aging) on the oxygen adsorption on the surface of SnO₂ particles, the electric properties and the sensor response to hydrogen in dry and humid atmospheres for SnO₂ resistive-type gas sensors were evaluated. The electric resistance in dry and wet atmospheres at 350 °C was strongly increased by humid aging. From the results of oxygen partial pressure dependence of the electric resistance, the oxygen adsorption equilibrium constants ( K ₁; for O - adsorption, K ₂; for O 2- adsorption) were estimated on the basis of the theoretical model of oxygen adsorption. The K ₁ and K ₂ in dry and wet atmospheres at 350 °C were increased by humid aging at 580 °C, indicating an increase in the adsorption amount of both O - and O 2- . These results suggest that hydroxyl poisoning on the oxygen adsorption is suppressed by humid aging. The sensor response to hydrogen in dry and wet atmosphere at 350 °C was clearly improved by humid aging. Such an improvement of the sensor response seems to be caused by increasing the oxygen adsorption amount. Thus, the humid aging offers an effective way to improve the sensor response of SnO₂ resistive-type gas sensors in dry and wet atmospheres.

  19. Effect of Humid Aging on the Oxygen Adsorption in SnO2 Gas Sensors

    Directory of Open Access Journals (Sweden)

    Koichi Suematsu

    2018-01-01

    Full Text Available To investigate the effect of aging at 580 °C in wet air (humid aging on the oxygen adsorption on the surface of SnO2 particles, the electric properties and the sensor response to hydrogen in dry and humid atmospheres for SnO2 resistive-type gas sensors were evaluated. The electric resistance in dry and wet atmospheres at 350 °C was strongly increased by humid aging. From the results of oxygen partial pressure dependence of the electric resistance, the oxygen adsorption equilibrium constants (K1; for O− adsorption, K2; for O2− adsorption were estimated on the basis of the theoretical model of oxygen adsorption. The K1 and K2 in dry and wet atmospheres at 350 °C were increased by humid aging at 580 °C, indicating an increase in the adsorption amount of both O− and O2−. These results suggest that hydroxyl poisoning on the oxygen adsorption is suppressed by humid aging. The sensor response to hydrogen in dry and wet atmosphere at 350 °C was clearly improved by humid aging. Such an improvement of the sensor response seems to be caused by increasing the oxygen adsorption amount. Thus, the humid aging offers an effective way to improve the sensor response of SnO2 resistive-type gas sensors in dry and wet atmospheres.

  20. Efficient oxygen electrocatalysis on special active sites

    DEFF Research Database (Denmark)

    Halck, Niels Bendtsen

    throughout this thesis to understand these local structure effects and their influence on surface reactions. The concept of these special active sites is used to explain how oxygen evolution reaction (OER) catalysts can have activities beyond the limits of what was previously thought possible. The concept...... stored in these bonds in an eco-friendly fashion in fuel cells. This thesis explores catalysts for oxygen electrocatalysis and how carefully designed local structures on catalysts surfaces termed special active sites can influence the activity. Density functional theory has been used as a method...... is used to explain the increase in activity observed for the OER catalyst ruthenium dioxide when it is mixed with nickel or cobalt. Manganese and cobalt oxides when in the vicinity of gold also display an increase in OER activity which can be explained by locally created special active sites. Density...

  1. Density functional theory studies of the adsorption of ethylene and oxygen on Pt(111) and Pt3Sn(111)

    DEFF Research Database (Denmark)

    Watwe, R.M.; Cortright, R.D.; Mavrikakis, Manos

    2001-01-01

    Density functional theory, employing periodic slab calculations, was used to investigate the interactions of ethylene and oxygen with Pt(111) and Pt3Sn(111). The predicted energetics and structures of adsorbed species on Pt(111) are in good agreement with experimental data. The binding energies...... more than adsorption on two-fold and one-fold sites. Oxygen atoms bond as strongly on Pt3Sn(111) as on Pt(111), and these atoms prefer to adsorb near Sn atoms on the surface. The addition of Sn to Pt(111) leads to a surface heterogeneity, wherein ethylidyne species prefer to adsorb away from Sn atoms...

  2. Density functional study the interaction of oxygen molecule with defect sites of graphene

    Energy Technology Data Exchange (ETDEWEB)

    Qi Xuejun [State Key Laboratory of Coal Combustion, Wuhan 430074 (China); Guo Xin, E-mail: guoxin@mail.hust.edu.cn [State Key Laboratory of Coal Combustion, Wuhan 430074 (China); Zheng Chuguang [State Key Laboratory of Coal Combustion, Wuhan 430074 (China)

    2012-10-15

    Highlights: Black-Right-Pointing-Pointer The defect sites existed on the graphite surface create active sites and enhance the reactivity of carbonaceous material. Black-Right-Pointing-Pointer Oxygen molecule more favor chemisorbed on the graphene surface contains defect sites than the perfect surface. Black-Right-Pointing-Pointer The single active oxygen atom adsorbed on the defect surfaces, it completely insert into the surface. - Abstract: The present article reports a theoretical study of oxygen interacted with graphene surface containing defect sites on the atomic level by employing the density functional theory combined with the graphene cluster model. It was founded that oxygen molecule prefers to be chemisorbed on the graphene surface containing defect sites compared to the perfect surface. The adsorption energy of O{sub 2} on the double defect site is about 2.5 times as large as that on the perfect graphene surface. Moreover, the oxygen molecule interacts with S-W defect site gives rise to stable epoxy structure, which pulling the carbon atom outward from the original site in the direction perpendicular to the surface. If the oxygen molecule is adsorbed on the single vacancy site, two C-O bonds are formed on the graphene surface. However, when the oxygen molecule is chemisorbed on the double vacancy site, the oxygen atoms substitute the missing carbon atom's position in the carbon plane and form a hexagonal structure on the graphene network. The results indicate that single active oxygen atom approaches the defect site, it's completely adsorbed in the plane and high energy is released. In all cases, the interaction of an oxygen atom with defect surface involves an exothermic process. The defect site creates active sites on the surface of graphene and produces catalytic effects during the process of oxidation of carbonaceous materials.

  3. A first principles investigation of the oxygen adsorption on Zr(0001) surface using cluster expansions

    Science.gov (United States)

    Samin, Adib J.; Taylor, Christopher D.

    2017-11-01

    The design of corrosion resistant zircalloys is important for a variety of technological applications ranging from medicine to the nuclear industry. Since corrosion resistance is mainly attributed to the formation of a surface oxide layer, developing a detailed understanding of this process may assist in future corrosion resistance design. In this work, we conduct a systematic multi-scale investigation of the early stages of oxide formation. This was accomplished by first using a database of fully relaxed DFT calculations to build a cluster-expansion description of the potential function. The developed potential was reasonably good at predicting DFT energies as evidenced by the cross-validation score of 4.4 meV/site. The effective cluster expansion parameters were indicative of repulsive adsorbate interactions in the adlayer in agreement with the literature. The potential then allowed for a systematic investigation of the oxygen configurations on the Zr(0001) surface via Monte Carlo simulations. The adsorption energy was recorded as a function of coverage and an increasing trend was observed in agreement with DFT predictions and the repulsive nature of interactions in the adlayer. The convex hull diagram was recorded indicating the most stable configuration to occur around a coverage of 0.6 ML. The adsorption isotherm was also recorded and contrasted for two temperatures relevant for different applications.

  4. The adsorption of NO on an oxygen pre-covered Pt(1 1 1) surface: in situ high-resolution XPS combined with molecular beam studies

    Science.gov (United States)

    Zhu, J. F.; Kinne, M.; Fuhrmann, T.; Tränkenschuh, B.; Denecke, R.; Steinrück, H.-P.

    2003-12-01

    Adsorption of NO on a Pt(1 1 1) surface pre-covered with a p(2 × 2) atomic oxygen layer has been studied in situ by high-resolution X-ray photoelectron spectroscopy and temperature-programmed XPS using third-generation synchrotron radiation at BESSY II, Berlin, combined with molecular beam techniques and ex situ by low energy electron diffraction and temperature-programmed desorption. O 1s XP spectra reveal that an ordered p(2 × 2)-O layer dramatically changes the adsorption behavior of NO as compared to the clean surface. The atomic oxygen occupies fcc hollow sites, and therefore blocks NO adsorption on these sites, which are energetically preferred on clean Pt(1 1 1). As a consequence, NO populates on-top sites at low coverage. At 110 K for higher coverages, NO can additionally adsorb on hcp hollow sites, thereby inducing a shift of the O 1s binding energy of atomic oxygen towards lower energies by about 0.25 eV. The bond strength of the hcp hollow NO species to the substrate is weakened by the presence of atomic oxygen. A sharp p(2 × 2) LEED pattern is observed for NO adsorption on the oxygen pre-covered surface, up to saturation coverage. The total saturation coverage of NO on Pt(1 1 1) pre-covered with varying amounts of oxygen (below 0.25 ML) decreases linearly with the coverage of oxygen. The initial sticking coefficient of NO is reduced from 0.96 on clean Pt(1 1 1) to 0.88 on a p(2 × 2) oxygen pre-covered surface.

  5. Probing adsorption phenomena on a single crystal Pt-alloy surface under oxygen reduction reaction conditions

    International Nuclear Information System (INIS)

    Bondarenko, Alexander S.; Stephens, Ifan E.L.; Bech, Lone; Chorkendorff, Ib

    2012-01-01

    Highlights: ► Impedance spectroscopy of Cu/Pt(1 1 1) near-surface alloy and Pt(1 1 1). ► Presence of oxygen changes little the adsorption dynamics. ► Adsorption dynamics similar on alloy and Pt(1 1 1). ► Electrosorption phenomena on alloy shifted in potential, relative to Pt(1 1 1). - Abstract: The adsorption dynamics of *OH and *O species at Pt(1 1 1) and Cu/Pt(1 1 1) near-surface alloy (NSA) surfaces in oxygen-free and O 2 -saturated 0.1 M HClO 4 was investigated. Subsurface Cu modifies the electronic structure at the Pt(1 1 1) surface resulting in weaker bonding to adsorbates like *OH, *H or *O. This provides a basis for the high oxygen reduction activity of the NSA, as predicted by density functional theory calculations. The shift in *OH adsorption of around 0.16 V towards more positive potentials can be clearly monitored in absence of O 2 and under the oxygen reduction reaction (ORR) conditions for the Cu/Pt(1 1 1) NSA. In both cases, for Pt(1 1 1) and NSA, the *OH(*O) adsorption dynamics is very similar in the absence of oxygen and under ORR conditions. Therefore, theoretical assumptions about the coverage of adsorbates in the absence of oxygen can be reasonably extrapolated to the situation when oxygen reduction takes place at the surface. A ∼5-fold improvement in the ORR activity over the Pt(1 1 1) at 0.9 V (RHE) was measured for the Cu/Pt(1 1 1) near-surface alloy.

  6. Effect of the surface oxygen groups on methane adsorption on coals

    Energy Technology Data Exchange (ETDEWEB)

    Hao Shixiong [Department of Chemical Engineering, Sichuan University, Chengdu 610065 (China); Department of Chemical Engineering, Sichuan University of Science and Engineering, Zigong 643000 (China); Wen Jie [Department of Chemical Engineering, Sichuan University, Chengdu 610065 (China); Yu Xiaopeng [Department of Chemical Engineering, Sichuan University, Chengdu 610065 (China); Department of Chemical Engineering, Sichuan University of Science and Engineering, Zigong 643000 (China); Chu Wei, E-mail: chuwei1965_scu@yahoo.com [Department of Chemical Engineering, Sichuan University, Chengdu 610065 (China)

    2013-01-01

    Highlights: Black-Right-Pointing-Pointer We modified one coal with H{sub 2}O{sub 2}, (NH{sub 4}){sub 2}S{sub 2}O{sub 8} and HNO{sub 3} respectively, to prepare coal samples with different surface properties. Black-Right-Pointing-Pointer The oxygen groups on coal surface were characterized by XPS. Black-Right-Pointing-Pointer The textures of the coal samples were investigated by N{sub 2} adsorption at 77 K. Black-Right-Pointing-Pointer The adsorption behaviors were measured by volumetric method. Black-Right-Pointing-Pointer There was a negative correlation between methane saturated adsorption capacity and the O{sub total}/C{sub total}. - Abstract: To investigate the influence of surface oxygen groups on methane adsorption on coals, one bituminous coal was modified with H{sub 2}O{sub 2}, (NH{sub 4}){sub 2}S{sub 2}O{sub 8} and HNO{sub 3} respectively, to prepare coal samples with different surface properties. The oxygen groups on coal surface were characterized by X-ray photoelectron spectroscopy (XPS). The textures of the coal samples were investigated by N{sub 2} adsorption at 77 K. Their surface morphologies were analyzed by scanning electron microscopy (SEM). The methane adsorption behaviors of these coal samples were measured at 303 K in pressure range of 0-5.3 MPa by volumetric method. The adsorption data of methane were fitted to the Langmuir model and Dubinin-Astakhov (D-A) model. The fitting results showed that the D-A model fitted the isotherm data better than the Langmuir model. It was observed that there was, in general, a positive correlation between the methane saturated adsorption capacity and the micropore volume of coals while a negative correlation between methane saturated adsorption capacity and the O{sub total}/C{sub total}. The methane adsorption capacity was determined by the coal surface chemistry when the microporosity parameters of two samples were similar. Coal with a higher amount of oxygen surface groups, and consequently with a less

  7. Adsorption of volatile sulphur compounds onto modified activated carbons: Effect of oxygen functional groups

    International Nuclear Information System (INIS)

    Vega, Esther; Lemus, Jesús; Anfruns, Alba; Gonzalez-Olmos, Rafael; Palomar, José; Martin, María J.

    2013-01-01

    Highlights: • HNO 3 oxidation incorporates a higher amount of functionalities than O 3 oxidation. • The loss of porosity is compensated by the massive incorporation of oxygen groups. • HNO 3 oxidation increases OH groups in AC and the ETM and DMS adsorption capacities. • The oxygen functional groups in the AC surface did not affect the DMDS adsorption. • COSMO-RS predicts the important role of OH groups for VSC adsorption. -- Abstract: The effect of physical and chemical properties of activated carbon (AC) on the adsorption of ethyl mercaptan, dimethyl sulphide and dimethyl disulphide was investigated by treating a commercial AC with nitric acid and ozone. The chemical properties of ACs were characterised by temperature programme desorption and X-ray photoelectron spectroscopy. AC treated with nitric acid presented a larger amount of oxygen functional groups than materials oxidised with ozone. This enrichment allowed a significant improvement on adsorption capacities for ethyl mercaptan and dimethyl sulphide but not for dimethyl disulphide. In order to gain a deeper knowledge on the effect of the surface chemistry of AC on the adsorption of volatile sulphur compounds, the quantum-chemical COSMO-RS method was used to simulate the interactions between AC surface groups and the studied volatile sulphur compounds. In agreement with experimental data, this model predicted a greater affinity of dimethyl disulphide towards AC, unaffected by the incorporation of oxygen functional groups in the surface. Moreover, the model pointed out to an increase of the adsorption capacity of AC by the incorporation of hydroxyl functional groups in the case of ethyl mercaptan and dimethyl sulphide due to the hydrogen bond interactions

  8. Adsorption of volatile sulphur compounds onto modified activated carbons: Effect of oxygen functional groups

    Energy Technology Data Exchange (ETDEWEB)

    Vega, Esther, E-mail: esther@lequia.udg.cat [LEQUIA, Institute of the Environment, University of Girona, Campus Montilivi, Girona, Catalonia E-17071 (Spain); Lemus, Jesús [Universidad de Madrid, Sección de Ingeniería Química, Cantoblanco, Madrid E-28049 (Spain); Anfruns, Alba; Gonzalez-Olmos, Rafael [LEQUIA, Institute of the Environment, University of Girona, Campus Montilivi, Girona, Catalonia E-17071 (Spain); Palomar, José [Universidad de Madrid, Sección de Ingeniería Química, Cantoblanco, Madrid E-28049 (Spain); Martin, María J. [LEQUIA, Institute of the Environment, University of Girona, Campus Montilivi, Girona, Catalonia E-17071 (Spain)

    2013-08-15

    Highlights: • HNO{sub 3} oxidation incorporates a higher amount of functionalities than O{sub 3} oxidation. • The loss of porosity is compensated by the massive incorporation of oxygen groups. • HNO{sub 3} oxidation increases OH groups in AC and the ETM and DMS adsorption capacities. • The oxygen functional groups in the AC surface did not affect the DMDS adsorption. • COSMO-RS predicts the important role of OH groups for VSC adsorption. -- Abstract: The effect of physical and chemical properties of activated carbon (AC) on the adsorption of ethyl mercaptan, dimethyl sulphide and dimethyl disulphide was investigated by treating a commercial AC with nitric acid and ozone. The chemical properties of ACs were characterised by temperature programme desorption and X-ray photoelectron spectroscopy. AC treated with nitric acid presented a larger amount of oxygen functional groups than materials oxidised with ozone. This enrichment allowed a significant improvement on adsorption capacities for ethyl mercaptan and dimethyl sulphide but not for dimethyl disulphide. In order to gain a deeper knowledge on the effect of the surface chemistry of AC on the adsorption of volatile sulphur compounds, the quantum-chemical COSMO-RS method was used to simulate the interactions between AC surface groups and the studied volatile sulphur compounds. In agreement with experimental data, this model predicted a greater affinity of dimethyl disulphide towards AC, unaffected by the incorporation of oxygen functional groups in the surface. Moreover, the model pointed out to an increase of the adsorption capacity of AC by the incorporation of hydroxyl functional groups in the case of ethyl mercaptan and dimethyl sulphide due to the hydrogen bond interactions.

  9. Combined adsorption of lithium and oxygen on (111) face of tungsten

    International Nuclear Information System (INIS)

    Lozovoj, Ya.B.; Smereka, T.P.; Babkin, G.V.; Payukh, B.M.

    1986-01-01

    A contact potential difference technique has been employed to study the electron-adsorption properties of lithium films on a (111) face of tungsten, preliminary coated with different doses of oxygen. At all the lithium coverages studied the presence of oxygen on the surface leads to a significant decrease of the work function φ min and an increase of the thermal stability of lithium films. For optimal coverage φ=1.8 eV, q=2.2 eV

  10. 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 *O....... This provides a basis for the high oxygen reduction activity of the NSA, as predicted by density functional theory calculations. The shift in *OH adsorption of around 0.16V towards more positive potentials can be clearly monitored in absence of O2 and under the oxygen reduction reaction (ORR) conditions...... for the Cu/Pt(111) NSA. In both cases, for Pt(111) and NSA, the *OH(*O) adsorption dynamics is very similar in the absence of oxygen and under ORR conditions. Therefore, theoretical assumptions about the coverage of adsorbates in the absence of oxygen can be reasonably extrapolated to the situation when...

  11. Density functional theory study of oxygen and water adsorption on SrTiO{sub 3}(001)

    Energy Technology Data Exchange (ETDEWEB)

    Guhl, Hannes

    2010-12-03

    Strontium titanate is an extensively studied material with a wide range of application, for instance in photo-catalysis and most importantly, it is used as a substrate in growth of functional oxides. The surface chemistry is crucial and hence understanding the surface structure on atomic scale is essential for gaining insight into the fundamental processes in the aforementioned applications. Moreover, there exist a lot of evidence that this surface chemistry might be controlled to considerably by extrinsic species, such as residual hydrogen and water. Investigating the properties of water and oxygen on the strontium titanate surface is certainly a natural starting point for a theoretical study based on density functional theory, because these species are practically present on the surface on a wide range of experimental conditions and they are computationally feasible. For the oxygen and water adsorption the binding energy is controlled by long-range surface relaxations leading to an effective repulsion of the adsorbed specimen. The isolated oxygen ad-atom forms a covalently bonded ''quasi-peroxide anion'' in combination with a lattice oxygen atom. Contrariwise, in all investigated configurations containing water molecules and hydroxyl groups, the respective oxygen atoms assumed positions close to the oxygen sites of the continued perovskite lattice of the substrate. Most remarkably, on the strontium oxide termination, the water molecules adsorbs and dissociates effortlessly leading to the formation of a pair of hydroxyl groups. For the titanium dioxide termination, a coverage dependent adsorption mode is observed. Densely packings stabilize water molecules, whereas at lower coverage and finite temperatures the formation of hydroxyl groups is found. The energetics responsible for this behavior is consistent with recent experiments by Iwahori and coworkers. (orig.)

  12. Density functional theory study of oxygen and water adsorption on SrTiO3(001)

    International Nuclear Information System (INIS)

    Guhl, Hannes

    2010-01-01

    Strontium titanate is an extensively studied material with a wide range of application, for instance in photo-catalysis and most importantly, it is used as a substrate in growth of functional oxides. The surface chemistry is crucial and hence understanding the surface structure on atomic scale is essential for gaining insight into the fundamental processes in the aforementioned applications. Moreover, there exist a lot of evidence that this surface chemistry might be controlled to considerably by extrinsic species, such as residual hydrogen and water. Investigating the properties of water and oxygen on the strontium titanate surface is certainly a natural starting point for a theoretical study based on density functional theory, because these species are practically present on the surface on a wide range of experimental conditions and they are computationally feasible. For the oxygen and water adsorption the binding energy is controlled by long-range surface relaxations leading to an effective repulsion of the adsorbed specimen. The isolated oxygen ad-atom forms a covalently bonded ''quasi-peroxide anion'' in combination with a lattice oxygen atom. Contrariwise, in all investigated configurations containing water molecules and hydroxyl groups, the respective oxygen atoms assumed positions close to the oxygen sites of the continued perovskite lattice of the substrate. Most remarkably, on the strontium oxide termination, the water molecules adsorbs and dissociates effortlessly leading to the formation of a pair of hydroxyl groups. For the titanium dioxide termination, a coverage dependent adsorption mode is observed. Densely packings stabilize water molecules, whereas at lower coverage and finite temperatures the formation of hydroxyl groups is found. The energetics responsible for this behavior is consistent with recent experiments by Iwahori and coworkers. (orig.)

  13. Study of the secondary electron energy spectrum of clean aluminium modification during oxygen adsorption, hydrogen adsorption or carbon segregation

    International Nuclear Information System (INIS)

    Pellerin, Francois

    1981-01-01

    The first part of this work is a review of both theoretical and experimental aspects of the fine structure appearing in the Secondary Electron Spectrum (SES) and in the electron energy loss spectrum. In the second part, we report the results of a study of the SES and ELS spectra of clean and gas covered aluminium. The use of very low primary electron energies (E p ≤ 30 eV) enables the detection of previously unobserved peaks in the ELS spectra of clean and oxygen covered aluminium. They are attributed to single electron excitations. Furthermore, a very large peak appears in the SES spectrum during oxygen or carbon adsorption on aluminium. It is interpreted in terms of interaction of the background electrons with the valence electrons of the surface. Molecular hydrogen adsorption is observed on Ta, Pt, Al 2 O 3 , Si. It is responsible for an ELS peak located 13 eV below the elastic peak. Furthermore, on silicon, the chemisorbed hydrogen form can be distinguished from the molecular form with the help of ELS. Finally, some examples are given of the application of these results to surface imaging. (author) [fr

  14. A supramolecular strategy for self-mobile adsorption sites in affinity membrane.

    Science.gov (United States)

    Lin, Ligang; Dong, Meimei; Liu, Chunyu; Wei, Chenjie; Wang, Yuanyuan; Sun, Hui; Ye, Hui

    2014-09-01

    Disclosed here is the design of a novel supramolecular membrane with self-mobile adsorption sites for biomolecules purification. In the 3D micropore channels of membrane matrix, the ligands are conjugated onto the cyclic compounds in polyrotaxanes for protein adsorption. During membrane filtration, the adsorption sites can rotate and/or slide along the axial chain, which results in the enhanced adsorption capacity. The excellent performance of supra-molecular membrane is related with the dynamic working manner of adsorption sites, which plays a crucial role on avoiding spatial mismatching and short-circuit effect. The supra-molecular strategy described here has general suggestions for the "sites" involved technologies such as catalysis, adsorption, and sensors, which is of broad interest. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Kinetics of oxygen adsorption on ZnS nanoparticles synthesized by precipitation process

    Directory of Open Access Journals (Sweden)

    Ahmadi Reza

    2016-06-01

    Full Text Available ZnS nanoparticles were synthesized through a one-step precipitation process. Effect of time and temperature on the formation reaction was investigated. The synthesized samples were characterized by X-ray diffraction (XRD, ultraviolet (UV visible absorption and photoluminescence (PL spectrophotometry. Based on XRD and UV-Vis data, the particles produced at 70 °C had a mean particle size of about 5 nm. Increasing time and temperature of the synthesis reaction resulted in photoluminescence intensification. PL spectroscopy helped understanding the adsorption kinetics of oxygen on ZnS nanoparticles during the precipitation synthesis process. Fabrication of ZnS structures with appropriate oxygen adsorption capacity was suggested as a means of PL emission intensity control.

  16. Oxygen adsorption on Cu(111) using low energy ion scattering spectroscopy

    International Nuclear Information System (INIS)

    Zhang, F.M.; Yao, J.; Shen, Y.G.; King, B.V.; O'Connor, D.J.

    1993-01-01

    The surface structure and oxygen adsorption of Cu(l 11) have been studied by 2 keV Li + , He + and Ar + ion scattering . Incident and azimuthal dependences were measured for the clean and O-covered surfaces, and the surface geometry was analysed on the basis of the shadowing features. Experimental results under different oxygen exposures at room temperature showed that the Cu(l 11) surface undergoes a roughening transition and results in a reconstruction where Cu atoms are vertically displaced by about 0.23 Angstroms. 4 refs., 4 figs

  17. Oxygen adsorption on Cu(111) using low energy ion scattering spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, F M; Yao, J; Shen, Y G; King, B V; O` Connor, D J [Newcastle Univ., NSW (Australia). Dept. of Physics

    1994-12-31

    The surface structure and oxygen adsorption of Cu(l 11) have been studied by 2 keV Li{sup +}, He{sup +} and Ar{sup +} ion scattering . Incident and azimuthal dependences were measured for the clean and O-covered surfaces, and the surface geometry was analysed on the basis of the shadowing features. Experimental results under different oxygen exposures at room temperature showed that the Cu(l 11) surface undergoes a roughening transition and results in a reconstruction where Cu atoms are vertically displaced by about 0.23 Angstroms. 4 refs., 4 figs.

  18. Oxygen adsorption on Cu(111) using low energy ion scattering spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, F.M.; Yao, J.; Shen, Y.G.; King, B.V.; O`Connor, D.J. [Newcastle Univ., NSW (Australia). Dept. of Physics

    1993-12-31

    The surface structure and oxygen adsorption of Cu(l 11) have been studied by 2 keV Li{sup +}, He{sup +} and Ar{sup +} ion scattering . Incident and azimuthal dependences were measured for the clean and O-covered surfaces, and the surface geometry was analysed on the basis of the shadowing features. Experimental results under different oxygen exposures at room temperature showed that the Cu(l 11) surface undergoes a roughening transition and results in a reconstruction where Cu atoms are vertically displaced by about 0.23 Angstroms. 4 refs., 4 figs.

  19. Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

    Energy Technology Data Exchange (ETDEWEB)

    Park, Sang-Won; Leckie, J.O. [Stanford Univ., CA (United States); Siegel, M.D. [Sandia National Labs., Albuquerque, NM (United States)

    1995-09-01

    Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption.

  20. Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

    International Nuclear Information System (INIS)

    Park, Sang-Won; Leckie, J.O.; Siegel, M.D.

    1995-09-01

    Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption

  1. Molecular origin of the selectivity differences between palladium and gold-palladium in benzyl alcohol oxidation: Different oxygen adsorption properties

    Energy Technology Data Exchange (ETDEWEB)

    Savara, Aditya Ashi [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Chan-Thaw, Carine E. [Univ. degli Studi di Milano, Milano (Italy); Sutton, Jonathan E. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Wang, Di [Karlsruhe Institute of Technology, Eggenstein-Leopoldshafen (Germany); Prati, Laura [Univ. degli Studi di Milano, Milano (Italy); Villa, Alberto [Univ. degli Studi di Milano, Milano (Italy)

    2016-12-22

    The same mechanism and microkinetic model used for benzyl alcohol oxidation over Pd/C was shown to apply to benzyl alcohol oxidation over AuPd/C. Almost all of the selectivity differences could be explained by a decrease in oxygen adsorption on AuPd. After isolating oxygen adsorption as being the origin of the selectivity differences, density functional theory was used to investigate the oxygen adsorption properties of a pure Pd surface, a pure Au surface, and an alloyed AuPd surface. Finally, the calculations showed that Au–Pd alloying decreased the oxygen adsorption properties relative to pure Pd, which explained the selectivity differences, consistent with the microkinetic modeling.

  2. ReaxFF Grand Canonical Monte Carlo simulation of adsorption and dissociation of oxygen on platinum (111)

    Science.gov (United States)

    Valentini, Paolo; Schwartzentruber, Thomas E.; Cozmuta, Ioana

    2011-12-01

    Atomic-level Grand Canonical Monte Carlo (GCMC) simulations equipped with a reactive force field (ReaxFF) are used to study atomic oxygen adsorption on a Pt(111) surface. The off-lattice GCMC calculations presented here rely solely on the interatomic potential and do not necessitate the pre-computation of surface adlayer structures and their interpolation. As such, they provide a predictive description of adsorbate phases. In this study, validation is obtained with experimental evidence (steric heats of adsorption and isotherms) as well as DFT-based state diagrams available in the literature. The ReaxFF computed steric heats of adsorption agree well with experimental data, and this study clearly shows that indirect dissociative adsorption of O2 on Pt(111) is an activated process at non-zero coverages, with an activation energy that monotonically increases with coverage. At a coverage of 0.25 ML, a highly ordered p(2 × 2) adlayer is found, in agreement with several low-energy electron diffraction observations. Isotherms obtained from the GCMC simulations compare qualitatively and quantitatively well with previous DFT-based state diagrams, but are in disagreement with the experimental data sets available. ReaxFF GCMC simulations at very high coverages show that O atoms prefer to bind in fcc hollow sites, at least up to 0.8 ML considered in the present work. At moderate coverages, little to no disorder appears in the Pt lattice. At high coverages, some Pt atoms markedly protrude out of the surface plane. This observation is in qualitative agreement with recent STM images of an oxygen covered Pt surface. The use of the GCMC technique based on a transferable potential is particularly valuable to produce more realistic systems (adsorbent and adsorbate) to be used in subsequent dynamical simulations (Molecular Dynamics) to address recombination reactions (via either Eley-Rideal or Langmuir-Hinshelwood mechanisms) on variously covered surfaces. By using GCMC and Molecular

  3. The effect of the oxygen dissolved in the adsorption of gold in activated carbon

    International Nuclear Information System (INIS)

    Navarro, P.; Wilkomirsky, I.

    1999-01-01

    The effect of the oxygen dissolved on the adsorption of gold in a activated carbon such as these used for carbon in pulp (CIP) and carbon in leach (CIL) processes were studied. The research was oriented to dilucidate the effect of the oxygen dissolved in the gold solution on the kinetics and distribution of the gold adsorbed in the carbon under different conditions of ionic strength, pH and gold concentration. It was found that the level of the oxygen dissolved influences directly the amount of gold adsorbed on the activated carbon, being this effect more relevant for low ionic strength solutions. The pH and initial gold concentration has no effect on this behavior. (Author) 16 refs

  4. Fluoride adsorption on goethite in relation to different types of surface sites

    NARCIS (Netherlands)

    Hiemstra, T.; Riemsdijk, van W.H.

    2000-01-01

    Metal (hydr)oxides have different types of surface groups. Fluoride ions have been used as a probe to assess the number of surface sites. We have studied the F− adsorption on goethite by measuring the F− and H interaction and F− adsorption isotherms. Fluoride ions exchange against singly coordinated

  5. Coverage-dependent adsorption and desorption of oxygen on Pd(100)

    Energy Technology Data Exchange (ETDEWEB)

    Dunnen, Angela den; Jacobse, Leon; Wiegman, Sandra; Juurlink, Ludo B. F., E-mail: l.juurlink@chem.leidenuniv.nl [Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, P.O. Box 9502, 2300 RA Leiden (Netherlands); Berg, Otto T. [Department of Chemistry, California State University Fresno, 2555 E. San Ramon Ave., Fresno, California 93740 (United States)

    2016-06-28

    We have studied the adsorption and desorption of O{sub 2} on Pd(100) by supersonic molecular beam techniques and thermal desorption spectroscopy. Adsorption measurements on the bare surface confirm that O{sub 2} initially dissociates for all kinetic energies between 56 and 380 meV and surface temperatures between 100 and 600 K via a direct mechanism. At and below 150 K, continued adsorption leads to a combined O/O{sub 2} overlayer. Dissociation of molecularly bound O{sub 2} during a subsequent temperature ramp leads to unexpected high atomic oxygen coverages, which are also obtained at high incident energy and high surface temperature. At intermediate temperatures and energies, these high final coverages are not obtained. Our results show that kinetic energy of the gas phase reactant and reaction energy dissipated during O{sub 2} dissociation on the cold surface both enable activated nucleation of high-coverage surface structures. We suggest that excitation of local substrate phonons may play a crucial role in oxygen dissociation at any coverage.

  6. 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.

  7. Xenon capture on silver-loaded zeolites: characterization of very strong adsorption sites

    International Nuclear Information System (INIS)

    Daniel, Cecile; Elbaraoui, Adnane; Aguado, Sonia; Schuurman, Yves; Farrusseng, David; Springuel-Huet, Marie-Anne; Nossov, Andrei; Fontaine, Jean-Pierre; Topin, Sylvain; Taffary, Thomas; Deliere, Ludovic

    2013-01-01

    The number and strength of adsorption sites for Xe in silver-modified zeolites are estimated from isotherm measurements at various temperatures over a broad range of pressure (from 1 ppm to atmospheric pressure). Fully and partially exchanged silver zeolites were synthesized starting from Na-ZSM-5(25), Na-ZSM-5(40), Na-Beta, NaX, and NaY. We have discovered that silver-modified zeolites may present one or two distinct adsorption sites depending on the nature of the material and silver loadings. The strongest adsorption sites are characterized by isosteric heat of adsorption in the order of -40 to -50 kJ.mol -1 . For Pentasil-type zeolites, we observe a linear 2:1 correlation between the total amount of silver and the number of strong sites. The highest concentration of strong sites is found for fully silver exchanged ZSM-5 (5.7 * 10 -4 mol/g), which presents the largest silver content for Pentasil-type zeolite. The equilibrium constant of Ag-ZSM-5 at low pressure is about 50 times larger than that of AgX. Qualitative correlations were established between Xe adsorption isotherms and Xe NMR signals. We show that Xe NMR could be used as a quantitative method for the characterization of the strength and of the number of strong Xe adsorption sites on silver-exchanged zeolites. The numbers of strong adsorption sites responsible for the Xe adsorption at 10-1000 ppm can be determined by the length of the plateau observed at low Xe uptake. In practice, our findings give guidelines for the discovery and optimization of silver-loaded zeolites for the capture of Xe at ppm levels. It appears that the amount of silver is a key parameter. Silver-modified ZSM-5 shows adsorption capacities 2-3 orders of magnitude larger than currently applied adsorbents for atmospheric Xe capture. (authors)

  8. Quantitative imaging of cation adsorption site densities in undisturbed soil

    Science.gov (United States)

    Keck, Hannes; Strobel, Bjarne W.; Gustafsson, Jon-Petter; Koestel, John

    2017-04-01

    The vast majority of present soil system models assume a homogeneous distribution and accessibility of cation adsorption sites (CAS) within soil structural units like e.g. soil horizons. This is however in conflict with several recent studies finding that CAS in soils are not uniformly but patchily distributed at and below the cm-scale. It is likely that the small-scale distribution of CAS has significant impact on the performance of these models. However, systematic approaches to map CAS densities in undisturbed soil with 3-D resolution that could lead to respective model improvements are still lacking. We therefore investigated the 3-D distribution of the CAS in undisturbed soils using X-ray scanning and barium ions as a contrast agent. We appraised the validity of the approach by comparing X-ray image-derived cation exchange coefficients (CEC) with ones obtained using the ammonium acetate method. In the process, we evaluated whether there were larger CAS concentrations at aggregate and biopore boundaries as it is often hypothesized. We sampled eight small soil cores (approx. 10 ccm) from different locations with contrasting soil texture and organic matter contents. The samples were first saturated with a potassium chloride solution (0.1 mol per liter), whereupon a 3-D X-ray image was taken. Then, the potassium chloride solution was flushed out with a barium chloride solution (0.3 mol per liter) with barium replacing the potassium from the CAS due to its larger exchange affinity. After X-ray images as well as electrical conductivity in the effluent indicated that the entire sample had been saturated with the barium chloride, the sample was again rinsed using the potassium chloride solution. When the rinsing was complete a final 3-D X-ray image was acquired. The difference images between final and initial 3-D X-ray images were interpreted as depicting the adsorbed barium as the density of barium exceeds the one of potassium by more than 2 times. The X-ray image

  9. Influence of porous texture and surface chemistry on the CO₂ adsorption capacity of porous carbons: acidic and basic site interactions.

    Science.gov (United States)

    Sánchez-Sánchez, Angela; Suárez-García, Fabián; Martínez-Alonso, Amelia; Tascón, Juan M D

    2014-12-10

    Doped porous carbons exhibiting highly developed porosity and rich surface chemistry have been prepared and subsequently applied to clarify the influence of both factors on carbon dioxide capture. Nanocasting was selected as synthetic route, in which a polyaramide precursor (3-aminobenzoic acid) was thermally polymerized inside the porosity of an SBA-15 template in the presence of different H3PO4 concentrations. The surface chemistry and the porous texture of the carbons could be easily modulated by varying the H3PO4 concentration and carbonization temperature. Porous texture was found to be the determinant factor on carbon dioxide adsorption at 0 °C, while surface chemistry played an important role at higher adsorption temperatures. We proved that nitrogen functionalities acted as basic sites and oxygen and phosphorus groups as acidic ones toward adsorption of CO2 molecules. Among the nitrogen functional groups, pyrrolic groups exhibited the highest influence, while the positive effect of pyridinic and quaternary functionalities was smaller. Finally, some of these N-doped carbons exhibit CO2 heats of adsorption higher than 42 kJ/mol, which make them excellent candidates for CO2 capture.

  10. Analysis of oxygen and hydrogen adsorption on Nb(100) surface by scanning tunneling microscopy

    International Nuclear Information System (INIS)

    An, Bai; Wen, Mao; Fukuyama, Seiji; Yokogawa, Kiyoshi; Ichimura, Shingo; Yoshimura, Masamichi

    2006-01-01

    The surface structure of Nb(100) under the condition of cleaning, oxidation and hydrogen adsorption is observed by STM (scanning tunneling microscopy). The results obtained are followings; (1) (3 x 1)-O→(4 x 1)-O→c(2 x 2)-O→clean(1 x 1)structure was observed by atom level, and these atomic models of structures and STM images were verified by the first-principles calculations, (2) when the clean(1 x 1) structure exposed to hydrogen, dissociative adsorption of hydrogen was observed and Nb hydride cluster formed on the surface at room temperature. It was heated at about 450 - 670 K in UHV, the cluster decomposed into hydrogen and (1 x 1) structure with linear defect was formed. The c(2 x 2)-O structure by oxygen adsorption transformed into (1 x 1)-H structure with OH and Nb hydride cluster under hydrogen gas at room temperature. When it was heated in UHV at 640 K, OH desorbed from the surface and (1 x 1) structure with linear defect was generated. The surface of (3 x 1)-O structure was not changed by hydrogen. (S.Y.)

  11. Adsorption site of ammonia on copper-exchanged Y-type zeolite under coexisting water vapor. Temperature-programed desorption and infrared adsorption spectra

    Energy Technology Data Exchange (ETDEWEB)

    Kasaoka, S.; Sasaoka, E.; Shiraga, T.; Ono, Y.

    1978-03-01

    Sodium Y zeolites were copper-exchanged with cupric nitrate in water, in aqueous ammonia, and in aqueous ammonia/ammonium chloride, and calcined at 500/sup 0/C. Temperature-programed desorption and IR spectroscopy showed three types of adsorption sites for 0.1-1.0% ammonia gas from nitrogen containing 0-12% water vapor: physisorption, adsorption as tetraamminocopper(II) on copper(II) sites (type 2 site), and adsorption as ammonium ion on hydroxyl sites (type 3 site). Adsorption on type 2 sites occurred only at high ammonia concentration; desorption occurred around 175/sup 0/C. Type 3 sites consisted of Cu(OH)/sup +/ and Al(OH)/sup +/, adsorbed ammonia from low concentrations, and at temperatures above 200/sup 0/C, were probably the active sites for the reduction of nitric oxide by ammonia.

  12. Surface sites on carbon-supported Ru, Co and Ni nanoparticles as determined by microcalorimetry of CO adsorption

    International Nuclear Information System (INIS)

    Cerro-Alarcon, M.; Maroto-Valiente, A.; Rodriguez-Ramos, I.; Guerrero-Ruiz, A.

    2005-01-01

    The adsorption of CO on carbon-supported metal (Ru, Co and Ni) catalysts was studied by microcalorimetry. A correlation of the results thus obtained with those reported for monocrystals or with other studies available in the scientific literature for supported metal catalysts, including infrared spectroscopy data, enables the determination of the type of exposed crystalline planes and/or of the different types of CO adsorbed species. The results obtained suggest that the energetic distribution of the surface sites depends on the carbon support material and on the applied reduction treatment. In this way, the use of a high surface area graphite (clean of surface oxygen groups) leads to an electron density enrichment on the small metal particles (Ru) and, in general, to a higher heterogeneity of the active surface sites. The elimination of surface oxygen functional groups (with the reduction treatment at the higher temperature) of the carbon molecular sieve support leads to changes in the surface structure of the metal particles and, consequently, to higher CO adsorption heats, particularly for Ru and Co

  13. Adsorption and dissociation of oxygen molecules on Si(111)-(7×7) surface

    International Nuclear Information System (INIS)

    Niu, Chun-Yao; Wang, Jian-Tao

    2013-01-01

    The adsorption and dissociation of O 2 molecules on Si(111)-(7×7) surface have been studied by first-principles calculations. Our results show that all the O 2 molecular species adsorbed on Si(111)-(7×7) surface are unstable and dissociate into atomic species with a small energy barrier about 0.1 eV. The single O 2 molecule adsorption tends to form an ins×2 or a new metastable ins×2* structure on the Si adatom sites and the further coming O 2 molecules adsorb on those structures to produce an ad-ins×3 structure. The ad-ins×3 structure is indeed highly stable and kinetically limited for diving into the subsurface layer to form the ins×3-tri structure by a large barrier of 1.3 eV. Unlike the previous views, we find that all the ad-ins, ins×2, and ad-ins×3 structures show bright images, while the ins×2*, ins×3, and ins×3-tri structures show dark images. The proposed oxidation pathways and simulated scanning tunneling microscope images account well for the experimental results and resolve the long-standing confusion and issue about the adsorption and reaction of O 2 molecules on Si(111) surface

  14. Periodic DFT study of acidic trace atmospheric gas molecule adsorption on Ca- and Fe-doped MgO(001) surface basic sites.

    Science.gov (United States)

    Baltrusaitis, Jonas; Hatch, Courtney; Orlando, Roberto

    2012-08-02

    The electronic properties of undoped and Ca- or Fe-doped MgO(001) surfaces, as well as their propensity toward atmospheric acidic gas (CO2, SO2, and NO2) uptake was investigated with an emphasis on gas adsorption on the basic MgO oxygen surface sites, O(surf), using periodic density functional theory (DFT) calculations. Adsorption energy calculations show that MgO doping will provide stronger interactions of the adsorbate with the O(surf) sites than the undoped MgO for a given adsorbate molecule. Charge transfer from the iron atom in Fe-doped MgO(001) to NO2 was shown to increase the binding interaction between adsorbate by an order of magnitude, when compared to that of undoped and Ca-doped MgO(001) surfaces. Secondary binding interactions of adsorbate oxygen atoms were observed with surface magnesium sites at distances close to those of the Mg-O bond within the crystal. These interactions may serve as a preliminary step for adsorption and facilitate further adsorbate transformations into other binding configurations. Impacts on global atmospheric chemistry are discussed as these adsorption phenomena can affect atmospheric gas budgets via altered partitioning and retention on mineral aerosol surfaces.

  15. Oxygen isotopic fractionation of O₂ during adsorption and desorption processes using molecular sieve at low temperatures.

    Science.gov (United States)

    Ahn, Insu; Kusakabe, Minoru; Lee, Jong Ik

    2014-06-15

    Cryogenic trapping using molecular sieves is commonly used to collect O2 extracted from silicates for (17)O/(16)O and (18)O/(16)O analyses. However, gases which interfere with (17)O/(16)O analysis, notably NF3, are also trapped and their removal is essential for accurate direct measurement of the (17)O/(16)O ratio. It is also necessary to identify and quantify any isotopic fractionation associated with the use of cryogenic trapping using molecular sieves. The oxygen isotopic compositions of O2 before and after desorption from, and adsorption onto, 13X and 5A molecular sieves (MS13X and MS5A) at 0°C, -78°C, -114°C, and -130°C were measured in order to determine the oxygen isotopic fractionation at these temperatures. We also investigated whether isotopic fractionation occurred when O2 gas was transferred sequentially into a second cold finger, also containing molecular sieve. It was confirmed that significant oxygen isotopic fractionation occurs between the gaseous O2 and that adsorbed onto molecular sieve, if desorption and adsorption are incomplete. As the fraction of released or untrapped O2 becomes smaller with decreasing trapping temperature (from 0 to -130°C), the isotopic fractionation becomes larger. Approximately half of the total adsorbed O2 is released from the molecular sieve during desorption at -114°C, which is the temperature recommended for separation from NF3 (retained on the molecular sieve), and this will interfere with (17)O/(16)O measurements. The use of a single cold finger should be avoided, because partial desorption is accompanied by oxygen isotopic fractionation, thereby resulting in inaccurate isotopic data. The use of a dual cold finger arrangement is recommended because, as we have confirmed, the transfer of O2 from the first trap to the second is almost 100%. However, even under these conditions, a small isotopic fractionation (0.18 ± 0.05‰ in δ(17)O values and 0.26 ± 0.06‰ in δ(18)O values) occurred, with O2 in

  16. Adsorption

    Directory of Open Access Journals (Sweden)

    Sushmita Banerjee

    2017-05-01

    Full Text Available Application of saw dust for the removal of an anionic dye, tartrazine, from aqueous solutions has been investigated. The experiments were carried out in batch mode. Effect of the parameters such as pH, initial dye concentration and temperature on the removal of the dye was studied. Equilibrium was achieved in 70 min. Maximum adsorption of dye was achieved at pH 3. Removal percent was found to be dependent on the initial concentration of dye solution, and maximum removal was found to be 97% at 1 mg/L of tartrazine. The removal increases from 71% to 97% when the initial concentration of dye solution decreases from 15 mg/L to 1 mg/L. The equilibrium adsorption data were analyzed by Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models. The (Langmuir adsorption capacity of the adsorbent is found to be 4.71 mg/g at 318 K. Kinetic modeling of the process of removal was carried out and the process of removal was found to follow a pseudo second order model and the value of rate constant for adsorption process was calculated as 2.7 × 10−3 g mg−1 min−1 at 318 K. The thermodynamic parameters such as change in free energy (ΔG°, enthalpy (ΔH° and entropy (ΔS° were determined and the negative values of ΔG° indicated that the process of removal was spontaneous at all values of temperatures. Further, the values of ΔH° indicated the endothermic nature of the process of removal.

  17. Competitive adsorption of copper(II), cadmium(II), lead(II) and zinc(II) onto basic oxygen furnace slag

    International Nuclear Information System (INIS)

    Xue Yongjie; Hou Haobo; Zhu Shujing

    2009-01-01

    Polluted and contaminated water can often contain more than one heavy metal species. It is possible that the behavior of a particular metal species in a solution system will be affected by the presence of other metals. In this study, we have investigated the adsorption of Cd(II), Cu(II), Pb(II), and Zn(II) onto basic oxygen furnace slag (BOF slag) in single- and multi-element solution systems as a function of pH and concentration, in a background solution of 0.01 M NaNO 3 . In adsorption edge experiments, the pH was varied from 2.0 to 13.0 with total metal concentration 0.84 mM in the single element system and 0.21 mM each of Cd(II), Cu(II), Pb(II), and Zn(II) in the multi-element system. The value of pH 50 (the pH at which 50% adsorption occurs) was found to follow the sequence Zn > Cu > Pb > Cd in single-element systems, but Pb > Cu > Zn > Cd in the multi-element system. Adsorption isotherms at pH 6.0 in the multi-element systems showed that there is competition among various metals for adsorption sites on BOF slag. The adsorption and potentiometric titrations data for various slag-metal systems were modeled using an extended constant-capacitance surface complexation model that assumed an ion-exchange process below pH 6.5 and the formation of inner-sphere surface complexes at higher pH. Inner-sphere complexation was more dominant for the Cu(II), Pb(II) and Zn(II) systems

  18. Competitive adsorption of copper(II), cadmium(II), lead(II) and zinc(II) onto basic oxygen furnace slag

    Energy Technology Data Exchange (ETDEWEB)

    Xue Yongjie [School of Resource and Environment Science, Wuhan University, Hubei, Wuhan (China); Wuhan Kaidi Electric Power Environmental Protection Co. Ltd., Hubei, Wuhan (China)], E-mail: xueyj@mail.whut.edu.cn; Hou Haobo; Zhu Shujing [School of Resource and Environment Science, Wuhan University, Hubei, Wuhan (China)

    2009-02-15

    Polluted and contaminated water can often contain more than one heavy metal species. It is possible that the behavior of a particular metal species in a solution system will be affected by the presence of other metals. In this study, we have investigated the adsorption of Cd(II), Cu(II), Pb(II), and Zn(II) onto basic oxygen furnace slag (BOF slag) in single- and multi-element solution systems as a function of pH and concentration, in a background solution of 0.01 M NaNO{sub 3}. In adsorption edge experiments, the pH was varied from 2.0 to 13.0 with total metal concentration 0.84 mM in the single element system and 0.21 mM each of Cd(II), Cu(II), Pb(II), and Zn(II) in the multi-element system. The value of pH{sub 50} (the pH at which 50% adsorption occurs) was found to follow the sequence Zn > Cu > Pb > Cd in single-element systems, but Pb > Cu > Zn > Cd in the multi-element system. Adsorption isotherms at pH 6.0 in the multi-element systems showed that there is competition among various metals for adsorption sites on BOF slag. The adsorption and potentiometric titrations data for various slag-metal systems were modeled using an extended constant-capacitance surface complexation model that assumed an ion-exchange process below pH 6.5 and the formation of inner-sphere surface complexes at higher pH. Inner-sphere complexation was more dominant for the Cu(II), Pb(II) and Zn(II) systems.

  19. Competitive adsorption of copper(II), cadmium(II), lead(II) and zinc(II) onto basic oxygen furnace slag.

    Science.gov (United States)

    Xue, Yongjie; Hou, Haobo; Zhu, Shujing

    2009-02-15

    Polluted and contaminated water can often contain more than one heavy metal species. It is possible that the behavior of a particular metal species in a solution system will be affected by the presence of other metals. In this study, we have investigated the adsorption of Cd(II), Cu(II), Pb(II), and Zn(II) onto basic oxygen furnace slag (BOF slag) in single- and multi-element solution systems as a function of pH and concentration, in a background solution of 0.01M NaNO(3). In adsorption edge experiments, the pH was varied from 2.0 to 13.0 with total metal concentration 0.84mM in the single element system and 0.21mM each of Cd(II), Cu(II), Pb(II), and Zn(II) in the multi-element system. The value of pH(50) (the pH at which 50% adsorption occurs) was found to follow the sequence Zn>Cu>Pb>Cd in single-element systems, but Pb>Cu>Zn>Cd in the multi-element system. Adsorption isotherms at pH 6.0 in the multi-element systems showed that there is competition among various metals for adsorption sites on BOF slag. The adsorption and potentiometric titrations data for various slag-metal systems were modeled using an extended constant-capacitance surface complexation model that assumed an ion-exchange process below pH 6.5 and the formation of inner-sphere surface complexes at higher pH. Inner-sphere complexation was more dominant for the Cu(II), Pb(II) and Zn(II) systems.

  20. A cluster DFT study of NH{sub 3} and NO adsorption on the (MoO{sub 2}){sup 2+}/HZSM-5 surface: Lewis versus Brønsted acid sites

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Zhifeng [College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); College of Material Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Zuo, Zhijun [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Li, Zhe, E-mail: lizhe@tyut.edu.cn [College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Zhang, Jinshan [College of Material Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China)

    2014-12-01

    Graphical abstract: - Highlights: • NH{sub 3} adsorption is found to be more favorable energetically than NO adsorption on both Lewis and Brønsted acid sites. • Lewis and Brønsted acid sites are competitive energetically for NH{sub 3} adsorption. • Reduced-state Mo{sup 5+} is suggested to play a key role in adsorption and activation of NO{sub x} together with the adsorbed NH{sub 4}{sup +}. - Abstract: A systematic DFT study was carried out to investigate NH{sub 3} and NO adsorption on both Lewis and Brønsted acid sites of (MoO{sub 2}){sup 2+}/HZSM-5 catalyst by using cluster models. The adsorption energy results indicate that NH{sub 3} could strongly adsorb on both Lewis and Brønsted acid sites in the form of coordinated NH{sub 3} and NH{sub 4}{sup +}, respectively, whereas NO represents poorer adsorption ability. It is also found that Lewis and Brønsted acid sites are competitive energetically for NH{sub 3} adsorption. According to the difference in the proposed mechanisms for NH{sub 3} adsorption on different acid sites, particular attention has been focused on the first dissociation of coordinated NH{sub 3} for Lewis acid site and the effect of Mo site on the introduction of NO for Brønsted acid site. For the coordinated NH{sub 3} on Lewis acid site, the more electron donation from NH{sub 3} is, the greater its adsorption stability is and the higher active its H atoms are. In addition, DOS results show that stability of the H atoms is enhanced by interacting with framework oxygen and especially the H atoms chemical-bonded with framework oxygen. For the NH{sub 4}{sup +} on Brønsted acid site, reduced-state Mo{sup 5+} holds stronger reducibility and oxidizability than terminal oxygen, which is suggested to play a key role in adsorption and activation of NO{sub x} together with the adsorbed NH{sub 4}{sup +}.

  1. Goethite surface reactivity: III. Unifying arsenate adsorption behavior through a variable crystal face - Site density model

    Science.gov (United States)

    Salazar-Camacho, Carlos; Villalobos, Mario

    2010-04-01

    We developed a model that describes quantitatively the arsenate adsorption behavior for any goethite preparation as a function of pH and ionic strength, by using one basic surface arsenate stoichiometry, with two affinity constants. The model combines a face distribution-crystallographic site density model for goethite with tenets of the Triple Layer and CD-MUSIC surface complexation models, and is self-consistent with its adsorption behavior towards protons, electrolytes, and other ions investigated previously. Five different systems of published arsenate adsorption data were used to calibrate the model spanning a wide range of chemical conditions, which included adsorption isotherms at different pH values, and adsorption pH-edges at different As(V) loadings, both at different ionic strengths and background electrolytes. Four additional goethite-arsenate systems reported with limited characterization and adsorption data were accurately described by the model developed. The adsorption reaction proposed is: lbond2 FeOH +lbond2 SOH +AsO43-+H→lbond2 FeOAsO3[2-]…SOH+HO where lbond2 SOH is an adjacent surface site to lbond2 FeOH; with log K = 21.6 ± 0.7 when lbond2 SOH is another lbond2 FeOH, and log K = 18.75 ± 0.9, when lbond2 SOH is lbond2 Fe 2OH. An additional small contribution of a protonated complex was required to describe data at low pH and very high arsenate loadings. The model considered goethites above 80 m 2/g as ideally composed of 70% face (1 0 1) and 30% face (0 0 1), resulting in a site density for lbond2 FeOH and for lbond2 Fe 3OH of 3.125/nm 2 each. Below 80 m 2/g surface capacity increases progressively with decreasing area, which was modeled by considering a progressively increasing proportion of faces (0 1 0)/(1 0 1), because face (0 1 0) shows a much higher site density of lbond2 FeOH groups. Computation of the specific proportion of faces, and thus of the site densities for the three types of crystallographic surface groups present in

  2. Interaction of oxygen with zirconia surface

    International Nuclear Information System (INIS)

    Ivankiv, L.I.; Ketsman, I.V.

    1999-01-01

    The influence of surface heat treatment, electron (50-800) eV irradiation and UV (180-300) nM illumination of adsorption system on the state of oxygen adsorbed on zirconia surface have been investigated. On the basis of experimental results obtained by investigation of photon emission accompanying oxygen adsorption (AL) and TPD data existence of adsorption sites on the surface is suggested on which irreversible dissociative adsorption of oxygen occurs. These very sites are associated with emission processes Conclusion is made that the only type of adsorption sites connected with anion vacancy is present on zirconia surface and this is its charge state that determines the state of adsorbed oxygen. One of the important mechanisms by which the electron and UV photon excitation affects the adsorption interaction is the change of the charge state of the adsorption site

  3. Oxygen adsorption on Cu-9 at. %Al(111) studied by low energy electron diffraction and Auger electron spectroscopy

    Science.gov (United States)

    Yoshitake, Michiko; Bera, Santanu; Yamauchi, Yasuhiro; Song, Weijie

    2003-07-01

    Cu-based alloys have been used for electric cables for long time. In the field of microelectronics, Al had been used for electrical wiring. However, it became clear that electromigration occurs in Al that causes breaking of wires in minute wirings. Due to this problem, Cu wiring is used in most advanced microprocessors. Cu metal is more corrosive than Al and Cu-based alloys with a small amount of Al is expected to solve problems both on electromigration and corrosion. The initial stage of corrosion is oxygen adsorption. We studied surface segregation of Al on Cu-9% Al(111) and oxygen adsorption on the surface with/without Al segregation in ultrahigh vacuum by low energy electron diffraction (LEED) and Auger electron spectroscopy. It was found that Al segregates on the surface to form (√3×√3)R30° structure and the structure vanishes above 595 K to give (1×1) structure while Al still segregates. The specimen was exposed to oxygen at different temperatures. The amount of oxygen uptake was not structure dependent but temperature dependent. Below 595 K, only a small amount of oxygen adsorbed. Between 595 and 870 K, oxygen adsorbed surface showed amorphous LEED pattern. The specimen was annealed at 1070 K after oxygen exposure. When the specimen was exposed oxygen below 870 K, the oxygen Auger intensity decreased significantly by annealing and the annealed surface showed (√3×√3)R30° structure at room temperature. When the specimen was exposed to oxygen at 870 K, diffused spots developed newly in LEED pattern but the pattern disappeared after 1070 K annealing while oxygen Auger intensity remained almost constant. Exposing the specimen to oxygen at 995 K resulted in clear spots in the LEED pattern, which were attributed to the (7/√3×7√3)R30° structure.

  4. A first-principles study of structure, orbital interactions and atomic oxygen and OH adsorption on Mo-, Sc- and Y-doped nickel bimetallic clusters

    International Nuclear Information System (INIS)

    Das, Nishith Kumar; Shoji, Tetsuo

    2013-01-01

    Highlights: •Mo-doped nickel clusters are energetically more stable than the Sc and Y-doped clusters (n ⩾ 10). •Mo atom exhibits center at the cluster rather than edge, while Sc and Y atom sit at the edge. •The metallic s, d orbitals are mainly dominated on the stability of nanoclusters. •The oxygen and OH adsorption energy of Mo-doped cluster are higher than those of other nanoclusters. •2p Orbitals are strongly bonds with Mo 4d, and a weakly interacts with Ni 3d, 4s and Mo 5s orbitals. -- Abstract: Density functional theory (DFT) has been used to study the stability, orbitals interactions and oxygen and hydroxyl chemisorption properties of Ni n M (1 ⩽ n ⩽ 12) clusters. A single atom doped-nickel clusters increase the stability, and icosahedral Ni 12 Mo cluster is the most stable structure. Molybdenum atom prefers to exhibit center at the cluster (n ⩾ 10) rather than edge, while Sc and Y atom remain at the edge. The Ni–Mo bond lengths are smaller than the Ni–Sc and Ni–Y. The pDOS results show that the d–d orbitals interactions are mainly dominating on the stability of clusters, while p orbitals have a small effect on the stability. The Mo-doped nanoclusters have the highest oxygen and OH chemisorption energy, and the most favorable adsorption site is on the top Mo site. The larger cluster distortion is found for the Sc- and Y-doped structures compared to other clusters. The oxygen 2p orbitals are strongly hybridizing with the Mo 4d orbitals (n < 9) and a little interaction between oxygen 2p and Ni 3d, 4s and Mo 5s orbitals. The Mo-doped clusters are significantly increased the chemisorption energies that might improve the passive film adherence of nanoalloys

  5. Spectroscopic link between adsorption site occupation and local surface chemical reactivity

    DEFF Research Database (Denmark)

    Baraldi, A.; Lizzit, S.; Comelli, G.

    2004-01-01

    rules, from which adsorption sites are directly determined. Theoretical calculations rationalize the results for transition metal surfaces in terms of the energy shift of the d-band center of mass and this proves that adsorbate-induced SCL shifts provide a spectroscopic measure of local surface...

  6. DFT study of oxygen adsorption on Mo{sub 2}C(001) and (201) surfaces at different conditions

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Lihong, E-mail: chenglihong001@126.com [School of Materials and Mechanical & Electrical Engineering, Jiangxi Science and Technology Normal University, Nanchang 330013, Jiangxi (China); Li, Wenkui; Chen, Zhiqin; Ai, Jianping; Zhou, Zehua [School of Materials and Mechanical & Electrical Engineering, Jiangxi Science and Technology Normal University, Nanchang 330013, Jiangxi (China); Liu, Jianwen, E-mail: liujw@nsccsz.gov.cn [National Supercomputing Center in Shenzhen, Shenzhen 518055 (China)

    2017-07-31

    Highlights: • O adsorption manners on Mo{sub 2}C surfaces were calculated by DFT method. • Stable oxygen adsorption states and coverage were identified at given T and p. • O{sub 2} results in full oxidation while H{sub 2}O and CO{sub 2} cause partial oxidation of Mo{sub 2}C surfaces. • Hydrogen could be used to avoid Mo{sub 2}C surface oxidation. - Abstract: Density functional theory (DFT) calculations were performed to investigate oxygen adsorption on Mo{sub 2}C(001) and (201)surfaces at different coverage. The energies and structures of oxygen from lowest to saturated coverages were clearly identified on each surface. Thermodynamics method was introduced to reveal the roles of temperature, pressure as well as oxygen sources (O{sub 2}, H{sub 2}O and CO{sub 2}) on the surface oxygen coverage, which is related to the surface oxidation. On the basis of phase diagram, we can easily identify the stable oxygen coverage at different defined conditions. In addition, it reveals that O{sub 2} is the strongest oxidant, which results in the full coverage of oxygen on both surfaces in a wide range of temperature and pressure. Then, H{sub 2}O and CO{sub 2} are weaker oxidants, which could only cause partial oxidation of Mo{sub 2}C surfaces. These results indicate the facile oxidation of Mo{sub 2}C catalyst. The possible ways to avoid surface oxidation are keeping higher temperature and H{sub 2} pressure in the gas phase.

  7. High-resolution insight into the competitive adsorption of heavy metals on natural sediment by site energy distribution.

    Science.gov (United States)

    Huang, Limin; Jin, Qiang; Tandon, Puja; Li, Aimin; Shan, Aidang; Du, Jiajie

    2018-04-01

    Investigating competitive adsorption on river/lake sediments is valuable for understanding the fate and transport of heavy metals. Most studies have studied the adsorption isotherms of competitive heavy metals, which mainly comparing the adsorption information on the same concentration. However, intrinsically, the concentration of each heavy metal on competitive adsorption sites is different, while the adsorption energy is identical. Thus, this paper introduced the site energy distribution theory to increase insight into the competitive adsorption of heavy metals (Cu, Cd and Zn). The site energy distributions of each metal with and without other coexisting heavy metals were obtained. It illustrated that site energy distributions provide much more information than adsorption isotherms through screening of the full energy range. The results showed the superior heavy metal in each site energy area and the influence of competitive metals on the site energy distribution of target heavy metal. Site energy distributions can further help in determining the competitive sites and ratios of coexisting metals. In particular, in the high-energy area, which has great environmental significance, the ratios of heavy metals in the competitive adsorption sites obtained for various competitive systems were as follows: slightly more than 3:1 (Cu-Cd), slightly less than 3:1 (Cu-Zn), slightly more than 1:1 (Cd-Zn), and nearly 7:2:2 (Cu-Cd-Zn). The results from this study are helpful to deeply understand competitive adsorption of heavy metals (Cu, Cd, Zn) on sediment. Therefore, this study was effective in presenting a general pattern for future reference in competitive adsorption studies on sediments. Copyright © 2018 Elsevier Ltd. All rights reserved.

  8. (La1-xSrx)0.98MnO3 perovskite with A-site deficiencies toward oxygen reduction reaction in aluminum-air batteries

    Science.gov (United States)

    Xue, Yejian; Miao, He; Sun, Shanshan; Wang, Qin; Li, Shihua; Liu, Zhaoping

    2017-02-01

    The strontium doped Mn-based perovskites have been proposed as one of the best oxygen reduction reaction catalysts (ORRCs) to substitute the noble metal. However, few studies have investigated the catalytic activities of LSM with the A-site deficiencies. Here, the (La1-xSrx)0.98MnO3 (LSM) perovskites with A-site deficiencies are prepared by a modified solid-liquid method. The structure, morphology, valence state and oxygen adsorption behaviors of these LSM samples are characterized, and their catalytic activities toward ORR are studied by the rotating ring-disk electrode (RRDE) and aluminum-air battery technologies. The results show that the appropriate doping with Sr and introducing A-site stoichiometry can effectively tailor the Mn valence and increase the oxygen adsorption capacity of LSM. Among all the LSM samples in this work, the (La0.7Sr0.3)0.98MnO3 perovskite composited with 50% carbon (50%LSM30) exhibits the best ORR catalytic activity due to the excellent oxygen adsorption capacity. Also, this catalyst has much higher durability than that of commercial 20%Pt/C. Moreover, the maximum power density of the aluminum-air battery using 50%LSM30 as the ORRC can reach 191.3 mW cm-2. Our work indicates that the LSM/C composite catalysts with A-site deficiencies can be used as a promising ORRC in the metal-air batteries.

  9. Water-induced adsorption of carbon monoxide and oxygen on the gold dimer cation.

    Science.gov (United States)

    Ito, Tomonori; Patwari, G Naresh; Arakawa, Masashi; Terasaki, Akira

    2014-09-18

    It is demonstrated, using tandem mass spectrometry and ion trap, that preadsorption of a H2O molecule on the gold dimer cation, Au2(+), enhances adsorption of CO and O2 molecules, which is otherwise inert toward these molecules. The rate of adsorption of CO on Au2(H2O)(+) was found to be higher by 2 orders of magnitude relative to bare Au2(+). The enhancement of the CO adsorption rate is due to the presence of a reaction channel, which cleaves the Au-Au bond, leading to the formation of Au(H2O)(CO)(+). Such an observation can be attributed to weakening of the Au-Au bond upon adsorption of a water molecule. Further, it was also observed that preadsorption of H2O leads to dramatic enhancement of O2 adsorption on the Au2(+) ion, which can be attributed to the changes in the electron density following water adsorption.

  10. Atomic oxygen adsorption and its effect on the oxidation behaviour of ZrB2-ZrC-SiC in air

    International Nuclear Information System (INIS)

    Gao Dong; Zhang Yue; Xu Chunlai; Song Yang; Shi Xiaobin

    2011-01-01

    Research highlights: → Atomic oxygen was adsorbed on the surface of ZrB 2 -ZrC-SiC ceramics. → Atomic oxygen was preferred reacted with borides according to XPS spectra. → The atomic oxygen adsorption is detrimental to the oxidation resistance. → The porosity should be the major reason which provides diffusion path for the atomic oxygen. → The structure evolution of the ceramics during oxidation is analyzed. - Abstract: Atomic oxygen is adsorbed on the surface of the hot-pressed ZrB 2 -ZrC-SiC ceramic composites, and then the ceramic composites are oxidized in air up to 1500 deg. C with the purpose of clarifying the effect of atomic oxygen adsorption on the oxidation behaviour of the ceramic composites. The XPS spectra are employed to identify the adsorption mechanism of atomic oxygen on the surface of the ceramic composites, and the formation of O-B, O-Zr, and O-Si bonds indicates that atomic oxygen is chemically adsorbed on the surface of the ceramic. In addition, atomic oxygen is preferred to be adsorbed on the surface of borides according to the Zr 3d core level spectrum. On the other hand, the atomic oxygen adsorption is detrimental to the oxidation resistance according to experimental results, and the porosity of the ceramic should be the major reason which provides diffusion path for the atomic oxygen. Furthermore, the structure evolution of the ceramic composites during oxidation process is analyzed.

  11. Adsorption/desorption of low concentration of carbonyl sulfide by impregnated activated carbon under micro-oxygen conditions

    International Nuclear Information System (INIS)

    Wang, Xueqian; Qiu, Juan; Ning, Ping; Ren, Xiaoguang; Li, Ziyan; Yin, Zaifei; Chen, Wei; Liu, Wei

    2012-01-01

    Highlights: ► Carbonyl sulfide can be catalytic oxidized by micro-oxygen in the off-gas. ► How to use the trace oxygen for the oxidation of carbonyl sulfide was a challenge. ► The SO 4 2− species in the adsorbent sample were generated by a catalytic oxidation process. - Abstract: Activated carbon modified with different impregnants has been studied for COS removal efficiency under micro-oxygen conditions. Activated carbon modified with Cu(NO 3 ) 2 –CoPcS–KOH (denoted as Cu–Co–KW) is found to have markedly enhanced adsorption purification ability. In the adsorption purification process, the reaction temperature, oxygen concentration, and relative humidity of the gas are determined to be three crucial factors. A breakthrough of 43.34 mg COS/g adsorbent at 60 °S and 30% relative humidity with 1.0% oxygen is shown in Cu–Co–KW for removing COS. The structures of the activated carbon samples are characterized using nitrogen adsorption, and their surface chemical structures are analyzed with X-ray photoelectron spectroscopy (XPS). Modification of Cu(NO 3 ) 2 –CoPcS–KOH appears to improve the COS removal capacity significantly, during which, SO 4 2− is presumably formed, strongly adsorbed, and present in the micropores ranging from 0.7 to 1.5 nm. TPD is used to identify the products containing sulfur species on the carbon surface, where SO 2 and COS are detected in the effluent gas generated from exhausted Cu–Co–KW (denoted Cu–Co–KWE). According to the current study results, the activated carbon impregnated with Cu(NO 3 ) 2 –CoPcS–KOH promises a good candidate for COS adsorbent, with the purified gas meeting requirements for desirable chemical feed stocks.

  12. Adsorption/desorption of low concentration of carbonyl sulfide by impregnated activated carbon under micro-oxygen conditions

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xueqian, E-mail: wxqian3000@yahoo.com.cn [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650093 (China); Qiu, Juan; Ning, Ping; Ren, Xiaoguang; Li, Ziyan; Yin, Zaifei; Chen, Wei; Liu, Wei [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650093 (China)

    2012-08-30

    Highlights: Black-Right-Pointing-Pointer Carbonyl sulfide can be catalytic oxidized by micro-oxygen in the off-gas. Black-Right-Pointing-Pointer How to use the trace oxygen for the oxidation of carbonyl sulfide was a challenge. Black-Right-Pointing-Pointer The SO{sub 4}{sup 2-} species in the adsorbent sample were generated by a catalytic oxidation process. - Abstract: Activated carbon modified with different impregnants has been studied for COS removal efficiency under micro-oxygen conditions. Activated carbon modified with Cu(NO{sub 3}){sub 2}-CoPcS-KOH (denoted as Cu-Co-KW) is found to have markedly enhanced adsorption purification ability. In the adsorption purification process, the reaction temperature, oxygen concentration, and relative humidity of the gas are determined to be three crucial factors. A breakthrough of 43.34 mg COS/g adsorbent at 60 Degree-Sign S and 30% relative humidity with 1.0% oxygen is shown in Cu-Co-KW for removing COS. The structures of the activated carbon samples are characterized using nitrogen adsorption, and their surface chemical structures are analyzed with X-ray photoelectron spectroscopy (XPS). Modification of Cu(NO{sub 3}){sub 2}-CoPcS-KOH appears to improve the COS removal capacity significantly, during which, SO{sub 4}{sup 2-} is presumably formed, strongly adsorbed, and present in the micropores ranging from 0.7 to 1.5 nm. TPD is used to identify the products containing sulfur species on the carbon surface, where SO{sub 2} and COS are detected in the effluent gas generated from exhausted Cu-Co-KW (denoted Cu-Co-KWE). According to the current study results, the activated carbon impregnated with Cu(NO{sub 3}){sub 2}-CoPcS-KOH promises a good candidate for COS adsorbent, with the purified gas meeting requirements for desirable chemical feed stocks.

  13. The nature of cationic adsorption sites in alkaline zeolites-single, dual and multiple cation sites

    Czech Academy of Sciences Publication Activity Database

    Nachtigall, P.; Delgado, M. R.; Nachtigallová, Dana; Arean, C. O.

    2012-01-01

    Roč. 14, č. 5 (2012), s. 1552-1569 ISSN 1463-9076 R&D Projects: GA ČR GA203/09/0143 Institutional research plan: CEZ:AV0Z40550506 Keywords : exchanged ZSM-5 zeolites * carbon-monoxide adsorption * low-temperature CO * solid-state NMR * high-silica zeolites Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.829, year: 2012

  14. Transient biouptake flux and accumulation by micro-organisms: The case of two types of sites with Langmuir adsorption

    NARCIS (Netherlands)

    Galceran, J.; Monne, J.; Puy, J.; Leeuwen, van H.P.

    2006-01-01

    The uptake of a chemical species by an aquatic microorganism is modelled considering two kinds of sites where Langmuirian adsorption is followed by first order internalisation kinetics. Simpler models, such as only one internalisation route (while most of the adsorption takes place on

  15. The influence of oxygen adsorption on the NEXAFS and core-level XPS spectra of the C60 derivative PCBM

    International Nuclear Information System (INIS)

    Brumboiu, Iulia Emilia; Eriksson, Olle; Brena, Barbara; Ericsson, Leif; Hansson, Rickard; Moons, Ellen

    2015-01-01

    Fullerenes have been a main focus of scientific research since their discovery due to the interesting possible applications in various fields like organic photovoltaics (OPVs). In particular, the derivative [6,6]-phenyl-C 60 -butyric acid methyl ester (PCBM) is currently one of the most popular choices due to its higher solubility in organic solvents compared to unsubstituted C 60 . One of the central issues in the field of OPVs is device stability, since modules undergo deterioration (losses in efficiency, open circuit voltage, and short circuit current) during operation. In the case of fullerenes, several possibilities have been proposed, including dimerization, oxidation, and impurity related deterioration. We have studied by means of density functional theory the possibility of oxygen adsorption on the C 60 molecular moiety of PCBM. The aim is to provide guidelines for near edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) measurements which can probe the presence of atomic or molecular oxygen on the fullerene cage. By analysing several configurations of PCBM with one or more adsorbed oxygen atoms, we show that a joint core level XPS and O1s NEXAFS investigation could be effectively used not only to confirm oxygen adsorption but also to pinpoint the bonding configuration and the nature of the adsorbate

  16. Molecular studies of Cs adsorption sites in inorganic layered materials: the influence of solution concentration.

    Science.gov (United States)

    Sato, Kiminori; Hunger, Michael

    2017-07-19

    Radioactive Cs released into a soil environment migrates along with groundwater in a manner dependent on Cs concentration. Data on the variation of Cs adsorption as a function of solution concentration are an essential prerequisite to successful decontamination work in Fukushima. To aid the ongoing decontamination work, the adsorption of Cs in aqueous solution across a wide Cs + molarity range is studied for the case of saponite clay as adsorbent, an inorganic layered material that is an abundant mineral in the soil environment. The local molecular structures, i.e. nanosheet surfaces, nanosheet edges, and oncoming hexagonal cavities, participating in Cs adsorption are qualitatively highlighted by means of a recently developed analytical method using data from a conventional elution test, 133 Cs magic-angle-spinning nuclear magnetic resonance (MAS NMR), and the radiocesium interception potential (RIP) [K. Sato, et al., J. Phys. Chem. C, 2016, 120, 1270]. The concentrations of nanosheet edges amount to between 100 and 400 mmol kg -1 , which are not substantially different from those of the nanosheet surfaces, generally regarded as the main decontamination sites. This unambiguously implies that the nanosheet edges should be targeted as the molecular sites for decontaminating radioactive Cs, in addition to the nanosheet surfaces.

  17. First-principles studies on the adsorption of molecular oxygen on Ba(110) surface

    International Nuclear Information System (INIS)

    Li, S.F.; Xue Xinlian; Li Pinglin; Li Xinjian; Jia Yu

    2006-01-01

    The adsorption of O 2 on Ba(110) surface is studied with first-principles calculations based on density functional theory. Our calculations predict that O 2 may prefer to dissociative adsorption on Ba(110) surface without obvious barrier. Also our results do not support the model of charge transfer from the surface to the molecule as a bond breaking mechanism. Instead, the increasing hybridization between O 2 orbitals and the d states of Ba(110) surface may play an important role in the dissociation adsorption

  18. Non-site-specific allosteric effect of oxygen on human hemoglobin under high oxygen partial pressure.

    Science.gov (United States)

    Takayanagi, Masayoshi; Kurisaki, Ikuo; Nagaoka, Masataka

    2014-04-08

    Protein allostery is essential for vital activities. Allosteric regulation of human hemoglobin (HbA) with two quaternary states T and R has been a paradigm of allosteric structural regulation of proteins. It is widely accepted that oxygen molecules (O2) act as a "site-specific" homotropic effector, or the successive O2 binding to the heme brings about the quaternary regulation. However, here we show that the site-specific allosteric effect is not necessarily only a unique mechanism of O2 allostery. Our simulation results revealed that the solution environment of high O2 partial pressure enhances the quaternary change from T to R without binding to the heme, suggesting an additional "non-site-specific" allosteric effect of O2. The latter effect should play a complementary role in the quaternary change by affecting the intersubunit contacts. This analysis must become a milestone in comprehensive understanding of the allosteric regulation of HbA from the molecular point of view.

  19. Precursor state of oxygen molecules on the Si(001) surface during the initial room-temperature adsorption

    Science.gov (United States)

    Hwang, Eunkyung; Chang, Yun Hee; Kim, Yong-Sung; Koo, Ja-Yong; Kim, Hanchul

    2012-10-01

    The initial adsorption of oxygen molecules on Si(001) is investigated at room temperature. The scanning tunneling microscopy images reveal a unique bright O2-induced feature. The very initial sticking coefficient of O2 below 0.04 Langmuir is measured to be ˜0.16. Upon thermal annealing at 250-600 °C, the bright O2-induced feature is destroyed, and the Si(001) surface is covered with dark depressions that seem to be oxidized structures with -Si-O-Si- bonds. This suggests that the observed bright O2-induced feature is an intermediate precursor state that may be either a silanone species or a molecular adsorption structure.

  20. Oxygen-induced Decrease in the Equilibrium Adsorptive Capacities of Activated Carbons

    OpenAIRE

    Ovín Ania, María Concepción; Parra Soto, José Bernardo; Pis Martínez, José Juan

    2004-01-01

    Special attention was paid in this work to the role of surface chemistry in the adsorption of phenol and salicylic acid onto activated carbons. To this end, two commercial activated carbons (granular and powdered) were oxidised using ammonium peroxodisulphate [(NH4) 2S2O8] and nitric acid in different concentrations. The structural and chemical properties of the oxidised adsorbents were characterised via nitrogen adsorption isotherms measured at –196 ° C and Boehm titrations. Phenol adsorptio...

  1. Evaluation of the Oxygen Concentrator Prototypes: Pressure Swing Adsorption Prototype and Electrochemical Prototype

    Science.gov (United States)

    Gilkey, Kelly M.; Olson, Sandra L.

    2015-01-01

    An oxygen concentrator is needed to provide enriched oxygen in support of medical contingency operations for future exploration human spaceflight programs. It would provide continuous oxygen to an ill or injured crew member in a closed cabin environment. Oxygen concentration technology is being pursued to concentrate oxygen from the ambient environment so oxygen as a consumable resource can be reduced. Because oxygen is a critical resource in manned spaceflight, using an oxygen concentrator to pull oxygen out of the ambient environment instead of using compressed oxygen can provide better optimization of resources. The overall goal of this project is to develop an oxygen concentrator module that minimizes the hardware mass, volume, and power footprint while still performing at the required clinical capabilities. Should a medical event occur that requires patient oxygenation, the release of 100 percent oxygen into a small closed cabin environment can rapidly raise oxygen levels to the vehicles fire limit. The use of an oxygen concentrator to enrich oxygen from the ambient air and concentrate it to the point where it can be used for medical purposes means no oxygen is needed from the ultra-high purity (99.5+% O2) oxygen reserve tanks. By not adding oxygen from compressed tanks to the cabin environment, oxygen levels can be kept below the vehicle fire limit thereby extending the duration of care provided to an oxygenated patient without environmental control system intervention to keep the cabin oxygen levels below the fire limits. The oxygen concentrator will be a Food and Drug Administration (FDA) clearable device. A demonstration unit for the International Space Station (ISS) is planned to verify the technology and provide oxygen capability. For the ISS, the demonstration unit should not exceed 10 kg (approximately 22 lb), which is the soft stowage mass limit for launch on resupply vehicles for the ISS. The unit's size should allow for transport within the

  2. Determination of deuterium adsorption site on palladium(1 0 0) using low energy ion recoil spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kambali, I. [Department of Physics, University of Newcastle, Callaghan (Australia); O' Connor, D.J. [Department of Physics, University of Newcastle, Callaghan (Australia)], E-mail: john.oconnor@newcastle.edu.au; Gladys, M.J. [Department of Physics, University of Newcastle, Callaghan (Australia); Karolewski, M.A. [Department of Chemistry, University of Brunei Darussalam, Gadong BE1410 (Brunei Darussalam)

    2008-05-15

    Ion beam analysis has been recently applied to study the adsorption phenomena of some adsorbates on metal surfaces. In this paper, surface recoils created by low energy Ne{sup +} ions are employed to study the adsorption site of deuterium (D) atoms on Pd(1 0 0). This technique is extremely surface sensitive with the capacity for atomic layer depth resolution. From azimuthal angle observations of Pd(1 0 0) specimen, it was found that at room temperature, D was adsorbed in the fourfold hollow site of Pd(1 0 0) at a height of 0.25 {+-} 0.05 A above the surface. The adsorbate remains in the hollow site at all temperatures to 383 K though the vertical height above the surface is found to depend on coverage and for the first time evidence is found of a transition to a p(2 x 2) structure for the adsorbate. There is no evidence of D sitting in the Pd(1 0 0) subsurface at room and higher temperatures.

  3. The effect of topological defects and oxygen adsorption on the electronic transport properties of single-walled carbon-nanotubes

    International Nuclear Information System (INIS)

    Grujicic, M.; Cao, G.; Singh, R.

    2003-01-01

    Ab initio density functional theory (DFT) calculations of the interactions between isolated infinitely-long semiconducting zig-zag (10, 0) or isolated infinitely-long metallic arm-chair (5, 5) single-walled carbon-nanotubes (SWCNTs) and single oxygen-molecules are carried out in order to determine the character of molecular-oxygen adsorption and its effect on electronic transport properties of these SWCNTs. A Green's function method combined with a nearest-neighbor tight-binding Hamiltonian in a non-orthogonal basis is used to compute the electrical conductance of SWCNTs and its dependence on the presence of topological defects in SWCNTs and of molecular-oxygen adsorbates. The computational results obtained show that in both semiconducting and metallic SWCNTs, oxygen-molecules are physisorbed to the defect-free nanotube walls, but when such walls contain topological defects, oxygen-molecules become strongly chemisorbed. In semiconducting (10, 0) SWCNTs, physisorbed O 2 -molecules are found to significantly increase electrical conductance while the effect of 7-5-5-7 defects is practically annulled by chemisorbed O 2 -molecules. In metallic (5, 5) SWCNTs, both O 2 adsorbates and 7-5-5-7 defects are found to have a relatively small effect on electrical conductance of these nanotubes

  4. Adsorption Energies of Carbon, Nitrogen, and Oxygen Atoms on the Low-temperature Amorphous Water Ice: A Systematic Estimation from Quantum Chemistry Calculations

    Science.gov (United States)

    Shimonishi, Takashi; Nakatani, Naoki; Furuya, Kenji; Hama, Tetsuya

    2018-03-01

    We propose a new simple computational model to estimate the adsorption energies of atoms and molecules to low-temperature amorphous water ice, and we present the adsorption energies of carbon (3 P), nitrogen (4 S), and oxygen (3 P) atoms based on quantum chemistry calculations. The adsorption energies were estimated to be 14,100 ± 420 K for carbon, 400 ± 30 K for nitrogen, and 1440 ± 160 K for oxygen. The adsorption energy of oxygen is consistent with experimentally reported values. We found that the binding of a nitrogen atom is purely physisorption, while that of a carbon atom is chemisorption, in which a chemical bond to an O atom of a water molecule is formed. That of an oxygen atom has a dual character, with both physisorption and chemisorption. The chemisorption of atomic carbon also implies the possibility of further chemical reactions to produce molecules bearing a C–O bond, though this may hinder the formation of methane on water ice via sequential hydrogenation of carbon atoms. These properties would have a large impact on the chemical evolution of carbon species in interstellar environments. We also investigated the effects of newly calculated adsorption energies on the chemical compositions of cold dense molecular clouds with the aid of gas-ice astrochemical simulations. We found that abundances of major nitrogen-bearing molecules, such as N2 and NH3, are significantly altered by applying the calculated adsorption energy, because nitrogen atoms can thermally diffuse on surfaces, even at 10 K.

  5. Formation of cerussite and hydrocerussite during adsorption of lead from aqueous solution on oxidized carbons by cold oxygen plasma

    Energy Technology Data Exchange (ETDEWEB)

    De Velasco Maldonado, Paola S. [Instituto Tecnologico de Aguascalientes, Av. Adolfo López Mateos No. 1801 Ote. C.P, Aguascalientes, Ags, 20256 (Mexico); Hernández-Montoya, Virginia, E-mail: virginia.hernandez@yahoo.com.mx [Instituto Tecnologico de Aguascalientes, Av. Adolfo López Mateos No. 1801 Ote. C.P, Aguascalientes, Ags, 20256 (Mexico); Concheso, A.; Montes-Morán, Miguel A. [Instituto Nacional del Carbon, INCAR-CSIC, Apartado 73, E-33080, Oviedo (Spain)

    2016-11-15

    Highlights: • The formation of cerussite and hydrocerussite was observed on the carbon surface. • Occurrence of CaCO{sub 3} on the carbons surface plays a crucial role in the formation. • The carbons were prepared by carbonization and oxidation with cold oxygen plasma. • Oxidation with cold oxygen plasma increases the formation of these compounds. - Abstract: A new procedure of elimination of Pb{sup 2+} from aqueous solution using carbon adsorbents, in which high amounts of cerussite and hydrocerussite are deposited on the carbon surfaces, is reported. The procedure includes the preparation of carbons from selected lignocellulosic wastes (pecan nut shells and peach stones) by single carbonization and further oxidation with cold oxygen plasma. The materials prior and after the oxidation treatment were characterized using elemental analysis, FT-IR spectroscopy, SEM/EDX analysis, adsorption of N{sub 2} at −196 °C and X-ray photoelectron spectroscopy. The adsorption of Pb{sup 2+} was carried out in batch systems under constant agitation. The formation of cerussite and hydrocerussite on the spent carbon surfaces was confirmed by XRD, SEM/EDX and FT-IR. A Pb{sup 2+} removal mechanism is proposed in which a co-precipitation of lead nitrate and calcium carbonate would render the formation of the lead carbonates. In such mechanism, the occurrence of CaCO{sub 3} on the surface of the adsorbents plays a crucial role. The presence of calcium carbonate on the precursors is understood on the basis of the thermal evolution of calcium oxalate originally present in the biomass. The oxygen plasma treatment helps to expose the calcium carbonate nanocrystals thus improving dramatically the removal capacity of Pb{sup 2+}. Accordingly, retention capacities as high as 63 mg of Pb{sup 2+} per gram of adsorbent have been attained.

  6. Formation of cerussite and hydrocerussite during adsorption of lead from aqueous solution on oxidized carbons by cold oxygen plasma

    International Nuclear Information System (INIS)

    De Velasco Maldonado, Paola S.; Hernández-Montoya, Virginia; Concheso, A.; Montes-Morán, Miguel A.

    2016-01-01

    Highlights: • The formation of cerussite and hydrocerussite was observed on the carbon surface. • Occurrence of CaCO_3 on the carbons surface plays a crucial role in the formation. • The carbons were prepared by carbonization and oxidation with cold oxygen plasma. • Oxidation with cold oxygen plasma increases the formation of these compounds. - Abstract: A new procedure of elimination of Pb"2"+ from aqueous solution using carbon adsorbents, in which high amounts of cerussite and hydrocerussite are deposited on the carbon surfaces, is reported. The procedure includes the preparation of carbons from selected lignocellulosic wastes (pecan nut shells and peach stones) by single carbonization and further oxidation with cold oxygen plasma. The materials prior and after the oxidation treatment were characterized using elemental analysis, FT-IR spectroscopy, SEM/EDX analysis, adsorption of N_2 at −196 °C and X-ray photoelectron spectroscopy. The adsorption of Pb"2"+ was carried out in batch systems under constant agitation. The formation of cerussite and hydrocerussite on the spent carbon surfaces was confirmed by XRD, SEM/EDX and FT-IR. A Pb"2"+ removal mechanism is proposed in which a co-precipitation of lead nitrate and calcium carbonate would render the formation of the lead carbonates. In such mechanism, the occurrence of CaCO_3 on the surface of the adsorbents plays a crucial role. The presence of calcium carbonate on the precursors is understood on the basis of the thermal evolution of calcium oxalate originally present in the biomass. The oxygen plasma treatment helps to expose the calcium carbonate nanocrystals thus improving dramatically the removal capacity of Pb"2"+. Accordingly, retention capacities as high as 63 mg of Pb"2"+ per gram of adsorbent have been attained.

  7. Probing adsorption sites of carbon dioxide in metal organic framework of [Zn(bdc)(dpds)]n: A molecular simulation study

    Science.gov (United States)

    Lu, Shih-I.; Liao, Jian-Min; Huang, Xiao-Zhuang; Lin, Chia-Hsun; Ke, Szu-Yu; Wang, Chih-Chieh

    2017-11-01

    We used force-field based grand-canonical Monte Carlo simulation method and density functional theory to study adsorption characteristics of carbon dioxide (CO2) molecules in a metal-organic framework (MOF) compound, [Zn(bdc)(dpds)]n. The studied MOF include a metal ion (Zn(II)), an anion organic linker (dianion of benzene dicarboxylicacid, bdc2-) and a neutral organic linker (4,4‧-dipyridyldisulfide, dpds). Results from calculated adsorption isotherms and enthalpies of adsorption agree with the experimental data. The interactions between the adsorbed CO2 and the organic linkers were examined in simulations. Calculated results show available absorption sites are surrounded by two dpds ligands in which an S-S bond as an N-N‧ spacer connect two pyridines. In contrast, the bdc2- ligand does not give a significant contribution to the substantial adsorption amount even though it contains the carboxylate group that provides available bonding site to CO2.

  8. Effect of pre-pyrolysis mode on simultaneous introduction of nitrogen/oxygen-containing functional groups into the structure of bagasse-based mesoporous carbon and its influence on Cu(II) adsorption.

    Science.gov (United States)

    Wan, Zeqing; Li, Kunquan

    2018-03-01

    A convenient effective microwave pre-pyrolysis treatment to synthesize biomass-based mesoporous carbon with higher nitrogen/oxygen-chelating adsorption for Cu(II) is reported here, in which phosphoric acid impregnated bagasse was used as a microwave absorber and porogen. For comparison, conventional electric-heating pyrolyzed carbon was prepared and doped with nitrogen/oxygen groups. Nitrogen adsorption, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy (XPS) and batch adsorption were employed to investigate the effects of the two pre-pyrolysis modes on the sample physicochemical and Cu(II) adsorptive properties. The 22-min-microwave-pyrolyzed bagasse mesoporous activated carbon (MBAC, 85.32% mesoporosity) contained 10.52% O, which is 3.94% more than electric-heating pyrolyzed mesoporous activated carbon (89.52% mesoporosity). After electrophilic aromatic substitutions of N/O doping, the former possessed more N (5.83%) and more O (21.40%), confirming that time-saving energy-efficient microwave pyrolysis favors the formation of defective C/O atoms in or at the edges of the graphite layer of MBAC, which are highly active and tend to act as preferred reactive positions for the doping of N/O-containing groups simultaneously compared with conventional electric-heating pyrolysis. These N and O species existed mainly as COOH, OH, NH and NH 2 functional groups, and were confirmed by XPS to be active sites for metal binding via electrostatic attraction, hydrogen bonding, a chelate effect and complexation, resulting in the great enhancement of Cu(II) adsorption. Langmuir isotherm and pseudo-second-order kinetic fitting further proved that Cu(II) adsorption by N/O-doped MBAC is ascribed mainly to chemisorption. Therefore, rapid microwave pre-pyrolysis provides a promising route to prepare excellent-performance N/O-doped carbon adsorbents. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Electrochemical quartz crystal microbalance analysis of the oxygen reduction reaction on Pt-based electrodes. Part 2: adsorption of oxygen species and ClO4(-) anions on Pt and Pt-Co alloy in HClO4 solutions.

    Science.gov (United States)

    Omura, J; Yano, H; Tryk, D A; Watanabe, M; Uchida, H

    2014-01-14

    To gain deeper insight into the role of adsorbed oxygenated species in the O2 reduction reaction (ORR) kinetics on platinum and platinum-cobalt alloys for fuel cells, we carried out a series of measurements with the electrochemical quartz crystal microbalance (EQCM) and the rotating disk electrode (RDE) in acid solution. The effects of anion adsorption on the activities for the ORR were first assessed in HClO4 and HF electrolyte solutions at various concentrations. In our previous work (Part 1), we reported that the perchlorate anion adsorbs specifically on bulk-Pt, with a Frumkin-Temkin isotherm, that is, a linear relationship between Δm and log[HClO4]. Here, we find that the specific adsorption on the Pt-skin/Pt3Co alloy was significantly stronger than that on bulk-Pt, in line with its modified electronic properties. The kinetically controlled current density j(k) for the O2 reduction at the Pt-skin/Pt3Co-RDE was about 9 times larger than that of the bulk-Pt-RDE in 0.01 M HClO4 saturated with air, but the j(k) values on Pt-skin/Pt3Co decreased with increasing [HClO4] more steeply than in the case of Pt, due to the blocking of the active sites by the specifically adsorbed ClO4(-). We have detected reversible mass changes for one or more adsorbed oxygen-containing species (Ox = O2, O, OH, H2O) on the Pt-skin/Pt3Co-EQCM and Pt-EQCM in O2-saturated and He-purged 0.01 M HClO4 solutions, in which the specific adsorption of ClO4(-) anions was negligible. The coverages of oxygen species θ(Ox) on the Pt-skin/Pt3Co in the potential range from 0.86 to 0.96 V in the O2-saturated solution were found to be larger than those on pure Pt, providing strong evidence that the higher O2 reduction activity on the Pt3Co is correlated with higher θ(Ox), contrary to the conventional view.

  10. Predicting Multicomponent Adsorption Isotherms in Open-Metal Site Materials Using Force Field Calculations Based on Energy Decomposed Density Functional Theory

    NARCIS (Netherlands)

    Heinen, J.; Burtch, N.; Walton, K.; Fonseca Guerra, C.; Dubbeldam, D.

    2016-01-01

    For the design of adsorptive-separation units, knowledge is required of the multicomponent adsorption behavior. Ideal adsorbed solution theory (IAST) breaks down for olefin adsorption in open-metal site (OMS) materials due to non-ideal donor–acceptor interactions. Using a

  11. Wrinkles and Folds of Activated Graphene Nanosheets as Fast and Efficient Adsorptive Sites for Hydrophobic Organic Contaminants.

    Science.gov (United States)

    Wang, Jun; Chen, Baoliang; Xing, Baoshan

    2016-04-05

    To create more wrinkles and folds as available adsorption sites, graphene nanosheets (GNS) were thermally treated with KOH for morphological alteration. The surface structures and properties of the activated graphene nanosheets (AGN) were characterized by BET-N2, SEM, TEM, Raman, XRD, XPS, and FTIR. After KOH etching, the highly crystal structure was altered, self-aggregation of graphene layers were evidently relieved, and more single to few layer graphene nanosheets were created with wrinkles and folds. Also both specific surface area and micropore volume of AGN increased relative to GNS. The adsorption of AGN toward p-nitrotoluene, naphthalene and phenanthrene were greatly enhanced in comparison with GNS, and gradually promoted with increasing degree of KOH etching. Adsorption rate of organic contaminants on AGN was very fast and efficient, whereas small molecules showed higher adsorption rates due to the more porous surface of graphene. In addition to π-π interaction, the high affinities of p-nitrotoluene to AGN are suggested from strong electron charge transfer interactions between nitro groups on p-nitrotoluene and defect sites of AGN. A positively linear correlation between organic molecule uptake and the micropore volume of AGN indicated that pore-filling mechanism may play an important role in adsorption. Morphological wrinkles and folds of graphene nanosheets can be regulated to enhance the adsorption capability and kinetics for efficient pollutant removal and to selectively preconcentrate adsorbates with different sizes for detection.

  12. Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado

    Science.gov (United States)

    Hyun, S.P.; Fox, P.M.; Davis, J.A.; Campbell, K.M.; Hayes, K.F.; Long, P.E.

    2009-01-01

    A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters. ?? 2009 American Chemical Society.

  13. Evaluation of an Oxygen-Diffusion Dressing for Accelerated Healing of Donor-Site Wounds

    Science.gov (United States)

    2014-06-01

    wounds in humans,8 but requires visits to facilities with trained personnel and is limited by oxygen toxicity issues. Compared with hyperbaric oxygen...open-label study to compare the effectiveness of OxyBand and Xeroform dress- ings used as dressings for autogenous skin donor sites in burn patients...donor sites. Epinephrine in lactated Ringer’s solu- tion at a concentration of 1:106 was injected subcu- taneously to prepare both donor sites for

  14. Influence of preadsorbed oxygen on the sign and magnitude of the chemisorption-induced resistance change for H2 adsorption onto Fe films

    Science.gov (United States)

    Shanabarger, M. R.

    1986-01-01

    Measurements have been made of the chemisorption-induced resistance change for H2 adsorbed onto Fe film substrates predosed with fixed coverages of chemisorbed oxygen. The measurements were made at temperatures from 295 to 340 K and for estimated oxygen coverages of less than 0.1 monolayers. Two distinct resistance change components were observed in both the adsorption kinetics and the equilibrium isotherms: a positive component which is associated with the adsorption of H2 onto a clean Fe surface, and a negative component which was correlated with the presence of the chemisorbed oxygen. The resistance change isotherms can be fit with a model which assumes that each of the resistance change components result from dissociative chemisorbed hydrogen. Possible mechanisms for the chemisorbed-oxygen-induced negative resistance change are discussed.

  15. On sulfur core level binding energies in thiol self-assembly and alternative adsorption sites: An experimental and theoretical study

    International Nuclear Information System (INIS)

    Jia, Juanjuan; Kara, Abdelkader; Pasquali, Luca; Bendounan, Azzedine; Sirotti, Fausto; Esaulov, Vladimir A.

    2015-01-01

    Characteristic core level binding energies (CLBEs) are regularly used to infer the modes of molecular adsorption: orientation, organization, and dissociation processes. Here, we focus on a largely debated situation regarding CLBEs in the case of chalcogen atom bearing molecules. For a thiol, this concerns the case when the CLBE of a thiolate sulfur at an adsorption site can be interpreted alternatively as due to atomic adsorption of a S atom, resulting from dissociation. Results of an investigation of the characteristics of thiol self-assembled monolayers (SAMs) obtained by vacuum evaporative adsorption are presented along with core level binding energy calculations. Thiol ended SAMs of 1,4-benzenedimethanethiol (BDMT) obtained by evaporation on Au display an unconventional CLBE structure at about 161.25 eV, which is close to a known CLBE of a S atom on Au. Adsorption and CLBE calculations for sulfur atoms and BDMT molecules are reported and allow delineating trends as a function of chemisorption on hollow, bridge, and atop sites and including the presence of adatoms. These calculations suggest that the 161.25 eV peak is due to an alternative adsorption site, which could be associated to an atop configuration. Therefore, this may be an alternative interpretation, different from the one involving the adsorption of atomic sulfur resulting from the dissociation process of the S–C bond. Calculated differences in S(2p) CLBEs for free BDMT molecules, SH group sulfur on top of the SAM, and disulfide are also reported to clarify possible errors in assignments

  16. On sulfur core level binding energies in thiol self-assembly and alternative adsorption sites: An experimental and theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Juanjuan [Institut des Sciences Moléculaires d’Orsay, Université-Paris Sud, 91405 Orsay (France); CNRS, UMR 8214, Institut des Sciences Moléculaires d’Orsay, Orsay ISMO, Bâtiment 351, Université Paris Sud, 91405 Orsay (France); Kara, Abdelkader, E-mail: abdelkader.kara@ucf.edu, E-mail: vladimir.esaulov@u-psud.fr [Department of Physics, University of Central Florida, Orlando, Florida 32816 (United States); Pasquali, Luca [Dipartimento di Ingegneria “E. Ferrari,” Università di Modena e Reggio Emilia, Via Vignolese 905, 41125 Modena (Italy); IOM-CNR, s.s. 14, Km. 163.5 in AREA Science Park, 34149 Basovizza, Trieste (Italy); Department of Physics, University of Johannesburg, P.O. Box 524, Auckland Park 2006 (South Africa); Bendounan, Azzedine; Sirotti, Fausto [Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin, BP 48, F-91192 Gif-sur-Yvette Cedex (France); Esaulov, Vladimir A., E-mail: abdelkader.kara@ucf.edu, E-mail: vladimir.esaulov@u-psud.fr [Institut des Sciences Moléculaires d’Orsay, Université-Paris Sud, 91405 Orsay (France); CNRS, UMR 8214, Institut des Sciences Moléculaires d’Orsay, Orsay ISMO, Bâtiment 351, Université Paris Sud, 91405 Orsay (France); IOM-CNR, s.s. 14, Km. 163.5 in AREA Science Park, 34149 Basovizza, Trieste (Italy)

    2015-09-14

    Characteristic core level binding energies (CLBEs) are regularly used to infer the modes of molecular adsorption: orientation, organization, and dissociation processes. Here, we focus on a largely debated situation regarding CLBEs in the case of chalcogen atom bearing molecules. For a thiol, this concerns the case when the CLBE of a thiolate sulfur at an adsorption site can be interpreted alternatively as due to atomic adsorption of a S atom, resulting from dissociation. Results of an investigation of the characteristics of thiol self-assembled monolayers (SAMs) obtained by vacuum evaporative adsorption are presented along with core level binding energy calculations. Thiol ended SAMs of 1,4-benzenedimethanethiol (BDMT) obtained by evaporation on Au display an unconventional CLBE structure at about 161.25 eV, which is close to a known CLBE of a S atom on Au. Adsorption and CLBE calculations for sulfur atoms and BDMT molecules are reported and allow delineating trends as a function of chemisorption on hollow, bridge, and atop sites and including the presence of adatoms. These calculations suggest that the 161.25 eV peak is due to an alternative adsorption site, which could be associated to an atop configuration. Therefore, this may be an alternative interpretation, different from the one involving the adsorption of atomic sulfur resulting from the dissociation process of the S–C bond. Calculated differences in S(2p) CLBEs for free BDMT molecules, SH group sulfur on top of the SAM, and disulfide are also reported to clarify possible errors in assignments.

  17. Oxygen reduction and evolution at single-metal active sites

    DEFF Research Database (Denmark)

    Calle-Vallejo, F.; Martínez, J.I.; García Lastra, Juan Maria

    2013-01-01

    A worldwide spread of clean technologies such as low-temperature fuel cells and electrolyzers depends strictly on their technical reliability and economic affordability. Currently, both conditions are hardly fulfilled mainly due to the same reason: the oxygen electrode, which has large overpotent...

  18. First Principles Calculations of Oxygen Adsorption on the UN(001) Surface

    International Nuclear Information System (INIS)

    Zhukovskii, Yuri F.; Bocharov, Dmitry; Kotomin, Eugene Alexej; Evarestov, Robert; Bandura, A.V.

    2009-01-01

    Fabrication, handling and disposal of nuclear fuel materials require comprehensive knowledge of their surface morphology and reactivity. Due to unavoidable contact with air components (even at low partial pressures), UN samples contain considerable amount of oxygen impurities affecting fuel properties. In this study we focus on reactivity of the energetically most stable (001) substrate of uranium nitride towards the atomic oxygen as one of initial stages for further UN oxidation. The basic properties of O atoms adsorbed on the UN(001) surface are simulated here combining the two first principles calculation methods based on the plane wave basis set and that of the localized orbitals.

  19. Kinetics of Cation and Oxyanion Adsorption and Desorption on Ferrihydrite: Roles of Ferrihydrite Binding Sites and a Unified Model

    Energy Technology Data Exchange (ETDEWEB)

    Tian, Lei [School of Environment and Energy, South China University of Technology, Guangzhou, Guangdong 510006, People’s Republic of China; The Key Lab of Pollution Control and Ecosystem Restoration in Industry; Shi, Zhenqing [School of Environment and Energy, South China University of Technology, Guangzhou, Guangdong 510006, People’s Republic of China; The Key Lab of Pollution Control and Ecosystem Restoration in Industry; Lu, Yang [School of Environment and Energy, South China University of Technology, Guangzhou, Guangdong 510006, People’s Republic of China; The Key Lab of Pollution Control and Ecosystem Restoration in Industry; Dohnalkova, Alice C. [Environmental; Lin, Zhang [School of Environment and Energy, South China University of Technology, Guangzhou, Guangdong 510006, People’s Republic of China; The Key Lab of Pollution Control and Ecosystem Restoration in Industry; Dang, Zhi [School of Environment and Energy, South China University of Technology, Guangzhou, Guangdong 510006, People’s Republic of China; The Key Lab of Pollution Control and Ecosystem Restoration in Industry

    2017-08-29

    Understanding the kinetics of toxic ion reactions with ferrihydrite is crucial for predicting the dynamic behavior of contaminants in soil environments. In this study, the kinetics of As(V), Cr(VI), Cu, and Pb adsorption and desorption on ferrihydrite were investigated with a combination of laboratory macroscopic experiments, microscopic investigation and mechanistic modeling. The rates of As(V), Cr(VI), Cu, and Pb adsorption and desorption on ferrihydrite, as systematically studied using a stirred-flow method, was highly dependent on the reaction pH and metal concentrations and varied significantly among four metals. Spherical aberration-corrected scanning transmission electron microscopy (Cs-STEM) showed, at sub-nano scales, all four metals were distributed within the ferrihydrite particle aggregates homogeneously after adsorption reactions, with no evidence of surface diffusion-controlled processes. Based on experimental results, we developed a unifying kinetics model for both cation and oxyanion adsorption/desorption on ferrihydrite based on the mechanistic-based equilibrium model CD-MUSIC. Overall, the model described the kinetic results well, and we quantitatively demonstrated how the equilibrium properties of the cation and oxyanion binding to various ferrihydrite sites affected the adsorption and desorption rates. Our results provided a unifying quantitative modeling method for the kinetics of both cation and oxyanion adsorption/desorption on iron minerals.

  20. Adsorption of SF6 decomposed gas on anatase (101) and (001) surfaces with oxygen defect: A density functional theory study

    Science.gov (United States)

    Zhang, Xiaoxing; Chen, Qinchuan; Tang, Ju; Hu, Weihua; Zhang, Jinbin

    2014-01-01

    The detection of partial discharge by analyzing the components of SF6 gas in gas-insulated switchgears is important to the diagnosis and assessment of the operational state of power equipment. A gas sensor based on anatase TiO2 is used to detect decomposed gases in SF6. In this paper, first-principle density functional theory calculations are adopted to analyze the adsorption of SO2, SOF2, and SO2F2, the primary decomposition by-products of SF6 under partial discharge, on anatase (101) and (001) surfaces. Simulation results show that the perfect anatase (001) surface has a stronger interaction with the three gases than that of anatase (101), and both surfaces are more sensitive and selective to SO2 than to SOF2 and SO2F2. The selection of a defect surface to SO2, SOF2, and SO2F2 differs from that of a perfect surface. This theoretical result is corroborated by the sensing experiment using a TiO2 nanotube array (TNTA) gas sensor. The calculated values are analyzed to explain the results of the Pt-doped TNTA gas sensor sensing experiment. The results imply that the deposited Pt nanoparticles on the surface increase the active sites of the surface and the gas molecules may decompose upon adsorption on the active sites. PMID:24755845

  1. Adsorption of atomic oxygen (N2O) on a clean Ge(001) surface

    NARCIS (Netherlands)

    Zandvliet, Henricus J.W.; Keim, Enrico G.; van Silfhout, Arend

    1990-01-01

    We present the results of a study concerning the interaction of atomic oxygen (as released by decomposition of N2O ) with the clean Ge(001)2×1 surface at 300 K. Ellipsometry in the photon energy range of 1.5–4 eV, surface conductance measurements and Auger electron spectroscopy(AES) have been used

  2. On-site Destruction of Radioactive Oily Wastes Using Adsorption Coupled with Electrochemical Regeneration - 12221

    Energy Technology Data Exchange (ETDEWEB)

    Brown, N.W. [Arvia Technology Ltd, Daresbury Innovation Centre, Daresbury, WA4 4FS (United Kingdom); Wickenden, D.A. [Magnox Ltd, Berkeley Centre, Gloucestershire, GL13 9PB (United Kingdom); Roberts, E.P.L. [School of Chemical Engineering, University of Manchester, Manchester, M60 1QD (United Kingdom)

    2012-07-01

    Arvia{sup R}, working with Magnox Ltd, has developed the technology of adsorption coupled with electrochemical regeneration for the degradation of orphan radioactive oil wastes. The process results in the complete destruction of the organic phase where the radioactivity is transferred to liquid and solid secondary wastes that can then be processed using existing authorised on-site waste-treatment facilities.. Following on from successful laboratory and pilot scale trials, a full scale, site based demonstrator unit was commissioned at the Magnox Trawsfynydd decommissioning site to destroy 10 l of LLW and ILW radioactive oils. Over 99% of the emulsified oil was removed and destroyed with the majority of activity (80 - 90%) being transferred to the aqueous phase. Secondary wastes were disposed of via existing routes with the majority being disposed of via the sites active effluent treatment plant. The regeneration energy required to destroy a litre of oil was 42.5 kWh/l oil. This on-site treatment approach eliminates the risks and cost associated with transporting the active waste oils off site for incineration or other treatment. The Arvia{sup R} process of adsorption coupled with electrochemical regeneration has successfully demonstrated the removal and destruction of LLW and ILW radioactive oils on a nuclear site. Over 99.9% of the emulsified oil was removed, with the majority of the radioactive species transferred to the aqueous, supernate, phase (typically 80 - 90 %). The exception to this is Cs-137 which appears to be more evenly distributed, with 43% associated with the liquid phase and 33 % with the Nyex, the remainder associated with the electrode bed. The situation with Plutonium may be similar, but this requires confirmation, hence further work is underway to understand the full nature of the electrode bed radioactive burden and its distribution within the body of the electrodes. - Tritium gaseous discharges were negligible; hence no off-gas treatment

  3. A three-site Langmuir adsorption model to elucidate the temperature, pressure, and support dependence of the hydrogen coverage on supported Pt particles

    NARCIS (Netherlands)

    Ji, Y.; Koot, V.; van der Eerden, A.M.J.; Weckhuysen, B.M.; Koningsberger, D.C.; Ramaker, D.E.

    2007-01-01

    The three-site adsorption model, previously developed to describe H adsorption on small Pt particles, was used to gain insight into dependence of hydrogen coverage on temperature, pressure, and support ionicity. The three sites, in order of decreasing PtH bond strength, involve H in an atop, a

  4. An investigation of Oxygen adsorption on W(110) using reflectance anisotropy spectroscopy

    International Nuclear Information System (INIS)

    Zeybek, O.

    2004-01-01

    The probe of metal surface electronic structure and results of the oxidation of a BCC material and the first Joint Density of States interpretation of the spectrum from same metal have been presented. The surface sensitivity of RAS has been exploited when applied to a cubic single crystal to study the surface electronic structure of W(110) and the resulting chemisorption-induced changes upon exposure to oxygen. Oxidation of the surface is monitored until a final exposure of 10 Langmuirs is reached. A decrease of reflectance anisotropy signal is obtained with increasing oxygen coverage on the substrate and a coverage of ∼0.75 ML results in zero anisotropy over the reflectance anisotropy energy range

  5. An investigation of Oxygen adsorption on W(110) using reflectance anisotropy spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zeybek, O [Department of Physics, Balikesir University, Balikesir (Turkey)

    2004-07-01

    The probe of metal surface electronic structure and results of the oxidation of a BCC material and the first Joint Density of States interpretation of the spectrum from same metal have been presented. The surface sensitivity of RAS has been exploited when applied to a cubic single crystal to study the surface electronic structure of W(110) and the resulting chemisorption-induced changes upon exposure to oxygen. Oxidation of the surface is monitored until a final exposure of 10 Langmuirs is reached. A decrease of reflectance anisotropy signal is obtained with increasing oxygen coverage on the substrate and a coverage of {approx}0.75 ML results in zero anisotropy over the reflectance anisotropy energy range.

  6. Theoretical study of oxygen adsorption on pure Au-n+1(+) and doped MAun+ cationic gold clusters for M = Ti, Fe and n=3-7

    DEFF Research Database (Denmark)

    Torres, M. Begona; Fernandez Sanchez, Eva; Balbas, Luis C.

    2008-01-01

    A comparative study of the adsorption of an O-2 molecule on pure Au-n+1(+) and doped MAun+ cationic gold clusters for n = 3-7 and M = Ti, Fe is presented. The simultaneous adsorption of two oxygen atoms also was studied. This work was performed by means of first principles calculations based...... with adsorption energies of 0.56 and 0.69 eV, respectively. The ground-state geometry of Au-n(+) is almost unperturbed after O-2 adsorption. The electronic charge flows towards O-2 when the molecule is adsorbed in bridge positions and towards the gold cluster when O-2 is adsorbed on top of An atoms, and both...... with size n are rationalized in terms of O-O and O-M bond distances, as well as charge transfer between oxygen and cluster substrates. The spin multiplicity of those (MAunO2+)(ad) complexes with the highest O-2 adsorption energy is a maximum (minimum) for M = Fe (Ti), corresponding to parallel (anti...

  7. Adsorption and magnetism of bilayer graphene on the MnO polar surface with oxygen vacancies in the interface: First principles study

    Science.gov (United States)

    Ilyasov, Victor V.; Ershov, Igor V.; Popova, Inna G.; Pham, Khang D.; Nguyen, Chuong V.

    2018-05-01

    In this paper, we investigate systematically the structural, electronic, magnetic and adsorption properties of Bernal-stacked bilayer graphene on MnO(111) surface terminated by an oxygen atom, as a function of nonstoichiometric composition of the BLG/MnOx(111) interface. For additional functionalization of the BLG/MnOx(111) system, we also studied the adsorption properties of oxygen adsorbed on the BLG/MnOx(111) interface. Our results showed that the BLG is bound to the MnOx(111) substrate by the weak interaction for both spin-up and spin-down. Furthermore, we found that BLG adsorbed on the MnOx(111) substrate with a reduced oxygen symmetry in the interface is accompanied with a downshift of the Fermi level, which identifies the band structure of BLG as a p-type semiconductor. Upon interaction between BLG and MnOx(111) substrate, a forbidden gap of about 350 meV was opened between its bonding and antibonding π bands. A forbidden gap and the local magnetic moments in bilayer graphene can be controlled by changing the oxygen nonstoichometry or by oxygen adsorption. Additionally, magnetism has been predicted in the bilayer graphene adsorbed on the polar MnOx(111) surface with oxygen vacancies in the BLG/MnOx(111) interface, and its nature has also been discussed in this work. These results showed that the adsorption of bilayer graphene on the MnO(111) substrate can be used for developing novel generation of electronic and spintronic devices.

  8. Molecular oxygen adsorption and dissociation on Au12M clusters with M = Cu, Ag or Ir

    Science.gov (United States)

    Jiménez-Díaz, Laura M.; Pérez, Luis A.

    2018-03-01

    In this work, we present a density functional theory study of the structural and electronic properties of isolated neutral clusters of the type Au12M, with M = Cu, Ag, or Ir. On the other hand, there is experimental evidence that gold-silver, gold-copper and gold-iridium nanoparticles have an enhanced catalytic activity for the CO oxidation reaction. In order to address these phenomena, we also performed density functional calculations of the adsorption and dissociation of O2 on these nanoparticles. Moreover, to understand the effects of Cu, Ag, and Ir impurity atoms on the dissociation of O2, we also analyze this reaction in the corresponding pure gold cluster. The results indicate that the substitution of one gold atom in a Au13 cluster by Ag, Cu or Ir diminishes the activation energy barrier for the O2 dissociation by nearly 1 eV. This energy barrier is similar for Au12Ag and Au12Cu, whereas for Au12Ir is even lower. These results suggest that the addition of other transition metal atoms to gold nanoclusters can enhance their catalytic activity towards the CO oxidation reaction, independently of the effect that the substrate could have on supported nanoclusters.

  9. Dissolved oxygen mapping: A powerful tool for site assessments and ground water monitoring

    International Nuclear Information System (INIS)

    Newman, W.A.; Kimball, G.

    1992-01-01

    Dissolved oxygen concentration profiles often provide an excellent indication of the natural biological activity of microorganisms in ground water. The analysis of dissolved oxygen in ground water also provides a rapid, inexpensive method for determining the areal extent of contaminant plumes containing aerobically degraded compounds such as petroleum hydrocarbons. Indigenous hydrocarbon degrading organisms are present at most petroleum product spills giving this technique an almost universal application for dissolved hydrocarbons in ground water. Data from several sites will be presented to demonstrate the relationship between oxygen and dissolved contaminant concentrations. The inverse relationship between oxygen concentrations and dissolved contaminants can be used in many ways. During the initial site assessment, rapid on-site testing of ground water can provide real time data to direct drilling by identification of potentially contaminated locations. Several analytical techniques are available that allow field analysis to be performed in less than five minutes. Dissolved oxygen testing also provides an inexpensive way to monitor hydrocarbon migration without expensive gas chromatography. Often a plume of oxygen depleted ground water extends farther downgradient than the dissolved hydrocarbon plume. The depletion of oxygen in a well can provide an early warning system that detects upgradient contamination before the well is impacted by detectable levels of contaminants. Another application is the measurement of the natural degradation potential for aerobic remediation. If an aerobic in-situ remediation is used, dissolved oxygen monitoring provides an inexpensive method to monitor the progress of the remediation

  10. Adsorption of arsenic by iron rich precipitates from two coal mine drainage sites on the West Coast of New Zealand

    International Nuclear Information System (INIS)

    Rait, R.; Trumm, D.; Pope, J.; Craw, D.; Newman, N.; MacKenzie, H.

    2010-01-01

    Dissolved As can be strongly adsorbed to fine grained Fe(III) minerals such as hydroxides, oxyhydroxides and hydroxysulphates. Therefore precipitates that form during neutralisation or treatment of acid mine drainage have potential to be useful for treatment of As-contaminated water because acid mine drainage is often Fe rich. We tested the adsorption properties of Fe(III) rich precipitates from two West Coast coal mines with As-contaminated water from an historic gold ore processing site near Reefton. Precipitates were collected from distinctly different settings, an active acid mine drainage treatment plant at Stockton mine and the neutralisation/oxidation zone of acid mine drainage discharge at the abandoned Blackball Coal Mine. The two mine sites produce precipitates with different compositions and mineralogy. Arsenic adsorption onto precipitates from each site was determined in batch and column tests under laboratory conditions. Batch experiments indicate As adsorption occurs rapidly during the first 5 h and reaches equilibrium after 24 h. At equilibrium, and for a dosing ratio of 50 g of precipitate per litre of water, As concentrations decreased from 99 mg/L to 0.0080 mg/L with precipitates from Stockton and to 0.0017 mg/L with precipitates from Blackball. Arsenic adsorption capacity is up to 12 mg/g on precipitates from Stockton sludge and 74 mg/g on precipitates from Blackball. The Blackball precipitate adsorbs more As than precipitates from Stockton which is probably due to the higher Fe oxide content but pH and surface structure could also play a role. The column experiment confirmed that adsorption of As from a continuous waste stream onto these precipitates is possible, and that passive remediation using this waste product mixed with gravel to enhance permeability could be a viable approach at As-contaminated mine sites. (author). 56 refs., 10 figs., 6 tabs.

  11. Simulation of oxygen-steam gasification with CO{sub 2} adsorption for hydrogen production from empty fruit bunch

    Energy Technology Data Exchange (ETDEWEB)

    Ahmad, M.M.; Inayat, A.; Yusup, S.; Sabil, K.M. [Universiti Teknologi Petronas, Bandar Seri Iskandar, Tronoh (Malaysia). Center of Biofuel and Biochemical, Green Technology Mission Oriented Research

    2011-07-01

    The world is facing a critical situation in which fossil fuel reservoir is depleting while the demand for energy is increasing worldwide. Scientists globally have shifted their effort towards developing alternative sustainable fuels and quite a number of technologies have been discovered. One potential alternative solution is to produce energy from hydrogen as its energy content per kilogram is three times larger than that of gasoline. The combustion of hydrogen produces water instead of greenhouse gases, along with energy, making hydrogen even more attractive as a clean fuel. Current study focuses on the process development of hydrogen production via gasification of Empty Fruit Bunch (EFB) with in-situ adsorption of CO{sub 2} based on equilibrium modeling approach. The process flowsheet simulation is performed using iCON, PETRONAS process simulation software. This work investigates the influence of the temperature within the range of 600 to 1000 C and steam/biomass ratio between 0.1 and 1.0 on the hydrogen yield and product gas composition. The importance of different reactions involved in the system is also discussed. Using the simulation, the optimal operating conditions are predicted to be at 800 C and steam/biomass ratio of 0.6. Hydrogen yield of 149g kg{sup -1} of EFB can be obtained at 1000 C. The preliminary economic potential per annum of the oxygen-steam gasification system coupled with in situ CO{sub 2} adsorption is RM 6.64 x 10{sup 6} or approximately USD 2 x 10{sup 6}.

  12. Oxygen adsorption and incorporation at irradiated GaN(0001) and GaN(0001¯) surfaces: First-principles density-functional calculations

    Science.gov (United States)

    Sun, Qiang; Selloni, Annabella; Myers, T. H.; Doolittle, W. Alan

    2006-11-01

    Density functional theory calculations of oxygen adsorption and incorporation at the polar GaN(0001) and GaN(0001¯) surfaces have been carried out to explain the experimentally observed reduced oxygen concentration in GaN samples grown by molecular beam epitaxy in the presence of high energy (˜10keV) electron beam irradiation [Myers , J. Vac. Sci. Technol. B 18, 2295 (2000)]. Using a model in which the effect of the irradiation is to excite electrons from the valence to the conduction band, we find that both the energy cost of incorporating oxygen impurities in deeper layers and the oxygen adatom diffusion barriers are significantly reduced in the presence of the excitation. The latter effect leads to a higher probability for two O adatoms to recombine and desorb, and thus to a reduced oxygen concentration in the irradiated samples, consistent with experimental observations.

  13. Hydrogen adsorption strength and sites in the metal organic framework MOF5: Comparing experiment and model calculations

    Science.gov (United States)

    Mulder, F. M.; Dingemans, T. J.; Schimmel, H. G.; Ramirez-Cuesta, A. J.; Kearley, G. J.

    2008-07-01

    Hydrogen adsorption in porous, high surface area, and stable metal organic frameworks (MOF's) appears a novel route towards hydrogen storage materials [N.L. Rosi, J. Eckert, M. Eddaoudi, D.T. Vodak, J. Kim, M. O'Keeffe, O.M. Yaghi, Science 300 (2003) 1127; J.L.C. Rowsell, A.R. Millward, K. Sung Park, O.M. Yaghi, J. Am. Chem. Soc. 126 (2004) 5666; G. Ferey, M. Latroche, C. Serre, F. Millange, T. Loiseau, A. Percheron-Guegan, Chem. Commun. (2003) 2976; T. Loiseau, C. Serre, C. Huguenard, G. Fink, F. Taulelle, M. Henry, T. Bataille, G. Férey, Chem. Eur. J. 10 (2004) 1373]. A prerequisite for such materials is sufficient adsorption interaction strength for hydrogen adsorbed on the adsorption sites of the material because this facilitates successful operation under moderate temperature and pressure conditions. Here we report detailed information on the geometry of the hydrogen adsorption sites, based on the analysis of inelastic neutron spectroscopy (INS). The adsorption energies for the metal organic framework MOF5 equal about 800 K for part of the different sites, which is significantly higher than for nanoporous carbon materials (˜550 K) [H.G. Schimmel, G.J. Kearley, M.G. Nijkamp, C.T. Visser, K.P. de Jong, F.M. Mulder, Chem. Eur. J. 9 (2003) 4764], and is in agreement with what is found in first principles calculations [T. Sagara, J. Klassen, E. Ganz, J. Chem. Phys. 121 (2004) 12543; F.M. Mulder, T.J. Dingemans, M. Wagemaker, G.J. Kearley, Chem. Phys. 317 (2005) 113]. Assignments of the INS spectra is realized using comparison with independently published model calculations [F.M. Mulder, T.J. Dingemans, M. Wagemaker, G.J. Kearley, Chem. Phys. 317 (2005) 113] and structural data [T. Yildirim, M.R. Hartman, Phys. Rev. Lett. 95 (2005) 215504].

  14. Quantitative imaging of the 3-D distribution of cation adsorption sites in undisturbed soil

    Science.gov (United States)

    Keck, Hannes; Strobel, Bjarne W.; Petter Gustafsson, Jon; Koestel, John

    2017-10-01

    Several studies have shown that the distribution of cation adsorption sites (CASs) is patchy at a millimetre to centimetre scale. Often, larger concentrations of CASs in biopores or aggregate coatings have been reported in the literature. This heterogeneity has implications on the accessibility of CASs and may influence the performance of soil system models that assume a spatially homogeneous distribution of CASs. In this study, we present a new method to quantify the abundance and 3-D distribution of CASs in undisturbed soil that allows for investigating CAS densities with distance to the soil macropores. We used X-ray imaging with Ba2+ as a contrast agent. Ba2+ has a high adsorption affinity to CASs and is widely used as an index cation to measure the cation exchange capacity (CEC). Eight soil cores (approx. 10 cm3) were sampled from three locations with contrasting texture and organic matter contents. The CASs of our samples were saturated with Ba2+ in the laboratory using BaCl2 (0.3 mol L-1). Afterwards, KCl (0.1 mol L-1) was used to rinse out Ba2+ ions that were not bound to CASs. Before and after this process the samples were scanned using an industrial X-ray scanner. Ba2+ bound to CASs was then visualized in 3-D by the difference image technique. The resulting difference images were interpreted as depicting the Ba2+ bound to CASs only. The X-ray image-derived CEC correlated significantly with results of the commonly used ammonium acetate method to determine CEC in well-mixed samples. The CEC of organic-matter-rich samples seemed to be systematically overestimated and in the case of the clay-rich samples with less organic matter the CEC seemed to be systematically underestimated. The results showed that the distribution of the CASs varied spatially within most of our samples down to a millimetre scale. There was no systematic relation between the location of CASs and the soil macropore structure. We are convinced that the approach proposed here will strongly

  15. Role of oxygen adsorption in modification of optical and surface electronic properties of MoS2

    Science.gov (United States)

    Shakya, Jyoti; Kumar, Sanjeev; Mohanty, Tanuja

    2018-04-01

    In this work, the effect of surface oxidation of molybdenum disulfide (MoS2) nanosheets induced by hydrogen peroxide (H2O2) on the work function and bandgap of MoS2 has been investigated for tuning its optical and electronic properties. Transmission electron microscopy studies reveal the existence of varying morphologies of few layers of MoS2 as well as quantum dots due to the different absorbing effects of two mixed solvents on MoS2. The X-ray diffraction, electron paramagnetic resonance, and Raman studies indicate the presence of physical as well as chemical adsorption of oxygen atoms in MoS2. The photoluminescence spectra show the tuning of bandgap arising from the passivation of trapping centers leading to radiative recombination of excitons. The value of work function obtained from scanning Kelvin probe microscopy of MoS2 in mixed solvents of H2O2 and N-methyl-2-pyrrolidone increases with an increase in the concentration of H2O2. A linear relationship could be established between H2O2 content in mixed solvent and measured values of work function. This work gives the alternative route towards the commercial use of defect engineered transition metal dichalcogenide materials in diverse fields.

  16. Mechanistic studies of mercury adsorption and oxidation by oxygen over spinel-type MnFe{sub 2}O{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Yingju [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Liu, Jing, E-mail: liujing27@mail.hust.edu.cn [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Shenzhen Institute of Huazhong University of Science and Technology, Shenzhen 518000 (China); Zhang, Bingkai; Liu, Feng [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2017-01-05

    Highlights: • Hg adsorption and oxidation mechanisms on MnFe{sub 2}O{sub 4} were studied using DFT method. • Hg{sup 0} adsorption on Mn-terminated MnFe{sub 2}O{sub 4} (100) surface is a chemisorption process. • HgO shows high chemical reactivity for its adsorption on MnFe{sub 2}O{sub 4} surface. • The reaction between adsorbed Hg and surface oxygen is the rate-determining step. - Abstract: MnFe{sub 2}O{sub 4} has been regarded as a very promising sorbent for mercury emission control in coal-fired power plants because of its high adsorption capacity, magnetic, recyclable and regenerable properties. First-principle calculations based on density functional theory (DFT) were used to elucidate the mercury adsorption and oxidation mechanisms on MnFe{sub 2}O{sub 4} surface. DFT calculations show that Mn-terminated MnFe{sub 2}O{sub 4} (1 0 0) surface is much more stable than Fe-terminated surface. Hg{sup 0} is physically adsorbed on Fe-terminated MnFe{sub 2}O{sub 4} (1 0 0) surface. Hg{sup 0} adsorption on Mn-terminated MnFe{sub 2}O{sub 4} (1 0 0) surface is a chemisorption process. The partial density of states (PDOS) analysis indicates that Hg atom interacts strongly with surface Mn atoms through the orbital hybridization. HgO is adsorbed on the MnFe{sub 2}O{sub 4} surface in a chemical adsorption manner. The small HOMO–LUMO energy gap implies that HgO molecular shows high chemical reactivity for HgO adsorption on MnFe{sub 2}O{sub 4} surface. The energy barriers of Hg{sup 0} oxidation by oxygen on Fe- and Mn-terminated MnFe{sub 2}O{sub 4} surfaces are 206.37 and 76.07 kJ/mol, respectively. Mn-terminated surface is much more favorable for Hg{sup 0} oxidation than Fe-terminated surface. In the whole Hg{sup 0} oxidation process, the reaction between adsorbed mercury and surface oxygen is the rate-determining step.

  17. Stability of muon-oxygen bond sites in RBa2Cu3O7

    International Nuclear Information System (INIS)

    Lichti, R.L.; Adams, T.R.; Gibson, T.L.

    1991-01-01

    Relative energies of muon probe sites in the chain region of RBa 2 Cu 3 O 7 (RBCO) are investigated using a molecular quantum chemistry calculation for (Oμ) - embedded in a cluster of point charges to simulate local charge distributions in RBCO. Partial Cu-O chain covalency results in a O-μ...O muon site between the chain and bridging oxygens. However, Cu-μ ''hydride''-like sites are suggested by results for nominally ionic clusters. (orig.)

  18. Sources of oxygen flux in groundwater during induced bank filtration at a site in Berlin, Germany

    Science.gov (United States)

    Kohfahl, Claus; Massmann, Gudrun; Pekdeger, Asaf

    2009-05-01

    The microbial degradation of pharmaceuticals found in surface water used for artificial recharge is strongly dependent on redox conditions of the subsurface. Furthermore the durability of production wells may decrease considerably with the presence of oxygen and ferrous iron due to the precipitation of trivalent iron oxides and subsequent clogging. Field measurements are presented for oxygen at a bank filtration site in Berlin, Germany, along with simplified calculations of different oxygen pathways into the groundwater. For a two-dimensional vertical cross-section, oxygen input has been calculated for six scenarios related to different water management strategies. Calculations were carried out in order to assess the amount of oxygen input due to (1) the infiltration of oxic lake water, (2) air entrapment as a result of water table oscillations, (3) diffusive oxygen flux from soil air and (4) infiltrating rainwater. The results show that air entrapment and infiltrating lake water during winter constitute by far the most important mechanism of oxygen input. Oxygen input by percolating rainwater and by diffusive delivery of oxygen in the gas phase is negligible. The results exemplify the importance of well management as a determining factor for water oscillations and redox conditions during artificial recharge.

  19. Adsorption studies on Pt(111)

    International Nuclear Information System (INIS)

    Hopster, H.

    1977-06-01

    The adsorption of O 2 , CO, and C 2 H 2 as well as the CO oxidation on Pt(111) were studied by high-resolution electron spectroscopy. Using a platinum monocrystal sample with a contonuous stage density, the adhesion coefficient for O 2 and the reaction probability for CO were determined as a function of stage density and oxygen cover by measuring the oxygen cover and its time behaviour. The study of vibrations of adsorbed CO showed that CO is bound in linear form on two different adsorption sites. The adsorption of acetylene was studied at 140 K and 300 K. The frequencies of the C-H stretching and flexural vibrations as well as the C-C-H bonding angle were determined. (orig./GSC) [de

  20. Effect of Adsorption on Ice Surfaces on the Composition of Enceladus' Plumes: Partitioning of Oxygen-Bearing Organics

    Science.gov (United States)

    Bouquet, A.; Teolis, B. D.; Waite, J. H., Jr.

    2017-12-01

    Introduction: The plumes of Enceladus offer an opportunity to access a sample of water from its internal ocean. However, to gain valuable insights into the ocean's composition, it is necessary to take into account any possible process that would alter the mixture between the water table and the geysers. The adsorption of refractory compounds on the ice walls in the vents could partition them depending on their properties. Evaluating the effect of this fractionation is critical in anticipating which organics could be detected by a future mission. Models: We used a model using the temkin isotherm and published experimental desorption energies for our compounds of interest. The model calculates how the coverage of an ice surface exposed to the flow can evolve with time and what is the final composition of the adsorbed mixture is. The model considers the ice walls and the ice grains, as the latter have the potential to gather the most sticky compounds and put them within reach of sampling by a spacecraft. Our list of species included formaldehyde, methanol, acetic acid, formic acid, ethanol, butanol, benzene and hexanal.Results: We found that simple hydrocarbons have a very short residence time on ice, and are expected to stay in gas phase. Oxygen-bearing organic compounds, though, stick to the ice and will be concentrated on the walls and ice grains, with the exception of formaldehyde. With the species listed above originally in equal abundance in gas phase, we found the ice surface to hold mostly formic acid, acetic acid and butanol, with a small amount of ethanol and hexanal. The high number of collisions in the closed space of a 1 meter wide vent allows for a gas/adsorbed equilibration within a second. Way forward: The possible impact of ammonia, detected in the plumes, is unknown. Ammonia can accumulate on the ice surface and influence adsorption of other species, and potentially create a liquid layer by depressing the freezing point of water. The impact of these

  1. High-Resolution Electron Energy Loss Studies of Oxygen, Hydrogen, Nitrogen, Nitric Oxide, and Nitrous Oxide Adsorption on Germanium Surfaces.

    Science.gov (United States)

    Entringer, Anthony G.

    The first high resolution electron energy loss spectroscopy (HREELS) studies of the oxidation and nitridation of germanium surfaces are reported. Both single crystal Ge(111) and disordered surfaces were studied. Surfaces were exposed to H, O_2, NO, N _2O, and N, after cleaning in ultra-high vacuum. The Ge surfaces were found to be non-reactive to molecular hydrogen (H_2) at room temperature. Exposure to atomic hydrogen (H) resulted hydrogen adsorption as demonstrated by the presence of Ge-H vibrational modes. The HREEL spectrum of the native oxide of Ge characteristic of nu -GeO_2 was obtained by heating the oxide to 200^circC. Three peaks were observed at 33, 62, and 106 meV for molecular oxygen (O_2) adsorbed on clean Ge(111) at room temperature. These peaks are indicative of dissociative bonding and a dominant Ge-O-Ge bridge structure. Subsequent hydrogen exposure resulted in a shift of the Ge-H stretch from its isolated value of 247 meV to 267 meV, indicative of a dominant +3 oxidation state. A high density of dangling bonds and defects and deeper oxygen penetration at the amorphous Ge surface result in a dilute bridge structure with a predominant +1 oxidation state for similar exposures. Molecules of N_2O decompose at the surfaces to desorbed N_2 molecules and chemisorbed oxygen atoms. In contrast, both oxygen and nitrogen are detected at the surfaces following exposure to NO molecules. Both NO and N_2O appear to dissociate and bond at the top surface layer. Molecular nitrogen (N_2) does not react with the Ge surfaces, however, a precursor Ge nitride is observed at room temperature following exposure to nitrogen atoms and ions. Removal of oxygen by heating of the NO-exposed surface to 550^circC enabled the identification of the Ge-N vibrational modes. These modes show a structure similar to that of germanium nitride. This spectrum is also identical to that of the N-exposed surface heated to 550^circC. Surface phonon modes of the narrow-gap semiconducting

  2. Carbon monoxide adsorption on low-silica zeolites: from single to dual and to multiple cation sites.

    Science.gov (United States)

    Otero Areán, C; Rodríguez Delgado, M; López Bauçà, C; Vrbka, L; Nachtigall, P

    2007-09-07

    Infrared spectra of CO adsorbed on the Al-rich Na-A zeolite were analysed by using a combined theoretical and experimental approach, showing that such spectra cannot be interpreted by assigning each IR band to CO interacting with a specific type of single cation site. This concept, which usually works well for high-silica zeolites, should not be uncritically extended to Al-rich zeolites that are crowded with cations in configurations which lead to preferential formation of CO adsorption complexes involving more than one cation site.

  3. Proceedings of the DOE/Yucca Mountain Site Characterization Project Radionuclde Adsorption Workshop at Los Alamos National Laboratory, September 11--12, 1990

    International Nuclear Information System (INIS)

    Canepa, J.A.

    1992-08-01

    Los Alamos National Laboratory hosted a workshop on radionuclide adsorption for the Department of Energy (DOE)/Yucca Mountain Site Characterization Project on September 11 and 12, 1990. The purpose of the workshop was to respond to a recommendation by the Nuclear Waste Technical Review Board that the DOE organize a radionuclide adsorption workshop to be attended by the DOE and its contractors involved in the measurement and modeling of such adsorption. The workshop would have two general purposes: (a) to determine the applicability of available radionuclide adsorption data on tuff and models for predicting such adsorption under existing and postclosure conditions at Yucca Mountain and (b) to establish what additional radionuclide adsorption research and model development are needed. Individual projects are processed separately for the databases

  4. Binding energy and preferred adsorption sites of CO on gold and silver-gold cluster cations: adsorption kinetics and quantum chemical calculations.

    Science.gov (United States)

    Neumaier, Marco; Weigend, Florian; Hampe, Oliver; Kappes, Manfred M

    2008-01-01

    We revisit the reactivity of trapped pure gold (Au(n)+, n cations (Ag(m)Au(n)+, m + n carbon monoxide as studied in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The experimental results are discussed in terms of ab initio computations which provide a comprehensive picture of the chemical binding behaviour (like binding energy, adsorption sites, associated vibrational frequencies) of CO to the noble metal as a function of cluster size and composition. Starting from results for pure gold cluster cations for which an overall decrease of CO binding energy with increasing cluster size was experimentally observed--from about 1.09 +/- 0.1 eV (for n = 6) to below 0.65 +/- 0.1 eV (for n > 26) we demonstrate that metal--CO bond energies correlate with the total electron density and with the energy of the lowest unoccupied molecular orbital (LUMO) on the bare metal cluster cation as obtained by density functional theory (DFT) computations. This is a consequence of the predominantly sigma-donating character of the CO-M bond. Further support for this concept is found by contrasting the predictions of binding energies to the experimental results for small alloy cluster cations (Ag(m)Au(n)+, 4 < m + n < 7) as a function of composition. Here, binding energy drops with increasing silver content, while CO still binds always in a head-on fashion to a gold atom. Finally we show how the CO stretch frequency of Ag(m)Au(n)CO+ may be used to identify possible adsorption sites and pre-screen favorable isomers.

  5. Conductance of Sidewall-Functionalized Carbon Nanotubes: Universal Dependence on Adsorption Sites

    DEFF Research Database (Denmark)

    García-Lastra, J.M.; Thygesen, Kristian Sommer; Strange, Mikkel

    2008-01-01

    We use density functional theory to study the effect of molecular adsorbates on the conductance of metallic carbon nanotubes (CNT). The five molecules considered (NO2, NH2, H, COOH, OH) lead to very similar scattering of the electrons. The adsorption of a single molecule suppresses one of the two...

  6. The effect of the oxygen dissolved in the adsorption of gold in activated carbon; Efecto del oxigeno disuelto en la adsorcion de oro en carbon activado

    Energy Technology Data Exchange (ETDEWEB)

    Navarro, P. [Universidad de Santiago. Chile (Chile); Wilkomirsky, I. [Universidad de Concepcion. Chile (Chile)

    1999-07-01

    The effect of the oxygen dissolved on the adsorption of gold in a activated carbon such as these used for carbon in pulp (CIP) and carbon in leach (CIL) processes were studied. The research was oriented to dilucidate the effect of the oxygen dissolved in the gold solution on the kinetics and distribution of the gold adsorbed in the carbon under different conditions of ionic strength, pH and gold concentration. It was found that the level of the oxygen dissolved influences directly the amount of gold adsorbed on the activated carbon, being this effect more relevant for low ionic strength solutions. The pH and initial gold concentration has no effect on this behavior. (Author) 16 refs.

  7. Facile and cost-effective preparation of PVA/modified calcium carbonate nanocomposites via ultrasonic irradiation: Application in adsorption of heavy metal and oxygen permeation property.

    Science.gov (United States)

    Mallakpour, Shadpour; Khadem, Elham

    2017-11-01

    This work is focused on the fabrication and determination of physicochemical behaviors of new poly(vinyl alcohol) (PVA) nanocomposites (NCs) containing various contents of calcium carbonate (CC) nanoparticles modified with γ-aminopropyl triethoxy silane (ATS) (henceforth designated as CC-ATS) which could be a crucial treatment for their application as gas barrier to O 2 gas and uptake of metal ions in waste waters. Samples were produced through the solution casting method under ultrasound irradiation. Thermal and mechanical performances were also evaluated for all ultrasonically synthesized nanocomposites and the results indicated that thermal and mechanical stability are dramatically enhanced by addition of a small amount of modified CC-ATS within PVA up to 5wt% and higher amounts has low effect on the composite properties. The result of oxygen gas permeability of PVA showed a 25.44% reduction by adding of 5wt% of CC-ATS into polymer matrix. Experimental adsorption isotherm data indicated that PVA NC has more efficiency for Cu(II) adsorption relative to pure PVA and well simulated by Langmuir model with maximum adsorption capacity of 45.45mgg -1 . Moreover, study of sorption kinetic indicated that the solute adsorption on PVA/CC-ATS NC 5wt% was well modeled using the pseudo-second-order. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Reactivity of a reduced metal oxide surface: hydrogen, water and carbon monoxide adsorption on oxygen defective rutile TiO 2( 1 1 0 )

    Science.gov (United States)

    Menetrey, M.; Markovits, A.; Minot, C.

    2003-02-01

    The reactivity at reduced surface differs from that on the stoichiometric perfect surfaces. This does not originate uniquely from the modification of the coordination; electron count also is determining. The general trend is a decrease of the heat of adsorption on the metal cations. The reactivity decreases at sites in the vicinity of the defects due to the reduction induced by the O vacancies. At the defect site the decrease is less pronounced for H, H 2, CO and molecular H 2O. In the case of H 2O dissociative adsorption, the defect site is more reactive than the perfect surface. Thus, a hydration converting the defective-reduced TiO 2 to the hydrogenated non-defective-reduced surface is easy. The resulting structure possesses surface hydroxyl groups. It is probably the easiest way to form the hydrogenated non-defective surface. On TiO 2, the defective surface requires very anhydrous conditions.

  9. Sites of reactive oxygen species generation by mitochondria oxidizing different substrates

    Directory of Open Access Journals (Sweden)

    Casey L. Quinlan

    2013-01-01

    Full Text Available Mitochondrial radical production is important in redox signaling, aging and disease, but the relative contributions of different production sites are poorly understood. We analyzed the rates of superoxide/H2O2 production from different defined sites in rat skeletal muscle mitochondria oxidizing a variety of conventional substrates in the absence of added inhibitors: succinate; glycerol 3-phosphate; palmitoylcarnitine plus carnitine; or glutamate plus malate. In all cases, the sum of the estimated rates accounted fully for the measured overall rates. There were two striking results. First, the overall rates differed by an order of magnitude between substrates. Second, the relative contribution of each site was very different with different substrates. During succinate oxidation, most of the superoxide production was from the site of quinone reduction in complex I (site IQ, with small contributions from the flavin site in complex I (site IF and the quinol oxidation site in complex III (site IIIQo. However, with glutamate plus malate as substrate, site IQ made little or no contribution, and production was shared between site IF, site IIIQo and 2-oxoglutarate dehydrogenase. With palmitoylcarnitine as substrate, the flavin site in complex II (site IIF was a major contributor (together with sites IF and IIIQo, and with glycerol 3-phosphate as substrate, five different sites all contributed, including glycerol 3-phosphate dehydrogenase. Thus, the relative and absolute contributions of specific sites to the production of reactive oxygen species in isolated mitochondria depend very strongly on the substrates being oxidized, and the same is likely true in cells and in vivo.

  10. The determination and analysis of site-specific rates of mitochondrial reactive oxygen species production

    DEFF Research Database (Denmark)

    Quinlan, Casey L; Perevoschikova, Irina V; Goncalves, Renata L S

    2013-01-01

    Mitochondrial reactive oxygen species (ROS) are widely implicated in physiological and pathological pathways. We propose that it is critical to understand the specific sites of mitochondrial ROS production and their mechanisms of action. Mitochondria possess at least eight distinct sites of ROS...... production in the electron transport chain and matrix compartment. In this chapter, we describe the nature of the mitochondrial ROS-producing machinery and the relative capacities of each site. We provide detailed methods for the measurement of H2O2 release and the conditions under which maximal rates from...

  11. Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction.

    Science.gov (United States)

    Zitolo, Andrea; Ranjbar-Sahraie, Nastaran; Mineva, Tzonka; Li, Jingkun; Jia, Qingying; Stamatin, Serban; Harrington, George F; Lyth, Stephen Mathew; Krtil, Petr; Mukerjee, Sanjeev; Fonda, Emiliano; Jaouen, Frédéric

    2017-10-16

    Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co-N-C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and electronic state of three porphyrinic moieties, CoN 4 C 12 , CoN 3 C 10,porp and CoN 2 C 5 . The O 2 electro-reduction and operando X-ray absorption response are measured in acidic medium on Co-N-C and compared to those of a Fe-N-C catalyst prepared similarly. We show that cobalt moieties are unmodified from 0.0 to 1.0 V versus a reversible hydrogen electrode, while Fe-based moieties experience structural and electronic-state changes. On the basis of density functional theory analysis and established relationships between redox potential and O 2 -adsorption strength, we conclude that cobalt-based moieties bind O 2 too weakly for efficient O 2 reduction.Nitrogen-doped carbon materials with atomically dispersed iron or cobalt are promising for catalytic use. Here, the authors show that cobalt moieties have a higher redox potential, bind oxygen more weakly and are less active toward oxygen reduction than their iron counterpart, despite similar coordination.

  12. Factors influencing U(VI adsorption onto soil from a candidate very low level radioactive waste disposal site in China

    Directory of Open Access Journals (Sweden)

    Zuo Rui

    2016-01-01

    Full Text Available The properties of soil at disposal sites are very important for geological disposal of very low level radioactive waste in terms of U(VI. In this study, soil from a candidate very low level radioactive waste disposal site in China was evaluated for its capacity on uranium sorption. Specifically, the equilibrium time, initial concentration, soil particle, pH, temperature, and carbonate were evaluated. The results indicated that after 15-20 days of sorption, the Kd value fluctuated and stabilized at 355-360 mL/g. The adsorptive capacity of uranium was increased as the initial uranium concentration increased, while it decreased as the soil particle size increased. The pH value played an important role in the U(VI sorption onto soil, especially under alkaline conditions, and had a great effect on the sorption capacity of soil for uranium. Moreover, the presence of carbonate decreased the sorption of U(VI onto soil because of the role of the strong complexation of carbonate with U(VI in the groundwater. Overall, this study assessed the behavior of U(VI sorption onto natural soil, which would be an important factor in the geological barrier of the repository, has contribution on mastering the characteristic of the adsorption of uranium in the particular soil media for the process of very low level radioactive waste disposal.

  13. Supplemental Perioperative Oxygen to Reduce Surgical Site Infection after High Energy Fracture Surgery

    Science.gov (United States)

    2017-10-01

    AWARD NUMBER: W81XWH-12-1-0588 TITLE: Supplemental Perioperative Oxygen to Reduce Surgical Site Infection after High- Energy Fracture Surgery...High- Energy Fracture Surgery 5a. CONTRACT NUMBER W81XWH-12-1-0588 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Robert V. O’Toole, MD...14 4 1. INTRODUCTION: The overall scope of this project is to address the treatment of high- energy military fractures, which has

  14. Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni

    Energy Technology Data Exchange (ETDEWEB)

    López-Moreno, S., E-mail: sinlopez@uacam.mx [Centro de Investigación en Corrosión, Universidad Autónoma de Campeche, Av. Héroe de Nacozari 480, Campeche, Campeche 24029 (Mexico); Romero, A. H. [Physics Department, West Virginia University, Morgantown, West Virginia 26506-6315 (United States)

    2015-04-21

    Density functional theory is used to investigate the reaction of oxygen with clean copper and nickel [111]-surfaces. We study several alternative adsorption sites for atomic and molecular oxygen on both surfaces. The minimal energy geometries and adsorption energies are in good agreement with previous theoretical studies and experimental data. From all considered adsorption sites, we found a new O{sub 2} molecular precursor with two possible dissociation paths on the Cu(111) surface. Cross barrier energies for the molecular oxygen dissociation have been calculated by using the climbing image nudge elastic band method, and direct comparison with experimental results is performed. Finally, the structural changes and adsorption energies of oxygen adsorbed on surface when there is a vacancy nearby the adsorption site are also considered.

  15. Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni

    Science.gov (United States)

    López-Moreno, S.; Romero, A. H.

    2015-04-01

    Density functional theory is used to investigate the reaction of oxygen with clean copper and nickel [111]-surfaces. We study several alternative adsorption sites for atomic and molecular oxygen on both surfaces. The minimal energy geometries and adsorption energies are in good agreement with previous theoretical studies and experimental data. From all considered adsorption sites, we found a new O2 molecular precursor with two possible dissociation paths on the Cu(111) surface. Cross barrier energies for the molecular oxygen dissociation have been calculated by using the climbing image nudge elastic band method, and direct comparison with experimental results is performed. Finally, the structural changes and adsorption energies of oxygen adsorbed on surface when there is a vacancy nearby the adsorption site are also considered.

  16. Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni

    International Nuclear Information System (INIS)

    López-Moreno, S.; Romero, A. H.

    2015-01-01

    Density functional theory is used to investigate the reaction of oxygen with clean copper and nickel [111]-surfaces. We study several alternative adsorption sites for atomic and molecular oxygen on both surfaces. The minimal energy geometries and adsorption energies are in good agreement with previous theoretical studies and experimental data. From all considered adsorption sites, we found a new O 2 molecular precursor with two possible dissociation paths on the Cu(111) surface. Cross barrier energies for the molecular oxygen dissociation have been calculated by using the climbing image nudge elastic band method, and direct comparison with experimental results is performed. Finally, the structural changes and adsorption energies of oxygen adsorbed on surface when there is a vacancy nearby the adsorption site are also considered

  17. Improving the capacity of lithium-sulfur batteries by tailoring the polysulfide adsorption efficiency of hierarchical oxygen/nitrogen-functionalized carbon host materials.

    Science.gov (United States)

    Schneider, Artur; Janek, Jürgen; Brezesinski, Torsten

    2017-03-22

    The use of monolithic carbons with structural hierarchy and varying amounts of nitrogen and oxygen functionalities as sulfur host materials in high-loading lithium-sulfur cells is reported. The primary focus is on the strength of the polysulfide/carbon interaction with the goal of assessing the effect of (surface) dopant concentration on cathode performance. The adsorption capacity - which is a measure of the interaction strength between the intermediate lithium polysulfide species and the carbon - was found to scale almost linearly with the nitrogen level. Likewise, the discharge capacity of lithium-sulfur cells increased linearly. This positive correlation can be explained by the favorable effect of nitrogen on both the chemical and electronic properties of the carbon host. The incorporation of additional oxygen-containing surface groups into highly nitrogen-functionalized carbon helped to further enhance the polysulfide adsorption efficiency, and therefore the reversible cell capacity. Overall, the areal capacity could be increased by almost 70% to around 3 mA h cm -2 . We believe that the design parameters described here provide a blueprint for future carbon-based nanocomposites for high-performance lithium-sulfur cells.

  18. Oxygen profile and clogging in vertical flow sand filters for on-site wastewater treatment.

    Science.gov (United States)

    Petitjean, A; Forquet, N; Boutin, C

    2016-04-01

    13 million people (about 20% of the population) use on-site wastewater treatment in France. Buried vertical sand filters are often built, especially when the soil permeability is not sufficient for septic tank effluent infiltration in undisturbed soil. Clogging is one of the main problems deteriorating the operation of vertical flow filters for wastewater treatment. The extent of clogging is not easily assessed, especially in buried vertical flow sand filters. We suggest examining two possible ways of detecting early clogging: (1) NH4-N/NO3-N outlet concentration ratio, and (2) oxygen measurement within the porous media. Two pilot-scale filters were equipped with probes for oxygen concentration measurements and samples were taken at different depths for pollutant characterization. Influent and effluent grab-samples were taken three times a week. The systems were operated using batch-feeding of septic tank effluent. Qualitative description of oxygen transfer processes under unclogged and clogged conditions is presented. NH4-N outlet concentration appears to be useless for early clogging detection. However, NO3-N outlet concentration and oxygen content allows us to diagnose the early clogging of the system. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. NH{sub 3} adsorption on the Lewis and Bronsted acid sites of MoO{sub 3} (0 1 0) surface: A cluster DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Zhifeng [College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); College of Material Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Fan, Junyan [Foundation Department, Shanxi Police Academy, No. 27 Second Section of Old Jinci Road, Taiyuan 030021, Shanxi (China); Zuo, Zhijun [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Li, Zhe, E-mail: lizhe@tyut.edu.cn [College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Zhang, Jinshan [College of Material Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China)

    2014-01-01

    The adsorption of NH{sub 3} on the Lewis and Bronsted acid sites of MoO{sub 3} (0 1 0) surface has been investigated based on the density functional theory (DFT) method using the clusters models. The calculated results indicate that NH{sub 3} could strongly adsorb on both the Lewis and Bronsted acid sites in the form of NH{sub 3} species and NH{sub 4}{sup +} respectively, whereas the adsorption on the Lewis acid site is found to be more favorable energetically than that on the Bronsted acid site. For the Lewis acid site Mulliken population analysis shows a donation of lone pairs from NH{sub 3} to the surface and activation of N–H bond. The overlaps of N-s, N-p and Mo-d orbitals suggest the strong interaction between N and Mo atoms. For the Bronsted acid site N–H bond is also activated by the formation of NH{sub 4}{sup +} species. The hybridizations between H and O atoms as well as N and H atoms are the major reasons for strong chemical adsorption of NH{sub 3} and the existence of NH{sub 4}{sup +} species, which partly attributed to the presence of N–H… O hydrogen bonds. Furthermore, the formation of a second Lewis acid site at adjacent or diagonal site results in slight changes of adsorption stability, structural changes and charge redistributions, suggesting its small influence on NH{sub 3} adsorption.

  20. Cations in Octahedral Sites: A Descriptor for Oxygen Electrocatalysis on Transition-Metal Spinels

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Chao; Feng, Zhenxing; Scherer, Günther G.; Barber, James; Shao-Horn, Yang; Xu, Zhichuan J. (Nanyang); (ICL); (Oregon State U.); (TUM-CREATE); (MIT)

    2017-04-10

    Exploring efficient and low-cost electrocatalysts for the oxygen-reduction reaction (ORR) and oxygen-evolution reaction (OER) is critical for developing renewable energy technologies such as fuel cells, metal–air batteries, and water electrolyzers. A rational design of a catalyst can be guided by identifying descriptors that determine its activity. Here, a descriptor study on the ORR/OER of spinel oxides is presented. With a series of MnCo2O4, the Mn in octahedral sites is identified as an active site. This finding is then applied to successfully explain the ORR/OER activities of other transition-metal spinels, including MnxCo3-xO4 (x = 2, 2.5, 3), LixMn2O4 (x = 0.7, 1), XCo2O4 (X = Co, Ni, Zn), and XFe2O4 (X = Mn, Co, Ni). A general principle is concluded that the eg occupancy of the active cation in the octahedral site is the activity descriptor for the ORR/OER of spinels, consolidating the role of electron orbital filling in metal oxide catalysis.

  1. Effects of NH4+, K+, Mg2+, and Ca2+ on the Cesium Adsorption/Desorption in Binding Sites of Vermiculitized Biotite.

    Science.gov (United States)

    Yin, Xiangbiao; Wang, Xinpeng; Wu, Hao; Takahashi, Hideharu; Inaba, Yusuke; Ohnuki, Toshihiko; Takeshita, Kenji

    2017-12-05

    The reversibility of cesium adsorption in contaminated soil is largely dependent on its interaction with micaceous minerals, which may be greatly influenced by various cations. Herein, we systematically investigated the effects of NH 4 + , K + , Mg 2+ , and Ca 2+ on the adsorption/desorption of Cs + into different binding sites of vermiculitized biotite (VB). Original VB was initially saturated by NH 4 + , K + , or Mg 2+ ; we then evaluated the adsorption of Cs + on three treated VBs, and the desorption by extraction with NH 4 + , K + , Mg 2+ , or Ca 2+ was further evaluated. Our structural analysis and Cs + extractability determinations showed that NH 4 + and K + both collapsed the interlayers of VB, resulting in the dominant adsorption of Cs + to external surface sites on which Cs + was readily extracted by NH 4 + , K + , Mg 2+ , or Ca 2+ irrespective of their species, whereas Mg 2+ maintained the VB with expanded interlayers, leading to the overwhelming adsorption of Cs + in collapsed interlayer sites on which the Cs + desorption was difficult and varied significantly by the cations used in extraction. The order of Cs + extraction ability from the collapsed interlayers was K + ≫ Mg 2+ ≈ Ca 2+ ≫ NH 4 + . These results could provide important insights into Cs migration in soil and its decontamination for soil remediation.

  2. The influence of oxygen and hydrogen adsorption on the magneticstructure of the ultrathin iron film on the Ir(001) surface

    Czech Academy of Sciences Publication Activity Database

    Máca, František; Kudrnovský, Josef; Drchal, Václav; Redinger, J.

    2013-01-01

    Roč. 88, č. 4 (2013), "045423-1"-"045423-7" ISSN 1098-0121 R&D Projects: GA AV ČR IAA100100912; GA ČR GA202/09/0775 Institutional support: RVO:68378271 Keywords : surface magnetism * magnetic overlayer * gas adsorption * magnetic phase stability * density functional calculation * STM Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.664, year: 2013

  3. Posttransplant oxygen inhalation improves the outcome of subcutaneous islet transplantation: A promising clinical alternative to the conventional intrahepatic site.

    Science.gov (United States)

    Komatsu, H; Rawson, J; Barriga, A; Gonzalez, N; Mendez, D; Li, J; Omori, K; Kandeel, F; Mullen, Y

    2018-04-01

    Subcutaneous tissue is a promising site for islet transplantation, due to its large area and accessibility, which allows minimally invasive procedures for transplantation, graft monitoring, and removal of malignancies as needed. However, relative to the conventional intrahepatic transplantation site, the subcutaneous site requires a large number of islets to achieve engraftment success and diabetes reversal, due to hypoxia and low vascularity. We report that the efficiency of subcutaneous islet transplantation in a Lewis rat model is significantly improved by treating recipients with inhaled 50% oxygen, in conjunction with prevascularization of the graft bed by agarose-basic fibroblast growth factor. Administration of 50% oxygen increased oxygen tension in the subcutaneous site to 140 mm Hg, compared to 45 mm Hg under ambient air. In vitro, islets cultured under 140 mm Hg oxygen showed reduced central necrosis and increased insulin release, compared to those maintained in 45 mm Hg oxygen. Six hundred syngeneic islets subcutaneously transplanted into the prevascularized graft bed reversed diabetes when combined with postoperative 50% oxygen inhalation for 3 days, a number comparable to that required for intrahepatic transplantation; in the absence of oxygen treatment, diabetes was not reversed. Thus, we show oxygen inhalation to be a simple and promising approach to successfully establishing subcutaneous islet transplantation. © 2017 The American Society of Transplantation and the American Society of Transplant Surgeons.

  4. Adsorption competition study between oxygenated compounds and hydrocarbons on molecular sieves; Etude de la competition d`adsorption entre les composes oxygenes et les hydrocarbures sur les tamis moleculaires

    Energy Technology Data Exchange (ETDEWEB)

    Kong Ming, L.

    1996-11-29

    The aim of this study is to determine the competitive behavior of methanol and l -hexene in an n-hexane solvent system using a 13-x and a molecular sieves as the adsorbent. Adsorption was carried out in liquid phase. Parameters such as concentration, flowrate, temperature and column, length were varied in order to assess their effects on the breakthrough curves. In methanol-n-hexane system, it was found that the concentration profiles of the breakthrough curves were not very much influenced by the parameters except for the amount of volume of feed processes. However, changes in the flowrate does not have a significant effect on the concentration profile. A higher flowrate, the profile assumes a more dispersive pattern which of course is expected due to lower contact time if internal diffusion is rate determining. In the case of l -hexane carries out at different temperatures and column lengths there were some differences in concentration profiles. This may be due to experimental difficulties in controlling the flowrate at the start of the experiment rather than inherent adsorption behavior. In the 3-component system, 1 -hexene breakthrough was very much earlier as compared to methanol. Desorption carried out at 383 k and with flowrate of 28{+-}l g/min and for 100 minutes for all cases showed little variation. Re-adsorption under various conditions showed marked reduction in the amount of feed processed. The breakthrough curves were simulated using an Institut Francais du Petrole (IFP) proprietary computer program which is based on selectivity and theoretical plates and which predicts very well for xylene separation. In the 1 -hexene-n-hexane system, the simulator predicted reasonably well in terms of bed volume processed, however, for the methanol-n-hexane system the simulator failed. For the program to be effective, some mathematical treatments needs to be done with respect to the handling of the numerical analysis. To describe the adsorption equilibrium, two

  5. Comparison of reactivity on step and terrace sites of Pd (3 3 2) surface for the dissociative adsorption of hydrogen: A quantum chemical molecular dynamics study

    International Nuclear Information System (INIS)

    Ahmed, Farouq; Nagumo, Ryo; Miura, Ryuji; Ai, Suzuki; Tsuboi, Hideyuki; Hatakeyama, Nozomu; Endou, Akira; Takaba, Hiromitsu; Kubo, Momoji; Miyamoto, Akira

    2011-01-01

    The notion of 'active sites' is fundamental to heterogeneous catalysis. However, the exact nature of the active sites, and hence the mechanism by which they act, are still largely a matter of speculation. In this study, we have presented a systematic quantum chemical molecular dynamics (QCMD) calculations for the interaction of hydrogen on different step and terrace sites of the Pd (3 3 2) surface. Finally the dissociative adsorption of hydrogen on step and terrace as well as the influence of surface hydrogen vacancy for the dissociative adsorption of hydrogen has been investigated through QCMD. This is a state-of-the-art method for calculating the interaction of atoms and molecules with metal surfaces. It is found that fully hydrogen covered (saturated) step sites can dissociate hydrogen moderately and that a monovacancy surface is suitable for significant dissociative adsorption of hydrogen. However in terrace site of the surface we have found that dissociation of hydrogen takes place only on Pd sites where the metal atom is not bound to any pre-adsorbed hydrogen atoms. Furthermore, from the molecular dynamics and electronic structure calculations, we identify a number of consequences for the interpretation and modeling of diffusion experiments demonstrating the coverage and directional dependence of atomic hydrogen diffusion on stepped palladium surface.

  6. Water on TiO2 studied by work function change: adsorption in cycles

    International Nuclear Information System (INIS)

    Bundaleski, Nenad; Silva, Ana G; Jean-Shaw, Bobbie; Teodoro, Orlando; Moutinho, Augusto

    2013-01-01

    The nature of water adsorption on TiO 2 (110) rutile surface attracts a lot of attention for quite some time. In spite of the considerable experimental and theoretical efforts a lot of details remain unclear. We have been using work function study to follow the adsorption of water on TiO 2 at room temperature, and interpreted the results in terms of fast dissociative adsorption on bridging oxygen vacancies (BOV) and much slower non-dissociative adsorption on Ti 5f rows. Additionally, we concluded that water from Ti 5f rows efficiently desorbs at room temperature which is not the case for BOV adsorption sites. Here we propose a novel experimental approach which consists of monitoring in real-time the work function change during cycles of water adsorption. Since desorption at BOVs does not take place at room temperature, this method allows us to resolve the adsorption dynamics on the two adsorption sites. The first results changed our understanding of the phenomenon: we show that both, adsorption on BOVs and Ti 5f are both very fast. Additionally, slow exponential decay of the work function is observed, which is not directly related to water adsorption. The possible explanation of the third slow contribution could be related to the migration of hydrogen atoms along the bridging oxygen rows.

  7. Density functional study of NO adsorption on undefected and oxygen defective Au–BaO(1 0 0) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Añez, Rafael, E-mail: ranez@ivic.gob.ve [Laboratorio de Química Física y Catálisis Computacional, Centro de Química, Instituto Venezolano de Investigaciones Científicas, Apartado, 21827 Caracas (Venezuela, Bolivarian Republic of); Sierraalta, Aníbal; Bastardo, Anelisse [Laboratorio de Química Física y Catálisis Computacional, Centro de Química, Instituto Venezolano de Investigaciones Científicas, Apartado, 21827 Caracas (Venezuela, Bolivarian Republic of); Coll, David [Laboratorio de Físico Química Teórica de Materiales, Centro de Química, Instituto Venezolano de Investigaciones Científicas, Apartado, 21827 Caracas (Venezuela, Bolivarian Republic of); Garcia, Belkis [Instituto Universitario de Tecnología de Valencia IUTVAL, Valencia, Edo. Carabobo (Venezuela, Bolivarian Republic of)

    2014-07-01

    A periodic density functional approach has been used in order to explore the interaction of NO with undoped and Au doped BaO(1 0 0) surface. Due to oxygen vacancies increase the interaction between the doping metal and the surface, F{sub S} and F{sub S}{sup +} vacancies were studied and compared with the results obtained on the undefected doped BaO(1 0 0). Our results indicate that the high basicity of the BaO surface, besides the electron density changes produced by the oxygen vacancies, modify considerably how the Au atom interacts with the surface increasing the ionic character of the interaction. F{sub S} vacancy shows to be a promise center to activate de NO bond on the BaO(1 0 0) surface.

  8. Predicting Multicomponent Adsorption Isotherms in Open-Metal Site Materials Using Force Field Calculations Based on Energy Decomposed Density Functional Theory.

    Science.gov (United States)

    Heinen, Jurn; Burtch, Nicholas C; Walton, Krista S; Fonseca Guerra, Célia; Dubbeldam, David

    2016-12-12

    For the design of adsorptive-separation units, knowledge is required of the multicomponent adsorption behavior. Ideal adsorbed solution theory (IAST) breaks down for olefin adsorption in open-metal site (OMS) materials due to non-ideal donor-acceptor interactions. Using a density-function-theory-based energy decomposition scheme, we develop a physically justifiable classical force field that incorporates the missing orbital interactions using an appropriate functional form. Our first-principles derived force field shows greatly improved quantitative agreement with the inflection points, initial uptake, saturation capacity, and enthalpies of adsorption obtained from our in-house adsorption experiments. While IAST fails to make accurate predictions, our improved force field model is able to correctly predict the multicomponent behavior. Our approach is also transferable to other OMS structures, allowing the accurate study of their separation performances for olefins/paraffins and further mixtures involving complex donor-acceptor interactions. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Combined quantum chemistry and Monte Carlo simulation of competitive adsorption of O{sub 2} and OH on Pt surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Li, Rui, E-mail: ruililcu@gmail.com [Department of Chemistry, Liaocheng University, Liaocheng 252059 (China); Li, Haibo; Xu, Shuling [Department of Chemistry, Liaocheng University, Liaocheng 252059 (China); Liu, Jifeng, E-mail: liujifeng111@gmail.com [Key Laboratory of Food Nutrition and Safety, Ministry of Education of China, Tianjin University of Science and Technology, Tianjin 300457 (China)

    2017-07-15

    Highlights: • Competitive adsorption of O{sub 2} and OH on different Pt surfaces was theoretically studied. • The adsorption energies of O{sub 2} and OH depend on the Pt surfaces and the adsorption sites. • The order of O{sub 2} adsorption efficiency was characterized. - Abstract: To obtain a microscopic explanation on the difference of oxygen reduction reaction activity on different Pt low index surfaces, we simulated competitive adsorptions of O{sub 2} and OH on four Pt low index surfaces. Firstly, all possible chemical adsorption configurations of the O{sub 2} and OH molecules on the three surfaces were acquired through density functional theory. The distribution of these configurations on the different surfaces was collected from Monte Carlo simulations. Our results demonstrated that the adsorption energy order of O{sub 2} on different surfaces was (110)(1 × 2) > (110) > (100) > (111) and that the adsorption energy order of the OH molecules on Pt surfaces was the same. Considering the competitive adsorption of O{sub 2} and OH on Pt surfaces, the final O{sub 2} adsorption efficiencies order of three surfaces was (111) > (110) > (100) > (110)(1 × 2), which was consistent with the experimental activities of oxygen reduction. Our study provided theoretical references for previous experimental studies and had important significance for the understanding of oxygen adsorption on Pt surfaces.

  10. Molecular simulation insights on the in vacuo adsorption of amino acids on graphene oxide surfaces with varying surface oxygen densities

    Energy Technology Data Exchange (ETDEWEB)

    Rahmani, Farzin; Nouranian, Sasan, E-mail: sasan@olemiss.edu; Mahdavi, Mina [University of Mississippi, Department of Chemical Engineering (United States); Al-Ostaz, Ahmed [University of Mississippi, Department of Civil Engineering (United States)

    2016-11-15

    In this fundamental study, a series of molecular dynamics simulations were performed in vacuo to investigate the energetics and select geometries of 20 standard amino acids (AAs) on pristine graphene (PG) and graphene oxide (GO) surfaces as a function of graphene surface oxygen density. These interactions are of key interest to graphene/biomolecular systems. Our results indicate that aromatic AAs exhibit the strongest total interactions with the PG surfaces due to π-π stacking. Tryptophan (Trp) has the highest aromaticity due to its indole side chain and, hence, has the strongest interaction among all AAs (−16.66 kcal/mol). Aliphatic, polar, and charged AAs show various levels of affinity to the PG sheets depending on the strength of their side chain hydrophobic interactions. For example, arginine (Arg) with its guanidinium side chain exhibits the strongest interaction with the PG sheets (−13.81 kcal/mol) following aromatic AAs. Also, glycine (Gly; a polar AA) has the weakest interaction with the PG sheets (−7.29 kcal/mol). When oxygen-containing functional groups are added to the graphene sheets, the π-π stacking in aromatic AAs becomes disrupted and perfect parallelism of the aromatic rings is lost. Moreover, hydrogen bonding and/or electrostatic interactions become more pronounced. Charged AAs exhibit the strongest interactions with the GO surfaces. In general, the AA-GO interactions increase with increasing surface oxygen density, and the effect is more pronounced at higher O/C ratios. This study provides a quantitative measure of AA-graphene interactions for the design and tuning of biomolecular systems suitable for biosensing, drug delivery, and gene delivery applications.

  11. Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials.

    Science.gov (United States)

    Qi, Xuejun; Song, Wenwu; Shi, Jianwei

    2017-01-01

    Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite's chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface.

  12. The correlation of adsorption behavior between ciprofloxacin hydrochloride and the active sites of Fe-doped MCM-41

    Science.gov (United States)

    Wu, Ying; Tang, Yiming; Li, Laisheng; Liu, Peihong; Li, Xukai; Chen, Weirui; Xue, Ying

    2018-02-01

    Fe-MCM-41s with various molar ratios of silicon to iron (20, 40, 80 and 160) were prepared to investigate adsorption properties of ciprofloxacin hydrochloride (CPX) in aqueous solutions. Fe-MCM-41s were characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption/desorption isotherms and infrared spectroscopy (FT-IR). Effects of silicon–iron ratio, adsorbent dosage, pH and temperature were conducted to explore the adsorption mechanism of CPX on Fe-MCM-41. The results showed that the introduction of iron facilitated the absorption quantity for CPX from 20.04 to 83.33 mg g-1 at 120 min of reaction time, which was mainly attributed to surface complexation. The promotion of hydrophobic effect, electrostatic interactions and π-π electron donor–acceptor interaction also played coordinate roles in the adsorption process. The experimental kinetic data followed both the pseudo-second-order and intra-particle diffusion models, while the adsorption isotherm data fit well to Freundlich model at high temperature. Thermodynamic study showed that the adsorption was spontaneous. Under the effect of electrostatic interaction, pH of the solution strongly affected CPX adsorption. Five representative metal cations (Ca, Cu, Ni, Pb and Cd) were chosen to study the effects on CPX adsorption and their complexation. The inhibiting effect of metal cations on CPX adsorption was sequenced in the order of Cu > Ni > Pb > Cd > Ca, which followed the same order as the complexation stability constants between CPX and cations. The Fe-MCM-41 adsorbent possessed excellent reusability for 4 cycles use, suggesting a potential applicability of Fe-MCM-41 to remove CPX in water.

  13. Adsorption of diuron and dichlobenil on multiwalled carbon nanotubes as affected by lead.

    Science.gov (United States)

    Chen, Guang-Cai; Shan, Xiao-Quan; Pei, Zhi-Guo; Wang, Huanhua; Zheng, Li-Rong; Zhang, Jing; Xie, Ya-Ning

    2011-04-15

    The effect of lead on the adsorption of diuron and dichlobenil on multiwalled carbon nanotubes (MWCNTs) was investigated to explore the possible application of MWCNTs for removal of both herbicides from contaminated water. The adsorption of diuron and dichlobenil on MWCNTs at pH 6 was nonlinear and fit the Polanyi-Manes model well. The adsorption of diuron and dichlobenil was closely correlated with specific surface areas and micropore volumes of MWCNTs. An increase in oxygen content of MWCNTs with same diameters and similar surface areas decreased the adsorption of diuron and dichlobenil, while increased the adsorption of lead. Micro-Fourier transform infrared spectroscopic study indicated that hydrogen bonding is a main mechanism responsible for the adsorption of diuron or dichlobenil onto MWCNTs-O. Oxygen containing groups, mainly carboxylic groups, significantly increased the adsorption of lead through the formations of outer-sphere and inner-sphere complexes, which are verified by X-ray absorption spectroscopic measurements. Oxygen containing groups and the presence of lead diminished the adsorption of diuron and dichlobenil. The suppression mechanisms of lead were ascribed to hydration and complexation of lead with carboxylic groups, which may occupy part of surface of MWCNTs-O. The large hydration shell of lead cations may intrude or shield hydrophobic and hydrophilic sites, resulting in a decreased adsorption of diuron and dichlobenil at the lead-complexed moieties. Copyright © 2011 Elsevier B.V. All rights reserved.

  14. Seasonal and inter-annual variations of dissolved oxygen in the northwestern Mediterranean Sea (DYFAMED site)

    Science.gov (United States)

    Coppola, Laurent; Legendre, Louis; Lefevre, Dominique; Prieur, Louis; Taillandier, Vincent; Diamond Riquier, Emilie

    2018-03-01

    Dissolved oxygen (O2) is a relevant tracer to interpret variations of both water mass properties in the open ocean and biological production in the surface layer of both coastal and open waters. Deep-water formation is very active in the northwestern Mediterranean Sea, where it influences intermediate and deep waters properties, nutrients replenishment and biological production. This study analyses, for the first time, the 20-year time series of monthly O2 concentrations at the DYFAMED long-term sampling site in the Ligurian Sea. Until the winters of 2005 and 2006, a thick and strong oxygen minimum layer was present between 200 and 1300 m because dense water formation was then local, episodic and of low intensity. In 2005-2006, intense and rapid deep convection injected 24 mol O2 m-2 between 350 and 2000 m from December 2005 to March 2006. Since this event, the deep layer has been mostly ventilated during winter time by newly formed deep water spreading from the Gulf of Lion 250 km to the west and by some local deep mixing in early 2010, 2012 and 2013. In the context of climate change, it is predicted that the intensity of deep convection will become weaker in the Mediterranean, which could potentially lead to hypoxia in intermediate and deep layers with substantial impact on marine ecosystems. With the exception of winters 2005 and 2006, the O2 changes in surface waters followed a seasonal trend that reflected the balance between air-sea O2 exchanges, changes in the depth of the mixed layer and phytoplankton net photosynthesis. We used the 20-year O2 time series to estimate monthly and annual net community production. The latter was 7.1 mol C m-2 yr-1, consistent with C-14 primary production determinations and sediment-trap carbon export fluxes at DYFAMED.

  15. The Correlation of Adsorption Behavior between Ciprofloxacin Hydrochloride and the Active Sites of Fe-doped MCM-41

    Directory of Open Access Journals (Sweden)

    Ying Wu

    2018-02-01

    Full Text Available HIGHLIGHTSFe incorporation significantly accelerated the adsorption of CPX on MCM-41.Fe leaching can be ignored when pH was higher than 4.0.pH played an important role in CPX adsorption on Fe-MCM-41.Co-effect of CPX and metal cations on Fe-MCM-41 was investigated.Fe-MCM-41s with various molar ratios of silicon to iron (20, 40, 80, and 160 were prepared to investigate adsorption properties of ciprofloxacin hydrochloride (CPX in aqueous solutions. Fe-MCM-41s were characterized by transmission electron microscope (TEM, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, nitrogen adsorption/desorption isotherms, and infrared spectroscopy (FT-IR. Effects of silicon-iron ratio, adsorbent dosage, pH, and temperature were conducted to explore the adsorption mechanism of CPX on Fe-MCM-41. The results showed that the introduction of iron facilitated the absorption quantity for CPX from 20.04 to 83.33 mg g−1 at 120 min of reaction time, which was mainly attributed to surface complexation. The promotion of hydrophobic effect, electrostatic interactions, and π-π electron donor-acceptor interaction also played coordinate roles in the adsorption process. The experimental kinetic data followed both the pseudo-second-order and intra-particle diffusion models, while the adsorption isotherm data fit well to Freundlich model at high temperature. Thermodynamic study showed that the adsorption was spontaneous. Under the effect of electrostatic interaction, pH of the solution strongly affected CPX adsorption. Five representative metal cations (Ca, Cu, Ni, Pb, and Cd were chosen to study the effects on CPX adsorption and their complexation. The inhibiting effect of metal cations on CPX adsorption was sequenced in the order of Cu > Ni > Pb > Cd > Ca, which followed the same order as the complexation stability constants between CPX and cations. The Fe-MCM-41 adsorbent possessed excellent reusability for 4 cycles use, suggesting a potential applicability of

  16. The role of the anionic and cationic pt sites in the adsorption site preference of water and ethanol on defected Pt4/Pt(111) substrates: A density functional theory investigation within the D3 van der waals corrections

    Science.gov (United States)

    Seminovski, Yohanna; Amaral, Rafael C.; Tereshchuk, Polina; Da Silva, Juarez L. F.

    2018-01-01

    Platinum (Pt) atoms in the bulk face-centered cubic structure have neutral charge because they are equivalent by symmetry, however, in clean Pt surfaces, the effective charge on Pt atoms can turn slightly negative (anionic) or positive (cationic) while increasing substantially in magnitude for defected (low-coordinated) Pt sites. The effective charge affect the adsorption properties of molecular species on Pt surfaces and it can compete in importance with the coupling of the substrate-molecule electronic states. Although several studies have been reported due to the importance of Pt for catalysis, our understanding of the role played by low-coordinated sites is still limited. Here, we employ density functional theory within the Perdew-Burke-Ernzerhof exchange-correlation functional and the D3 van der Waals (vdW) correction to investigate the role of the cationic and anionic Pt sites on the adsorption properties of ethanol and water on defected Pt4/Pt(111) substrates. Four substrates were carefully selected, namely, two two-dimensional (2D) Pt4 configurations (2D-strand and 2D-island) and two tri-dimensional (3D) Pt4 (3D-fcc and 3D-hcp), to understand the role of coordination, effective charge, and coupling of the electronic states in the adsorption properties. From the Bader charge analysis, we identified the cationic and anionic sites among the Pt atoms exposed to the vacuum region in the Pt4/Pt(111) substrates. We found that ethanol and water bind via the anionic O atoms to the low-coordinated defected Pt sites of the substrates, where the angle PtOH is nearly 100° for most configurations. In the 3D-fcc or 3D-hcp defected configurations, the lowest-coordinated Pt atoms are anionic, hence, those Pt sites are not preferable for the adsorption of O atoms. The charge transfer from water and ethanol to the Pt substrates has similar magnitude for all cases, which implies similar Coulomb contribution to the adsorption energy. Moreover, we found a correlation of the

  17. Adsorption and separation of CO{sub 2} on Fe(II)-MOF-74: Effect of the open metal coordination site

    Energy Technology Data Exchange (ETDEWEB)

    Lou, Wolong; Yang, Jiangfeng; Li, Libo; Li, Jinping, E-mail: Jpli211@hotmail.com

    2014-05-01

    We describe the successful synthesis of Fe{sub 2}(dobdc) (dobdc{sup 4−}=2, 5-dioxido-1, 4-benzenedicarboxylate), which has an open metal coordination site Fe(II), and investigate the adsorption properties of three important molecules CO{sub 2}, CH{sub 4} and N{sub 2} on Fe{sub 2}(dobdc) and an oxidized analog, Fe{sub 2}(O{sub 2})(dobdc). We found that CO{sub 2} adsorption isotherm of Fe{sub 2}(dobdc) at 10 bar was very different from Fe{sub 2}(O{sub 2})(dobdc), with the capacities of 144.5 cm{sup 3} g{sup −1} and 98.1 cm{sup 3} g{sup −1}, respectively. The adsorption capacities for CH{sub 4} were 75.8 cm{sup 3} g{sup −1} and 36.8 cm{sup 3} g{sup −1}, respectively, at 10 bar in these materials. Using ideal adsorbed solution theory (IAST), we obtain the adsorption selectivity for CO{sub 2} using equimolar mixtures of CO{sub 2}/CH{sub 4} and CO{sub 2}/N{sub 2} with Fe{sub 2}(dobdc) and Fe{sub 2}(O{sub 2})(dobdc) as a function of pressure. Fe{sub 2}(dobdc) has a higher, more stable separation factor. - Graphical abstract: The selectivity of CO{sub 2}/CH{sub 4} mixture (50%/50%) on Fe{sub 2}(dobdc) and Fe{sub 2}(O{sub 2})(dobdc). - Highlights: • We explored the contrastive adsorption of CO{sub 2}, CH{sub 4}, and N{sub 2} in Fe{sub 2}(dobdc) and Fe{sub 2}(O{sub 2})(dobdc) for the first time. • Through IAST, we obtain the adsorption selectivity for CO{sub 2} from the equimolar mixture of CO{sub 2}/CH{sub 4} and CO{sub 2}/N{sub 2} for Fe{sub 2}(dobdc) and Fe{sub 2}(O{sub 2})(dobdc). • We determined that the open coordination site of Fe(II) is the main reason for different adsorption performances.

  18. Coupling of anodic oxidation and adsorption by granular activated carbon for chemical oxygen demand removal from 4,4'-diaminostilbene-2,2'-disulfonic acid wastewater.

    Science.gov (United States)

    Wang, Lizhang; Zhao, Yuemin

    2010-01-01

    Experiments were performed to reduce chemical oxygen demand (COD) from 4,4'-diaminostilbene-2,2'-disulfonic (DSD) acid manufacturing wastewater using electrochemical oxidation coupled with adsorption by granular activated carbon. The COD removal is affected by the residence time and applied voltage. When the residence time is increased, lower value of COD effluent could be obtained, however, the average current efficiency (ACE) decreased rapidly, and so does the applied voltage. In addition, aeration could effectively enhance COD removal efficiency and protect anodes from corrosion. Furthermore, the acidic condition is beneficial to the rapid decrease of COD and the values of pH effluent are independent of the initial solution pH. The optimization conditions obtained from these experiments are applied voltage of 4.8 V, residence time of 180 min and air-liquid ratio of 4.2 with the COD effluent of about 690 mg L⁻¹. In these cases, the ACE and energy consumption are 388% and 4.144 kW h kg⁻¹ COD, respectively. These perfect results from the experiments illustrate that the combined process is a considerable alternative for the treatment of industrial wastewater containing high concentration of organic pollutants and salinity.

  19. The role of oxygen and water on molybdenum nanoclusters for electro catalytic ammonia production

    Directory of Open Access Journals (Sweden)

    Jakob G. Howalt

    2014-01-01

    Full Text Available The presence of water often gives rise to oxygen adsorption on catalyst surfaces through decomposition of water and the adsorbed oxygen or hydroxide species often occupy important surfaces sites, resulting in a decrease or a total hindrance of other chemical reactions taking place at that site. In this study, we present theoretical investigations of the influence of oxygen adsorption and reduction on pure and nitrogen covered molybdenum nanocluster electro catalysts for electrochemical reduction of N2 to NH3 with the purpose of understanding oxygen and water poisoning of the catalyst. Density functional theory calculations are used in combination with the computational hydrogen electrode approach to calculate the free energy profile for electrochemical protonation of O and N2 species on cuboctahedral Mo13 nanoclusters. The calculations show that the molybdenum nanocluster will preferentially bind oxygen over nitrogen and hydrogen at neutral bias, but under electrochemical reaction conditions needed for nitrogen reduction, oxygen adsorption is severely weakened and the adsorption energy is comparable to hydrogen and nitrogen adsorption. The potentials required to reduce oxygen off the surface are −0.72 V or lower for all oxygen coverages studied, and it is thus possible to (reactivate (partially oxidized nanoclusters for electrochemical ammonia production, e.g., using a dry proton conductor or an aqueous electrolyte. At lower oxygen coverages, nitrogen molecules can adsorb to the surface and electrochemical ammonia production via the associative mechanism is possible at potentials as low as −0.45 V to −0.7 V.

  20. Oxygen isotope evidence for sorption of molecular oxygen to pyrite surface sites and incorporation into sulfate in oxidation experiments

    International Nuclear Information System (INIS)

    Tichomirowa, Marion; Junghans, Manuela

    2009-01-01

    Experiments were conducted to investigate (i) the rate of O-isotope exchange between SO 4 and water molecules at low pH and surface temperatures typical for conditions of acid mine drainage (AMD) and (ii) the O- and S-isotope composition of sulfates produced by pyrite oxidation under closed and open conditions (limited and free access of atmospheric O 2 ) to identify the O source/s in sulfide oxidation (water or atmospheric molecular O 2 ) and to better understand the pyrite oxidation pathway. An O-isotope exchange between SO 4 and water was observed over a pH range of 0-2 only at 50 deg. C, whereas no exchange occurred at lower temperatures over a period of 8 a. The calculated half-time of the exchange rate for 50 deg. C (pH = 0 and 1) is in good agreement with former experimental data for higher and lower temperatures and excludes the possibility of isotope exchange for typical AMD conditions (T ≤ 25 deg. C, pH ≥ 3) for decades. Pyrite oxidation experiments revealed two dependencies of the O-isotope composition of dissolved sulfates: O-isotope values decreased with longer duration of experiments and increasing grain size of pyrite. Both changes are interpreted as evidence for chemisorption of molecular O 2 to pyrite surface sites. The sorption of molecular O 2 is important at initial oxidation stages and more abundant in finer grained pyrite fractions and leads to its incorporation in the produced SO 4 . The calculated bulk contribution of atmospheric O 2 in the dissolved SO 4 reached up to 50% during initial oxidation stages (first 5 days, pH 2, fine-grained pyrite fraction) and decreased to less than 20% after about 100 days. Based on the direct incorporation of molecular O 2 in the early-formed sulfates, chemisorption and electron transfer of molecular O 2 on S sites of the pyrite surface are proposed, in addition to chemisorption on Fe sites. After about 10 days, the O of all newly-formed sulfates originates only from water, indicating direct interaction

  1. Effects of chemical functional groups on elemental mercury adsorption on carbonaceous surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Liu Jing, E-mail: liujing27@mail.hust.edu.cn [State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074 (China); Cheney, Marcos A. [Department of Natural Sciences, University of Maryland Eastern Shore, Princess Anne, MD 21853 (United States); Wu Fan; Li Meng [State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2011-02-15

    A systematic theoretical study using density functional theory is performed to provide molecular-level understanding of the effects of chemical functional groups on mercury adsorption on carbonaceous surfaces. The zigzag and armchair edges were used in modeling the carbonaceous surfaces to simulate different adsorption sites. The edge atoms on the upper side of the models are unsaturated to simulate active sites. All calculations (optimizations, energies, and frequencies) were made at B3PW91 density functional theory level, using RCEP60VDZ basis set for mercury and 6-31G(d) pople basis set for other atoms. The results indicate that the embedding of halogen atom can increase the activity of its neighboring site which in turn increases the adsorption capacity of the carbonaceous surface for Hg{sup 0}. The adsorption belongs to chemisorptions, which is in good agreement with the experimental results. For the effects of oxygen functional groups, lactone, carbonyl and semiquinone favor Hg{sup 0} adsorption because they increase the neighboring site's activity for mercury adsorption. On the contrary, phenol and carboxyl functional groups show a physisorption of Hg{sup 0}, and reduce Hg capture. This result can explain the seemingly conflicting experimental results reported in the literature concerning the influence of oxygen functional groups on mercury adsorption on carbonaceous surface.

  2. One year of Seaglider dissolved oxygen concentration profiles at the PAP site

    Science.gov (United States)

    Binetti, Umberto; Kaiser, Jan; Heywood, Karen; Damerell, Gillian; Rumyantseva, Anna

    2015-04-01

    Oxygen is one of the most important variables measured in oceanography, influenced both by physical and biological factors. During the OSMOSIS project, 7 Seagliders were used in 3 subsequent missions to measure a multidisciplinary suite of parameters at high frequency in the top 1000 m of the water column for one year, from September 2012 to September 2013. The gliders were deployed at the PAP time series station (nominally at 49° N 16.5° W) and surveyed the area following a butterfly-shaped path. Oxygen concentration was measured by Aanderaa optodes and calibrated using ship CTD O2 profiles during 5 deployment and recovery cruises, which were in turn calibrated by Winkler titration of discrete samples. The oxygen-rich mixed layer deepens in fall and winter and gets richer in oxygen when the temperature decreases. The spring bloom did not happen as expected, but instead the presence of a series of small blooms was measured throughout spring and early summer. During the summer the mixed layer become very shallow and oxygen concentrations decreased. A Deep Oxygen Maximum (DOM) developed along with a deep chlorophyll maximum during the summer and was located just below the mixed layer . At this depth, phytoplankton had favourable light and nutrient conditions to grow and produce oxygen, which was not subject to immediate outgassing. The oxygen concentration in the DOM was not constant, but decreased, then increased again until the end of the mission. Intrusions of oxygen rich water are also visible throughout the mission. These are probably due to mesoscale events through the horizontal transport of oxygen and/or nutrients that can enhance productivity, particularly at the edge of the fronts. We calculate net community production (NCP) by analysing the variation in oxygen with time. Two methods have been proposed. The classical oxygen budget method assumes that changes in oxygen are due to the sum of air-sea flux, isopycnal advection, diapycnal mixing and NCP. ERA

  3. Preferential adsorption of NH3 gas molecules on MWCNT defect sites probed using in situ Raman spectroscopy

    CSIR Research Space (South Africa)

    Chimowa, George

    2017-06-01

    Full Text Available The preferential adsorption of NH(sub3) gas molecules on multi-walled carbon nanotubes (MWCNTs) was studied using in situ Raman spectroscopy. It was observed that the full widths at half maximum of the G band and the intensity ratio I(sub2D...

  4. Theoretical investigation of site-specific characteristics of CO adsorption complexes in the Li+-FER zeolite

    Czech Academy of Sciences Publication Activity Database

    Nachtigall, Petr; Bulánek, R.

    2006-01-01

    Roč. 307, č. 1 (2006), s. 118-127 ISSN 0926-860X R&D Projects: GA MŠk(CZ) LC512 Institutional research plan: CEZ:AV0Z40550506 Keywords : adsorption * spectroscopy * DFT Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.630, year: 2006

  5. Adsorption of SO2 on bituminous coal char and activated carbon fiber

    Science.gov (United States)

    DeBarr, Joseph A.; Lizzio, Anthony A.; Daley, Michael A.

    1997-01-01

    The SO2 adsorption behaviors of activated carbons produced from Illinois coal and of commercially prepared activated carbon fibers (ACFs) were compared. There was no relation between surface area of coal-based carbons and SO2 adsorption, whereas adsorption of SO2 on the series of ACFs was inversely proportional to N2 BET surface area. Higher surface area ACFs had wider pores and adsorbed less SO2; thus, pore size distribution is thought to play a significant role in SO2 adsorption for these materials. Oxidation with HNO3 and/or H2SO4, followed by heat treatment at 700−925°C to remove carbon−oxygen complexes, resulted in increased SO2 adsorption for both coal chars and ACFs. This behavior was explained by an increase in the available number of free sites, previously occupied by oxygen and now available for SO2 adsorption. The use of nitrogen-containing functional groups on ACFs of proper pore size shows promise for further increasing SO2 adsorption capacities. Knowledge of the relationship among the number of free sites, pore size, and surface chemistry on corresponding SO2 adsorption should lead to the development of more efficient adsorbents prepared from either coal or ACFs.

  6. Site blocking in silver-exchanged zeolite Y by carbon monoxide and ethene using xenon adsorption and 129Xe NMR spectroscopy

    Science.gov (United States)

    Boddenberg, B.; Watermann, J.

    1993-03-01

    The adsorption isotherms and 129Xe NMR chemical shifts of xenon in the zeolites NaY, AgY, and in AgY preloaded with ≈ 1 molecule/supercage ethene and carbon monoxide were measured at 25°C. The experimental data reveal the blocking of the silver-cation sites for xenon by the preadsorbed molecules. Ethene and CO are found to block the previously postulated two types of silver-cation species in the supercages of AgY in a different way.

  7. Combined Theoretical and Experimental Investigation of CO Adsorption on Coordinatively Unsaturated Sites in CuBTC MOF

    Czech Academy of Sciences Publication Activity Database

    Rubeš, M.; Grajciar, L.; Bludský, Ota; Wiersum, A. D.; Llewellyn, P. L.; Nachtigall, P.

    2012-01-01

    Roč. 13, č. 2 (2012), s. 488-495 ISSN 1439-4235 R&D Projects: GA MŠk LC512 Grant - others:GA MŠk(CZ) 7E09111; 7th framework programme(XE) 228862 Institutional research plan: CEZ:AV0Z40550506 Keywords : ab initio calculations * adsorption * density functional calculations * metal-organic frameworks * microcalorimetry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.349, year: 2012

  8. Carbon monoxide adsorption on low-silica zeolites-from single to dual and to multiple cation sites

    Czech Academy of Sciences Publication Activity Database

    Otero Areán, C.; Rodríguez Delgado, M.; López Bauca, C.; Vrbka, Luboš; Nachtigall, Petr

    2007-01-01

    Roč. 9, č. 33 (2007), s. 4657-4661 ISSN 1463-9076 R&D Projects: GA MŠk LC512; GA ČR GA203/06/0324 Grant - others:UIB(ES) MAT2005-05350 Institutional research plan: CEZ:AV0Z40550506 Keywords : zeolite * adsorption * DFT Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.343, year: 2007

  9. High-temperature equilibrium study of the oxygen-site occupancy in YBa2Cu3O7-δ by positron annihilation

    International Nuclear Information System (INIS)

    Hermes, H.; Forster, M.; Schaefer, H.

    1991-01-01

    Measurements of the positron lifetime and the Doppler broadening of the annihilation γ line were performed on sintered YBa 2 Cu 3 O 7-δ specimens between ambient temperature and 1140 K at oxygen partial pressures, p O2 , between 10 2 and 10 5 Pa in order to study the atomic processes of changes of the oxygen content in thermal equilibrium. Above 680 K the positron lifetime increases with increasing temperature and decreasing oxygen partial pressure. It is found that the normalized positron annihilation rate λ 1 * depends exclusively on the oxygen deficiency δ and decreases linearly with increasing δ. Our results demonstrate that the positrons are annihilated predominantly on the sites of the Cu(1)-O(1) chains where the oxygen atoms are removed (oxygen-deficient sites), as suggested by theoretical studies. A simple atomistic model of oxygen exchange is confirmed by the experimentally observed variation of the positron annihilation rate with (p O2 ) -0.27

  10. SR-Site: Oxygen ingress in the rock at Forsmark during a glacial cycle

    Energy Technology Data Exchange (ETDEWEB)

    Sidborn, Magnus (Kemakta Konsult AB (Sweden)); Sandstroem, Bjoern (WSP Sverige AB (Sweden)); Tullborg, Eva-Lena (Terralogica AB (Sweden)); Salas, Joaquin; Maia, Flavia; Delos, Anne; Molinero, Jorge (Amphos21 (Spain)); Hallbeck, Lotta; Pedersen, Karsten (Microbial Analytics Sweden AB (Sweden))

    2010-11-15

    The aim of this report is to assess the possibility for oxygen to be transported by glacial melt-water to canister positions in a final repository for spent nuclear fuel at the proposed location in Forsmark. The approach for this assessment is to combine reactive transport modelling with geological observations of present and historical indications of oxygen ingress. For safety assessment purposes a cautious approach in the modelling is required when estimating the extent of oxygen ingress. In this report, a cautious approach has been applied both in the conceptualisation of the problem and in the choice of input parameters used in the models. Oxygen consuming processes are only neglected in the modelling if they are expected to further decrease the extent of oxygen ingress. Several oxygen consuming processes have been identified, each of which may play an important role in the scavenging of oxygen along recharge flow paths in the rock. These processes include biological pathways with degradation of organic material of ground surface origin, and biotically mediated reactions with reduced rock minerals and with various materials expected to be present in the backfilled repository volume. In the absence of microbes most of these reactions may also follow abiotic pathways. Present day observations show that degradation of organic material is the most powerful oxygen scavenging process. At Forsmark, oxygen is generally depleted within a few metres under present day temperate conditions. Although biological activity is likely to exist also during different phases of a glaciation, large uncertainties exist regarding e.g. the population growth dynamics, the biotic reaction rates and the availability of organic material under the highly varying conditions expected. Microbial activity and degradation of organic material is therefore pessimistically neglected in the calculations in this report. In the absence of organic material, ferrous iron present in minerals in the rock

  11. SR-Site: Oxygen ingress in the rock at Forsmark during a glacial cycle

    International Nuclear Information System (INIS)

    Sidborn, Magnus; Sandstroem, Bjoern; Tullborg, Eva-Lena; Salas, Joaquin; Maia, Flavia; Delos, Anne; Molinero, Jorge; Hallbeck, Lotta; Pedersen, Karsten

    2010-11-01

    The aim of this report is to assess the possibility for oxygen to be transported by glacial melt-water to canister positions in a final repository for spent nuclear fuel at the proposed location in Forsmark. The approach for this assessment is to combine reactive transport modelling with geological observations of present and historical indications of oxygen ingress. For safety assessment purposes a cautious approach in the modelling is required when estimating the extent of oxygen ingress. In this report, a cautious approach has been applied both in the conceptualisation of the problem and in the choice of input parameters used in the models. Oxygen consuming processes are only neglected in the modelling if they are expected to further decrease the extent of oxygen ingress. Several oxygen consuming processes have been identified, each of which may play an important role in the scavenging of oxygen along recharge flow paths in the rock. These processes include biological pathways with degradation of organic material of ground surface origin, and biotically mediated reactions with reduced rock minerals and with various materials expected to be present in the backfilled repository volume. In the absence of microbes most of these reactions may also follow abiotic pathways. Present day observations show that degradation of organic material is the most powerful oxygen scavenging process. At Forsmark, oxygen is generally depleted within a few metres under present day temperate conditions. Although biological activity is likely to exist also during different phases of a glaciation, large uncertainties exist regarding e.g. the population growth dynamics, the biotic reaction rates and the availability of organic material under the highly varying conditions expected. Microbial activity and degradation of organic material is therefore pessimistically neglected in the calculations in this report. In the absence of organic material, ferrous iron present in minerals in the rock

  12. Towards identifying the active sites on RuO2(110) in catalyzing oxygen evolution  

    DEFF Research Database (Denmark)

    Rao, Reshma R.; Kolb, Manuel J.; Halck, Niels Bendtsen

    2017-01-01

    While the surface atomic structure of RuO2 has been well studied in ultra high vacuum, much less is known about the interaction between water and RuO2 in aqueous solution. In this work, in situ surface X-ray scattering measurements combined with density functional theory (DFT) were used to determ......While the surface atomic structure of RuO2 has been well studied in ultra high vacuum, much less is known about the interaction between water and RuO2 in aqueous solution. In this work, in situ surface X-ray scattering measurements combined with density functional theory (DFT) were used...... on the coordinatively unsaturated Ru sites (CUS) and hydrogen adsorbed to the bridging oxygen sites. At potentials relevant to the oxygen evolution reaction (OER), an –OO species on the Ru CUS sites was detected, which was stabilized by a neighboring –OH group on the Ru CUS or bridge site. Combining potential...

  13. Adsorption of polycyclic aromatic hydrocarbons by graphene and graphene oxide nanosheets.

    Science.gov (United States)

    Wang, Jun; Chen, Zaiming; Chen, Baoliang

    2014-05-06

    The adsorption of naphthalene, phenanthrene, and pyrene onto graphene (GNS) and graphene oxide (GO) nanosheets was investigated to probe the potential adsorptive sites and molecular mechanisms. The microstructure and morphology of GNS and GO were characterized by elemental analysis, XPS, FTIR, Raman, SEM, and TEM. Graphene displayed high affinity to the polycyclic aromatic hydrocarbons (PAHs), whereas GO adsorption was significantly reduced after oxygen-containing groups were attached to GNS surfaces. An unexpected peak was found in the curve of adsorption coefficients (Kd) with the PAH equilibrium concentrations. The hydrophobic properties and molecular sizes of the PAHs affected the adsorption of G and GO. The high affinities of the PAHs to GNS are dominated by π-π interactions to the flat surface and the sieving effect of the powerful groove regions formed by wrinkles on GNS surfaces. In contrast, the adsorptive sites of GO changed to the carboxyl groups attaching to the edges of GO because the groove regions disappeared and the polar nanosheet surfaces limited the π-π interactions. The TEM and SEM images initially revealed that after loading with PAH, the conformation and aggregation of GNS and GO nanosheets dramatically changed, which explained the observations that the potential adsorption sites of GNS and GO were unusually altered during the adsorption process.

  14. Lack of conventional oxygen-linked proton and anion binding sites does not impair allosteric regulation of oxygen binding in dwarf caiman hemoglobin

    Science.gov (United States)

    Fago, Angela; Malte, Hans; Storz, Jay F.; Gorr, Thomas A.

    2013-01-01

    In contrast to other vertebrate hemoglobins (Hbs) whose high intrinsic O2 affinities are reduced by red cell allosteric effectors (mainly protons, CO2, organic phosphates, and chloride ions), crocodilian Hbs exhibit low sensitivity to organic phosphates and high sensitivity to bicarbonate (HCO3−), which is believed to augment Hb-O2 unloading during diving and postprandial alkaline tides when blood HCO3− levels and metabolic rates increase. Examination of α- and β-globin amino acid sequences of dwarf caiman (Paleosuchus palpebrosus) revealed a unique combination of substitutions at key effector binding sites compared with other vertebrate and crocodilian Hbs: β82Lys→Gln, β143His→Val, and β146His→Tyr. These substitutions delete positive charges and, along with other distinctive changes in residue charge and polarity, may be expected to disrupt allosteric regulation of Hb-O2 affinity. Strikingly, however, P. palpebrosus Hb shows a strong Bohr effect, and marked deoxygenation-linked binding of organic phosphates (ATP and DPG) and CO2 as carbamate (contrasting with HCO3− binding in other crocodilians). Unlike other Hbs, it polymerizes to large complexes in the oxygenated state. The highly unusual properties of P. palpebrosus Hb align with a high content of His residues (potential sites for oxygenation-linked proton binding) and distinctive surface Cys residues that may form intermolecular disulfide bridges upon polymerization. On the basis of its singular properties, P. palpebrosus Hb provides a unique opportunity for studies on structure-function coupling and the evolution of compensatory mechanisms for maintaining tissue O2 delivery in Hbs that lack conventional effector-binding residues. PMID:23720132

  15. Apparent oxygen utilization rates calculated from tritium and helium-3 profiles at the Bermuda Atlantic Time-series Study site

    Directory of Open Access Journals (Sweden)

    R. H. R. Stanley

    2012-06-01

    Full Text Available We present three years of Apparent Oxygen Utilization Rates (AOUR estimated from oxygen and tracer data collected over the ocean thermocline at monthly resolution between 2003 and 2006 at the Bermuda Atlantic Time-series Study (BATS site. We estimate water ages by calculating a transit time distribution from tritium and helium-3 data. The vertically integrated AOUR over the upper 500 m, which is a regional estimate of export, during the three years is 3.1 ± 0.5 mol O2 m−2 yr−1. This is comparable to previous AOUR-based estimates of export production at the BATS site but is several times larger than export estimates derived from sediment traps or 234Th fluxes. We compare AOUR determined in this study to AOUR measured in the 1980s and show AOUR is significantly greater today than decades earlier because of changes in AOU, rather than changes in ventilation rates. The changes in AOU are likely a methodological artefact associated with problems with early oxygen measurements.

  16. Combined DFT and XPS investigation of iodine anions adsorption on the sulfur terminated (001) chalcopyrite surface

    Energy Technology Data Exchange (ETDEWEB)

    Li, Kui, E-mail: likui9606@stu.xjtu.edu.cn [School of Nuclear Science and Technology, Xi’an Jiaotong University, Xi’an 710049 (China); Zhao, Yaolin, E-mail: zhaoyaolin@mail.xjtu.edu.cn [School of Nuclear Science and Technology, Xi’an Jiaotong University, Xi’an 710049 (China); Zhang, Peng, E-mail: zp32@qq.com [Sino Shaanxi Nuclear Industry Group, Xi’an 710100 (China); He, Chaohui, E-mail: hechaohui@mail.xjtu.edu.cn [School of Nuclear Science and Technology, Xi’an Jiaotong University, Xi’an 710049 (China); Deng, Jia, E-mail: djkokocase@stu.xjtu.edu.cn [School of Nuclear Science and Technology, Xi’an Jiaotong University, Xi’an 710049 (China); Ding, Shujiang, E-mail: dingsj@mail.xjtu.edu.cn [Department of Applied Chemistry, School of Science, Xi’an Jiaotong University, Xi’an 710049 (China); Shi, Weiqun, E-mail: shiwq@ihep.ac.cn [Key Laboratory of Nuclear Radiation and Nuclear Energy Technology and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)

    2016-12-30

    Highlights: • Metal surface sites of (001)-S surface of chalcopyrite show significant chemical affinity to iodide and iodate. • The energetically favorable active site is copper for iodide adsorption and iron for iodate adsorption, respectively. • Iodate undergoes a dissociative adsorption on the copper site of chalcopyrite surface. - Abstract: The adsorption of iodine anions (iodide and iodate) on the sulfur terminated (001) chalcopyrite surface has been systematically investigated combining first-principles calculations based on density functional theory (DFT) with X-ray photoelectron spectroscopy (XPS) measurements. Based on the total energy calculations and geometric optimization, the thermodynamically preferred site was copper atom for iodide adsorption and iron atom for iodate adsorption, respectively. In the case of Cu site mode, the iodate underwent a dissociative adsorption, where one I−O bond of iodate ion was broken and the dissociative oxygen atom adsorbed on the adjacent sulphur site. Projected density of states (PDOS) analysis further clarified the interaction mechanism between active sites of chalcopyrite surface and adsorbates. In addition, full-range XPS spectra qualitatively revealed the presence of iodine on chalcopyrite surface. High resolution XPS spectra of the I 3d peaks after adsorption verified the chemical environment of iodine. The binding energies of 618.8 eV and 623.5 eV for I 3d{sub 5/2} peaks unveiled that the adsorption of iodide and iodate ions on copper-iron sulfide minerals was the result of formation of low solubility metal iodides precipitate. Also two I 3d peaks with low intensity around 618 eV and 630 eV might be related to the inorganic reduction of iodate to iodide by reducing S{sup 2−} ion of chalcopyrite.

  17. The Importance of Surface-Binding Site towards Starch-Adsorptivity Level in α-Amylase: A Review on Structural Point of View

    Directory of Open Access Journals (Sweden)

    Umi Baroroh

    2017-01-01

    Full Text Available Starch is a polymeric carbohydrate composed of glucose. As a source of energy, starch can be degraded by various amylolytic enzymes, including α-amylase. In a large-scale industry, starch processing cost is still expensive due to the requirement of high temperature during the gelatinization step. Therefore, α-amylase with raw starch digesting ability could decrease the energy cost by avoiding the high gelatinization temperature. It is known that the carbohydrate-binding module (CBM and the surface-binding site (SBS of α-amylase could facilitate the substrate binding to the enzyme’s active site to enhance the starch digestion. These sites are a noncatalytic module, which could interact with a lengthy substrate such as insoluble starch. The major interaction between these sites and the substrate is the CH/pi-stacking interaction with the glucose ring. Several mutation studies on the Halothermothrix orenii, SusG Bacteroides thetaiotamicron, Barley, Aspergillus niger, and Saccharomycopsis fibuligera α-amylases have revealed that the stacking interaction through the aromatic residues at the SBS is essential to the starch adsorption. In this review, the SBS in various α-amylases is also presented. Therefore, based on the structural point of view, SBS is suggested as an essential site in α-amylase to increase its catalytic activity, especially towards the insoluble starch.

  18. New developments for localized adsorption

    International Nuclear Information System (INIS)

    Boudh-hir, M.E.

    1989-02-01

    Using the diagrammatic expansion, new developments for localized adsorption are found. It is proved that the correlations in the system, in the absence of the attractive site potential, and the periodicity of the sites play a fundamental role in the adsorption phenomena. 14 refs, 2 figs, 2 tabs

  19. Single-Site Active Iron-Based Bifunctional Oxygen Catalyst for a Compressible and Rechargeable Zinc-Air Battery.

    Science.gov (United States)

    Ma, Longtao; Chen, Shengmei; Pei, Zengxia; Huang, Yan; Liang, Guojin; Mo, Funian; Yang, Qi; Su, Jun; Gao, Yihua; Zapien, Juan Antonio; Zhi, Chunyi

    2018-02-27

    The exploitation of a high-efficient, low-cost, and stable non-noble-metal-based catalyst with oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) simultaneously, as air electrode material for a rechargeable zinc-air battery is significantly crucial. Meanwhile, the compressible flexibility of a battery is the prerequisite of wearable or/and portable electronics. Herein, we present a strategy via single-site dispersion of an Fe-N x species on a two-dimensional (2D) highly graphitic porous nitrogen-doped carbon layer to implement superior catalytic activity toward ORR/OER (with a half-wave potential of 0.86 V for ORR and an overpotential of 390 mV at 10 mA·cm -2 for OER) in an alkaline medium. Furthermore, an elastic polyacrylamide hydrogel based electrolyte with the capability to retain great elasticity even under a highly corrosive alkaline environment is utilized to develop a solid-state compressible and rechargeable zinc-air battery. The creatively developed battery has a low charge-discharge voltage gap (0.78 V at 5 mA·cm -2 ) and large power density (118 mW·cm -2 ). It could be compressed up to 54% strain and bent up to 90° without charge/discharge performance and output power degradation. Our results reveal that single-site dispersion of catalytic active sites on a porous support for a bifunctional oxygen catalyst as cathode integrating a specially designed elastic electrolyte is a feasible strategy for fabricating efficient compressible and rechargeable zinc-air batteries, which could enlighten the design and development of other functional electronic devices.

  20. Effect of high perioperative oxygen fraction on surgical site infection and pulmonary complications after abdominal surgery: the PROXI randomized clinical trial

    DEFF Research Database (Denmark)

    Meyhoff, Christian S; Wetterslev, Jørn; Jorgensen, Lars N

    2009-01-01

    Control and Prevention. Secondary outcomes included atelectasis, pneumonia, respiratory failure, and mortality. RESULTS: Surgical site infection occurred in 131 of 685 patients (19.1%) assigned to receive 80% oxygen vs 141 of 701 (20.1%) assigned to receive 30% oxygen (odds ratio [OR], 0.94; 95...

  1. An experimental and theoretical approach on the effect of presence of oxygen in milled graphite as lithium storage material

    International Nuclear Information System (INIS)

    Robledo, C.B.; Thomas, J.E.; Luque, G.; Leiva, E.P.M.; Cámara, O.; Barraco, D.; Visintin, A.

    2014-01-01

    The effect of milling time on the morphology of graphite is characterized by XRD, SEM, BET, FTIR and XPS and the electrochemical response of the resulting materials upon lithium-ion absorption is analyzed using different techniques. As milling time is increased, the particle size diminishes and the amount of oxygen content increases. Concomitantly, the capacity for lithium adsorption also increases because new adsorption sites become available due to more surface area and oxygen functional groups. These effects are interpreted using first-principles calculations, which show that the presence of oxygenated species promotes lithium adsorption at higher potentials. This capacity increase is probably not relevant for lithium-ion batteries since there is no intercalation process but rather an adsorption one, but may be of interest for supercapacitive applications. Diffusion coefficients of lithium for different graphite particle sizes are evaluated. The effects of diffusion, particle size and oxygen content are discussed

  2. Oxygen Sorption and Desorption Properties of Selected Lanthanum Manganites and Lanthanum Ferrite Manganites

    DEFF Research Database (Denmark)

    Nielsen, Jimmi; Skou, Eivind M.; Jacobsen, Torben

    2015-01-01

    Temperature‐programmed desorption (TPD) with a carrier gas was used to study the oxygen sorption and desorption properties of oxidation catalysts and solid‐oxide fuel cell (SOFC) cathode materials (La0.85Sr0.15)0.95MnO3+δ (LSM) and La0.60Sr0.40Fe0.80Mn0.20O3‐δ (LSFM). The powders were characterized...... by X‐ray diffractometry, atomic force microscopy (AFM), and BET surface adsorption. Sorbed oxygen could be distinguished from oxygen originating from stoichiometry changes. The results indicated that there is one main site for oxygen sorption/desorption. The amount of sorbed oxygen was monitored over...... time at different temperatures. Furthermore, through data analysis it was shown that the desorption peak associated with oxygen sorption is described well by second‐order desorption kinetics. This indicates that oxygen molecules dissociate upon adsorption and that the rate‐determining step...

  3. The New World Health Organization Recommendations on Perioperative Administration of Oxygen to Prevent Surgical Site Infections: A Dangerous Reductionist Approach?

    Science.gov (United States)

    Wenk, Manuel; Van Aken, Hugo; Zarbock, Alexander

    2017-08-01

    In October 2016, the World Health Organization (WHO) published recommendations for preventing surgical site infections (SSIs). Among those measures is a recommendation to administer oxygen at an inspired fraction of 80% intra- and postoperatively for up to 6 hours. SSIs have been identified as a global health problem, and the WHO should be commended for their efforts. However, this recommendation focuses only on the patient's "wound," ignores other organ systems potentially affected by hyperoxia, and may ultimately worsen patient outcomes.The WHO advances a "strong recommendation" for the use of a high inspired oxygen fraction even though the quality of evidence is only moderate. However, achieving this goal by disregarding other potentially lethal complications seems inappropriate, particularly in light of the weak evidence underpinning the use of high fractions of oxygen to prevent SSI. Use of such a strategy thus should be intensely discussed by anesthesiologists and perioperative physicians.Normovolemia, normotension, normoglycemia, normothermia, and normoventilation can clearly be safely applied to most patients in most clinical scenarios. But the liberal application of hyperoxemia intraoperatively and up to 6 hours postoperatively, as suggested by the WHO, is questionable from the viewpoint of anesthesia and perioperative medicine, and its effects will be discussed in this article.

  4. Mutations at the Qo-Site of the Cytochrome bc1 Complex Strongly Affect Oxygen Binding

    DEFF Research Database (Denmark)

    Husen, Peter; Solov'yov, Ilia A

    2017-01-01

    The homodimeric bc1 protein complex is embedded in membranes of mitochondria and photosynthetic bacteria, where it transports protons across the membrane to maintain an electrostatic potential used to drive ATP synthesis as part of the respiratory or photosynthetic pathways. The reaction cycle...... at the Qo-sites, and, moreover, different behavior of the two monomers of the bc1 complex is observed. The conformational differences at the Qo-sites of the two monomers are studied in detail and discussed. The anionic form of semiquinone was identified as leading to the greatest opportunity for side...

  5. Electrochemical probing into the active sites of graphitic-layer encapsulated iron oxygen reduction reaction electrocatalysts

    DEFF Research Database (Denmark)

    Zhong, Lijie; Jensen, Jens Oluf; Cleemann, Lars Nilausen

    2018-01-01

    is still unclear compared with the well-recognized surface coordinated FeNx/C structure. Using the strong complexing effect of the iron component with anions, cyanide (CN−) in alkaline and thiocyanate (SCN−) in acidic media, the metal containing active sites are electrochemically probed. Three...

  6. The effect of entrainment site and inspiratory pressure on the delivery of oxygen therapy during non-invasive mechanical ventilation (NIMV in acute COPD patients

    Directory of Open Access Journals (Sweden)

    Sundeep Kaul

    2006-12-01

    Full Text Available Supplemental O2 is frequently added to bi-level non-invasive ventilation circuits to maintain Sa,O2 >90%. Oxygen can be added at several points & in the presence of different inspiratory pressures. The effect of varying entrainment sites and inspiratory pressures (IPAP on PO2, PCO2, Fio2, inspiratory triggering and expiratory triggering in COPD patients is unknown. 18 patients with stable COPD (mean FEV1 47% participated in the study. Oxygen was added at 4 sites in the ventilatory circuit (site 1: between mask and exhalation port; site 2: just distal to exhalation port; site 3: at ventilator outlet; site 4: directly into the mask via an inlet. The effect of varying entrainment sites and inspiratory pressures on arterial PO2, PCO2, FIO2, was recorded at 3 mins. The same full face mask (Respironics, Image 3 & ventilator (Respironics, BIPAP ST 30 was used.

  7. The impact of moisture sources on the oxygen isotope composition of precipitation at a continental site in central Europe

    Science.gov (United States)

    Krklec, Kristina; Domínguez-Villar, David; Lojen, Sonja

    2018-06-01

    The stable isotope composition of precipitation records processes taking place within the hydrological cycle. Potentially, moisture sources are important controls on the stable isotope composition of precipitation, but studies focused on this topic are still scarce. We studied the moisture sources contributing to precipitation at Postojna (Slovenia) from 2009 to 2013. Back trajectory analyses were computed for the days with precipitation at Postojna. The moisture uptake locations were identified along these trajectories using standard hydrometeorological formulation. The moisture uptake locations were integrated in eight source regions to facilitate its comparison to the monthly oxygen isotope composition (δ18O values) of precipitation. Nearly half of the precipitation originated from continental sources (recycled moisture), and >40% was from central and western Mediterranean. Results show that moisture sources do not have a significant impact on the oxygen isotope composition at this site. We suggest that the large proportion of recycled moisture originated from transpiration rather than evaporation, which produced water vapour with less negative δ18O values. Thus the difference between the oceanic and local vapour source was reduced, which prevented the distinction of the moisture sources based on their oxygen isotope signature. Nevertheless, δ18O values of precipitation are partially controlled by climate parameters, which is of major importance for paleoclimate studies. We found that the main climate control on Postojna δ18O values of precipitation is the surface temperature. Amount effect was not recorded at this site, and the winter North Atlantic Oscillation (NAO) does not impact the δ18O values of precipitation. The Western Mediterranean Oscillation (WeMO) was correlated to oxygen stable isotope composition, although this atmospheric pattern was not a control. Instead we found that the link to δ18O values results from synoptic scenarios affecting We

  8. Crystal Structures, Surface Stability, and Water Adsorption Energies of La-Bastnäsite via Density Functional Theory and Experimental Studies

    Energy Technology Data Exchange (ETDEWEB)

    Srinivasan, Sriram Goverapet [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Shivaramaiah, Radha [Univ. of California, Davis, CA (United States); Kent, Paul R. C. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Stack, Andrew G. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Navrotsky, Alexandra [Univ. of California, Davis, CA (United States); Riman, Richard [State Univ. of New Jersey, Piscataway, NJ (United States); Anderko, Andre [OLI Systems, Inc., Cedar Knolls, NJ (United States); Bryantsev, Vyacheslav S. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2016-07-11

    Bastnasite is a fluoro-carbonate mineral that is the largest source of rare earth elements such as Y, La and Ce. With increasing demand for REE in many emerging technologies, there is an urgent need for improving the efficiency of ore beneficiation by froth flotation. In order to design improved flotation agents that can selectively bind to the mineral surface, a fundamental understanding of the bulk and surface properties of bastnasite is essential. Density functional theory calculations using the PBEsol exchange correlation functional and the DFT-D3 dispersion correction reveal that the most stable form of La bastnsite is isomorphic to the structure of Ce bastnasite belonging to the P2c space group, while the Inorganic Crystal Structure Database structure in the P2m space group is ca. 11.3 kJ/mol higher in energy per LaFCO3 formula unit. We report powder X-ray diffraction measurements on synthetic of La bastnasite to support these theoretical findings. Six different surfaces are studied by DFT, namely [100], [0001], [101], [102], [104] and [112]. Among these, the [100] surface is the most stable with a surface energy of 0.73 J/m2 in vacuum and 0.45 J/m2 in aqueous solution. We predicted the shape of a La bastnasite nanoparticle via thermodynamic Wulff construction to be a hexagonal prism with [100] and [0001] facets, chiseled at its ends by the [101] and [102] facets. The average surface energy of the nanoparticle in the gas phase is estimated to be 0.86 J/m2, in good agreement with a value of 1.11 J/m2 measured by calorimetry. The calculated adsorption energy of a water molecule varies widely with the surface plane and specific adsorption sites on a given surface. Moreover, the first layer of water molecules is predicted to adsorb strongly on the La-bastnasite surface, in agreement with water adsorption calorimetry experiments. Our work provides an important step towards a detailed atomistic understanding of

  9. Adsorption site and structure determination of c(2x2) N{sub 2}/Ni(100) using angle-resolved photoemission extended fine structure

    Energy Technology Data Exchange (ETDEWEB)

    Moler, E.J.; Kellar, S.A.; Huff, W.R.A. [Lawrence Berkeley National Lab., CA (United States)] [and others

    1997-04-01

    The authors have determined the atomic spatial structure of c(2x2) N2Ni(100) with Angle-Resolved Photoemission Extended Fine Structure (ARPEFS) from the nitrogen 1s core level using monochromatized x-rays from beamline 6.1 at SSRL and beamline 9.3.2 at the ALS. The chemically shifted N 1s peak intensities were summed together to obtain ARPEFS curves for both nitrogen atoms in the molecule. They used a new, highly-optimized program based on the Rehr-Albers scattering matrix formalism to find the adsorption site and to quantitatively determine the bond-lengths. The nitrogen molecule stands upright at an atop site, with a N-Ni bond length of 2.25(1) {angstrom}, a N-N bond length of 1.10(7) {angstrom}, and a first layer Ni-Ni spacing of 1.76(4) {angstrom}. The shake-up peak shows an identical ARPEFS diffraction pattern, confirming its intrinsic nature and supporting a previous use of this feature to decompose the peak into contributions from the chemically inequivalent nitrogen atoms. Comparison to a previously published theoretical treatment of N-N-Ni and experimental structures of analogous adsorbate systems demonstrates the importance of adsorbate-adsorbate interactions in weakly chemisorbed systems.

  10. Evaluation of adsorption and Fenton-adsorption processes for landfill leachate treatment

    OpenAIRE

    San Pedro-Cedillo, L.; Méndez-Novelo, R.I.; Rojas-Valencia, M.N.; Barceló-Quintal, M.; Castillo-Borges, E.R.; Sauri-Riancho, M.R.; Marrufo-Gómez, J.M.

    2015-01-01

    The objective of this research was to compare the adsorption and Fenton-adsorption treatments for the removal of contaminants in leachate from landfills and thus determine the most efficient one. The adsorption process with granular activated carbon was tested in two types of samples: raw leachate and leachate treated by Fenton. The results showed color, chemical oxygen demand (COD), total nitrogen and total organic carbon (TOC) removal rates higher than 99% through the Fenton-adsorption proc...

  11. Adsorption characteristics of N-nitrosodimethylamine from aqueous solution on surface-modified activated carbons

    Energy Technology Data Exchange (ETDEWEB)

    Xiaodong, Dai [Chemistry and Chemical Engineering School, China University of Petroleum, Dongying 257061, Shandong (China); Institute for Sustainability and Innovation, Victoria University, Melbourne, VIC 8001 (Australia); Zou, Linda [SA Water Centre for Water Management and Reuse, University of South Australia, Adelaide, SA5095 (Australia); Zifeng, Yan [Chemistry and Chemical Engineering School, China University of Petroleum, Dongying 257061, Shandong (China); Millikan, Mary [Institute for Sustainability and Innovation, Victoria University, Melbourne, VIC 8001 (Australia)

    2009-08-30

    This study investigated the removal of N-nitrosodimethylamine (NDMA) by an adsorption mechanism using commercially available activated carbons and surface-modified activated carbons. The effects of the modification on the properties of the activated carbon were studied by N{sub 2} adsorption/desorption, Diffuse Reflectance Infrared Fourier Transmission (DRIFT) analysis and X-Ray Photoelectron Spectroscopy (XPS). Adsorption experiments revealed that the activated carbons demonstrated a greater capacity for NDMA adsorption capacity than can be achieved using zeolite. The equilibrium data was fitted to the Freundlich equation and it was found that the adsorption capacity was significantly influenced by the micropore size, relative pore volume and surface characteristics. Adsorption experiments were conducted using unmodified and modified activated carbons. The results indicated that the adsorption capacity of NDMA can be significantly improved by heat treatment and doping of TiO{sub 2} particles. This was because the surface treatments yielded more hydrophobic sites and fewer oxygen-containing surface functional groups, and consequently an increased capacity for NDMA adsorption.

  12. Adsorption characteristics of N-nitrosodimethylamine from aqueous solution on surface-modified activated carbons

    International Nuclear Information System (INIS)

    Dai Xiaodong; Zou, Linda; Yan Zifeng; Millikan, Mary

    2009-01-01

    This study investigated the removal of N-nitrosodimethylamine (NDMA) by an adsorption mechanism using commercially available activated carbons and surface-modified activated carbons. The effects of the modification on the properties of the activated carbon were studied by N 2 adsorption/desorption, Diffuse Reflectance Infrared Fourier Transmission (DRIFT) analysis and X-Ray Photoelectron Spectroscopy (XPS). Adsorption experiments revealed that the activated carbons demonstrated a greater capacity for NDMA adsorption capacity than can be achieved using zeolite. The equilibrium data was fitted to the Freundlich equation and it was found that the adsorption capacity was significantly influenced by the micropore size, relative pore volume and surface characteristics. Adsorption experiments were conducted using unmodified and modified activated carbons. The results indicated that the adsorption capacity of NDMA can be significantly improved by heat treatment and doping of TiO 2 particles. This was because the surface treatments yielded more hydrophobic sites and fewer oxygen-containing surface functional groups, and consequently an increased capacity for NDMA adsorption.

  13. Adsorption and activation of methane and methanol on Pt(100) surface: a density functional study

    International Nuclear Information System (INIS)

    Moussounda, P.S.

    2006-11-01

    The activation of methane (CH 4 ) and methanol (CH 3 OH) on Pt(100) surface has been investigated using density functional theory calculations based on plane-wave basis and pseudo-potential. We optimised CH 4 /Pt(100) system. The calculated adsorption energies over the top, bridge and hollow sites are small, weakly dependent on the molecular orientation. The nature of the CH 4 -Pt interaction was examined through the electronic structure changes. The adsorption of methyl (CH 3 ) and hydrogen (H) and the co-adsorption of CH 3 +H were also calculated. From these results, we examined the dissociation of CH 4 to CH 3 +H, and the activation energies found are in good agreement with the experimental and theoretical values. The activation of CH 3 OH/Pt(100) has been studied. All the sites have almost the same adsorption energy. The adsorption of oxygen (O) and the co-adsorption of CH 4 and O were also examined. In addition, the formation of CH 3 OH assuming a one-step mechanism step via the co-adsorption of CH 4 +O has been studied and the barrier height was found to be high. (authors)

  14. Reactive adsorption of SO2 on activated carbons with deposited iron nanoparticles.

    Science.gov (United States)

    Arcibar-Orozco, Javier A; Rangel-Mendez, J Rene; Bandosz, Teresa J

    2013-02-15

    The effect of iron particle size anchored on the surface of commercial activated carbon on the removal of SO(2) from a gas phase was studied. Nanosize iron particles were deposited using forced hydrolysis of FeCl(3) with or without H(3)PO(4) as a capping agent. Dynamic adsorption experiments were carried out on either dry or pre-humidified materials and the adsorption capacities were calculated. The surface of the initial and exhausted materials was extensively characterized by microscopic, porosity, thermogravimetric and surface chemistry. The results indicate that the SO(2) adsorption capacity increased two and half times after the prehumidification process owing to the formation of H(2)SO(4) in the porous system. Iron species enhance the SO(2) adsorption capacity only when very small nanoparticles are deposited on the pore walls as a thin layer. Large iron nanoparticles block the ultramicropores decreasing the accessibility of the active sites and consuming oxygen that rest adsorption centers for SO(2) molecules. Iron nanoparticles of about 3-4 nm provide highly dispersed adsorption sites for SO(2) molecules and thus increase the adsorption capacity of about 80%. Fe(2)(SO(4))(3) was detected on the surface of exhausted samples. Copyright © 2012 Elsevier B.V. All rights reserved.

  15. Establishing efficient cobalt based catalytic sites for oxygen evolution on a Ta3N5 photocatalyst

    KAUST Repository

    Nurlaela, Ela; Ould-Chikh, Samy; Llorens, Isabelle; Hazemann, Jean-louis; Takanabe, Kazuhiro

    2015-01-01

    In a photocatalytic suspension system with a powder semiconductor, the interface between the photocatalyst semiconductor and catalyst should be constructed to minimize resistance for charge transfer of excited carriers. This study demonstrates an in-depth understanding of pretreatment effects on the photocatalytic O2 evolution reaction (OER) activity of visible-light-responsive Ta3N5 decorated with CoOx nanoparticles. The CoOx/Ta3N5 sample was synthesized by impregnation followed by sequential heat treat-ments under NH3 flow and air flow at various temperatures. Various characterization techniques, including X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), scanning transmission electron microscopy (STEM), and X-ray photoelectron spec-troscopy (XPS), were used to clarify the state and role of cobalt. No improvement in photocatalytic activity for OER over the bare Ta3N5 was observed for the as-impregnated CoOx/Ta3N5, likely because of insufficient contact between CoOx and Ta3N5. When the sample was treated in NH3 at high temperature, a substantial improvement in the photocatalytic activity was observed. After NH3 treatment at 700 °C, the Co0-CoOx core-shell agglomerated cobalt structure was identified by XAS and STEM. No metallic cobalt species was evident after the photocatalytic OER, indicating that the metallic cobalt itself is not essential for the reaction. Accordingly, mild oxidation (200 °C) of the NH3-treated CoOx/Ta3N5 sample enhanced photocatalytic OER activity. Oxidation at higher temperatures drastically eliminated the photocatalytic activity, most likely because of unfavorable Ta3N5 oxidation. These results suggest that the intimate contact between cobalt species and Ta3N5 facilitated at high temperature is beneficial to enhancing hole transport and that the cobalt oxide provides electrocatalytic sites for OER.

  16. Establishing efficient cobalt based catalytic sites for oxygen evolution on a Ta3N5 photocatalyst

    KAUST Repository

    Nurlaela, Ela

    2015-08-05

    In a photocatalytic suspension system with a powder semiconductor, the interface between the photocatalyst semiconductor and catalyst should be constructed to minimize resistance for charge transfer of excited carriers. This study demonstrates an in-depth understanding of pretreatment effects on the photocatalytic O2 evolution reaction (OER) activity of visible-light-responsive Ta3N5 decorated with CoOx nanoparticles. The CoOx/Ta3N5 sample was synthesized by impregnation followed by sequential heat treat-ments under NH3 flow and air flow at various temperatures. Various characterization techniques, including X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), scanning transmission electron microscopy (STEM), and X-ray photoelectron spec-troscopy (XPS), were used to clarify the state and role of cobalt. No improvement in photocatalytic activity for OER over the bare Ta3N5 was observed for the as-impregnated CoOx/Ta3N5, likely because of insufficient contact between CoOx and Ta3N5. When the sample was treated in NH3 at high temperature, a substantial improvement in the photocatalytic activity was observed. After NH3 treatment at 700 °C, the Co0-CoOx core-shell agglomerated cobalt structure was identified by XAS and STEM. No metallic cobalt species was evident after the photocatalytic OER, indicating that the metallic cobalt itself is not essential for the reaction. Accordingly, mild oxidation (200 °C) of the NH3-treated CoOx/Ta3N5 sample enhanced photocatalytic OER activity. Oxidation at higher temperatures drastically eliminated the photocatalytic activity, most likely because of unfavorable Ta3N5 oxidation. These results suggest that the intimate contact between cobalt species and Ta3N5 facilitated at high temperature is beneficial to enhancing hole transport and that the cobalt oxide provides electrocatalytic sites for OER.

  17. Copper adsorption in tropical oxisols

    Directory of Open Access Journals (Sweden)

    Silveira Maria Lucia Azevedo

    2003-01-01

    Full Text Available Cu adsorption, at concentrations between 0 to 800 mg L-1, was evaluated in surface and subsurface samples of three Brazilian soils: a heavy clayey-textured Rhodic Hapludalf (RH, a heavy clayey-textured Anionic ''Rhodic'' Acrudox (RA and a medium-textured Anionic ''Xanthic'' Acrudox (XA. After adsorption, two consecutive extractions were performed to the samples which received 100 mg L-1 copper. Surface samples adsorbed higher amounts of Cu than the subsurface, and exhibited lower Cu removed after the extractions, reinforcing the influence of the organic matter in the reactions. Cu adsorption was significant in the subsurface horizons of the Oxisols, despite the positive balance of charge, demonstrating the existence of mechanisms for specific adsorption, mainly related to the predominance of iron and aluminum oxides in the mineral fractions. In these samples, Cu was easily removed from the adsorption sites. RH demonstrated a higher capacity for the Cu adsorption in both horizons.

  18. From 3D to 2D Co and Ni Oxyhydroxide Catalysts: Elucidation of the Active Site and Influence of Doping on the Oxygen Evolution Activity

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Hansen, Heine Anton; Vegge, Tejs

    2017-01-01

    Layered oxyhydroxides (ox-hys) of Ni and Co are among the most active catalysts for oxygen evolution in alkaline media. Their activities can be further tuned by delamination into single-layer oxide sheets or by means of doping. The active site for the reaction and how doping and delamination...... investigate the role of terrace and edge sites and use stability, catalytic activity, and electronic conductivity as evaluation criteria to pinpoint the best catalysts. We arrive at several important conclusions: the ox-hy surface is fully oxidized under oxygen evolution conditions, bulk terraces...

  19. Adsorption of ethanol on V2O5 (010) surface for gas-sensing applications: Ab initio investigation

    International Nuclear Information System (INIS)

    Qin, Yuxiang; Cui, Mengyang; Ye, Zhenhua

    2016-01-01

    Highlights: • Ethanol adsorbed on V 2 O 5 (010) surface was investigated by ab initio calculations. • Ethanol prefers to adsorb on “Hill”-like surface, rather than“Valley”-like region. • Surface O 1(H) site plays a key role to dominate the ethanol adsorption process. • Sensing mechanism is related with electronic structure and electron redistribution. • Gas sensitivity is reflected by quantitative electron population analysis. - Abstract: The adsorption of ethanol on V 2 O 5 (010) surface was investigated by means of density functional theory (DFT) with a combined generalized gradient approximation (GGA) plus Hubbard U approach to exploit the potential sensing applications. The adsorption configurations were first constructed by considering different orientations of ethanol molecule to V and O sites on the “Hill”- and “Valley”-like regions of corrugated (010) surface. It is found that ethanol molecule can adsorb on whole surface in multiple stable configurations. Nevertheless the molecular adsorption on the “Hill”-like surface is calculated to occur preferentially, and the single coordinated oxygen on “Hill”-like surface (O 1(H) ) acting as the most energetically favorable adsorption site shows the strongest adsorption ability to ethanol molecule. Surface adsorption of ethanol tunes the electronic structure of V 2 O 5 and cause an n-doping effect. As a consequence, the Fermi levels shift toward the conductive bond increasing the charge carrier concentration of electrons in adsorbed V 2 O 5 . The sensitive electronic structure and the multiple stable configurations to ethanol adsorption highlight the high adsorption activity and then the potential of V 2 O 5 (010) surface applied to high sensitive sensor for ethanol vapor detection. Further Mulliken population and Natural bond orbital (NBO) calculations quantify the electron transfer from the adsorbed ethanol to the surface, and correlates the adsorption ability of surface sites

  20. Calcium-manganese oxides as structural and functional models for active site in oxygen evolving complex in photosystem II: lessons from simple models.

    Science.gov (United States)

    Najafpour, Mohammad Mahdi

    2011-01-01

    The oxygen evolving complex in photosystem II which induces the oxidation of water to dioxygen in plants, algae and certain bacteria contains a cluster of one calcium and four manganese ions. It serves as a model to split water by sunlight. Reports on the mechanism and structure of photosystem II provide a more detailed architecture of the oxygen evolving complex and the surrounding amino acids. One challenge in this field is the development of artificial model compounds to study oxygen evolution reaction outside the complicated environment of the enzyme. Calcium-manganese oxides as structural and functional models for the active site of photosystem II are explained and reviewed in this paper. Because of related structures of these calcium-manganese oxides and the catalytic centers of active site of the oxygen evolving complex of photosystem II, the study may help to understand more about mechanism of oxygen evolution by the oxygen evolving complex of photosystem II. Copyright © 2010 Elsevier B.V. All rights reserved.

  1. Kinetic Study of Oxygen Adsorption over Nanosized Au/γ-Al2O3 Supported Catalysts under Selective CO Oxidation Conditions

    Directory of Open Access Journals (Sweden)

    George Karaiskakis

    2012-04-01

    Full Text Available O2 adsorption is a key process for further understanding the mechanism of selective CO oxidation (SCO on gold catalysts. Rate constants related to the elementary steps of O2 adsorption, desorption and surface bonding, as well as the respective activation energies, over a nanosized Au/γ-Al2O3 catalyst, were determined by Reversed-Flow Inverse Gas Chromatography (RF-IGC. The present study, carried-out in a wide temperature range (50–300 °C, both in excess as well as in the absence of H2, resulted in mechanistic insights and kinetic as well as energetic comparisons, on the sorption processes of SCO reactants. In the absence of H2, the rate of O2 binding, over Au/γ-Al2O3, drastically changes with rising temperature, indicating possible O2 dissociation at elevated temperatures. H2 facilitates stronger O2 bonding at higher temperatures, while low temperature binding remains practically unaffected. The lower energy barriers observed, under H2 rich conditions, can be correlated to O2 dissociation after hydrogenation. Although, H2 enhances both selective CO reactant’s desorption, O2 desorption is more favored than that of CO, in agreement with the well-known mild bonding of SCO reactant’s at lower temperatures. The experimentally observed drastic change in the strength of CO and O2 binding is consistent both with well-known high activity of SCO at ambient temperatures, as well as with the loss of selectivity at higher temperatures.

  2. Kinetic Study of Oxygen Adsorption over Nanosized Au/γ-Al2O3 Supported Catalysts under Selective CO Oxidation Conditions

    Directory of Open Access Journals (Sweden)

    George Karaiskakis

    2012-04-01

    Full Text Available O2 adsorption is a key process for further understanding the mechanism of selective CO oxidation (SCO on gold catalysts. Rate constants related to the elementary steps of O2 adsorption, desorption and surface bonding, as well as the respective activation energies, over a nanosized Au/γ-Al2O3 catalyst, were determined by Reversed-Flow Inverse Gas Chromatography (RF-IGC. The present study, carried-out in a wide temperature range (50–300 °C, both in excess as well as in the absence of H2, resulted in mechanistic insights and kinetic as well as energetic comparisons, on the sorption processes of SCO reactants. In the absence of H2, the rate of O2 binding, over Au/γ-Al2O3, drastically changes with rising temperature, indicating possible O2 dissociation at elevated temperatures. H2 facilitates stronger O2 bonding at higher temperatures, while low temperature binding remains practically unaffected. The lower energy barriers observed, under H2 rich conditions, can be correlated to O2 dissociation after hydrogenation. Although, H2 enhances both selective CO reactant’s desorption, O2 desorption is more favored than that of CO, in agreement with the well-known mild bonding of SCO reactant’s at lower temperatures. The experimentally observed drastic change in the strength of CO and O2 binding is consistent both with well-known high activity of SCO at ambient temperatures, as well as with the loss of selectivity at higher temperatures.

  3. Oxygen enriched combustion system performance study. Phase 2: 100 percent oxygen enriched combustion in regenerative glass melters, Final report

    Energy Technology Data Exchange (ETDEWEB)

    Tuson, G.B.; Kobayashi, H.; Campbell, M.J.

    1994-08-01

    The field test project described in this report was conducted to evaluate the energy and environmental performance of 100% oxygen enriched combustion (100% OEC) in regenerative glass melters. Additional objectives were to determine other impacts of 100% OEC on melter operation and glass quality, and to verify on a commercial scale that an on-site Pressure Swing Adsorption oxygen plant can reliably supply oxygen for glass melting with low electrical power consumption. The tests constituted Phase 2 of a cooperative project between the United States Department of Energy, and Praxair, Inc. Phase 1 of the project involved market and technical feasibility assessments of oxygen enriched combustion for a range of high temperature industrial heating applications. An assessment of oxygen supply options for these applications was also performed during Phase 1, which included performance evaluation of a pilot scale 1 ton per day PSA oxygen plant. Two regenerative container glass melters were converted to 100% OEC operation and served as host sites for Phase 2. A 75 ton per day end-fired melter at Carr-Lowrey Glass Company in Baltimore, Maryland, was temporarily converted to 100% OEC in mid- 1990. A 350 tpd cross-fired melter at Gallo Glass Company in Modesto, California was rebuilt for permanent commercial operation with 100% OEC in mid-1991. Initially, both of these melters were supplied with oxygen from liquid storage. Subsequently, in late 1992, a Pressure Swing Adsorption oxygen plant was installed at Gallo to supply oxygen for 100% OEC glass melting. The particular PSA plant design used at Gallo achieves maximum efficiency by cycling the adsorbent beds between pressurized and evacuated states, and is therefore referred to as a Vacuum/Pressure Swing Adsorption (VPSA) plant.

  4. Novel Phosphorylation and Ubiquitination Sites Regulate Reactive Oxygen Species-dependent Degradation of Anti-apoptotic c-FLIP Protein*

    Science.gov (United States)

    Wilkie-Grantham, Rachel P.; Matsuzawa, Shu-Ichi; Reed, John C.

    2013-01-01

    The cytosolic protein c-FLIP (cellular Fas-associated death domain-like interleukin 1β-converting enzyme inhibitory protein) is an inhibitor of death receptor-mediated apoptosis that is up-regulated in a variety of cancers, contributing to apoptosis resistance. Several compounds found to restore sensitivity of cancer cells to TRAIL, a TNF family death ligand with promising therapeutic potential, act by targeting c-FLIP ubiquitination and degradation by the proteasome. The generation of reactive oxygen species (ROS) has been implicated in c-FLIP protein degradation. However, the mechanism by which ROS post-transcriptionally regulate c-FLIP protein levels is not well understood. We show here that treatment of prostate cancer PPC-1 cells with the superoxide generators menadione, paraquat, or buthionine sulfoximine down-regulates c-FLIP long (c-FLIPL) protein levels, which is prevented by the proteasome inhibitor MG132. Furthermore, pretreatment of PPC-1 cells with a ROS scavenger prevented ubiquitination and loss of c-FLIPL protein induced by menadione or paraquat. We identified lysine 167 as a novel ubiquitination site of c-FLIPL important for ROS-dependent degradation. We also identified threonine 166 as a novel phosphorylation site and demonstrate that Thr-166 phosphorylation is required for ROS-induced Lys-167 ubiquitination. The mutation of either Thr-166 or Lys-167 was sufficient to stabilize c-FLIP protein levels in PPC-1, HEK293T, and HeLa cancer cells treated with menadione or paraquat. Accordingly, expression of c-FLIP T166A or K167R mutants protected cells from ROS-mediated sensitization to TRAIL-induced cell death. Our findings reveal novel ROS-dependent post-translational modifications of the c-FLIP protein that regulate its stability, thus impacting sensitivity of cancer cells to TRAIL. PMID:23519470

  5. Understanding cation ordering and oxygen vacancy site preference in Ba3CaNb2O9 from first-principles

    Science.gov (United States)

    Ding, Hepeng; Virkar, Anil; Liu, Feng

    2014-03-01

    We investigate the physical mechanism underlying the formation of the B-site cation ordering and the oxygen vacancy site selection in Ba3CaNb2O9 using density functional theory calculations. We found that either cation site exchange or oxygen vacancy formation induces negligible lattice strain. This implies that the ionic radius plays an insignificant role in governing these two processes. Furthermore, the electrostatic interactions are found dominant in the ordering of mixed valence species on one or more sites, the ionic bond strength is identified as the dominant force in governing both the 1:2 B-site cation ordering along the direction and the oxygen vacancy site preference in Ba3CaNb2O9. Specifically, the cation ordering can be rationalized by the increased mixing bonding energy of the Ca-O-Nb bonds over the Ca-O-Ca and Nb-O-Nb bonds, i.e., 1/2(Ca-O-Ca + Nb-O-Nb) Grant Number DE-SC0001061 as a flow through from the University of South Carolina.

  6. Numerical evaluation of Cs adsorption in PB column by extended Langmuir formula and one-dimensional adsorption model

    International Nuclear Information System (INIS)

    Hiroshi Ogawa; Akiko Kitajima; Hisashi Tanaka; Tohru Kawamoto

    2015-01-01

    Adsorption property of granulated Prussian blue adsorbent on radioactive cesium was evaluated for efficient decontamination in Fukushima area. The adsorbent was found to show an inflective adsorption isotherm, which was expressed by extended Langmuir formula with three adsorption sites. Adsorption speeds of each site were evaluated by time-dependent batch experiment. The simulation using derived parameters and one-dimensional adsorption model successfully reproduced the experimental data of cesium decontamination by small and large columns. (author)

  7. High coverage hydrogen adsorption on the Fe{sub 3}O{sub 4}(1 1 0) surface

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Xiaohu, E-mail: yuxiaohu950203@126.com [College of Physics and Electrical Engineering, Anyang Normal University, Anyang, Henan 455000 (China); State Key laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001 (China); Zhang, Xuemei [College of Physics and Electrical Engineering, Anyang Normal University, Anyang, Henan 455000 (China); Wang, Shengguang [State Key laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001 (China); Synfuels China Co., Ltd., Huairou, Beijing 101407 (China)

    2015-10-30

    Graphical abstract: - Highlights: • Hydrogen adsorption on the A and B termination layers of the Fe{sub 3}O{sub 4}(1 1 0) surface at different coverage has been studied by DFT + U method. • The adsorption of hydrogen prefers surface oxygen atoms on both Fe{sub 3}O{sub 4}(1 1 0) surface layers. • The more stable A layer has stronger adsorption energy than the less stable B layer. • The saturation coverage has two dissociatively adsorbed H{sub 2} on the A layer, and one dissociatively adsorbed H{sub 2} on the B layer. - Abstract: Hydrogen adsorption on the A and B termination layers of the Fe{sub 3}O{sub 4}(1 1 0) surface at different coverage has been systematically studied by density functional theory calculations including an on-site Hubbard term (GGA + U). The adsorption of hydrogen prefers surface oxygen atoms on both layers. The more stable A layer has stronger adsorption energy than the less stable B layer. The saturation coverage has two dissociatively adsorbed H{sub 2} on the A layer, and one dissociatively adsorbed H{sub 2} on the B layer. The adsorption mechanism has been analyzed on the basis of projected density of states (PDOS).

  8. Insights into the importance of oxygen functional groups in carbon reactions with oxygen containing gases

    International Nuclear Information System (INIS)

    John Zhu, Max Lu

    2005-01-01

    The role of pore structure of carbon in carbon-related adsorptions and reactions has been extensively investigated. However the studies on the role of surface chemistry of carbon are limited. In this paper, we present the importance of oxygen functional groups in carbon reactions with oxygen-containing gases. It is found that there is a good correlation between the electronic structures and reactivities of carbon edge sites. Zigzag sites are more active in oxygen adsorption because of the unpaired electrons and armchair sites are less active in oxygen adsorption due to the triple character. However, the desorption of semi-quinone oxygen from zigzag sites needs a bond energy ca. 30% higher than that of o-quinone oxygen from armchair edge sites. CO 2 and H 2 O adsorb on carbon surface much less favorably than O 2 . H 2 O is first physically adsorbed on the virgin graphite surface followed by chemisorption through oxygen atom approaching the carbon edge site and the movements of two hydrogen atoms to produce H 2 . The adsorption mechanism of H 2 O is different from that for CO 2 , but the final result is quite similar, i.e. producing only semi-quinone oxygen. Based upon the above studies, a new generalized mechanism, as shown in Fig. 1, is developed and can account for all the important kinetic phenomena of carbon-gas reactions. The key point is that in CO 2 /H 2 O-carbon reaction only semi-quinone formed; while, in O 2 -carbon reaction, semi-quinone, o-quinone (at lower pressure), and off-plane epoxy oxygen (at relatively higher pressure) can be formed. This is the main reason for the different reaction kinetics of O 2 -carbon reaction and CO 2 /H 2 O-carbon reactions as observed experimentally. The oxygen functional groups of carbon can be characterized by XPS, PZC (point of zero charge), IEP (isoelectric point) and TPD (temperature-programmed desorption), which were used in our previous studies. We treated the carbon surface with different acids, finding that HNO 3

  9. Toxicity of nano-TiO2 on algae and the site of reactive oxygen species production

    International Nuclear Information System (INIS)

    Li, Fengmin; Liang, Zhi; Zheng, Xiang; Zhao, Wei; Wu, Miao; Wang, Zhenyu

    2015-01-01

    Highlights: • The growth of two species of algae was inhibited under nano-TiO 2 exposure. • Oxidative stress was one of the mechanisms of toxicity of nano-TiO 2 on algae. • The site of ROS production was the electron transfer chain of chloroplast. - Abstract: Given the extensive use of nanomaterials, they may enter aquatic environments and harm the growth of algae, which are primary producers in an aquatic ecosystem. Thus, the balance of an aquatic ecosystem may be destroyed. In this study, Karenia brevis and Skeletonema costatum were exposed to nano-TiO 2 (anatase, average particle size of 5–10 nm, specific surface area of 210 ± 10 m 2 g −1 ) to assess the effects of nano-TiO 2 on algae. The findings of transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDX) and scanning electron microscopy (SEM) demonstrate aggregation of nano-TiO 2 in the algal suspension. Nano-TiO 2 was also found to be inside algal cells. The growth of the two species of algae was inhibited under nano-TiO 2 exposure. The 72 h EC 50 values of nano-TiO 2 to K. brevis and S. costatum were 10.69 and 7.37 mg L −1 , respectively. TEM showed that the cell membrane of K. brevis was destroyed and its organelles were almost undistinguished under nano-TiO 2 exposure. The malondialdehyde (MDA) contents of K. brevis and S. costatum significantly increased compared with those of the control (p < 0.05). Meanwhile, superoxide dismutase (SOD) and catalase activities (CAT) of K. brevis and S. costatum changed in different ways. The reactive oxygen species (ROS) levels in both species were significantly higher than those of the control (p < 0.05). The site of ROS production and accumulation in K. brevis and S. costatum under nano-TiO 2 exposure was explored with the addition of inhibitors of different electron transfer chains. This study indicated that nano-TiO 2 in algal suspensions inhibited the growth of K. brevis and S. costatum. This effect was attributed to oxidative

  10. Toxicity of nano-TiO{sub 2} on algae and the site of reactive oxygen species production

    Energy Technology Data Exchange (ETDEWEB)

    Li, Fengmin, E-mail: lifengmin@ouc.edu.cn [Key Laboratory of Marine Environmental Science and Ecology, Ministry of Education, College of Environmental Science and Technology, Ocean University of China, Qingdao 266100 (China); Liang, Zhi [Key Laboratory of Marine Environmental Science and Ecology, Ministry of Education, College of Environmental Science and Technology, Ocean University of China, Qingdao 266100 (China); Zheng, Xiang, E-mail: zhengxiang7825@sina.com [School of Environment and Natural Resources, Renmin University of China, Beijing 100872 (China); Zhao, Wei; Wu, Miao; Wang, Zhenyu [Key Laboratory of Marine Environmental Science and Ecology, Ministry of Education, College of Environmental Science and Technology, Ocean University of China, Qingdao 266100 (China)

    2015-01-15

    Highlights: • The growth of two species of algae was inhibited under nano-TiO{sub 2} exposure. • Oxidative stress was one of the mechanisms of toxicity of nano-TiO{sub 2} on algae. • The site of ROS production was the electron transfer chain of chloroplast. - Abstract: Given the extensive use of nanomaterials, they may enter aquatic environments and harm the growth of algae, which are primary producers in an aquatic ecosystem. Thus, the balance of an aquatic ecosystem may be destroyed. In this study, Karenia brevis and Skeletonema costatum were exposed to nano-TiO{sub 2} (anatase, average particle size of 5–10 nm, specific surface area of 210 ± 10 m{sup 2} g{sup −1}) to assess the effects of nano-TiO{sub 2} on algae. The findings of transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDX) and scanning electron microscopy (SEM) demonstrate aggregation of nano-TiO{sub 2} in the algal suspension. Nano-TiO{sub 2} was also found to be inside algal cells. The growth of the two species of algae was inhibited under nano-TiO{sub 2} exposure. The 72 h EC{sub 50} values of nano-TiO{sub 2} to K. brevis and S. costatum were 10.69 and 7.37 mg L{sup −1}, respectively. TEM showed that the cell membrane of K. brevis was destroyed and its organelles were almost undistinguished under nano-TiO{sub 2} exposure. The malondialdehyde (MDA) contents of K. brevis and S. costatum significantly increased compared with those of the control (p < 0.05). Meanwhile, superoxide dismutase (SOD) and catalase activities (CAT) of K. brevis and S. costatum changed in different ways. The reactive oxygen species (ROS) levels in both species were significantly higher than those of the control (p < 0.05). The site of ROS production and accumulation in K. brevis and S. costatum under nano-TiO{sub 2} exposure was explored with the addition of inhibitors of different electron transfer chains. This study indicated that nano-TiO{sub 2} in algal suspensions inhibited the growth

  11. Macromolecule simulation and CH4 adsorption mechanism of coal vitrinite

    Science.gov (United States)

    Yu, Song; Yan-ming, Zhu; Wu, Li

    2017-02-01

    The microscopic mechanism of interactions between CH4 and coal macromolecules is of significant practical and theoretical importance in CBM development and methane storage. Under periodic boundary conditions, the optimal energy configuration of coal vitrinite, which has a higher torsion degree and tighter arrangement, can be determined by the calculation of molecular mechanics (MM) and molecular dynamics (MD), and annealing kinetics simulation based on ultimate analysis, 13C NMR, FT IR and HRTEM. Macromolecular stabilization is primarily due to the van der Waals energy and covalent bond energy, mainly consisting of bond torsion energy and bond angle energy. Using the optimal configuration as the adsorbent, GCMC simulation of vitrinite adsorption of CH4 is conducted. A saturated state is reached after absorbing 17 CH4s per coal vitrinite molecule. CH4 is preferentially adsorbed on the edge, and inclined to gathering around the branched chains of the inner vitrinite sites. Finally, the adsorption parameters are calculated through first principle DFT. The adsorbability order is as follows: aromatic structure> heteroatom rings > oxygen functional groups. The adsorption energy order is as follows: Top graphene. However, the energy of the most preferential location is much lower than that of graphite/graphene. CH4 is more easily absorbed on the surface of vitrinite. Adsorbability varies considerably at different adsorption locations and sites on the surface of vitrinite. Crystal parameter of vitrinite is a = b = c = 15.8 Å and majority of its micropores are blow 15.8 Å, indicating that the vitrinite have the optimum adsorption aperture. It can explain its higher observed adsorption capacities for CH4 compared with graphite/graphene.

  12. Theoretical insights into the uranyl adsorption behavior on vanadium carbide MXene

    Science.gov (United States)

    Zhang, Yu-Juan; Zhou, Zhang-Jian; Lan, Jian-Hui; Ge, Chang-Chun; Chai, Zhi-Fang; Zhang, Peihong; Shi, Wei-Qun

    2017-12-01

    Remediation of the contamination by long-lived actinide wastes is extremely important but also challenging. Adsorption based techniques have attracted much research attention for their potential as low-cost and effective methods to reduce the radioactive waste from solution. In this work, we have investigated the adsorption behavior of uranyl species [with the general form UO2(L1)x(L2)y(L3)z, where L1, L2 and L3 stand for ligands H2O, OH and CO3, respectively] on hydroxylated vanadium carbide V2C(OH)2 MXene nanosheets using density functional theory based simulation methods We find that all studied uranyl species can stably bond to hydroxylated MXene with binding energies ranging from -3.3 to -4.6 eV, suggesting that MXenes could be effective adsorbers for uranyl ions. The strong adsorption is achieved by forming two Usbnd O bonds with the hydroxylated Mxene. In addition, the axial oxygen atoms from the uranyl ions form hydrogen bonds with the hydroxylated V2C, further strengthening the adsorption. We have also investigated the effects of F termination on the uranyl adsorption properties of V2C nanosheets. Usbnd F bonds are in general weaker than Usbnd O bonds on the adsorption site, suggesting that F terminated Mexne is less favorable for uranyl adsorption applications.

  13. Water Induced Surface Reconstruction of the Oxygen (2x1) covered Ru(0001)

    Energy Technology Data Exchange (ETDEWEB)

    Maier, Sabine; Cabrera-Sanfelix, Pepa; Stass, Ingeborg; Sanchez-Portal, Daniel; Arnau, Andres; Salmeron, Miquel

    2010-08-06

    Low temperature scanning tunneling microscopy (STM) and density functional theory (DFT) were used to study the adsorption of water on a Ru(0001) surface covered with half monolayer of oxygen. The oxygen atoms occupy hcp sites in an ordered structure with (2x1) periodicity. DFT predicts that water is weakly bound to the unmodified surface, 86 meV compared to the ~;;200 meV water-water H-bond. Instead, we found that water adsorption causes a shift of half of the oxygen atoms from hcp sites to fcc sites, creating a honeycomb structure where water molecules bind strongly to the exposed Ru atoms. The energy cost of reconstructing the oxygen overlayer, around 230 meV per displaced oxygen atom, is more than compensated by the larger adsorption energy of water on the newly exposed Ru atoms. Water forms hydrogen bonds with the fcc O atoms in a (4x2) superstructure due to alternating orientations of the molecules. Heating to 185 K results in the complete desorption of the water layer, leaving behind the oxygen honeycomb structure, which is metastable relative to the original (2x1). This stable structure is not recovered until after heating to temperatures close to 260K.

  14. Forms of adsorption and transition states of oxidation of carbon monoxide by molecular oxygen and dissociation of nitrogen monooxide, catalyzed by monovalent copper

    Science.gov (United States)

    Ermakov, A. I.; Mashutin, V. Y.; Vishnjakov, A. V.

    With the help of the results of semiempirical (parametric method 3) and ab initio (second-order Møller-Plesset [MP2] unrestricted Hartree-Fock [UHF] 6-31G**, unrestricted density functional theory [UDFT] 6-31G** Becke's three-parameter exchange functional and the gradient-corrected functional of Lee, Yang, and Paar [B3LYP] and UDFT LANL2DZ B3LYP) quantum-chemical calculations has been studied the complexation CO and NO with molecular hydroxide of copper(I). The influence of charge defects has been simulated by the calculations of anionic, neutral, and cationic systems. It is shown that CO and NO are mainly coordinated by nonoxygen atom on an atom of copper(I) hydroxide as one- and two-center forms. These forms are suitable for appearance of prereactionary complexes of catalytic oxidation CO by molecular oxygen and decomposition NO into atoms of nitrogen and oxygen. The corresponding prereactionary complexes for systems with participation of copper(II) hydroxide and copper(III) hydroxide are not revealed. The calculations predict inhibiting impact of copper(II) and copper(III) of the observed reactions. Computed stability of complexes CO and NO with copper(I) hydroxide and activation energy of catalytic conversion of monooxides essentially depend on an excessive charge of the system. Introduction of electron-donating additives into copper(I) hydroxide promotes rise of catalytic activity of copper(I) compound.

  15. Effect of oxygen potential on sulphur dioxide activation of oil sands fluid coke and characteristics of activated coke in mercury adsorption

    International Nuclear Information System (INIS)

    Morris, E.A.; Jia, C.Q.; Tong, S.

    2007-01-01

    A sulphur-impregnated activated carbon (SIAC) technology was modified for use in copper smelters in order to mitigate mercury and sulphur dioxide (SO 2 ) emissions. Elemental sulphur was captured as a co-product. The study examined the feasibility of reducing levels of SO 2 using fluid coke in the copper smelter flue. SIAC properties were optimized in order to capture vapour phase mercury. Raw fluid coke samples were used to measure SO 2 flow rates. Gas composition was varied to mimic concentrations found during normal operation of copper converters. Gas chromatography was used to analyze reactions products and to prove the hypothesis that mercury capacity is influenced by the oxygen potential of the activation gas due to changes in surface sulphur types developed from reduced sulphur species. Results of the study showed that oxygen levels at 5 per cent did not play a significant role in pore development. It was concluded that increased residence times contributed to reductions in SO 2 and elemental S yields. 13 refs., 1 tab., 7 figs

  16. Study of the influence of adsorption of oxygen, hydrogen and water on radiation-induced thermally activated currents of magnesium oxide

    International Nuclear Information System (INIS)

    Wysocki, S.

    1985-01-01

    Recently, radiation-induced thermally activated currents (RITAC) have been studied in purified and magnesium-doped lithium fluoride. In the RITAC method, the electric field is applied at low temperature, only during irradiation. The present paper deals with the dipolar complexes generated by γ-radiations in the surface region of magnesium oxide in vacuum and in the presence of oxygen, hydrogen and water. Spectrally pure MgO single crystal spectrally pure oxygen and hydrogen and doubly distilled water were used. The electrodes were deposited on the (100) surface of MgO single crystal by vacuum evaporation of gold. Experimental details are given. A figure shows the thermally activated depolarization (TAD) curve for MgO in vacuum. In a TAD experiment, the sample was subjected to a constant electric field at 700 K and cooled. Upon reaching room temperature the electric field was removed In this case we observed a single peak at Tsub(max) = 511 K. A figure shows RITAC curves for an MgO sample in vacuum after irradiation. The results are shown and discussed. (author)

  17. Hydrogen sulfide adsorption on activated carbon fiber. Tests on Parisian subway; Elimination du sulfure d'hydrogene par adsorption sur tissu de charbon actif. Essais sur site RATP

    Energy Technology Data Exchange (ETDEWEB)

    Bouzaza, A.; Marsteau, St.; Laplanche, A. [Ecole Nationale Superieure de Chimie, Lab. Chimie des Nuissances et Genie de l' Environnement - CNGE, 35 - Rennes (France); Garrot, B. [RATP, Dept. Environnement et Securite-Domaines d' Expertises de l' Environnement-Entite Qualite de l' Air, 75 - Paris (France)

    2003-06-01

    Hydrogen sulfide has an unpleasant odor and may cause damage to the electrical materials of the Parisian subway. The activated carbon has some intrinsic catalytic activity, so the removal of hydrogen sulfide is due to an adsorption-oxidation process. In a laboratory scale, some kinetic parameters were acquired, which allowed us to build up two dynamic reactors. These continuous reactors, equipped with activated carbon fibers, were tested on the Madeleine station of the Parisian subway. The feasibility of the elimination of H{sub 2}S by continuous adsorption-oxidation was confirmed. The relative humidity of the gas phase was found to play an important role in the performance of the elimination. The durability of the pilot tested was compatible with an industrial exploitation of the process. (authors)

  18. Adsorption and activation of methane and methanol on Pt(100) surface: a density functional study; Adsorption et activation du methane et du methanol sur la surface (100) du platine: une etude par la fonctionnelle de la densite

    Energy Technology Data Exchange (ETDEWEB)

    Moussounda, P.S

    2006-11-15

    The activation of methane (CH{sub 4}) and methanol (CH{sub 3}OH) on Pt(100) surface has been investigated using density functional theory calculations based on plane-wave basis and pseudo-potential. We optimised CH{sub 4}/Pt(100) system. The calculated adsorption energies over the top, bridge and hollow sites are small, weakly dependent on the molecular orientation. The nature of the CH{sub 4}-Pt interaction was examined through the electronic structure changes. The adsorption of methyl (CH{sub 3}) and hydrogen (H) and the co-adsorption of CH{sub 3}+H were also calculated. From these results, we examined the dissociation of CH{sub 4} to CH{sub 3}+H, and the activation energies found are in good agreement with the experimental and theoretical values. The activation of CH{sub 3}OH/Pt(100) has been studied. All the sites have almost the same adsorption energy. The adsorption of oxygen (O) and the co-adsorption of CH{sub 4} and O were also examined. In addition, the formation of CH{sub 3}OH assuming a one-step mechanism step via the co-adsorption of CH{sub 4}+O has been studied and the barrier height was found to be high. (authors)

  19. Oxygen vacancies as active sites for water dissociation on rutile TiO2(110)

    DEFF Research Database (Denmark)

    Schaub, R.; Thostrup, P.; Lopez, Nuria

    2001-01-01

    to dissociate H2O through the transfer of one proton to a nearby oxygen atom, forming two hydroxyl groups for every vacancy. The amount of water dissociation is limited by the density of oxygen vacancies present on the clean surface exclusively. The dissociation process sets in as soon as molecular water...

  20. Adsorption of guaiacol on Fe (110) and Pd (111) from first principles

    Science.gov (United States)

    Hensley, Alyssa J. R.; Wang, Yong; McEwen, Jean-Sabin

    2016-06-01

    The catalytic properties of surfaces are highly dependent upon the effect said surfaces have on the geometric and electronic structure of adsorbed reactants, products, and intermediates. It is therefore crucial to have a surface-level understanding of the adsorption of the key species in a reaction in order to design active and selective catalysts. Here, we study the adsorption of guaiacol on Fe (110) and Pd (111) using dispersion-corrected density functional theory calculations as both of these metals are of interest as hydrodeoxygenation catalysts for the conversion of bio-oils to useable biofuels. Both vertical (via the oxygen functional groups) and horizontal (via the aromatic ring) adsorption configurations were examined and the resulting adsorption and molecular distortion energies showed that the vertical sites were only physisorbed while the horizontal sites were chemisorbed on both metal surfaces. A comparison of guaiacol's horizontal adsorption on Fe (110) and Pd (111) showed that guaiacol had a stronger adsorption on Pd (111) while the Fe (110) surface distorted the Csbnd O bonds to a greater degree. Electronic analyses on the horizontal systems showed that the greater adsorption strength for guaiacol on Pd (111) was likely due to the greater charge transfer between the aromatic ring and the surface Pd atoms. Additionally, the greater distortion of the Csbnd O bonds in adsorbed guaiacol on Fe (110) is likely due to the greater degree of interaction between the oxygen and surface Fe atoms. Overall, our results show that the Fe (110) surface has a greater degree of interaction with the functional groups and the Pd (111) surface has a greater degree of interaction with the aromatic ring.

  1. Strong Selective Adsorption of Polymers.

    Science.gov (United States)

    Ge, Ting; Rubinstein, Michael

    2015-06-09

    A scaling theory is developed for selective adsorption of polymers induced by the strong binding between specific monomers and complementary surface adsorption sites. By "selective" we mean specific attraction between a subset of all monomers, called "sticky", and a subset of surface sites, called "adsorption sites". We demonstrate that, in addition to the expected dependence on the polymer volume fraction ϕ bulk in the bulk solution, selective adsorption strongly depends on the ratio between two characteristic length scales, the root-mean-square distance l between neighboring sticky monomers along the polymer, and the average distance d between neighboring surface adsorption sites. The role of the ratio l / d arises from the fact that a polymer needs to deform to enable the spatial commensurability between its sticky monomers and the surface adsorption sites for selective adsorption. We study strong selective adsorption of both telechelic polymers with two end monomers being sticky and multisticker polymers with many sticky monomers between sticky ends. For telechelic polymers, we identify four adsorption regimes at l / d 1, we expect that the adsorption layer at exponentially low ϕ bulk consists of separated unstretched loops, while as ϕ bulk increases the layer crosses over to a brush of extended loops with a second layer of weakly overlapping tails. For multisticker chains, in the limit of exponentially low ϕ bulk , adsorbed polymers are well separated from each other. As l / d increases, the conformation of an individual polymer changes from a single-end-adsorbed "mushroom" to a random walk of loops. For high ϕ bulk , adsorbed polymers at small l / d are mushrooms that cover all the adsorption sites. At sufficiently large l / d , adsorbed multisticker polymers strongly overlap. We anticipate the formation of a self-similar carpet and with increasing l / d a two-layer structure with a brush of loops covered by a self-similar carpet. As l / d exceeds the

  2. Different effects of surface heterogeneous atoms of porous and non-porous carbonaceous materials on adsorption of 1,1,2,2-tetrachloroethane in aqueous environment.

    Science.gov (United States)

    Chen, Weifeng; Ni, Jinzhi

    2017-05-01

    The surface heterogeneous atoms of carbonaceous materials (CMs) play an important role in adsorption of organic pollutants. However, little is known about the surface heterogeneous atoms of CMs might generate different effect on adsorption of hydrophobic organic compounds by porous carbonaceous materials - activated carbons (ACs) and non-porous carbonaceous materials (NPCMs). In this study, we observed that the surface oxygen and nitrogen atoms could decrease the adsorption affinity of both ACs and NPCMs for 1,1,2,2-tetrachloroethane (TeCA), but the degree of decreasing effects were very different. The increasing content of surface oxygen and nitrogen ([O + N]) caused a sharper decrease in adsorption affinity of ACs (slope of lg (k d /SA) vs [O + N]: -0.098∼-0.16) than that of NPCMs (slope of lg (k d /SA) vs [O + N]: -0.025∼-0.059) for TeCA. It was due to the water cluster formed by the surface hydrophilic atoms that could block the micropores and generate massive invalid adsorption sites in the micropores of ACs, while the water cluster only occupied the surface adsorption sites of NPCMs. Furthermore, with the increasing concentration of dissolved TeCA, the effect of surface area on adsorption affinity of NPCMs for TeCA kept constant while the effect of [O + N] decreased due to the competitive adsorption between water molecule and TeCA on the surface of NPCMs, meanwhile, both the effects of micropore volume and [O + N] on adsorption affinity of ACs for TeCA were decreased due to the mechanism of micropore volume filling. These findings are valuable for providing a deep insight into the adsorption mechanisms of CMs for TeCA. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Adsorption of simple molecules on clean metal surfaces

    International Nuclear Information System (INIS)

    Na Lamphun, O.-A.

    1980-06-01

    The adsorption of nitric oxide, oxygen, krypton and xenon on evaporated tungsten, nickel and iron films is studied. The theoretical and experimental aspects of adsorption are reviewed, a preliminary study of adsorption by the volumetric method is presented, surface potential and sticking probability studies of adsorption using ion gauges are investigated and an analysis of residual gases, sticking probability and surface potential studies using quadrupole mass spectrometry, given. (author)

  4. Formation of reactive oxygen by N2O decomposition over binuclear cationic sites of Fe-ferrierite zeolite: Periodic DFT + U study

    Science.gov (United States)

    Avdeev, Vasilii I.; Bedilo, Alexander F.

    2018-03-01

    The electronic nature of sites over Fe-ferrierite zeolite stabilizing active α-oxygen is analyzed by the periodic DFT + U approach. It is shown that two antiferromagnetically coupled Fe2+ cations with bridging OH-bonds form a stable bi-nuclear site of the [Fe2+Fe2+] doped FER complex. Frontier orbitals of this complex populated by two electrons with minority spins are localized in the bandgap. As a result, [Fe2+Fe2+] unit acquires the properties of a binuclear Lewis acid dipolarophile for 1,3-dipole N2O. First reaction step of N2O decomposition follows the Huisgen‧s concept of the 1,3-dipolar cycloaddition concept followed by the formation of reactive oxygen species Fesbnd O.

  5. Effect of oxygen on decomposition of nitrous oxide over various metal oxide catalysts

    International Nuclear Information System (INIS)

    Satsuma, Atsushi; Maeshima, Hajime; Watanabe, Kiyoshi; Hattori, Tadashi

    2001-01-01

    The inhibitory effect of oxygen on decomposition of nitrous oxide over various metal oxide catalysts was investigated. The activity of nitrous oxide decomposition significantly decreased over CuO, Co 3 O 4 , NiO, Fe 2 O 3 , SnO 2 , In 2 O 3 and Cr 2 O 3 by reversible adsorption of oxygen onto the active sites. On the contrary to this, there was no or small change in the activity of TiO 2 , Al 2 O 3 , MgO, La 2 O 3 and CaO. A good correlation was observed between the degree of inhibition and the heat of formation of metal oxides. On the basis of kinetic model, the reduction of catalytic activity in the presence of oxygen was rationalized with the strength of oxygen adsorption on the metal oxide surface. (author)

  6. Adsorption of Cd(II) from aqueous solutions by rape straw biochar derived from different modification processes.

    Science.gov (United States)

    Li, Bing; Yang, Lan; Wang, Chang-Quan; Zhang, Qing-Pei; Liu, Qing-Cheng; Li, Yi-Ding; Xiao, Rui

    2017-05-01

    In order to deal with cadmium (Cd(II)) pollution, three modified biochar materials: alkaline treatment of biochar (BC-NaOH), KMnO 4 impregnation of biochar (BC-MnO x ) and FeCl 3 magnetic treatment of biochar (BC-FeO x ), were investigated. Nitrogen adsorption-desorption isotherms, Fourier transform infrared spectroscopy (FTIR), Boehm titration, and scanning electron microscopy (SEM) were used to determine the characteristics of adsorbents and explore the main adsorption mechanism. The results show that manganese oxide particles are carried successfully within the biochar, contributing to micropore creation, boosting specific surface area and forming innersphere complexes with oxygen-containing groups, while also increasing the number of oxygen-containing groups. The adsorption sites created by the loaded manganese oxide, rather than specific surface areas, play the most important roles in cadmium adsorption. Batch adsorption experiments demonstrate a Langmuir model fit for Cd(II), and BC-MnO x provided the highest sorption capacity (81.10 mg g -1 ). The sorption kinetics of Cd(II) on adsorbents follows pseudo-second-order kinetics and the adsorption rate of the BC-MnO x material was the highest (14.46 g (mg·h) -1 ). Therefore, biochar modification methods involving KMnO 4 impregnation may provide effective ways of enhancing Cd(II) removal from aqueous solutions. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Adsorption of guanidinium collectors on aluminosilicate minerals - a density functional study.

    Science.gov (United States)

    Nulakani, Naga Venkateswara Rao; Baskar, Prathab; Patra, Abhay Shankar; Subramanian, Venkatesan

    2015-10-07

    In this density functional theory based investigation, we have modelled and studied the adsorption behaviour of guanidinium cations and substituted (phenyl, methoxy phenyl, nitro phenyl and di-nitro phenyl) guanidinium cationic collectors on the basal surfaces of kaolinite and goethite. The adsorption behaviour is assessed in three different media, such as gas, explicit water and pH medium, to understand the affinity of GC collectors to the SiO4 tetrahedral and AlO6 octahedral surfaces of kaolinite. The tetrahedral siloxane surface possesses a larger binding affinity to GC collectors than the octahedral sites due to the presence of surface exposed oxygen atoms that are active in the intermolecular interactions. Furthermore, the inductive electronic effects of substituted guanidinium cations also play a key role in the adsorption mechanism. Highly positive cations result in a stronger electrostatic interaction and preferential adsorption with the kaolinite surfaces than low positive cations. Computed interaction energies and electron densities at the bond critical points suggest that the adsorption of guanidinium cations on the surfaces of kaolinite and goethite is due to the formation of intra/inter hydrogen bonding networks. Also, the electrostatic interaction favours the high adsorption ability of GC collectors in the pH medium than gas phase and water medium. The structures and energies of GC collectors pave an intuitive view for future experimental studies on mineral flotation.

  8. Computational study of ibuprofen removal from water by adsorption in realistic activated carbons.

    Science.gov (United States)

    Bahamon, Daniel; Carro, Leticia; Guri, Sonia; Vega, Lourdes F

    2017-07-15

    Molecular simulations using the Grand Canonical Monte Carlo (GCMC) method have been performed in order to obtain physical insights on how the interaction between ibuprofen (IBP) and activated carbons (ACs) in aqueous mixtures affects IBP removal from water by ACs. A nanoporous carbon model based on units of polyaromatic molecules with different number of rings, defects and polar-oxygenated sites is described. Individual effects of factors such as porous features and chemical heterogeneities in the adsorbents are investigated and quantified. Results are in good agreement with experimental adsorption data, highlightening the ability of GCMC simulation to describe the macroscopic adsorption performance in drug removal applications, while also providing additional insights into the IBP/water adsorption mechanism. The simulation results allow finding the optimal type of activated carbon material for separating this pollutant in water treatment. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Fast Prediction of Adsorption Properties for Platinum Nanocatalysts with Generalized Coordination Numbers

    DEFF Research Database (Denmark)

    Calle-Vallejo, Federico; Martinez, Jose I.; García Lastra, Juan Maria

    2014-01-01

    of the generalized coordination numbers of the surface sites. This simple and predictive descriptor links the geometric arrangement of a surface to its adsorption properties. It generates linear adsorption-energy trends, captures finite-size effects, and provides more accurate descriptions than d-band centers...... in simple terms, while being able to compare these trends with those of extended surfaces. The trends in the adsorption energies of small oxygen- and hydrogen-containing adsorbates on Pt nanoparticles of various sizes and on extended surfaces were analyzed through DFT calculations by making use...... and usual coordination numbers. Unlike electronic-structure descriptors, which require knowledge of the densities of states, it is calculated manually. Finally, it was shown that an approximate equivalence exists between generalized coordination numbers and d-band centers....

  10. Stable isotopes of hydrogen and oxygen in surface water and ground water at selected sites on or near the Idaho National Engineering Laboratory, Idaho

    International Nuclear Information System (INIS)

    Ott, D.S.; Cecil, L.D.; Knobel, L.L.

    1994-01-01

    Relative stable isotopic ratios for hydrogen and oxygen compared to standard mean ocean water are presented for water from 4 surface-water sites and 38 ground-water sites on or near the Idaho National Engineering Laboratory (INEL). The surface-water samples were collected monthly from March 1991 through April 1992 and after a storm event on June 18, 1992. The ground-water samples either were collected during 1991 or 1992. These data were collected as part of the US Geological Survey's continuing hydrogeological investigations at the INEL. The relative isotopic ratios of hydrogen and oxygen are reported as delta 2 H (δ 2 H) and as delta 18 O (δ 18 O), respectively. The values of δ 2 H and δ 18 O in water from the four surface-water sites ranged from -143.0 to -122 and from -18.75 to -15.55, respectively. The values of δ 2 H and δ 18 O in water from the 38 ground-water sites ranged from -141.0 to -120.0 and from -18.55 to -14.95, respectively

  11. Achieving high-powered Zn/air fuel cell through N and S co-doped hierarchically porous carbons with tunable active-sites as oxygen electrocatalysts

    Science.gov (United States)

    Tang, Qiaowei; Wang, Luming; Wu, Mingjie; Xu, Nengneng; Jiang, Lei; Qiao, Jinli

    2017-10-01

    Electrochemical reduction of oxygen is the heart of the next-generation energy technologies to fuel cells and metal-air batteries, of which the reference catalysts suffer from two critical bottlenecks lying in their insufficient electroactivities and unclear active site structures. Herein, we introduce the effectively hierarchically porous carbons (HPCs) as the active-sites enriched platform for oxygen electroreduction. Three quaternized copolymers (PUB, PAADDA and PICP) with different chemical structures are used to pursue Fe/N/S-tailored ORR electrocatalysts. The most efficient one prepared by PAADDA gives the onset potential of 0.94 V and a half-wave potential of 0.85 V in basic solution, as well as superb electroactivities of low H2O2% and high electron transfer number in both alkaline and acidic medium. Surprisingly, they all display high discharge power density as applied to Zn-air fuel cells, and the HPCs-PAADDA catalyst thrillingly reaches 516.3 mW cm-2 when catalyst loading is optimized to 5.0 mg cm-2. The results elucidate that the polymer with long aliphatic chain is propitious to trap metals to create active sites and enwrap silica template to construct uniform pore structure. Only two kinds of nitrogen configuration (pyridinic-N and graphitic-N) are found with distinct structure in these HPCs, which happens to be active sites.

  12. Intracrystalline fractionation of oxygen isotopes between hydroxyl and non-hydroxyl sites in kaolinite measured by thermal dehydroxylation and partial fluorination

    Science.gov (United States)

    Girard, Jean-Pierre; Savin, Samuel M.

    1996-02-01

    Thermal dehydroxylation and partial fluorination techniques were used to measure intracrystalline fractionation of oxygen isotopes between hydroxyl and non-hydroxyl sites in kaolinite. Several aliquots of a well characterized, fine-grained (rates, and target temperatures. Measured δ18O values of both the liberated water and the dehydroxylated residue are consistent over a wide range of temperatures (550 850°C) when dehydroxylation is performed in a single-step fashion at a rapid heating rate (>50°C/min.). Similar dehydroxylation experiments indicate that brucite dehydroxylation occurs without any significant isotopic fractionation of the oxygen isotopes. By extrapolation we postulate that no significant fractionation occurs during single-step thermal dehydroxylation of fine-grained kaolinite, provided that dehydroxylation is performed under well controlled conditions. In contrast, gibbsite dehydroxylation is accompanied by substantial isotopic fractionation. This is probably the result of the complex, multi-pathway dehydroxylation reaction of this mineral. Similarly, thermal dehydroxylation of coarsegrained (>1 μm) kaolinites and dickites of weathering and hydrothermal origin yield results that are dependent on the temperature of dehydroxylation. We suggest that this effect may be caused by isotopic exchange during diffusion of water molecules through coarse particles. Partial fluorination of fine-grained kaolinite in the presence of excess F2 at low temperatures (rate of reaction of hydroxyl oxygen than of non-hydroxyl oxygen, but examination of the isotopic data as well as XRD and IR analyses of the residues after partial fluorination indicates that the separation between the two types of oxygen is not complete. The results, therefore, do not yield a reliable δ18O value of the hydroxyl oxygen. The results of this study suggest that the thermal dehydroxylation technique may be appropriate for analysis of OH groups in fine-grained kaolinite. The partial

  13. Adsorption of aromatic compounds by carbonaceous adsorbents: a comparative study on granular activated carbon, activated carbon fiber, and carbon nanotubes.

    Science.gov (United States)

    Zhang, Shujuan; Shao, Ting; Kose, H Selcen; Karanfil, Tanju

    2010-08-15

    Adsorption of three aromatic organic compounds (AOCs) by four types of carbonaceous adsorbents [a granular activated carbon (HD4000), an activated carbon fiber (ACF10), two single-walled carbon nanotubes (SWNT, SWNT-HT), and a multiwalled carbon nanotube (MWNT)] with different structural characteristics but similar surface polarities was examined in aqueous solutions. Isotherm results demonstrated the importance of molecular sieving and micropore effects in the adsorption of AOCs by carbonaceous porous adsorbents. In the absence of the molecular sieving effect, a linear relationship was found between the adsorption capacities of AOCs and the surface areas of adsorbents, independent of the type of adsorbent. On the other hand, the pore volume occupancies of the adsorbents followed the order of ACF10 > HD4000 > SWNT > MWNT, indicating that the availability of adsorption site was related to the pore size distributions of the adsorbents. ACF10 and HD4000 with higher microporous volumes exhibited higher adsorption affinities to low molecular weight AOCs than SWNT and MWNT with higher mesopore and macropore volumes. Due to their larger pore sizes, SWNTs and MWNTs are expected to be more efficient in adsorption of large size molecules. Removal of surface oxygen-containing functional groups from the SWNT enhanced adsorption of AOCs.

  14. Oxygen Reduction Reaction on PtCo Nanocatalyst: (Bi)sulfate Anion Poisoning

    Science.gov (United States)

    Liu, Jie; Huang, Yan

    2018-05-01

    Pt alloy electrocatalysts are susceptible to anion adsorption in the working environment of fuel cells. In this work, the unavoidable bisulfate and sulfate ((bi)sulfate) poisoning of the oxygen reduction reaction (ORR) on a common PtCo nanocatalyst was studied by the rotating disk electrode (RDE) technique, for the first time to the best of our knowledge. The specific activity decreases linearly with the logarithm of (bi)sulfate concentration under various high potentials. This demonstrates that the (bi)sulfate adsorption does not affect the free energy of ORR activation at a given potential. Moreover, it is speculated that these two conditions, the adsorption of one O2 molecule onto two Pt sites and this adsorption as a rate-determining step of ORR reaction, are unlikely to exist simultaneously.

  15. Adsorption of H atoms on cubic Er2O3 (0 0 1) surface: A DFT study

    International Nuclear Information System (INIS)

    Mao, Wei; Chikada, Takumi; Shimura, Kenichiro; Suzuki, Akihiro; Yamaguchi, Kenji; Terai, Takayuki

    2013-01-01

    First-principles plane wave calculations based on spin-polarized density functional theory (DFT) and generalized gradient approximation (GGA) have been used to study the adsorption of H atoms on cubic Er 2 O 3 (0 0 1) surface. We identify stable adsorption positions and find that H preferentially adsorbs on top of fourfold-hollow sites and transfers electrons to the surface, resulting in the formations of covalent bonds to the nearest neighboring four oxygen atoms. In the most energetically favorable adsorption sites, It was found that H bonds with O atoms at the cubic Er 2 O 3 (0 0 1) surface with an adsorption energy of −295.68 kJ mol −1 at coverage 1/8 ML, and the adsorption energy is inclined to decrease with the increase of H coverage (>1/4 ML). In addition, our calculations indicate that the dissociative H atom configurations have adsorption energies that are at least 152.64 kJ mol −1 greater than the H 2 molecule configurations on the surface. These results discussed in the context of erbium oxide slabs are employed to rationalize some processes regarding to the hydrogen isotope permeation behavior of tritium permeation barrier

  16. Intra-Operative Inspired Fraction of Oxygen and the Risk of Surgical Site Infections in Patients with Type 1 Surgical Incisions.

    Science.gov (United States)

    Wanta, Brendan T; Hanson, Kristine T; Hyder, Joseph A; Stewart, Thomas M; Curry, Timothy B; Berbari, Elie F; Habermann, Elizabeth B; Kor, Daryl J; Brown, Michael J

    2018-04-02

    Whether the fraction of inspired oxygen (F I O 2 ) influences the risk of surgical site infection (SSI) is controversial. The World Health Organization and the World Federation of Societies of Anesthesiologists offer conflicting recommendations. In this study, we evaluate simultaneously three different definitions of F I O 2 exposure and the risk of SSI in a large surgical population. Patients with clean (type 1) surgical incisions who developed superficial and deep organ/space SSI within 30 days after surgery from January 2003 through December 2012 in five surgical specialties were matched to specialty-specific controls. Fraction of inspired oxygen exposure was defined as (1) nadir F I O 2 , (2) percentage of operative time with F I O 2 greater than 50%, and (3) cumulative hyperoxia exposure, calculated as the area under the curve (AUC) of F I O 2 by time for the duration in which F I O 2 greater than 50%. Stratified univariable and multivariable logistic regression models tested associations between F I O 2 and SSI. One thousand two hundred fifty cases of SSI were matched to 3,248 controls. Increased oxygen exposure, by any of the three measures, was not associated with the outcome of any SSI in a multivariable logistic regression model. Elevated body mass index (BMI; 35+ vs. operative oxygen exposure was associated with higher odds of SSI in the neurosurgical and spine populations. Increased intra-operative inspired fraction of oxygen was not associated with a reduction in SSI. These findings do not support the practice of increasing F I O 2 for the purpose of SSI reduction in patients with clean surgical incisions.

  17. The role of mineral surface chemistry in modified dextrin adsorption.

    Science.gov (United States)

    Beaussart, Audrey; Mierczynska-Vasilev, Agnieszka M; Harmer, Sarah L; Beattie, David A

    2011-05-15

    The adsorption of two modified dextrins (phenyl succinate dextrin--PS Dextrin; styrene oxide dextrin--SO Dextrin) on four different mineral surfaces has been studied using X-ray photoelectron spectroscopy (XPS), in situ atomic force microscopy (AFM) imaging, and captive bubble contact angle measurements. The four surfaces include highly orientated pyrolytic graphite (HOPG), freshly cleaved synthetic sphalerite (ZnS), and two surfaces produced through surface reactions of sphalerite: one oxidized in alkaline solution (pH 9, 1 h immersion); and one subjected to metal ion exchange between copper and zinc (i.e. copper activation: exposed to 1×10(-3) M CuSO(4) solution for 1 h). XPS measurements indicate that the different sphalerite surfaces contain varying amounts of sulfur, zinc, oxygen, and copper, producing substrates for polymer adsorption with a range of possible binding sites. AFM imaging has shown that the two polymers adsorb to a similar extent on HOPG, and that the two polymers display very different propensities for adsorption on the three sphalerite surface types, with freshly cleaved sphalerite encouraging the least adsorption, and copper activated and oxidized sphalerite encouraging significantly more adsorption. Contact angle measurements of the four surfaces indicate that synthetic sphalerite has a low contact angle upon fracture, and that oxidation on the timescale of one hour substantially alters the hydrophobicity. HOPG and copper-activated sphalerite were the most hydrophobic, as expected due to the carbon and di/poly-sulfide rich surfaces of the two samples, respectively. SO Dextrin is seen to have a significant impact on the wettability of HOPG and the surface reacted sphalerite samples, highlighting the difficulty in selectively separating sphalerite from carbonaceous unwanted minerals in flotation. PS Dextrin has the least effect on the hydrophobicity of the reacted sphalerite surfaces, whilst still significantly increasing the wettability of

  18. Catalysis on singly dispersed bimetallic sites

    Science.gov (United States)

    Zhang, Shiran; Nguyen, Luan; Liang, Jin-Xia; Shan, Junjun; Liu, Jingyue; Frenkel, Anatoly I.; Patlolla, Anitha; Huang, Weixin; Li, Jun; Tao, Franklin

    2015-08-01

    A catalytic site typically consists of one or more atoms of a catalyst surface that arrange into a configuration offering a specific electronic structure for adsorbing or dissociating reactant molecules. The catalytic activity of adjacent bimetallic sites of metallic nanoparticles has been studied previously. An isolated bimetallic site supported on a non-metallic surface could exhibit a distinctly different catalytic performance owing to the cationic state of the singly dispersed bimetallic site and the minimized choices of binding configurations of a reactant molecule compared with continuously packed bimetallic sites. Here we report that isolated Rh1Co3 bimetallic sites exhibit a distinctly different catalytic performance in reduction of nitric oxide with carbon monoxide at low temperature, resulting from strong adsorption of two nitric oxide molecules and a nitrous oxide intermediate on Rh1Co3 sites and following a low-barrier pathway dissociation to dinitrogen and an oxygen atom. This observation suggests a method to develop catalysts with high selectivity.

  19. Immunity of the Fe-N-C catalysts to electrolyte adsorption: phosphate but not perchloric anions

    DEFF Research Database (Denmark)

    Hu, Yang; Jensen, Jens Oluf; Pan, Chao

    2018-01-01

    often carried out, like for Pt-based catalysts, in dilute perchloric acid by assuming its non-adsorbing nature on the active sites. The assumption is however not true. In this work, a typical Fe-N-C catalyst was first synthesized by high-pressure pyrolysis in the presence of carbon support...... and thoroughly characterized in terms of morphology, structure and active site distribution. The subsequent electrochemical characterization of the catalyst shows strong adsorption and poisoning effect of, in addition to the known Cl-, perchloric anions on the oxygen reduction reaction (ORR) activity...

  20. Particle size distribution of nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs on traffic and suburban sites of a European megacity: Paris (France

    Directory of Open Access Journals (Sweden)

    J. Ringuet

    2012-09-01

    Full Text Available The size distribution of particulate nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs was determined during two field campaigns at a traffic site in summer 2010 and at a suburban site during the MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation experiment in summer 2009. Both, OPAHs and NPAHs were strongly associated (>85% to fine particles (Dp< 2.5 μm increasing the interest of their study on a sanitary point of view. Results showed really different NPAH and OPAH particle size distributions between both sites. At traffic site, clearly bimodal (notably for NPAHs particle size distributions (Dp = 0.14 and 1.4 μm were observed, while the particle size distributions were more scattered at the suburban site, especially for OPAHs. Bimodal particle size distribution observed at traffic site for the NPAH could be assigned to the vehicle emissions and the particle resuspension. Broadest distribution observed at the suburban site could be attributed to the mass transfer of compounds by volatilization/sorption processes during the transport of particles in the atmosphere. Results also showed that the combination of the study of particle size distributions applied to marker compounds (primary: 1-nitropyrene; secondary: 2-nitrofluoranthene and to NPAH or OPAH chemical profiles bring some indications on their primary and/or secondary origin. Indeed, 1,4-anthraquinone seemed only primary emitted by vehicles while 7-nitrobenz[a]anthracene, benz[a]antracen7,12-dione and benzo[b]fluorenone seemed secondarily formed in the atmosphere.

  1. Effect of phytoremediation on concentrations of benzene, toluene, naphthalene, and dissolved oxygen in groundwater at a former manufactured gas plant site, Charleston, South Carolina, USA, 1998–2014

    Science.gov (United States)

    Landmeyer, James E.; Effinger, Thomas N.

    2016-01-01

    Concentrations of benzene, toluene, naphthalene, and dissolved oxygen in groundwater at a former manufactured gas plant site near Charleston, South Carolina, USA, have been monitored since the installation of a phytoremediation system of hybrid poplar trees in 1998. Between 2000 and 2014, the concentrations of benzene, toluene, and naphthalene (BT&N) in groundwater in the planted area have decreased. For example, in the monitoring well containing the highest concentrations of BT&N, benzene concentrations decreased from 10,200 µg/L to less than 4000 µg/L, toluene concentrations decreased from 2420 µg/L to less than 20 µg/L, and naphthalene concentrations decreased from 6840 µg/L to less than 3000 µg/L. Concentrations of BT&N in groundwater in all wells were observed to be lower during the summer months relative to the winter months of a particular year during the first few years after installing the phytoremediation system, most likely due to increased transpiration and contaminant uptake by the hybrid poplar trees during the warm summer months; this pathway of uptake by trees was confirmed by the detection of benzene, toluene, and naphthalene in trees during sampling events in 2002, and later in the study in 2012. These data suggest that the phytoremediation system affects the groundwater contaminants on a seasonal basis and, over multiple years, has resulted in a cumulative decrease in dissolved-phase contaminant concentrations in groundwater. The removal of dissolved organic contaminants from the aquifer has resulted in a lower demand on dissolved oxygen supplied by recharge and, as a result, the redox status of the groundwater has changed from anoxic to oxic conditions. This study provides much needed information for water managers and other scientists on the viability of the long-term effectiveness of phytoremediation in decreasing groundwater contaminants and increasing dissolved oxygen at sites contaminated by benzene, toluene, and naphthalene.

  2. IMPLANTABLE RESONATORS – A TECHNIQUE FOR REPEATED MEASUREMENT OF OXYGEN AT MULTIPLE DEEP SITES WITH IN VIVO EPR

    Science.gov (United States)

    Li, Hongbin; Hou, Huagang; Sucheta, Artur; Williams, Benjamin B.; Lariviere, Jean P.; Khan, Nadeem; Lesniewski, Piotr N.; Swartz, Harold M.

    2013-01-01

    EPR oximetry using implantable resonators allow measurements at much deeper sites than are possible with surface resonators (> 80 mm vs. 10 mm) and have greater sensitivity at any depth. We report here the development of an improvement of the technique that now enables us to obtain the information from multiple sites and at a variety of depths. The measurements from the various sites are resolved using a simple magnetic field gradient. In the rat brain multi-probe implanted resonators measured pO2 at several sites simultaneously for over 6 months to record under normoxic, hypoxic and hyperoxic conditions. This technique also facilitates measurements in moving parts of the animal such as the heart, because the orientation of the paramagnetic material relative to the sensitive small loop is not altered by the motion. The measured response is very fast, enabling measurements in real time of physiological and pathological changes such as experimental cardiac ischemia in the mouse heart. The technique also is quite useful for following changes in tumor pO2, including applications with simultaneous measurements in tumors and adjacent normal tissues. PMID:20204802

  3. Modification of polystyrene-based activated carbon spheres to improve adsorption of dibenzothiophene

    Science.gov (United States)

    Wang, Qin; Liang, Xiaoyi; Qiao, Wenming; Liu, Chaojun; Liu, Xiaojun; Zhang, Rui; Ling, Licheng

    2009-01-01

    Polystyrene-based activated carbon spheres (PACS) were modified with either air, HNO 3, (NH 4) 2S 2O 8, H 2O 2 or H 2 to improve their adsorption properties of dibenzothiophene (DBT). The texture and surface chemistry of PACS were characterized by N 2 adsorption, scanning electron microscopy (SEM), temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), acid-base titration and elemental analysis. The results showed that HNO 3 and (NH 4) 2S 2O 8 treatments introduced large amount of acidic groups such as carboxylic, lactones and anhydride groups, while air and H 2O 2 had relatively mild effects and introduced a small quantity of phenol, carbonyl and ether groups. In the HNO 3 treatment, the acidic groups might be fixed on the internal and external surface of PACS, which may act as active sites of adsorption, resulting in increase of the adsorption amount by 45%. Whereas H 2O 2 and (NH 4) 2S 2O 8 treatments might fix more oxygen-containing groups on the external surface, which may hinder DBT molecule enter into micropores, leading to rather lower adsorption capacity with the extent of oxidation. So, the concentration, distribution and types of the acidic functional groups are responsible for the removal of DBT.

  4. Factors Influencing NO2 Adsorption/Reduction on Microporous Activated Carbon: Porosity vs. Surface Chemistry

    Directory of Open Access Journals (Sweden)

    Imen Ghouma

    2018-04-01

    Full Text Available The textural properties and surface chemistry of different activated carbons, prepared by the chemical activation of olive stones, have been investigated in order to gain insight on the NO2 adsorption mechanism. The parent chemical activated carbon was prepared by the impregnation of olive stones in phosphoric acid followed by thermal carbonization. Then, the textural properties and surface chemistry were modified by chemical treatments including nitric acid, sodium hydroxide and/or a thermal treatment at 900 °C. The main properties of the parent and modified activated carbons were analyzed by N2-adsorption, scanning electron microscopy (SEM, and Fourier transform infrared spectroscopy (FTIR techniques, in order to enlighten the modifications issued from the chemical and thermal treatments. The NO2 adsorption capacities of the different activated carbons were measured in fixed bed experiments under 500 ppmv NO2 concentrations at room temperature. Temperature programmed desorption (TPD was applied after adsorption tests in order to quantify the amount of the physisorbed and chemisorbed NO2. The obtained results showed that the development of microporosity, the presence of oxygen-free sites, and the presence of basic surface groups are key factors for the efficient adsorption of NO2.

  5. Physisorption and desorption of H2, HD and D2 on amorphous solid water ice. Effect on mixing isotopologue on statistical population of adsorption sites.

    Science.gov (United States)

    Amiaud, Lionel; Fillion, Jean-Hugues; Dulieu, François; Momeni, Anouchah; Lemaire, Jean-Louis

    2015-11-28

    We study the adsorption and desorption of three isotopologues of molecular hydrogen mixed on 10 ML of porous amorphous water ice (ASW) deposited at 10 K. Thermally programmed desorption (TPD) of H2, D2 and HD adsorbed at 10 K have been performed with different mixings. Various coverages of H2, HD and D2 have been explored and a model taking into account all species adsorbed on the surface is presented in detail. The model we propose allows to extract the parameters required to fully reproduce the desorption of H2, HD and D2 for various coverages and mixtures in the sub-monolayer regime. The model is based on a statistical description of the process in a grand-canonical ensemble where adsorbed molecules are described following a Fermi-Dirac distribution.

  6. [Effect of oxygen tubing connection site on percutaneous oxygen partial pressure and percutaneous carbon dioxide partial pressure in patients with chronic obstructive pulmonary disease during noninvasive positive pressure ventilation].

    Science.gov (United States)

    Mi, S; Zhang, L M

    2017-04-12

    Objective: We evaluated the effects of administering oxygen through nasal catheters inside the mask or through the mask on percutaneous oxygen partial pressure (PcO(2))and percutaneous carbon dioxide partial pressure (PcCO(2)) during noninvasive positive pressure ventilation (NPPV) to find a better way of administering oxygen, which could increase PcO(2) by increasing the inspired oxygen concentration. Methods: Ten healthy volunteers and 9 patients with chronic obstructive pulmonary disease complicated by type Ⅱ respiratory failure were included in this study. Oxygen was administered through a nasal catheter inside the mask or through the mask (oxygen flow was 3 and 5 L/min) during NPPV. PcO(2) and PcCO(2) were measured to evaluate the effects of administering oxygen through a nasal catheter inside the mask or through the mask, indirectly reflecting the effects of administering oxygen through nasal catheter inside the mask or through the mask on inspired oxygen concentration. Results: Compared to administering oxygen through the mask during NPPV, elevated PcO(2) was measured in administering oxygen through the nasal catheter inside the mask, and the differences were statistically significant ( P 0.05). Conclusion: Administering oxygen through a nasal catheter inside the mask during NPPV increased PcO(2) by increasing the inspired oxygen concentration but did not increase PcCO(2). This method of administering oxygen could conserve oxygen and be suitable for family NPPV. Our results also provided theoretical basis for the development of new masks.

  7. Influence of the precursor chemical composition on heavy metal adsorption properties of hemp (Cannabis Sativa fibers based biocarbon

    Directory of Open Access Journals (Sweden)

    Vukčević Marija M.

    2017-01-01

    Full Text Available Waste hemp (Cannabis sativa fibers were used as sustainable and renewable raw materials for production of low-cost biocarbon sorbent for heavy metals removal. Carbon precursors of different chemical composition were obtained by oxidative and alkaline treatments of hemp fibers. Influence of lignocellulosic precursor chemical composition on hemp fibers-based biocarbon (HFB characteristics was examined by BET surface area measurement, scanning electron microscopy and mass titration. It was found that lignin content and polymorphic transformation of cellulose increase the SBET of microporous HFBs, while hemicelluloses induce more homogeneous distribution of adsorption active sites. Heavy metal ions adsorption onto HFBs is primarily influenced by the amount of surface oxygen groups, while specific surface area plays a secondary role. Equilibrium data obtained for lead ions adsorption were analyzed by different nonlinear adsorption isotherms, and the best fitting model was chosen using standard deviation and Akaike information criterion (AICC. The maximum adsorption capacities of HFBs ranged from 103.1 to 116.3 mg Pb/g. Thermodynamic parameters showed that Pb2+ adsorption onto HFBs is a spontaneous and complex endothermic process, suggesting the coexistence of physisorption and chemisorption mechanisms. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. 172007 and Grant no. 172029

  8. Spectroscopic characterization of TeF and oxygen chemisorption onto silicon (111)

    International Nuclear Information System (INIS)

    Newlin, D.E.

    1979-01-01

    Chemiluminescence from the reactions of H 2 Te and D 2 Te with fluorine was observed at 3900 to 8600 A. Two separate band systems are attributed to the B 2 Σ-X 2 π and A 2 π-X 2 π transitions of the TeF radical. Moessbauer spectra were obtained of H 2 Te and D 2 Te in an argon matrix, and of TeF produced in the reaction of hydrogen telluride with fluorine. These are discussed with respect to the isotope effect and electron density calculations for the tellurium nucleus. Kinetics of chemisorption of oxygen on a silicon (111) surface were studied at 298 to 473 0 K using ESCA. Results are interpreted assuming immobile adsorption requiring two nearest neighbor surface sites. The initial sticking coefficient (theta << 1) is found to be S approx. = 0.1, and the activation energy of adsorption is determined as E/sub a/ = 1.6 +- 0.3 kcal/mole at theta = 0.4. Higher values of the sticking coefficient are obtained when the surface is contaminated with carbon produced at heated filaments in the vacuum system, so any consideration of oxygen adsorption onto an atomically clean silicon surface should use the lower values of the sticking coefficient reported in the literature. Results of this study are consistent with a model for oxygen chemisorption involving two surface sites per oxygen molecule

  9. Oxygen-Poor Microzones as Potential Sites of Microbial N2 Fixation in Nitrogen-Depleted Aerobic Marine Waters

    Science.gov (United States)

    Paerl, Hans W.; Prufert, Leslie E.

    1987-01-01

    The nitrogen-deficient coastal waters of North Carolina contain suspended bacteria potentially able to fix N2. Bioassays aimed at identifying environmental factors controlling the development and proliferation of N2 fixation showed that dissolved organic carbon (as simple sugars and sugar alcohols) and particulate organic carbon (derived from Spartina alterniflora) additions elicited and enhanced N2 fixation (nitrogenase activity) in these waters. Nitrogenase activity occurred in samples containing flocculent, mucilage-covered bacterial aggregates. Cyanobacterium-bacterium aggregates also revealed N2 fixation. In all cases bacterial N2 fixation occurred in association with surficial microenvironments or microzones. Since nitrogenase is oxygen labile, we hypothesized that the aggregates themselves protected their constituent microbes from O2. Microelectrode O2 profiles revealed that aggregates had lower internal O2 tensions than surrounding waters. Tetrazolium salt (2,3,5-triphenyl-3-tetrazolium chloride) reduction revealed that patchy zones existed both within microbes and extracellularly in the mucilage surrounding microbes where free O2 was excluded. Triphenyltetrazolium chloride reduction also strongly inhibited nitrogenase activity. These findings suggest that N2 fixation is mediated by the availability of the appropriate types of reduced microzones. Organic carbon enrichment appears to serve as an energy and structural source for aggregate formation, both of which were required for eliciting N2 fixation responses of these waters. Images PMID:16347337

  10. A density functional study on the adsorption of hydrogen molecule ...

    Indian Academy of Sciences (India)

    tive adsorption of H2 onto the minimum energy copper clusters by using the density ... theoretical study of molecular oxygen and atomic oxy- gen adsorption onto small ...... the values for all singlet spin states are zero, indicating that no ...

  11. A DFT study on benzene adsorption over tungsten sulfides: surface model and adsorption geometries

    NARCIS (Netherlands)

    Koide, R.; Hensen, E.J.M.; Paul, J.F.; Cristol, S.; Payen, E.; Nakamura, H.; Santen, van R.A.

    2007-01-01

    Benzene adsorption on a WS2(100) surface was studied by ab initio periodic DFT computations. Benzene adsorption is facile on the bridge site of the bare W edge via ¿2 or ¿3 coordination. Taking into account the stable configuration at the W edge under typical hydrotreating reaction conditions (623

  12. Adsorption and decomposition of dimethyl methylphosphonate (DMMP) on expanded graphite/metal oxides

    Science.gov (United States)

    Hung, Wei-Che; Wang, Je-Chuang; Wu, Kuo-Hui

    2018-06-01

    Composites based on expanded graphite (EG) and metal oxides (MOs) were prepared by an explosive combustion and blending method. A metal oxide (Ag2O, CuO or ZnO)-containing phase was employed as a component with reactive functionality, which was supported on EG as a component with adsorptive functionality. The physical properties of the EG/MO composites were examined using SEM and FTIR spectroscopy, the results of which indicated that the MOs were incorporated in the EG matrix after impregnation. Solid state magic angle spinning (MAS) 1H, 31P and cross polarization (CP) MAS 13C NMR studies of the EG/MO composites were performed after adsorption of dimethyl methylphosphonate (DMMP). The FTIR and NMR data showed that the initial uptake occurred through both molecular and reactive adsorption. Molecular adsorption occurred by van der Waals interaction of M(Zn, Cu, Ag)⋯Odbnd P and hydrogen-bond formation to isolated hydroxyl groups. Reactive chemisorption appeared to occur through interaction with both Lewis acid sites and active oxygen species present on the MO surface. The FTIR and NMR results exhibited a trend of reactivity towards DMMP in the order Ag2O > ZnO > CuO, which indicated stronger interaction between the Lewis acid sites and the phosphoryl O atom of DMMP for Ag2O as compared with ZnO and CuO, with concomitant formation of surface-coordinated DMMP and bridge-bonded Osbnd Psbnd O phosphorus oxide species.

  13. Adsorption of water on O(2x2)/Ru(0001): thermal stability and inhibition of dissociation by H2O-O bonding

    Energy Technology Data Exchange (ETDEWEB)

    Mugarza, Aitor; Shimizu, Tomoko; Cabrera-Sanfelix, Pepa; Sanchez-Portal, Daniel; Arnau, Andres; Salmeron, Miquel

    2008-08-01

    The effect of preadsorbed oxygen on the subsequent adsorption and reactions of water on Ru(0001) has been studied using low temperature scanning tunneling microscopy and DFT calculations. Experiments were carried out for O coverages close to 0.25 ML. It was found that no dissociation of water takes place up to the desorption temperature of {approx}180-230 K. DFT calculations show that intact water on O(2x2)/Ru(0001) is {approx} 0.49 eV more stable than the dissociation products, H and OH, at their preferred fcc and top adsorption sites.

  14. Does intraoperative low arterial partial pressure of oxygen increase the risk of surgical site infection following emergency exploratory laparotomy in horses?

    Science.gov (United States)

    Costa-Farré, Cristina; Prades, Marta; Ribera, Thaïs; Valero, Oliver; Taurà, Pilar

    2014-04-01

    Decreased tissue oxygenation is a critical factor in the development of wound infection as neutrophil mediated oxidative killing is an essential mechanism against surgical pathogens. The objective of this prospective case series was to assess the impact of intraoperative arterial partial pressure of oxygen (PaO2) on surgical site infection (SSI) in horses undergoing emergency exploratory laparotomy for acute gastrointestinal disease. The anaesthetic and antibiotic protocol was standardised. Demographic data, surgical potential risk factors and PaO2, obtained 1h after induction of anaesthesia were recorded. Surgical wounds were assessed daily for infection during hospitalisation and follow up information was obtained after discharge. A total of 84 adult horses were included. SSI developed in 34 (40.4%) horses. Multivariate logistic regression showed that PaO2, anaesthetic time and subcutaneous suture material were predictors of SSI (AUC=0.76, sensitivity=71%, specificity=65%). The use of polyglycolic acid sutures increased the risk and horses with a PaO2 value 2h had the highest risk of developing SSI (OR=9.01; 95% CI 2.28-35.64). The results of this study confirm the hypothesis that low intraoperative PaO2 contributes to the development of SSI following colic surgery. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. Supplemental Peri-Operative Oxygen and Incision Site Infection after Surgery for Perforated Peptic Ulcer: A Randomized, Double-Blind Monocentric Trial.

    Science.gov (United States)

    Schietroma, Mario; Cecilia, Emanuela Marina; De Santis, Giuseppe; Carlei, Francesco; Pessia, Beatrice; Amicucci, Gianfranco

    2016-02-01

    The clinical role of hyperoxia for preventing surgical site infection (SSI) remains uncertain because randomized controlled trials on this topic have reported disparate results. One of the principal reasons for this outcome may be that prior trials have entered heterogeneous populations of patients and a variety of procedures. The aim of our study was to assess the influence of hyperoxygenation on SSI using a homogeneous study population. From January 2004 to April 2013, we studied, in a randomized trial, 239 patients, who underwent open surgery for perforated peptic ulcer (PPU). The surgical procedure was performed through an upper abdominal midline incision, and closure of PPU was achieved by suture alone or in combination with an omental patch. Patients were assigned randomly to an oxygen/air mixture with a fraction of inspired oxygen (FiO2) of 30% (n = 120) or 80% (n = 119). Administration was commenced after induction of anesthesia and maintained for 6 hours after surgery. The overall incision infection rate was 38.4% (92 of 239): 61 patients (50.8%) had an infection in the 30% FiO2 group and 31 (26%) in the 80% FiO2 group (p operative SSI, should be considered part of ongoing quality improvement activities related to surgical care, with few risks to the patient and little associated cost.

  16. Hydrogen adsorption on and solubility in graphites

    International Nuclear Information System (INIS)

    Kanashenko, S.L.; Wampler, W.R.

    1996-01-01

    The experimental data on adsorption and solubility of hydrogen isotopes in graphite over a wide range of temperatures and pressures are reviewed. Langmuir adsorption isotherms are proposed for the hydrogen-graphite interaction. The entropy and enthalpy of adsorption are estimated, allowing for effects of relaxation of dangling sp 2 bonds. Three kinds of traps are proposed: edge carbon atoms of interstitial loops with an adsorption enthalpy relative to H 2 gas of -4.4 eV/H 2 (unrelaxed, Trap 1), edge carbon atoms at grain surfaces with an adsorption enthalpy of -2.3 eV/H 2 (relaxed, Trap 2), and basal plane adsorption sites with an enthalpy of +2.43 eV/H 2 (Trap 3). The adsorption capacity of different types of graphite depends on the concentration of traps which depends on the crystalline microstructure of the material. The number of potential sites for the 'true solubility' (Trap 3) is assumed to be about one site per carbon atom in all types of graphite, but the endothermic character of this solubility leads to a negligible H inventory compared to the concentration of hydrogen in type 1 and type 2 traps for temperatures and gas pressures used in the experiments. Irradiation with neutrons or carbon atoms increases the concentration of type 1 and type 2 traps from about 20 and 200 appm respectively for unirradiated (POCO AXF-5Q) graphite to about 1500 and 5000 appm, respectively, at damage levels above 1 dpa. (orig.)

  17. Oxygen Reduction on Platinum

    DEFF Research Database (Denmark)

    Nesselberger, Markus

    . The influence of the ion adsorption strength, which is observed in the “particle size studies” on the oxygen reduction rate on Pt/C catalysts, is further investigated under similar reaction conditions by infrared spectroscopy. The designed in situ electrochemical ATR-FTIR setup features a high level...... of instrument automation and online data treatment, and provides welldefined mass transport conditions enabling kinetic measurements. A modified electrochemical / spectroscopic interface is presented allowing the exclusive investigation of the Pt/C catalyst layer. Three types of potential dependent adsorption...... adsorption on Pt does not block the ORR directly. Instead, the onset of oxide formation with the concomitant conversion of the anion adsorbate layer is the decisive blocking mechanism....

  18. Site of mitochondrial reactive oxygen species production in skeletal muscle of chronic obstructive pulmonary disease and its relationship with exercise oxidative stress.

    Science.gov (United States)

    Puente-Maestu, Luis; Tejedor, Alberto; Lázaro, Alberto; de Miguel, Javier; Alvarez-Sala, Luis; González-Aragoneses, Federico; Simón, Carlos; Agustí, Alvar

    2012-09-01

    Exercise triggers skeletal muscle oxidative stress in patients with chronic obstructive pulmonary disease (COPD). The objective of this research was to study the specific sites of reactive oxygen species (ROS) production in mitochondria isolated from skeletal muscle of patients with COPD and its relationship with local oxidative stress induced by exercise. Vastus lateralis biopsies were obtained in 16 patients with COPD (66 ± 10 yr; FEV(1), 54 ± 12% ref) and in 14 control subjects with normal lung function who required surgery because of lung cancer (65 ± 7 yr; FEV(1), 91 ± 14% ref) at rest and after exercise. In these biopsies we isolated mitochondria and mitochondrial membrane fragments and determined in vitro mitochondrial oxygen consumption (Mit$$\\stackrel{.}{\\hbox{ V }}$$o(2)) and ROS production before and after inhibition of complex I (rotenone), complex II (stigmatellin), and complex III (antimycin-A). We related the in vitro ROS production during state 3 respiration), which mostly corresponds to the mitochondria respiratory state during exercise, with skeletal muscle oxidative stress after exercise, as measured by thiobarbituric acid reactive substances.State 3 Mit$$\\stackrel{.}{\\hbox{ V }}$$o(2) was similar in patients with COPD and control subjects (191 ± 27 versus 229 ± 46 nmol/min/mg; P = 0.058), whereas H(2)O(2) production was higher in the former (147 ± 39 versus 51 ± 8 pmol/mg/h; P release by mitochondria in patients with COPD and in control subjects. The mitochondrial production of H(2)O(2) in state 3 respiration was related (r = 0.69; P < 0.001) to postexercise muscle thiobarbituric acid reactive substance levels. Our results show that complex III is the main site of the enhanced mitochondrial H(2)O(2) production that occurs in skeletal muscle of patients with COPD, and the latter appears to contribute to muscle oxidative damage.

  19. Activated Carbon Preparation and Modification for Adsorption

    Science.gov (United States)

    Cao, Yuhe

    Butanol is considered a promising, infrastructure-compatible biofuel. Butanol has a higher energy content than ethanol and can be used in conventional gas engines without modifications. Unfortunately, the fermentation pathway for butanol production is restricted by its toxicity to the microbial strains used in the process. Butanol is toxic to the microbes, and this can slow fermentation rates and reduce butanol yields. Gas stripping technology can efficiently remove butanol from the fermentation broth as it is produced, thereby decreasing its inhibitory effects. Traditional butanol separation heavily depends on the energy intensive distillation method. One of the main issues in acetone-butanol-ethanol fermentation is that butanol concentrations in the fermentation broth are low, ranging from 1 to 1.2 percent in weight, because of its toxicity to the microorganisms. Therefore distillation of butanol is even worse than distillation of corn ethanol. Even new separation methods, such as solid- extraction methods involve adding substances, such as polymer resin and zeolite or activated carbon, to biobutanol fermentatioon broth did not achieve energy efficient separation of butanol due to low adsorption selectivity and fouling in broth. Gas-stripping - condensation is another new butanol recovery method, however, the butanol in gas-stripping stream is too low to be condensed without using expensive and energy intensive liquid nitrogen. Adsorption can then be used to recover butanol from the vapor phase. Activated carbon (AC) samples and zeolite were investigated for their butanol vapor adsorption capacities. Commercial activated carbon was modified via hydrothermal H2O2 treatment, and the specific surface area and oxygen-containing functional groups of activated carbon were tested before and after treatment. Hydrothermal H2O 2 modification increased the surface oxygen content, Brunauer-Emmett-Teller surface area, micropore volume, and total pore volume of active carbon

  20. Theoretical study of the adsorption of rhodium on a TiO{sub 2}(1 1 0)-1 Multiplication-Sign 1 surface

    Energy Technology Data Exchange (ETDEWEB)

    Mutombo, P., E-mail: mutombo@fzu.cz [Institute of Physics of Academy of Sciences of the Czech Republic, Cukrovarnicka 10, 16253 Praha 6 (Czech Republic); Balazs, N. [Reaction Kinetics Laboratory, Institute of Nanochemistry and Catalysis, CRC of the Hungarian Academy of Sciences, University of Szeged, P.O. Box 168, H-6701 Szeged (Hungary); Majzik, Z. [Institute of Physics of Academy of Sciences of the Czech Republic, Cukrovarnicka 10, 16253 Praha 6 (Czech Republic); Reaction Kinetics Laboratory, Institute of Nanochemistry and Catalysis, CRC of the Hungarian Academy of Sciences, University of Szeged, P.O. Box 168, H-6701 Szeged (Hungary); Berko, A. [Reaction Kinetics Laboratory, Institute of Nanochemistry and Catalysis, CRC of the Hungarian Academy of Sciences, University of Szeged, P.O. Box 168, H-6701 Szeged (Hungary); Chab, V. [Institute of Physics of Academy of Sciences of the Czech Republic, Cukrovarnicka 10, 16253 Praha 6 (Czech Republic)

    2012-03-01

    Density functional theory (DFT) calculations were used to study the adsorption of rhodium on a TiO{sub 2}(1 1 0)-1 Multiplication-Sign 1 surface as a function of coverage. It was found that Rh atom prefers the hollow site between a bridging oxygen atom, a threefold oxygen atom and a fivefold coordinated Ti atom, regardless of the coverage used. DFT calculations also suggest that Rh-Rh interaction is attractive along the [0 0 1] direction, implying that the Rh 1D nanostructure should grow preferentially along this direction. Simulated Rh dimer clusters resemble strongly Pd dimers resolved in STM experiments suggesting that both metals occupy the same adsorption site at the TiO{sub 2}(1 1 0) surface.

  1. Theoretical study of the adsorption of rhodium on a TiO2(1 1 0)-1 × 1 surface

    International Nuclear Information System (INIS)

    Mutombo, P.; Balázs, N.; Majzik, Z.; Berkó, A.; Cháb, V.

    2012-01-01

    Density functional theory (DFT) calculations were used to study the adsorption of rhodium on a TiO 2 (1 1 0)-1 × 1 surface as a function of coverage. It was found that Rh atom prefers the hollow site between a bridging oxygen atom, a threefold oxygen atom and a fivefold coordinated Ti atom, regardless of the coverage used. DFT calculations also suggest that Rh-Rh interaction is attractive along the [0 0 1] direction, implying that the Rh 1D nanostructure should grow preferentially along this direction. Simulated Rh dimer clusters resemble strongly Pd dimers resolved in STM experiments suggesting that both metals occupy the same adsorption site at the TiO 2 (1 1 0) surface.

  2. Arsenic Adsorption Equilibrium Concentration and Adsorption Rate of Activated Carbon Coated with Ferric-Aluminum Hydroxides

    Science.gov (United States)

    Zhang, M.; Sugita, H.; Oguma, T.; Hara, J.; Takahashi, S.

    2015-12-01

    In some areas of developing countries, ground or well water contaminated with arsenic has been reluctantly used as drinking water. It is highly desirable that effective and inexpensive arsenic removal agents should be developed and provided to reduce the potential health risk. Previous studies demonstrated that activated carbon coated with ferric-aluminum hydroxides (Fe-Al-C) has high adsorptive potential for removal of arsenic. In this study, a series of experiments using Fe-Al-C were carried to discuss adsorption equilibrium time, adsorption equilibrium concentration and adsorption rate of arsenic for Fe-Al-C. Fe-Al-C used in this study was provided by Astec Co., Ltd. Powder reagent of disodium hydrogen arsenate heptahydrate was dissolved into ion-exchanged water. The solution was then further diluted with ion-exchanged water to be 1 and 10 mg/L as arsenic concentration. The pH of the solution was adjusted to be around 7 by adding HCl and/or NaOH. The solution was used as artificial arsenic contaminated water in two types of experiments (arsenic adsorption equilibrium and arsenic adsorption rate tests). The results of the arsenic equilibrium tests were showed that a time period of about 3 days to reach apparent adsorption equilibrium for arsenic. The apparent adsorption equilibrium concentration and adsorbed amount of arsenic on Fe-Al-C adsorbent could be estimated by application of various adsorption isotherms, but the distribution coefficient of arsenic between solid and liquid varies with experimental conditions such as initial concentration of arsenic and addition concentration of adsorbent. An adsorption rate equation that takes into account the reduction in the number of effective adsorption sites on the adsorbent caused by the arsenic adsorption reaction was derived based on the data obtained from the arsenic adsorption rate tests.

  3. In situ characterization of cofacial Co(IV) centers in Co4O4 cubane: Modeling the high-valent active site in oxygen-evolving catalysts.

    Science.gov (United States)

    Brodsky, Casey N; Hadt, Ryan G; Hayes, Dugan; Reinhart, Benjamin J; Li, Nancy; Chen, Lin X; Nocera, Daniel G

    2017-04-11

    The Co 4 O 4 cubane is a representative structural model of oxidic cobalt oxygen-evolving catalysts (Co-OECs). The Co-OECs are active when residing at two oxidation levels above an all-Co(III) resting state. This doubly oxidized Co(IV) 2 state may be captured in a Co(III) 2 (IV) 2 cubane. We demonstrate that the Co(III) 2 (IV) 2 cubane may be electrochemically generated and the electronic properties of this unique high-valent state may be probed by in situ spectroscopy. Intervalence charge-transfer (IVCT) bands in the near-IR are observed for the Co(III) 2 (IV) 2 cubane, and spectroscopic analysis together with electrochemical kinetics measurements reveal a larger reorganization energy and a smaller electron transfer rate constant for the doubly versus singly oxidized cubane. Spectroelectrochemical X-ray absorption data further reveal systematic spectral changes with successive oxidations from the cubane resting state. Electronic structure calculations correlated to experimental data suggest that this state is best represented as a localized, antiferromagnetically coupled Co(IV) 2 dimer. The exchange coupling in the cofacial Co(IV) 2 site allows for parallels to be drawn between the electronic structure of the Co 4 O 4 cubane model system and the high-valent active site of the Co-OEC, with specific emphasis on the manifestation of a doubly oxidized Co(IV) 2 center on O-O bond formation.

  4. Toxicity of nano-TiO2 on algae and the site of reactive oxygen species production.

    Science.gov (United States)

    Li, Fengmin; Liang, Zhi; Zheng, Xiang; Zhao, Wei; Wu, Miao; Wang, Zhenyu

    2015-01-01

    Given the extensive use of nanomaterials, they may enter aquatic environments and harm the growth of algae, which are primary producers in an aquatic ecosystem. Thus, the balance of an aquatic ecosystem may be destroyed. In this study, Karenia brevis and Skeletonema costatum were exposed to nano-TiO2 (anatase, average particle size of 5-10 nm, specific surface area of 210±10 m(2) g(-1)) to assess the effects of nano-TiO2 on algae. The findings of transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDX) and scanning electron microscopy (SEM) demonstrate aggregation of nano-TiO2 in the algal suspension. Nano-TiO2 was also found to be inside algal cells. The growth of the two species of algae was inhibited under nano-TiO2 exposure. The 72 h EC50 values of nano-TiO2 to K. brevis and S. costatum were 10.69 and 7.37 mg L(-1), respectively. TEM showed that the cell membrane of K. brevis was destroyed and its organelles were almost undistinguished under nano-TiO2 exposure. The malondialdehyde (MDA) contents of K. brevis and S. costatum significantly increased compared with those of the control (pTiO2 exposure was explored with the addition of inhibitors of different electron transfer chains. This study indicated that nano-TiO2 in algal suspensions inhibited the growth of K. brevis and S. costatum. This effect was attributed to oxidative stress caused by ROS production inside algal cells. The levels of anti-oxidative enzymes changed, which destroyed the balance between oxidation and anti-oxidation. Thus, algae were damaged by ROS accumulation, resulting in lipid oxidation and inhibited algae growth. The inhibitors of the electron transfer chain showed that the site of ROS production and accumulation in K. brevis cells was the chloroplast. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Ozone adsorption on carbon nanoparticles

    Science.gov (United States)

    Chassard, Guillaume; Gosselin, Sylvie; Visez, Nicolas; Petitprez, Denis

    2014-05-01

    Carbonaceous particles produced by incomplete combustion or thermal decomposition of hydrocarbons are ubiquitous in the atmosphere. On these particles are adsorbed hundreds of chemical species. Those of great concern to health are polycyclic aromatic hydrocarbons (PAHs). During atmospheric transport, particulate PAHs react with gaseous oxidants. The induced chemical transformations may change toxicity and hygroscopicity of these potentially inhalable particles. The interaction between ozone and carbon particles has been extensively investigated in literature. However ozone adsorption and surface reaction mechanisms are still ambiguous. Some studies described a fast catalytic decomposition of ozone initiated by an atomic oxygen chemisorption followed by a molecular oxygen release [1-3]. Others suggested a reversible ozone adsorption according to Langmuir-type behaviour [4,5]. The aim of this present study is a better understanding of ozone interaction with carbon surfaces. An aerosol of carbon nanoparticles was generated by flowing synthetic air in a glass tube containing pure carbon (primary particles studied. Accordingly to literature, it has been observed that the number of gas-phase ozone molecules lost per unit particle surface area tends towards a plateau for high ozone concentration suggesting a reversible ozone adsorption according to a Langmuir mechanism. We calculated the initial reaction probability between O3 and carbon particles.An initial uptake coefficient of 1.10-4 was obtained. Similar experiments were realized by selecting the particles size with a differential mobility analyser. We observed a strong size-dependent increase in reactivity with the decrease of particles size. This result is relevant for the health issues. Indeed the smallest particles are most likely to penetrate deep into the lungs. Competitive reactions between ozone and other species like H2O or atomic oxygen were also considered. Oxygen atoms were generated by photolysis of O3

  6. Facile Assembly of 3D Porous Reduced Graphene Oxide/Ultrathin MnO2 Nanosheets-S Aerogels as Efficient Polysulfide Adsorption Sites for High-Performance Lithium-Sulfur Batteries.

    Science.gov (United States)

    Zhao, Xiaojun; Wang, Hui; Zhai, Gaohong; Wang, Gang

    2017-05-23

    Rechargeable lithium-sulfur (Li-S) batteries are receiving much attention due to their high specific capacity, low cost, and environmental friendliness. Nonetheless, fast capacity decay and low specific capacity still limit their practical implementation. Herein, we report a facile strategy to overcome these challenges by the design and fabrication of 3D porous reduced graphene oxide/ultrathin MnO 2 nanosheets-S aerogel (rGM-SA) composites for Li-S batteries. By a simple solvothermal reaction process, nanosized S atoms are homogeneously decorated into the 3D scaffold formed by reduced graphene oxide (rGO) and MnO 2 nanosheets, which can form the homogeneous rGM-SA composites. In this porous network architecture, rGO serves as an electron and ion transfer pathway, a physical adsorption site for polysulfides, and provides structural stability. The ultrathin MnO 2 nanosheets provide strong binding sites for trapping polysulfide intermediates. The 3D porous rGO/MnO 2 architecture enables rapid ion transport and buffers volume expansion of sulfur during discharge. The rGM-SA composites can be directly used as lithium-sulfur battery cathodes without using binder and conductive additive. As a result of this multifunctional arrangement, the rGM-SA composites exhibit high and stable-specific capacities over 200 cycles and excellent high-rate performances. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Density functional theory study of the adsorption and dissociation of O{sub 2} on CuO(1 1 1) surface

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Shujuan, E-mail: sunshujuan@hebut.edu.cn [School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130 (China); Li, Chunyu [Science and Technology Innovation Center, Datang Technologies Industry Group Company Limited, Beijing (China); Zhang, Dongsheng [School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130 (China); Wang, Yanji, E-mail: yjwang@hebut.edu.cn [School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130 (China)

    2015-04-01

    Highlights: • The dissociation mechanisms of O{sub 2} on the CuO(1 1 1) surface have been obtained. • The energy barriers and reaction energies are calculated. • The presence of oxygen vacancy can obviously improve the catalytic activity of CuO. - Abstract: Density functional theory (DFT) have been performed to investigate the adsorption and dissociation of O{sub 2} on the perfect and oxygen-deficient CuO(1 1 1) surfaces. The calculated results indicate that the bridge site of two Cu{sub sub} atoms is the most favorable site for O adsorption on the perfect CuO(1 1 1) surface. But on the oxygen-deficient CuO(1 1 1) surface, the O atom adsorbed on O{sub vacancy} site after optimization. On the perfect and oxygen-deficient CuO(1 1 1) surfaces, the O{sub 2} are all paralleling to the surface after optimization. Possible dissociation pathways of molecularly adsorbed O{sub 2} on the two surfaces are identified. The calculated results suggest that the presence of oxygen vacancy exhibits a strong chemical reactivity towards the dissociation of O{sub 2} and can obviously improve the catalytic activity of CuO.

  8. Adsorption of Zn(II) on the kaolinite(001) surfaces in aqueous environment: A combined DFT and molecular dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Qiang; Kong, Xiang-Ping; Zhang, Bao-Hua; Wang, Juan, E-mail: juaner80@163.com

    2017-08-31

    Highlights: • Zn(II) adsorption on two types of neutral kaolinite(001) surfaces is investigated. • Surface “Ou” is found the preferred site for mono- and bi-dentate complexes. • Both Zn(II) and surface oxygen accept electrons from aqua oxygens. • Coupling of O 2p with Zn sp{sup 3}d{sup 2} (or sp{sup 3}) hybridization states is the bonding nature. - Abstract: Adsorption of Zn(II) on two types of neutral (001) surfaces of kaolinite, tetrahedral Si(t) and octahedral Al(o), was studied by means of DFT calculations and classical molecular dynamics simulations. The position and structure for both outer-sphere and mono-/bi-dentate inner-sphere complexes of Zn(II) in aqueous environment were examined, with binding energy and radial distribution function calculated. Outer-sphere complex on the Si(t) surface, monodentate inner-sphere complex of “O{sub u}” (surface oxygen with “upright” hydrogen) site and bidentate complex of “O{sub u}-O{sub u}” site of neighboring Al centers on the Al(o) surface are considered to be the dominant adsorption species. The outer-sphere complex is found six-coordinated with distorted octahedral geometry, while both the inner-sphere complexes exhibit the tetrahedral structure with coordination number of four. Hydrogen bonding interactions between oxygen or hydrogen of the kaolinite(001) surfaces and the aqua ligands of Zn(II) act as the key role for the structure and stability of adsorption complexes. Upon the Mulliken population analysis and partial density of states, both Zn(II) and surface oxygen accept electrons from aqua oxygens, and coupling of O 2p with the sp{sup 3}d{sup 2} or sp{sup 3} hybridization states of Zn(II) is the primary bonding nature of Zn(II) with oxygen in outer- and inner-sphere complexes, respectively.

  9. Adsorption and Photodesorption of CO from Charged Point Defects on TiO 2 (110)

    Energy Technology Data Exchange (ETDEWEB)

    Mu, Rentao; Dahal, Arjun P.; Wang, Zhitao; Dohnalek, Zdenek; Kimmel, Gregory A.; Petrik, Nikolay G.; Lyubinetsky, Igor V.

    2017-09-12

    Adsorption and photodesorption of weakly-bound carbon monoxide, CO, from reduced and hydroxylated rutile TiO2(110) (r- and h- TiO2(110)) at sub-monolayer coverages is studied with atomically-resolved scanning tunneling microscopy (STM) along with ensemble-averaged temperature-programmed desorption (TPD) and angle-resolved photon-stimulated desorption (PSD) at low temperatures ( 50 K). STM data weighted by the concentration of each kind of adsorption sites on r-TiO2(110) give an adsorption probability which is the highest for the bridging oxygen vacancies (VO) and very low for the Ti5c sites closest to VO. Occupancy of the remaining Ti5c sites with CO is significant, but smaller than for VO. The probability distribution for the different adsorption sites corresponds to a very small difference in CO adsorption energies: < 0.02 eV. We also find that UV irradiation stimulates both diffusion and desorption of CO at low temperature. CO photodesorbs primarily from the vacancies with a bi-modal angular distribution. In addition to a major, normal to the surface component, there is a broader cosine component indicating scattering from the surface which likely also leads to photo-stimulated diffusion. Hydroxylation of VO’s does not significantly change the CO PSD yield and angular distribution, indicating that not atomic but rather electronic surface defects are involved in the site-specific PSD process. We suggest that photodesorption can be initiated by recombination of photo-generated holes with excess unpaired electrons localized near the surface point-defect (either VO or bridging hydroxyl), leading to the surface atoms rearrangement and ejection of the weakly-bound CO molecules.

  10. Two-dimensional boron: Lightest catalyst for hydrogen and oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Mir, Showkat H. [Centre for Nano Science, Central University of Gujarat, Gandhinagar 382030 (India); Chakraborty, Sudip, E-mail: sudiphys@gmail.com, E-mail: prakash.jha@cug.ac.in; Wärnå, John [Condensed Matter Theory Group, Department of Physics and Astronomy, Uppsala University, Uppsala 75120 (Sweden); Jha, Prakash C., E-mail: sudiphys@gmail.com, E-mail: prakash.jha@cug.ac.in [School of Applied Material Sciences, Central University of Gujarat, Gandhinagar 382030 (India); Soni, Himadri [Lehrstuhl für Theoretische Chemie, Friedrich-Alexander Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen (Germany); Jha, Prafulla K. [Department of Physics, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara 390 002 (India); Ahuja, Rajeev [Condensed Matter Theory Group, Department of Physics and Astronomy, Uppsala University, Uppsala 75120 (Sweden); Department of Materials and Engineering, Royal Institute of Technology (KTH), 10044 Stockholm (Sweden)

    2016-08-01

    The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) have been envisaged on a two-dimensional (2D) boron sheet through electronic structure calculations based on a density functional theory framework. To date, boron sheets are the lightest 2D material and, therefore, exploring the catalytic activity of such a monolayer system would be quite intuitive both from fundamental and application perspectives. We have functionalized the boron sheet (BS) with different elemental dopants like carbon, nitrogen, phosphorous, sulphur, and lithium and determined the adsorption energy for each case while hydrogen and oxygen are on top of the doping site of the boron sheet. The free energy calculated from the individual adsorption energy for each functionalized BS subsequently guides us to predict which case of functionalization serves better for the HER or the OER.

  11. Cesium adsorption on In0.53Ga0.47As (1 0 0) β2 (2 × 4) surface: A first-principles research

    International Nuclear Information System (INIS)

    Guo, Jing; Chang, Benkang; Jin, Muchun; Wang, Honggang; Wang, MeiShan

    2015-01-01

    Highlights: • Eight different cesium adsorption In 0.53 Ga 0.47 As (1 0 0) β 2 (2 × 4) surface models have been built. • Surface characteristics of the cesium adsorption In 0.53 Ga 0.47 As (1 0 0) β 2 (2 × 4) surfaces are investigated based on the first principle. • New energy bands appear and band gap is narrowed after adsorption. • The cesium adsorption enhances the surface ionization. • T 2 and T 3 are the reasonable adsorption sites relatively. - Abstract: In 0.53 Ga 0.47 As is a perfect III–V compound semiconductor for the photoemissive layer of the infrared-extension negative electron affinity photocathode. It is the key step for the formation of negative electron affinity that the cesium atoms and oxygen atoms activate the photocathode surface alternately. Geometry optimizations based on the first principles have been carried out for the In 0.53 Ga 0.47 As (1 0 0) β 2 (2 × 4) surfaces with a cesium atom adsorbed on 8 different possible sites named as D, D′, T 2 , T 2 ′, T 3 , T 3 ′, T 4 and T 4 ′. The surfaces characteristics have been investigated before and after adsorption from the point of negative electron affinity formation. Meanwhile, the surface atom structure, the adsorption energy, work function, surface energy bands, charge transfer and the dipole generation of the 8 different adsorption surfaces have been compared to each other. The work function and the surface energy bands have been analyzed in detail, which are closely related with the photoelectrons escaping from the surface. The surface work functions are all decreased in varying degrees and energy band bends all appear at the 8 different adsorption sites due to the surface charge transfer and the dipole formation. In conclusion, T 2 and T 3 are the favorable adsorption sites relatively. The surfaces with a cesium atom adsorbed on these two sites are most stable and have much lower work functions, which generates reasonable energy band bend and is benefit for the

  12. Hemoglobin Rahere, a human hemoglobin variant with amino acid substitution at the 2,3-diphosphoglycerate binding site. Functional consequences of the alteration and effects of bezafibrate on the oxygen bindings.

    OpenAIRE

    Sugihara, J; Imamura, T; Nagafuchi, S; Bonaventura, J; Bonaventura, C; Cashon, R

    1985-01-01

    We encountered an abnormal hemoglobin (Rahere), with a threonine residue replacing the beta 82 (EF6) lysine residue at the binding site of 2,3-diphosphoglycerate, which was responsible for overt erythrocytosis in two individuals of a Japanese family. Hemoglobin Rahere shows a lower oxygen affinity on the binding of 2,3-diphosphoglycerate or chloride ions than hemoglobin A. Although a decrease in the positive charge density at the binding sites of 2,3-diphosphoglycerate in hemoglobin Rahere ap...

  13. The Adsorption Mechanism of Modified Activated Carbon on Phenol

    Directory of Open Access Journals (Sweden)

    Lin J. Q.

    2016-01-01

    Full Text Available Modified activated carbon was prepared by thermal treatment at high temperature under nitrogen flow. The surface properties of the activated carbon were characterized by Boehm titration, BET and point of zero charge determination. The adsorption mechanism of phenol on modified activated carbon was explained and the adsorption capacity of modified activated carbon for phenol when compared to plain activated carbon was evaluated through the analysis of adsorption isotherms, thermodynamic and kinetic properties. Results shows that after modification the surface alkaline property and pHpzc value of the activated carbon increase and the surface oxygen-containing functional groups decrease. The adsorption processes of the plain and modified carbon fit with Langmuir isotherm equation well, and the maximum adsorption capacity increase from 123.46, 111.11, 103.09mg/g to 192.31, 178.57, 163,93mg/g under 15, 25 and 35°C after modification, respectively. Thermodynamic parameters show that the adsorption of phenol on activated carbon is a spontaneously exothermic process of entropy reduction, implying that the adsorption is a physical adsorption. The adsorption of phenol on activated carbon follows the pseudo-second-order kinetics (R2>0.99. The optimum pH of adsorption is 6~8.

  14. Adsorption behavior of Am(III) on granite

    International Nuclear Information System (INIS)

    Zhang Yingjie; Feng Xiaogui; Liang Junfu; Chen Jing; Su Rui; Wang Ju; Liu Chunli

    2009-01-01

    The adsorption behavior of Am(III) on granite (sampled from drilling well BS01 at Beishan (BS) area--a potential candidate site for China's high-level radioactive waste repository, the granite sample's depth about 300 m) was studied in BS03 well groundwater by a batch technique at (25±1) degree C. The influences of pH, sulphate ion, total carbonate ion, humic acid, and concentration of the Am(III) on the adsorption behavior were also studied, and the possible adsorption mechanism was discussed. Experimental results show that the adsorption distribution rate of Am(III) on granite increases with increasing pH of aqueous phase. The chemical composition of the groundwater is the main factor which influences the species of Am(III) and adsorption behavior. The adsorption mechanism of Am(III) on granite is surface complexation. The adsorption isotherm of Am(III) on granite can be described by Freundlich's equation. (authors)

  15. Hydrogen adsorption on bimetallic PdAu(111) surface alloys

    DEFF Research Database (Denmark)

    Takehiro, Naoki; Liu, Ping; Bergbreiter, Andreas

    2014-01-01

    The adsorption of hydrogen on structurally well defined PdAu-Pd(111) monolayer surface alloys was investigated in a combined experimental and theoretical study, aiming at a quantitative understanding of the adsorption and desorption properties of individual PdAu nanostructures. Combining...... the structural information obtained by high resolution scanning tunneling microscopy (STM), in particular on the abundance of specific adsorption ensembles at different Pd surface concentrations, with information on the adsorption properties derived from temperature programmed desorption (TPD) spectroscopy...... and high resolution electron energy loss spectroscopy (HREELS) provides conclusions on the minimum ensemble size for dissociative adsorption of hydrogen and on the adsorption energies on different sites active for adsorption. Density functional theory (DFT) based calculations give detailed insight...

  16. Synergistic interaction and controllable active sites of nitrogen and sulfur co-doping into mesoporous carbon sphere for high performance oxygen reduction electrocatalysts

    Science.gov (United States)

    Oh, Taeseob; Kim, Myeongjin; Park, Dabin; Kim, Jooheon

    2018-05-01

    Nitrogen and sulfur co-doped mesoporous carbon sphere (NSMCS) was prepared as a metal-free catalyst by an economical and facile pyrolysis process. The mesoporous carbon spheres were derived from sodium carboxymethyl cellulose as the carbon source and the nitrogen and sulfur dopants were derived from urea and p-benzenedithiol, respectively. The doping level and chemical states of nitrogen and sulfur in the prepared NSMCS can be easily adjusted by controlling the pyrolysis temperature. The NSMCS pyrolyzed at 900 °C (NSMCS-900) exhibited higher oxygen reduction reaction activity than the mesoporous carbon sphere doped solely with nitrogen or sulfur, due to the synergistic effect of co-doping. Among all the NSMCS samples, NSMCS-900 exhibited excellent ORR catalytic activity owing to the presence of a highly active site, consisting of pyridinic N, graphitic N, and thiophene S. Remarkably, the NSMCS-900 catalyst was comparable with commercial Pt/C, in terms of the onset and the half-wave potentials and showed better durability than Pt/C for ORR in an alkaline electrolyte. The approach demonstrated in this work could be used to prepare promising metal-free electrocatalysts for application in energy conversion and storage.

  17. Interfacial adsorption of insulin - Conformational changes and reversibility of adsorption

    NARCIS (Netherlands)

    Mollmann, SH; Jorgensen, L; Bukrinsky, JT; Elofsson, U; Norde, W; Frokjaer, S

    The adsorption of human insulin to Teflon particles was studied with respect to conformational changes and the reversibility of adsorption was examined by total internal reflection fluorescence (TIRF). Adsorption isotherms for the adsorption of human insulin indicated high affinity adsorption, even

  18. Adsorption of ethanol on V{sub 2}O{sub 5} (010) surface for gas-sensing applications: Ab initio investigation

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Yuxiang, E-mail: qinyuxiang@tju.edu.cn [School of Electronics and Information Engineering, Tianjin University, Tianjin 300072 (China); Key Laboratory for Advanced Ceramics and Machining Technology, Ministry of Education, School of Materials Science and Engineering, Tianjin University, Tianjin 300072 (China); Cui, Mengyang; Ye, Zhenhua [School of Electronics and Information Engineering, Tianjin University, Tianjin 300072 (China)

    2016-08-30

    Highlights: • Ethanol adsorbed on V{sub 2}O{sub 5} (010) surface was investigated by ab initio calculations. • Ethanol prefers to adsorb on “Hill”-like surface, rather than“Valley”-like region. • Surface O{sub 1(H)} site plays a key role to dominate the ethanol adsorption process. • Sensing mechanism is related with electronic structure and electron redistribution. • Gas sensitivity is reflected by quantitative electron population analysis. - Abstract: The adsorption of ethanol on V{sub 2}O{sub 5} (010) surface was investigated by means of density functional theory (DFT) with a combined generalized gradient approximation (GGA) plus Hubbard U approach to exploit the potential sensing applications. The adsorption configurations were first constructed by considering different orientations of ethanol molecule to V and O sites on the “Hill”- and “Valley”-like regions of corrugated (010) surface. It is found that ethanol molecule can adsorb on whole surface in multiple stable configurations. Nevertheless the molecular adsorption on the “Hill”-like surface is calculated to occur preferentially, and the single coordinated oxygen on “Hill”-like surface (O{sub 1(H)}) acting as the most energetically favorable adsorption site shows the strongest adsorption ability to ethanol molecule. Surface adsorption of ethanol tunes the electronic structure of V{sub 2}O{sub 5} and cause an n-doping effect. As a consequence, the Fermi levels shift toward the conductive bond increasing the charge carrier concentration of electrons in adsorbed V{sub 2}O{sub 5}. The sensitive electronic structure and the multiple stable configurations to ethanol adsorption highlight the high adsorption activity and then the potential of V{sub 2}O{sub 5} (010) surface applied to high sensitive sensor for ethanol vapor detection. Further Mulliken population and Natural bond orbital (NBO) calculations quantify the electron transfer from the adsorbed ethanol to the surface, and

  19. Lithium Mediated Benzene Adsorption on Graphene and Graphene Nanoribbons

    OpenAIRE

    Krepel, Dana; Hod, Oded

    2013-01-01

    The anchoring of benzene molecules on lithium adsorption sites at the surface of graphene and nanoribbons thereof are investigated. The effects of adsorbate densities, specific adsorption locations, and spin states on the structural stability and electronic properties of the underlying graphene derivatives are revealed. At sufficiently high densities, bare lithium adsorption turns armchair graphene nanoribbons metallic and their zigzag counterparts half-metallic due to charge transfer from th...

  20. Random and cooperative sequential adsorption

    Science.gov (United States)

    Evans, J. W.

    1993-10-01

    Irreversible random sequential adsorption (RSA) on lattices, and continuum "car parking" analogues, have long received attention as models for reactions on polymer chains, chemisorption on single-crystal surfaces, adsorption in colloidal systems, and solid state transformations. Cooperative generalizations of these models (CSA) are sometimes more appropriate, and can exhibit richer kinetics and spatial structure, e.g., autocatalysis and clustering. The distribution of filled or transformed sites in RSA and CSA is not described by an equilibrium Gibbs measure. This is the case even for the saturation "jammed" state of models where the lattice or space cannot fill completely. However exact analysis is often possible in one dimension, and a variety of powerful analytic methods have been developed for higher dimensional models. Here we review the detailed understanding of asymptotic kinetics, spatial correlations, percolative structure, etc., which is emerging for these far-from-equilibrium processes.

  1. Hemoglobin Rahere, a human hemoglobin variant with amino acid substitution at the 2,3-diphosphoglycerate binding site. Functional consequences of the alteration and effects of bezafibrate on the oxygen bindings.

    Science.gov (United States)

    Sugihara, J; Imamura, T; Nagafuchi, S; Bonaventura, J; Bonaventura, C; Cashon, R

    1985-09-01

    We encountered an abnormal hemoglobin (Rahere), with a threonine residue replacing the beta 82 (EF6) lysine residue at the binding site of 2,3-diphosphoglycerate, which was responsible for overt erythrocytosis in two individuals of a Japanese family. Hemoglobin Rahere shows a lower oxygen affinity on the binding of 2,3-diphosphoglycerate or chloride ions than hemoglobin A. Although a decrease in the positive charge density at the binding sites of 2,3-diphosphoglycerate in hemoglobin Rahere apparently shifts the allosteric equilibrium toward the low affinity state, it greatly diminishes the cofactor effects by anions. The oxygen affinity of the patient's erythrocytes is substantially lowered by the presence of bezafibrate, which combines with sites different from those of 2,3-diphosphoglycerate in either hemoglobin Rahere or hemoglobin A.

  2. Adsorption. What else?

    OpenAIRE

    Rodrigues, Alirio E.

    2012-01-01

    [EN] Chemical Engineering today combines Molecular and Materials Engineerig and Process and Product Engineering (ChE=M2P2). Cyclic adsorptive processes (Simulated Moving Bed –SMB and Pressure Swing Adsorption-PSA) will be discussed for “old” and “new” applications making use of “old” and “new” (MOFs) adsorbent materials. After revisiting my memory as PhD student and the First Brazilian Adsorption meeting I will review the basic concepts involved in adsorption processes and then...

  3. Enhanced photocatalytic activity for degrading pollutants of g-C{sub 3}N{sub 4} by promoting oxygen adsorption after H{sub 3}BO{sub 3} modification

    Energy Technology Data Exchange (ETDEWEB)

    Li, Chengming; Raziq, Fazal; Liu, Chong; Li, Zhijun [Key Laboratory of Functional Inorganic Materials Chemistry (Heilongjiang University), Ministry of Education, School of Chemistry and Materials Science, Harbin 150080 (China); Sun, Liqun [Key Laboratory of Functional Inorganic Materials Chemistry (Heilongjiang University), Ministry of Education, School of Chemistry and Materials Science, Harbin 150080 (China); College of Chemical Engineering, Daqing Normal University, Daqing 163712 (China); Jing, Liqiang, E-mail: jinglq@hlju.edu.cn [Key Laboratory of Functional Inorganic Materials Chemistry (Heilongjiang University), Ministry of Education, School of Chemistry and Materials Science, Harbin 150080 (China)

    2015-12-15

    Graphical abstract: - Highlights: • G-C{sub 3}N{sub 4} is modified by a hydrothermal post treatment with orthoboric acid. • The surface modification could enhance the separation of photogenerated charges. • This leads to the enhanced photocatalytic activities for degrading pollutants. • The borate acid modification favors O{sub 2} adsorption to promote charge separation. - Abstract: The g-C{sub 3}N{sub 4} has been modified by a hydrothermal post treatment with orthoboric acid. It is shown that the surface modification with an appropriate amount of orthoboric acid obviously enhances the surface photovoltage responses of g-C{sub 3}N{sub 4}, clearly indicating that the separation of photogenerated charges is greatly improved. This is well responsible for the enhanced photocatalytic activities for degrading representative gas-phase acetaldehyde, and liquid-phase phenol. Moreover, it is demonstrated that the amount of O{sub 2} adsorbed on the surfaces of g-C{sub 3}N{sub 4} is greatly increased after H{sub 3}BO{sub 3} modification based on the O{sub 2} temperature-programmed desorption curves. It is suggested that the orthoboric acid modification favors O{sub 2} adsorption to promote the photogenerated electrons captured for improved photocatalytic activities. This work would provide feasible routes to further improve the photocatalytic performance of semiconductors for degrading pollutants.

  4. Hydrogen peroxide reduction in the oxygen vacancies of ZnO nanotubes

    International Nuclear Information System (INIS)

    Peyghan, Ali Ahmadi; Laeen, Shima Parizad; Aslanzadeh, Saeed Amir; Moradi, Morteza

    2014-01-01

    The adsorption of a H 2 O 2 molecule on the pristine and O-vacancy defected ZnO nanotubes was investigated by means of density functional calculations. It was found that the molecule prefers to attach to two zinc atoms of the tube from its two oxygen atoms with the adsorption energy of 254.1 kJ/mol. Attachment of the H 2 O 2 to the wall of the tube does not have any significant influence on its highest occupied molecular orbital/lowest unoccupied molecular orbital gap (E g ). The presence of oxygen vacancy defect causes a decrease in the E g of the tube and, as a consequence, may cause an increase in the conductivity of the tube. The zinc atoms of the defect are more reactive toward H 2 O 2 reduction to H 2 O than perfect ones with the adsorption energy of 617.4 kJ/mol. During the adsorption process, the H 2 O 2 was reoriented in such a way that its O atom has diffused into vacancy site, so that O-O and O-H bonds of the molecule were dissociated and an H 2 O is formed. Thus, we think that ZnO-NTs may be a candidate for electrochemical reduction and detection of H 2 O 2 . - Highlights: • H 2 O 2 adsorption on pristine and O-vacancy defected ZnO nanotubes was studied by DFT. • H 2 O 2 does not have any significant influence on the gap of the tube. • Presence of oxygen vacancy defect causes a decrease in the gap of the tube. • ZnO nanotubes may be a candidate for electrochemical reduction and detection of H 2 O 2

  5. Effect of intra-operative high inspired oxygen fraction on surgical site infection: a meta-analysis of randomized controlled trials.

    Science.gov (United States)

    Yang, W; Liu, Y; Zhang, Y; Zhao, Q-H; He, S-F

    2016-08-01

    Surgical site infection (SSI) causes significant mortality and morbidity. Administration of a high inspired oxygen fraction (FiO2) to patients undergoing surgery may represent a potential preventive strategy. To conduct a meta-analysis of randomized controlled trials in which high FiO2 was compared with normal FiO2 in patients undergoing surgery to estimate the effect on the development of SSI. A comprehensive search was undertaken for randomized controlled trials (until December 2015) that compared high FiO2 with normal FiO2 in adults undergoing surgery with general anaesthesia and reported on SSI. This study included 17 randomized controlled trials with 8093 patients. Infection rates were 13.11% in the control group and 11.53% in the hyperoxic group, while the overall risk ratio was 0.893 [95% confidence interval (CI) 0.794-1.003; P = 0.057]. Subgroup analyses stratified by country, definition of SSI, and type of surgery were also performed, and showed similar results. However, high FiO2 was found to be of significant benefit in patients undergoing colorectal surgery, with a risk ratio of 0.735 (95% CI 0.573-0.944; P=0.016). There is moderate evidence to suggest that administration of high FiO2 to patients undergoing surgery, especially colorectal surgery, reduces the risk of SSI. Further studies with better adherence to the intervention may affect the results of this meta-analysis. Copyright © 2016 The Healthcare Infection Society. Published by Elsevier Ltd. All rights reserved.

  6. Assessment of tissue oxygen saturation during a vascular occlusion test using near-infrared spectroscopy: the role of probe spacing and measurement site studied in healthy volunteers

    NARCIS (Netherlands)

    Bezemer, R.; Lima, A.; Myers, D.; Klijn, E.; Heger, M.; Goedhart, P.T.; Bakker, J.; Ince, C.

    2009-01-01

    INTRODUCTION: To assess potential metabolic and microcirculatory alterations in critically ill patients, near-infrared spectroscopy (NIRS) has been used, in combination with a vascular occlusion test (VOT), for the non-invasive measurement of tissue oxygen saturation (StO2), oxygen consumption, and

  7. [Adsorption kinetics and mechanism of lead (II) on polyamine-functionalized mesoporous activated carbon].

    Science.gov (United States)

    Li, Kun-Quan; Wang, Yan-Jin; Yang, Mei-Rong; Zhu, Zhi-Qiang; Zheng, Zheng

    2014-08-01

    Bagasse mesoporous carbon was prepared by microwave assisted H3 PO4 activation. Amido and imido groups were modified with ethanediamine on the channels' surface of mesoporous carbon through nitric oxidation and amide reaction. The influence of Pb(II) concentration, adsorption time on Pb(II) adsorption on the ethanediamine-modified mesoporous carbon (AC-EDA) was investigated. The adsorption kinetics and mechanism were also discussed. The results showed that AC-EDA had a great performance for Pb(II) adsorption, and more than 70% of Pb(II) was adsorbed in 5 minutes. The adsorption amount of Pb(II) on the carbon increased with the increase of solution pH in acidic conditions. It was found that AC-EDA had different binding energies on different adsorption sites for Pb(II) separation. The Pb(II) adsorption process on AC-EDA was controlled by intra-particle diffusion in the first 3 min, and then film diffusion played the important pole on the adsorption. The adsorption amount increased with the increase of temperature, indicating the adsorption was an endothermic reaction. The high adsorption energy (> 11 kJ x mol(-1)) implied that the) adsorption was a chemical adsorption. The XPS of AC-EDA before and after Pb(II) adsorption showed that the polyamine group was involved in the adsorption, and should be a main factor of the high efficient adsorption.

  8. Adsorption of Cr(III) on ozonised activated carbon. Importance of Cpi-cation interactions.

    Science.gov (United States)

    Rivera-Utrilla, J; Sánchez-Polo, M

    2003-08-01

    The adsorption of Cr(III) in aqueous solution was investigated on a series of ozonised activated carbons, analysing the effect of oxygenated surface groups on the adsorption process. A study was carried out to determine the adsorption isotherms and the influence of the pH on the adsorption of this metal. The adsorption capacity and affinity of the adsorbent for Cr(III) increased with the increase in oxygenated acid groups on the surface of the activated carbon. These findings imply that electrostatic-type interactions predominate in the adsorption process, although the adsorption of Cr(III) on the original (basic) carbon indicates that other forces also participate in the adsorption process. Thus, the ionic exchange of protons in the -Cpi-H3O(+) interaction for Cr(III) accounts for the adsorption of cationic species in basic carbons with positive charge density. Study of the influence of pH on the adsorption of Cr(III) showed that, in each system, the maximum adsorption occurred when the charge of the carbon surface was opposite that of the species of Cr(III) present at the pH of the experiment. These results confirmed that electrostatic interactions predominate in the adsorption process.

  9. Macromolecule simulation and CH{sub 4} adsorption mechanism of coal vitrinite

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Song, E-mail: songyu10094488@126.com [School of Resources and Earth Science, China University of Mining & Technology, Xuzhou 221116 (China); Key Laboratory of Coal bed Methane Resource & Reservoir Formation Process, Ministry of Education, Xuzhou 221008 (China); Yan-ming, Zhu; Wu, Li [School of Resources and Earth Science, China University of Mining & Technology, Xuzhou 221116 (China); Key Laboratory of Coal bed Methane Resource & Reservoir Formation Process, Ministry of Education, Xuzhou 221008 (China)

    2017-02-28

    Highlights: • Molecular model of single maceral vitrinite was obtained by {sup 13}C NMR, FT IR and HRTEM. • An optimal configuration was obtained through calculation of MM and MD. • The adsorption parameters for methane and vitrinite were determined with DFT and GCMC. - Abstract: The microscopic mechanism of interactions between CH{sub 4} and coal macromolecules is of significant practical and theoretical importance in CBM development and methane storage. Under periodic boundary conditions, the optimal energy configuration of coal vitrinite, which has a higher torsion degree and tighter arrangement, can be determined by the calculation of molecular mechanics (MM) and molecular dynamics (MD), and annealing kinetics simulation based on ultimate analysis, {sup 13}C NMR, FT IR and HRTEM. Macromolecular stabilization is primarily due to the van der Waals energy and covalent bond energy, mainly consisting of bond torsion energy and bond angle energy. Using the optimal configuration as the adsorbent, GCMC simulation of vitrinite adsorption of CH{sub 4} is conducted. A saturated state is reached after absorbing 17 CH{sub 4}s per coal vitrinite molecule. CH{sub 4} is preferentially adsorbed on the edge, and inclined to gathering around the branched chains of the inner vitrinite sites. Finally, the adsorption parameters are calculated through first principle DFT. The adsorbability order is as follows: aromatic structure> heteroatom rings > oxygen functional groups. The adsorption energy order is as follows: Top < Bond < Center, Up < Down. The order of average RDF better reflects the adsorption ability and that of [-COOH] is lower than those of [−C=O] and [C−O−C]. CH{sub 4} distributed in the distance of 0.99–16 Å to functional groups in the type of monolayer adsorption and the average distance order manifest as [−C=O] (1.64 Å) < [C−O−C] (1.89 Å) < [−COOH] (3.78 Å) < [-CH{sub 3}] (4.11 Å) according to the average RDF curves. CH{sub 4} enriches

  10. Oxygen injection facility

    International Nuclear Information System (INIS)

    Ota, Masamoto; Hirose, Yuki

    1998-01-01

    A compressor introduces air as a starting material and sends it to a dust removing device, a dehumidifying device and an adsorption/separation system disposed downstream. The facility of the present invention is disposed in the vicinity of an injection point and installed in a turbine building of a BWR type reactor having a pipeline of a feedwater system to be injected. The adsorbing/separation system comprises an adsorbing vessel and an automatic valve, and the adsorbing vessel is filled with an adsorbent for selectively adsorbing nitrogen. Zeolite is used as the adsorbent. Nitrogen in the air passing through the adsorbing vessel is adsorbed and removed under a pressurized condition, and a highly concentrated oxygen gas is formed. The direction of the steam of the adsorbed nitrogen is changed by an opening/closing switching operation of an automatic valve and released to the atmosphere (the pressure is released). Generated oxygen gas is stored under pressure in a tank, and injected to the pipeline of the feedwater system by an oxygen injection conduit by way of a flow rate control valve. In the adsorbing vessel, steps of adsorption, separation and storage under pressure are repeated successively. (I.N.)

  11. Propylene/propane mixture adsorption on faujasite sorbents

    NARCIS (Netherlands)

    Van Miltenburg, A.; Gascon, J.; Zhu, W.; Kapteijn, F.; Moulijn, J.A.

    2008-01-01

    The adsorption of propylene and propane on zeolite NaX with and without a saturated (36 wt%) amount of CuCl have been investigated. The single component adsorption isotherms could be well described with a Dual-Site Langmuir model. The dispersion of CuCl results in a decrease of the maximum

  12. Water Adsorption on TiO2

    DEFF Research Database (Denmark)

    Hammer, Bjørk; Wendt, Stefan; Besenbacher, Flemming

    2010-01-01

    Scanning Tunneling Microscopy (STM) studies and Density Functional Theory (DFT) investigations of the interaction of water with the rutile TiO2 (110) surface are summarized. From high-resolution STM the following reactions have been revealed: water adsorption and diffusion in the Ti troughs, water...... dissociation in bridging oxygen vacancies, assembly of adsorbed water monomers into rapidly diffusing water dimers, and formation of water dimers by reduction of oxygen molecules. The STM results are rationalized based on DFT calculations, revealing the bonding geometries and reaction pathways of the water...

  13. Adsorption of VOCs on reduced graphene oxide.

    Science.gov (United States)

    Yu, Lian; Wang, Long; Xu, Weicheng; Chen, Limin; Fu, Mingli; Wu, Junliang; Ye, Daiqi

    2018-05-01

    A modified Hummer's method was adopted for the synthesis of graphene oxide (GO) and reduced graphene oxide (rGO). It was revealed that the modified method is effective for the production of GO and rGO from graphite. Transmission electron microscopy (TEM) images of GO and rGO showed a sheet-like morphology. Because of the presence of oxygenated functional groups on the carbon surface, the interlayer spacing of the prepared GO was higher than that of rGO. The presence of OH and CO groups in the Fourier transform infrared spectra (FTIR) spectrum and G-mode and 2D-mode in Raman spectra confirmed the synthesis of GO and rGO. rGO (292.6m 2 /g) showed higher surface area than that of GO (236.4m 2 /g). The prepared rGO was used as an adsorbent for benzene and toluene (model pollutants of volatile organic compounds (VOCs)) under dynamic adsorption/desorption conditions. rGO showed higher adsorption capacity and breakthrough times than GO. The adsorption capacity of rGO for benzene and toluene was 276.4 and 304.4mg/g, respectively. Desorption experiments showed that the spent rGO can be successfully regenerated by heating at 150.0°C. Its excellent adsorption/desorption performance for benzene and toluene makes rGO a potential adsorbent for VOC adsorption. Copyright © 2017. Published by Elsevier B.V.

  14. The behaviour of radionuclides in gas adsorption chromatographic processes with superimposed chemical reactions (chlorides)

    International Nuclear Information System (INIS)

    Eichler, B.

    1996-01-01

    Thermochemical relationships are derived describing the gas adsorption chromatographic transport of carrier-free radionuclides. Especially, complex adsorption processes such as dissociative, associative and substitutive adsorption are dealt with. The comparison of experimental with calculated data allows the determination of the type of adsorption reaction, which is the basis of the respective gas chromatographic process. The behaviour of carrier-free radionuclides of elements Pu, Ce, Ru, Co and Cr in thermochromatographic experiments with chlorinating carrier gases can be described as dissociative adsorption of chlorides in higher oxidation states. The gas adsorption chromatographic transport of Zr with oxygen and chlorine containing carrier gas is shown to be a substitutive adsorption process. The consequences of superimposed chemical reactions on the interpretation of results and the conception of gas adsorption chromatographic experiments with carrier-free radionuclides in isothermal columns and in temperature gradient tubes is discussed. (orig.)

  15. Adsorbtion of oxygen and cesium on lanthanum hexaboride

    International Nuclear Information System (INIS)

    Gorodetskij, D.A.; Tskhakaya, V.K.; Shchudlo, Yu.G.; Yarygin, V.I.; Yas'ko, A.A.

    1982-01-01

    Oxygen and cesium adsorption on lanthanum hexaboride was investigated. Especial attention was paid to structural investigations of the LaB 6 (100)-O system. Diffraction pictures and curves of changes in work function in the process of oxygen disorption have been obtained. At oxygen adsorption on a crystal heated up to different temperatures in the range of 900-1400 K the same diffraction pictures as at corresponding annealing temperatures observed were. It is noted that adsorption heat changes slightly in the LaB 6 -O-Cs system

  16. A Simple Adsorption Experiment

    Science.gov (United States)

    Guirado, Gonzalo; Ayllon, Jose A.

    2011-01-01

    The study of adsorption phenomenon is one of the most relevant and traditional physical chemistry experiments performed by chemistry undergraduate students in laboratory courses. In this article, we describe an easy, inexpensive, and straightforward way to experimentally determine adsorption isotherms using pieces of filter paper as the adsorbent…

  17. Adsorption of palladium ions by modified carbons from rice husks

    International Nuclear Information System (INIS)

    Mostafa, M.R.

    1994-01-01

    Steam activated carbon of high surface area does not show palladium ions adsorption. Treatment of this carbon with HF acid increases to a great extent the gas adsorption capacity expressed as nitrogen surface area as well as the adsorption capacity of palladium ions from aqueous solution. HHB was loaded in different amounts on to these carbons. The acid sites represent the active fraction of the surface on which the adsorption palladium ions proceed. The uptake of palladium ions by HHB treated carbons is related to the total number of HHB molecules loaded on the carbon surface. (author)

  18. Modification of polystyrene-based activated carbon spheres to improve adsorption of dibenzothiophene

    Energy Technology Data Exchange (ETDEWEB)

    Wang Qin [State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Meilong Road 130, Shanghai 200237 (China); Liang Xiaoyi [State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Meilong Road 130, Shanghai 200237 (China)], E-mail: xyliang@ecust.edu.cn; Qiao Wenming; Liu Chaojun; Liu Xiaojun; Zhang Rui; Ling Licheng [State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Meilong Road 130, Shanghai 200237 (China)

    2009-01-01

    Polystyrene-based activated carbon spheres (PACS) were modified with either air, HNO{sub 3}, (NH{sub 4}){sub 2}S{sub 2}O{sub 8}, H{sub 2}O{sub 2} or H{sub 2} to improve their adsorption properties of dibenzothiophene (DBT). The texture and surface chemistry of PACS were characterized by N{sub 2} adsorption, scanning electron microscopy (SEM), temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), acid-base titration and elemental analysis. The results showed that HNO{sub 3} and (NH{sub 4}){sub 2}S{sub 2}O{sub 8} treatments introduced large amount of acidic groups such as carboxylic, lactones and anhydride groups, while air and H{sub 2}O{sub 2} had relatively mild effects and introduced a small quantity of phenol, carbonyl and ether groups. In the HNO{sub 3} treatment, the acidic groups might be fixed on the internal and external surface of PACS, which may act as active sites of adsorption, resulting in increase of the adsorption amount by 45%. Whereas H{sub 2}O{sub 2} and (NH{sub 4}){sub 2}S{sub 2}O{sub 8} treatments might fix more oxygen-containing groups on the external surface, which may hinder DBT molecule enter into micropores, leading to rather lower adsorption capacity with the extent of oxidation. So, the concentration, distribution and types of the acidic functional groups are responsible for the removal of DBT.

  19. Radioactive nuclide adsorption

    International Nuclear Information System (INIS)

    Fukushima, Kimichika.

    1982-01-01

    Purpose: To improve the efficiency of a radioactive nuclide adsorption device by applying a nickel plating on a nickel plate to render the surface active. Constitution: A capturing device for radioactive nuclide such as manganese 54, cobalt 60, 58 and the like is disposed to the inside of a pipeway provided on the upper portion of fuel assemblies through which liquid sodium as the coolant for LMFBR type reactor is passed. The device comprises a cylindrical adsorption body and spacers. The adsorption body is made of nickel and applied with a nickel plating on the surface thereof. The surface of the adsorption body is unevened to result in disturbance in the coolant and thereby improve the adsorptive efficiency. (Kawakami, Y.)

  20. Irreversible adsorption of particles on heterogeneous surfaces.

    Science.gov (United States)

    Adamczyk, Zbigniew; Jaszczółt, Katarzyna; Michna, Aneta; Siwek, Barbara; Szyk-Warszyńska, Lilianna; Zembala, Maria

    2005-12-30

    Methods of theoretical and experimental evaluation of irreversible adsorption of particles, e.g., colloids and globular proteins at heterogeneous surfaces were reviewed. The theoretical models were based on the generalized random sequential adsorption (RSA) approach. Within the scope of these models, localized adsorption of particles occurring as a result of short-ranged attractive interactions with discrete adsorption sites was analyzed. Monte-Carlo type simulations performed according to this model enabled one to determine the initial flux, adsorption kinetics, jamming coverage and the structure of the particle monolayer as a function of the site coverage and the particle/site size ratio, denoted by lambda. It was revealed that the initial flux increased significantly with the site coverage theta(s) and the lambda parameter. This behavior was quantitatively interpreted in terms of the scaled particle theory. It also was demonstrated that particle adsorption kinetics and the jamming coverage increased significantly, at fixed site coverage, when the lambda parameter increased. Practically, for alpha = lambda2theta(s) > 1 the jamming coverage at the heterogeneous surfaces attained the value pertinent to continuous surfaces. The results obtained prove unequivocally that spherically shaped sites were more efficient in binding particles in comparison with disk-shaped sites. It also was predicted that for particle size ratio lambda charge. Particle deposition occurred under diffusion-controlled transport conditions and their coverage was evaluated by direct particle counting using the optical and electron microscopy. Adsorption kinetics was quantitatively interpreted in terms of numerical solutions of the governing diffusion equation with the non-linear boundary condition derived from Monte-Carlo simulations. It was proven that for site coverage as low as a few percent the initial flux at heterogeneous surfaces attained the maximum value pertinent to homogeneous

  1. Adsorption of Remazol Black B dye on Activated Carbon Felt

    Directory of Open Access Journals (Sweden)

    Donnaperna Lucio

    2008-11-01

    Full Text Available The adsorption of Remazol Black B (anionic dye on a microporous activated carbon felt is investigated from its aqueous solution. The surface chemistry of activated carbon is studied using X-ray microanalysis, "Boehm" titrations and pH of PZC measurements which indicates that the surface oxygenated groups are mainly acidic in nature. The kinetics of Remazol Black B adsorption is observed to be pH dependent and governed by the diffusion of the dye molecules. The experimental data can be explained by "intra-particle diffusion model". For Remazol Black B, the Khan model is best suited to simulate the adsorption isotherms.

  2. Oxygen toxicity

    Directory of Open Access Journals (Sweden)

    C. A. van der Westhuizen

    1990-07-01

    Full Text Available Oxygen has been discovered about 200 years ago. Since then the vital physiological involvement of oxygen in various biologi­cal processes, mainly energy production, has been established. However, in the body molecular oxygen can be converted to toxic oxygen metabolites such as superoxide anion, hydrogen peroxide, the hydroxyl radical and singlet oxygen. These toxic metabolites are produced mainly in the mitochondria, plasma membranes and endoplasmic reticulum.

  3. Adsorption of glyphosate in chilean soils and its relationship with unoccupied phosphate binding sites Adsorção de glifosato em solos chilenos e sua relação com sítios de adsorção disponíveis para adsorção de fosfato

    Directory of Open Access Journals (Sweden)

    Marcelo Kogan

    2003-04-01

    Full Text Available The objective of this work was to investigate glyphosate adsorption by soils and its relationship with unoccupied binding sites for phosphate adsorption. Soil samples of three Chilean soils series - Valdivia (Andisol, Clarillo (Inceptisol and Chicureo (Vertisol - were incubated with different herbicide concentrations. Glyphosate remaining in solution was determined by adjusting a HPLC method with a UV detector. Experimental maximum adsorption capacity were 15,000, 14,300 and 4,700 mg g¹ for Valdivia, Clarillo, and Chicureo soils, respectively. Linear, Freundlich, and Langmuir models were used to describe glyphosate adsorption. Isotherms describing glyphosate adsorption differed among soils. Maximum adjusted adsorption capacity with the Langmuir model was 231,884, 17,874 and 5,670 mg g-1 for Valdivia, Clarillo, and Chicureo soils, respectively. Glyphosate adsorption on the Valdivia soil showed a linear behavior at the range of concentrations used and none of the adjusted models became asymptotic. The high glyphosate adsorption capacity of the Valdivia soil was probably a result of its high exchangeable Al, extractable Fe, and alophan and imogolite clay type. Adsorption was very much related to phosphate dynamics in the Valdivia soil, which showed the larger unoccupied phosphate binding sites. However relationship between unoccupied phosphate binding sites and glyphosate adsorption in the other two soils (Clarillo and Chicureo was not clear.O objetivo deste trabalho foi investigar a adsorção de glifosato em solos e sua relação com os sítios disponíveis para adsorção de fosfato. Amostras de três solos chilenos - Valdivia (Andisol, Clarillo (Inceptisol e Chicureo (Vertisol - foram incubadas com diferentes concentrações do herbicida. O glifosato remanescente na solução foi determinado pelo método de HPLC com detector de UV modificado. A capacidade de adsorção máxima experimental foi de 15.000, 14.300 e 4.700 mg g-1 para os solos de

  4. Adsorption of zinc(II) on hydrous iron oxides

    International Nuclear Information System (INIS)

    Music, S.; Ristic, M.

    1992-01-01

    The adsorption of Zn 2+ ions on amorphous Fe(OH 3 ) and α-Fe 2 O 3 , as a function of pH, has been investigated. In the pH region corresponding to the formation of positively charged Zn-hydroxy complexes, an abrupt increase in adsorption was observed. The influence of EDTA and glycine on the adsorption of Zn 2+ by α-Fe 2 O 3 has also been investigated. Strong suppression of the adsorption of Zn 2+ was observed for high [EDTA or Gly]/[Zn 2+ ] concentration ratios. The results of the adsorption of Zn 2+ in the presence of an organic ligand were explained by the formation of Zn-EDTA or Zn-glycine complexes and also by the occupation of adsorption sites by the free organic ligand. (author) 26 refs.; 6 figs

  5. Palladium nanoparticles/defective graphene composites as oxygen reduction electrocatalysts: A first-principles study

    KAUST Repository

    Liu, Xin

    2012-02-02

    The impact of graphene substrate-Pd nanoparticle interaction on the O, OH, and OOH adsorption that is directly related to the electrocatalytic performance of these composites in oxygen reduction reaction (ORR) has been investigated by first-principles-based calculations. The calculated binding energy of a Pd 13 nanoparticle on a single vacancy graphene is as high as -6.10 eV, owing to the hybridization between the dsp states of the Pd particles with the sp 2 dangling bonds at the defect sites. The strong interaction results in the averaged d-band center of the deposited Pd nanoparticles shifted away from the Fermi level from -1.02 to -1.45 eV. Doping the single vacancy graphene with B or N will further tune the average d-band center and also the activity of the composite toward O, OH, and OOH adsorption. The adsorption energies of O, OH, and OOH are reduced from -4.78, -4.38, and -1.56 eV on the freestanding Pd 13 nanoparticle to -4.57, -2.66, and -1.39 eV on Pd 13/single vacancy graphene composites, showing that the defective graphene substrate will not only stabilize the Pd nanoparticles but also reduce the adsorption energies of the O-containing species to the Pd particle, and so as the poisoning of the ORR active sites. © 2011 American Chemical Society.

  6. Enhanced fluoride adsorption using Al (III) modified calcium hydroxyapatite

    International Nuclear Information System (INIS)

    Nie, Yulun; Hu, Chun; Kong, Chuipeng

    2012-01-01

    Highlights: ► Al modified hydroxyapatite possessed a higher defluoridation capacity of 32.57 mg/g. ► Hydroxyl groups on the surface of Al-HAP was the adsorption sites for F − removal. ► Enhanced F − removal over Al-HAP was attributed to the modification with aluminum. - Abstract: Aluminum-modified hydroxyapatite (Al-HAP) was prepared and characterized using XRD and BET analyses. Al-HAP possessed higher defluoridation capacity (DC) of 32.57 mgF − /g than unmodified hydroxyapatite (HAP) which showed a DC of 16.38 mgF − /g. The effect of Al/Ca atomic ratio in Al-HAP, solution pH and co-existing anions was further studied. The results indicated that the adsorption data could be well described by the Langmuir isotherm model and the adsorption kinetic followed the pseudo-second-order model. The pH changes during the adsorption process suggested that the -OH on the surface of Al-HAP was the adsorption sites. The more adsorption sites were formed on Al modified HAP, which possessed abundant surface hydroxyl groups, resulting in higher efficiency of F − removal. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were calculated in order to understand the nature of adsorption process. The results revealed that the adsorption reaction was a spontaneous and endothermic process.

  7. Study on Shale Adsorption Equation Based on Monolayer Adsorption, Multilayer Adsorption, and Capillary Condensation

    Directory of Open Access Journals (Sweden)

    Qing Chen

    2017-01-01

    Full Text Available Shale gas is an effective gas resource all over the world. The evaluation of pore structure plays a critical role in exploring shale gas efficiently. Nitrogen adsorption experiment is one of the significant approaches to analyze pore size structure of shale. Shale is extremely heterogeneous due to component diversity and structure complexity. Therefore, adsorption isotherms for homogeneous adsorbents and empirical isotherms may not apply to shale. The shape of adsorption-desorption curve indicates that nitrogen adsorption on shale includes monolayer adsorption, multilayer adsorption, and capillary condensation. Usually, Langmuir isotherm is a monolayer adsorption model for ideal interfaces; BET (Brunauer, Emmett, Teller adsorption isotherm is a multilayer adsorption model based on specific assumptions; Freundlich isotherm is an empirical equation widely applied in liquid phase adsorption. In this study, a new nitrogen adsorption isotherm is applied to simultaneously depict monolayer adsorption, multilayer adsorption, and capillary condensation, which provides more real and accurate representation of nitrogen adsorption on shale. In addition, parameters are discussed in relation to heat of adsorption which is relevant to the shape of the adsorption isotherm curve. The curve fitting results indicate that our new nitrogen adsorption isotherm can appropriately describe the whole process of nitrogen adsorption on shale.

  8. Modelling phosphate adsorption to the soil: Application of the non-ideal competitive adsorption model

    International Nuclear Information System (INIS)

    Abou Nohra, Joumana S.; Madramootoo, Chandra A.; Hendershot, William H.

    2007-01-01

    Phosphorus (P) transport in subsurface runoff has increased despite the limited mobility of P in soils. This study investigated the ability of the non-ideal competitive adsorption (NICA) model to describe phosphate (PO 4 ) adsorption for soils in southern Quebec (Canada). We measured the surface charge and PO 4 adsorption capacity for 11 agricultural soils. Using the experimental data and a nonlinear fitting function, we derived the NICA model parameters. We found that the NICA model described accurately the surface charge of these soils with a mean R 2 > 0.99, and described the adsorption data with a mean R 2 = 0.96. We also found that the variable surface charge was distributed over the two binding sites with the low pH sites demonstrating a stronger binding energy for hydroxyl and PO 4 ions. We established that the NICA model is able to describe P adsorption for the soils considered in this study. - The NICA model accurately described the adsorption of phosphate to some southern Quebec soils

  9. The investigation of adsorption and dissociation of H2O on Li2O (111) by ab initio theory

    Science.gov (United States)

    Kong, Xianggang; Yu, You; Ma, Shenggui; Gao, Tao; Lu, Tiecheng; Xiao, Chengjian; Chen, Xiaojun; Zhang, Chuanyu

    2017-06-01

    The adsorption and dissociation mechanism of H2O molecule on the Li2O (111) surface have been systematically studied by using the density functional theory calculations. The parallel and vertical configurations of H2O at six different symmetry adsorption sites on the Li2O (111) surface are considered. In our calculations, it is suggested that H2O can dissociate on the perfect Li2O surface, of which the corresponding adsorption energy is 1.118 eV. And the adsorption energy decrease to be 0.241 eV when oxygen atom of H2O bonds to lithium atom of the slab. The final configurations are sensitive to the initial molecular orientation. By Bader charge analysis, the charge transfer from slab to adsorbed H2O/OH can be found due to the downward shift of lowest-unoccupied molecular orbital. We also analyze the vibrational frequencies at the Brillouin Zone centre for H2O molecule adsorbed on the stoichiometric surface. Due to the slightly different structure parameters, the calculated values of the vibrational frequencies of hydroxyl group range from 3824 to 3767 cm-1. Our results agree well with experimental results performed in FT-IR spectrum, which showed that an absorption peak of OH group appeared at 3677 cm-1 at room temperature.

  10. adsorption, eosin, humic, peat

    OpenAIRE

    anshar, andi muhammad

    2015-01-01

    Eosin is one of the dyes commonly used in the industry and has the potential to cause pollution of the water environment. The Eosin pollution treatment methods used in this study was the adsorption method using humin fraction obtained from the peat land comes from Kalimantan. From the research data showed that the adsorption of eosin in humin result of washing with HCl / HF optimum at pH 4 and a contact time of 60 minutes with the adsorption-order rate was 8,4 x 10-3 min-1

  11. Oxygen-induced restructuring with release of gold atoms from Au(111)

    International Nuclear Information System (INIS)

    Min, B.K.; Deng, X.; Schalek, R.; Pinnaduwage, D.; Friend, C.M.

    2005-01-01

    Adsorption of oxygen atoms, achieved via electron-induced dissociation of nitrogen dioxide, induces restructuring of the 'herringbone' to a striped, soliton-wall structure accompanied by release of gold from the 'elbows' in the herringbone structure. The number density of 'elbows' (dislocations corresponding to a change in direction of the reconstruction) decreases as a function of increasing atomic oxygen coverage while the long range order observed in low energy electron diffraction (LEED) changes from (√(3)x22)-rec. to (1x22) in the limit of saturation coverage. Small islands and serrated step edges were formed due to the release of gold atoms from elbow sites of Au(111). The overall structural change of the Au(111) surface may result from the reduction of anisotropy related to the tensile stress relief of the Au(111) surface by oxygen atoms

  12. Competitive Protein Adsorption - Multilayer Adsorption and Surface Induced Protein Aggregation

    DEFF Research Database (Denmark)

    Holmberg, Maria; Hou, Xiaolin

    2009-01-01

    In this study, competitive adsorption of albumin and IgG (immunoglobulin G) from human serum solutions and protein mixtures onto polymer surfaces is studied by means of radioactive labeling. By using two different radiolabels (125I and 131I), albumin and IgG adsorption to polymer surfaces...... is monitored simultaneously and the influence from the presence of other human serum proteins on albumin and IgG adsorption, as well as their mutual influence during adsorption processes, is investigated. Exploring protein adsorption by combining analysis of competitive adsorption from complex solutions...... of high concentration with investigation of single protein adsorption and interdependent adsorption between two specific proteins enables us to map protein adsorption sequences during competitive protein adsorption. Our study shows that proteins can adsorb in a multilayer fashion onto the polymer surfaces...

  13. Adsorption mechanism and kinetics of azo dye chemicals on oxide nanotubes: a case study using porous CeO_2 nanotubes

    International Nuclear Information System (INIS)

    Wu, Junshu; Wang, Jinshu; Du, Yucheng; Li, Hongyi; Jia, Xinjian

    2016-01-01

    Metal oxide nanotubes are believed to be promising materials with adsorption functionality for water purification due to their synergistic effect of the overall microscale morphology for easy separation and nanoscale surface characters providing enough surface active absorption sites. This work shows the synthesis of uniform hierarchical porous CeO_2 nanotubes via nanowire-directed templating method and describes the adsorption behavior of CeO_2 nanotubes for a typical azo dye Congo red which has resistance to oxidation and decoloration in natural conditions. Fourier transform infrared spectroscopy spectra provided the evidence that Congo red was successfully coated on the surface of CeO_2 nanotubes by both bidentate-type bridge link of Ce"4"+ cations from sulfonate SO_3"− groups and the electrostatic attraction between the protonated surface generated by oxygen vacancies and dissociated sulfonate groups. The adsorption kinetic data fitted well to the pseudo-second-order kinetic equation, whereas the Langmuir isotherm equation exhibited better correlation with the experimental data. The calculated maximum adsorption capacity from the isothermal model was 362.32 mg/g. In addition, the prepared CeO_2 nanotubes exhibited good recyclability and reusability as highly efficient adsorbents for Congo red removal after regeneration. These favorable performances enable the obtained CeO_2 nanotubes to be promising materials for dye removal from aqueous solution.Graphical AbstractCeO_2 nanotubes composed of crystallized nanoparticles exhibit well adsorption ability for a typical azo dye Congo red.

  14. Nicotine adsorption on single wall carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Girao, Eduardo C. [Departamento de Fisica, Universidade Federal do Ceara, Caixa Postal 6030, Campus do Pici, 60455-900 Fortaleza, Ceara (Brazil); Fagan, Solange B.; Zanella, Ivana [Area de Ciencias Tecnologicas, Centro Universitario Franciscano - UNIFRA, 97010-032 Santa Maria, RS (Brazil); Filho, Antonio G. Souza, E-mail: agsf@fisica.ufc.br [Departamento de Fisica, Universidade Federal do Ceara, Caixa Postal 6030, Campus do Pici, 60455-900 Fortaleza, Ceara (Brazil)

    2010-12-15

    This work reports a theoretical study of nicotine molecules interacting with single wall carbon nanotubes (SWCNTs) through ab initio calculations within the framework of density functional theory (DFT). Different adsorption sites for nicotine on the surface of pristine and defective (8,0) SWCNTs were analyzed and the total energy curves, as a function of molecular position relative to the SWCNT surface, were evaluated. The nicotine adsorption process is found to be energetically favorable and the molecule-nanotube interaction is intermediated by the tri-coordinated nitrogen atom from the nicotine. It is also predicted the possibility of a chemical bonding between nicotine and SWCNT through the di-coordinated nitrogen.

  15. Ab initio Studies of O2 Adsorption on (110 Nickel-Rich Pentlandite (Fe4Ni5S8 Mineral Surface

    Directory of Open Access Journals (Sweden)

    Peace P. Mkhonto

    2015-10-01

    Full Text Available Ab initio density functional theory was used to investigate the adsorption of oxygen molecule on the nickel-rich pentlandite (110 surface, which is important for mineral extraction. The three most reactive adsorption sites: Fe-top, Ni-top, and fcc-hollow have been considered. Firstly, the non-adsorbed pentlandite surface reflects the Ni atoms relaxing inwards. Consequently, their electronic structure showed high Fe 3d-orbital contribution than the Ni 3d-orbitals at the EF (indicating that the Fe atoms are more reactive than Ni. Secondly, the O2-adsorbed surface predicted lowest adsorption energy for Fe-top (-1.902 eV, as a more spontaneous reaction is likely to occur than on fcc-hollow (-1.891 eV and Ni-top (-0.040 eV sites, suggesting Fe preferential oxidation. The density of states indicates that the O2 show prevalence of electrons in the πp* antibonding orbitals, and are reduced to zero states at the valence band on metal-bonded oxygen (O1. The πp* orbital is observed to reside just above the EF for Fe-top and fcc-hollow site, while on Ni-top is half-occupied for both metal-bonded oxygen (O1 and terminal oxygen (O2. Finally, the isosurface charge density difference showed electron (charge depletion on Ni/Fe metals and accumulation on the O2 molecule. Bader analysis indicated that the oxidized Fe and Ni atoms adopt more positive charge, while O2 on Fe-top atoms possesses more negative charge than on Ni-top, resulting with O1 possessing a smaller charge than O2 atom.

  16. How strong is the edge effect in the adsorption of anticancer drugs on a graphene cluster?

    Science.gov (United States)

    Rungnim, Chompoonut; Chanajaree, Rungroj; Rungrotmongkol, Thanyada; Hannongbua, Supot; Kungwan, Nawee; Wolschann, Peter; Karpfen, Alfred; Parasuk, Vudhichai

    2016-04-01

    The adsorption of nucleobase-analog anticancer drugs (fluorouracil, thioguanine, and mercaptopurine) on a graphene flake (C54H18) was investigated by shifting the site at which adsorption occurs from one end of the sheet to the other end. The counterpoise-corrected M06-2X/cc-pVDZ binding energies revealed that the binding stability decreases in the sequence thioguanine > mercaptopurine > fluorouracil. We found that adsorption near the middle of the sheet is more favorable than adsorption near the edge due to the edge effect. This edge effect is stronger for the adsorption of thioguanine or mercaptopurine than for fluorouracil adsorption. However, the edge effect reduces the binding energy of the drug to the flake by only a small amount, <5 kcal/mol, depending on the adsorption site and the alignment of the drug at this site.

  17. Hybrid adsorptive membrane reactor

    Science.gov (United States)

    Tsotsis, Theodore T [Huntington Beach, CA; Sahimi, Muhammad [Altadena, CA; Fayyaz-Najafi, Babak [Richmond, CA; Harale, Aadesh [Los Angeles, CA; Park, Byoung-Gi [Yeosu, KR; Liu, Paul K. T. [Lafayette Hill, PA

    2011-03-01

    A hybrid adsorbent-membrane reactor in which the chemical reaction, membrane separation, and product adsorption are coupled. Also disclosed are a dual-reactor apparatus and a process using the reactor or the apparatus.

  18. Co adsorption in kaolinite

    International Nuclear Information System (INIS)

    Souza, Eliel S.; Silva, Paulo S.C.

    2017-01-01

    Adsorption of metal ions in clay minerals has been used as an alternative to water and effluents treatment. Kaolinite is a clay mineral that presents low specific surface area and exchange ion capacity. Nevertheless, structural modifications can be achieved by means of acid or thermal activation. In this paper, it was studied the surface area of kaolinite/bentonite, kaolinite/activated carbon mixtures, thermal activated kaolinite and thermal activated kaolinite/activated carbon mixture. The mixture of kaolinite/activated carbon was tested for pH, contact time, interfering ions and initial concentration effects in the cobalt adsorption. Results showed that the optimized parameters are pH 6 and contact time of 30 min. Chromium acted as a competitive ion, zinc does not appear to have affected adsorption while iron seems to have favored it. Langmuir and Freundlich isotherms indicated that the adsorption of Co in the mixture of kaolinite/activated carbon is a spontaneous process. (author)

  19. Co adsorption in kaolinite

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Eliel S.; Silva, Paulo S.C., E-mail: eliel201019@hotmail.com, E-mail: pscsilva@ipen.br [Instituto de Pesquisas Energética s e Nucleares (IPEN/CNEN-SP), São Paulo, SP (Brazil)

    2017-07-01

    Adsorption of metal ions in clay minerals has been used as an alternative to water and effluents treatment. Kaolinite is a clay mineral that presents low specific surface area and exchange ion capacity. Nevertheless, structural modifications can be achieved by means of acid or thermal activation. In this paper, it was studied the surface area of kaolinite/bentonite, kaolinite/activated carbon mixtures, thermal activated kaolinite and thermal activated kaolinite/activated carbon mixture. The mixture of kaolinite/activated carbon was tested for pH, contact time, interfering ions and initial concentration effects in the cobalt adsorption. Results showed that the optimized parameters are pH 6 and contact time of 30 min. Chromium acted as a competitive ion, zinc does not appear to have affected adsorption while iron seems to have favored it. Langmuir and Freundlich isotherms indicated that the adsorption of Co in the mixture of kaolinite/activated carbon is a spontaneous process. (author)

  20. Adsorption mechanism of microcrystalline cellulose as green adsorbent for the removal of cationic methylene blue dye

    International Nuclear Information System (INIS)

    Tan, K.B.; Salamatinia, B.

    2016-01-01

    The adsorption mechanism of pure cellulose is yet to be explored. Thus, in this study, the adsorption mechanism of Microcrystalline Cellulose (MCC), a polysaccharide which is renewable, low cost and non-toxic, was studied on the adsorption of model dye Methylene blue (MB). It was found that the main adsorption mechanism of MB on MCC was due to the electrostatic attraction between the positively charged MB dye and negatively charged MCC. Thus, physical adsorption was the dominant effect, since electrostatic attraction is categorized as physical adsorption. This was verified by Dubinin-Radushkevich isotherm, whereby mean free energy adsorption value was found to be less than 8 kJ/mol. The values of Gibbs free energy for thermodynamics studies were found to be within the range of -20 kJ/mol and 0 kJ/mol, which also indicated physical adsorption. It was due to the electrostatic attraction as adsorption mechanism of this adsorption process which resulted rapid adsorption of MB dye. It was found that equilibrium dye concentration was achieved between 1-3 minutes, depending on the adsorption temperature. The rapid adsorption, as compared to a lot of materials, showed the potential of MCC as the future of green adsorbent. The adsorption of Methylene Blue on MCC fitted well in Langmuir Isotherm, with R2 values of higher than 0.99, while fitted moderately in Freundlich Isotherm, with R2 values between 0.9224 and 0.9223. Comparatively, the adsorption of MB on MCC fitted best Langmuir Isotherm as compared to Freundlich Isotherm which monolayer adsorption occurred at the homogenous surface of MCC. This also indicated adsorbed MB molecules do not interact with each other at neighboring adsorption sites. The maximum adsorption capacity calculated from Langmuir Isotherm was found to be 4.95 mg/g. Despite the potential of MCC as green adsorbent, the challenge of low adsorption capacity has to be addressed in the future. (author)

  1. Structure sensitivity in adsorption

    DEFF Research Database (Denmark)

    Hammer, Bjørk; Nielsen, Ole Holm; Nørskov, Jens Kehlet

    1997-01-01

    The structure sensitivity of CO adsorption on different flat, stepped, kinked and reconstructed Pt surfaces is studied using large-scale density-functional calculations. We find an extremely strong structure sensitivity in the adsorption energy with variations up to 1 eV (or 100%) from one...... structure to the next. We propose a model to explain this behavior, and use it to discuss more generally the origin of structure sensitivity in heterogeneous catalysis....

  2. Oxygen Therapy

    Science.gov (United States)

    ... their breathing to dangerously low levels. Will I need oxygen when I sleep? Usually if you use supplemental oxygen during the ... your health care provider tells you you only need to use oxygen for exercise or sleep. Even if you feel “fine” off of your ...

  3. Number of outer electrons as descriptor for adsorption processes on transition metals and their oxides

    DEFF Research Database (Denmark)

    Calle-Vallejo, Federico; Inoglu, Nilay G.; Su, Hai-Yan

    2013-01-01

    The trends in adsorption energies of the intermediates of the oxygen reduction and evolution reactions on transition metals and their oxides are smoothly captured by the number of outer electrons. This unique descriptor permits the construction of predictive adsorption-energy grids and explains t...

  4. Oxidized amino acid residues in the vicinity of Q(A and Pheo(D1 of the photosystem II reaction center: putative generation sites of reducing-side reactive oxygen species.

    Directory of Open Access Journals (Sweden)

    Laurie K Frankel

    Full Text Available Under a variety of stress conditions, Photosystem II produces reactive oxygen species on both the reducing and oxidizing sides of the photosystem. A number of different sites including the Mn4O5Ca cluster, P680, PheoD1, QA, QB and cytochrome b559 have been hypothesized to produce reactive oxygen species in the photosystem. In this communication using Fourier-transform ion cyclotron resonance mass spectrometry we have identified several residues on the D1 and D2 proteins from spinach which are oxidatively modified and in close proximity to QA (D1 residues (239F, (241Q, (242E and the D2 residues (238P, (239T, (242E and (247M and PheoD1 (D1 residues (130E, (133L and (135F. These residues may be associated with reactive oxygen species exit pathways located on the reducing side of the photosystem, and their modification may indicate that both QA and PheoD1 are sources of reactive oxygen species on the reducing side of Photosystem II.

  5. Adsorption on metal oxides Studies with the metastable impact electron spectroscopy

    CERN Document Server

    Krischok, S; Kempter, V

    2002-01-01

    An overview is given on the application of metastable impact electron spectroscopy, in combination with UPS, to the study of clean magnesia and titania surfaces and their interaction with metal atoms and small molecules. The mechanisms for metal adsorption on reducible (titania) and non-reducible (magnesia) substrates are different: while on titania the metal atom often bonds by electron transfer to Ti3d states, it is hybridization of the adsorbate and anion wavefunctions which accounts for the bonding on MgO. In the case of H sub 2 O, molecular adsorption takes place both on MgO and TiO sub 2; on the other hand, water-alkali coadsorption leads to hydroxide formation. In the case of CO sub 2 , chemisorption takes place in form of carbonate (CO sub 3) species. These originate from the CO sub 2 interaction with O sup 2 sup - surface anions. While for CaO chemisorption takes place at regular oxygen sites, for MgO this occurs at low-coordinated oxygen ions only; for TiO sub 2 chemisorption requires alkali coadsor...

  6. Adsorption on metal oxides: Studies with the metastable impact electron spectroscopy

    International Nuclear Information System (INIS)

    Krischok, S.; Hoefft, O.; Kempter, V.

    2002-01-01

    An overview is given on the application of metastable impact electron spectroscopy, in combination with UPS, to the study of clean magnesia and titania surfaces and their interaction with metal atoms and small molecules. The mechanisms for metal adsorption on reducible (titania) and non-reducible (magnesia) substrates are different: while on titania the metal atom often bonds by electron transfer to Ti3d states, it is hybridization of the adsorbate and anion wavefunctions which accounts for the bonding on MgO. In the case of H 2 O, molecular adsorption takes place both on MgO and TiO 2 ; on the other hand, water-alkali coadsorption leads to hydroxide formation. In the case of CO 2 , chemisorption takes place in form of carbonate (CO 3 ) species. These originate from the CO 2 interaction with O 2- surface anions. While for CaO chemisorption takes place at regular oxygen sites, for MgO this occurs at low-coordinated oxygen ions only; for TiO 2 chemisorption requires alkali coadsorption

  7. A review on adsorption refrigeration technology and adsorption deterioration in physical adsorption systems

    Energy Technology Data Exchange (ETDEWEB)

    Wang, D.C.; Li, Y.H. [College of Electromechanical Engineering, Qingdao University, 308 Ningxia Road, Qingdao 266071 (China); Laboratory of Fiber Materials and Modern Textile, the Growing Base for State Key Laboratory, Qingdao University, 308 Ningxia Road, Qingdao 266071 (China); Li, D.; Zhang, J.P. [College of Electromechanical Engineering, Qingdao University, 308 Ningxia Road, Qingdao 266071 (China); Xia, Y.Z. [Laboratory of Fiber Materials and Modern Textile, the Growing Base for State Key Laboratory, Qingdao University, 308 Ningxia Road, Qingdao 266071 (China)

    2010-01-15

    As one kind of environmentally friendly refrigeration, the adsorption refrigeration has attracted many attentions in resent decades. This paper introduces the researches of adsorption refrigeration systems with the commonly used working pairs, advanced adsorption cycles, heat and mass transfer enhancement and attempts of adsorption refrigeration applications. Poor heat and mass transfer problem is a bottleneck to prevent the improvements of the adsorption refrigeration technique. Two ways to enhance the heat and mass transfer are discussed in this paper. The adsorption deterioration of adsorbent, another obstacle to physical adsorption refrigeration applications, is also pointed out. And the possible reasons and the possible methods are analyzed. (author)

  8. Gas separation by pressure swing adsorption

    International Nuclear Information System (INIS)

    Martin, J.R.; Gottzman, C.F.; Notaro, F.; Stewart, H.A.

    1986-01-01

    Over the past twenty years separation processes based upon pressure swing adsorption have replaced cryogenic processes in a number of selected applications such as air separation for production of moderate quantities of nitrogen and oxygen and recovery of hydrogen from refinery and chemical plant gases. Key events contributing to the emergence of PSA as an important process option have been the development of synthetic zeolite molecular sieves by Union Carbide Corporation in the USA and of carbon molecular sieves by Bergbau-Forschung in Germany. Today PSA processes enjoy significant commercial use producing oxygen from 0.1 Nm 3 /h for medical application to 1500 Nm 3 /h for steel mill use, for making nitrogen up to 1000 Nm 3 /h for inerting and in purifying hydrogen streams of up to 100,000 Nm 3 /h for refinery use. In this paper some of the principles of adsorptive separations are reviewed. The history of the technology is traced briefly with emphasis on key material, process and application events. The major commercial processes in the application of adsorption to bulk separation of air and hydrogen purification are reviewed in more detail with comparisons made to cryogenic alternatives in terms of specific characteristics, advantages and disadvantages where appropriate. Information on performance, reliability and comparative economics are discussed where available

  9. Microcalorimetric and potentiometric titration studies on the adsorption of copper by P. putida and B. thuringiensis and their composites with minerals

    International Nuclear Information System (INIS)

    Fang Linchuan; Cai Peng; Li Pengxiang; Wu Huayong; Liang Wei; Rong Xingmin; Chen Wenli; Huang Qiaoyun

    2010-01-01

    In order to have a better understanding of the interactions of heavy metals with bacteria and minerals in soil and associated environments, isothermal titration calorimetry (ITC), potentiometric titration and equilibrium sorption experiments were conducted to investigate the adsorption behavior of Cu(II) by Bacillus thuringiensis, Pseudomonas putida and their composites with minerals. The interaction of montmorillonite with bacteria increased the reactive sites and resulted in greater adsorption for Cu(II) on their composites, while decreased adsorption sites and capacities for Cu(II) were observed on goethite-bacteria composites. A gram-positive bacterium B. thuringiensis played a more important role than a gram-negative bacterium P. putida in determining the properties of the bacteria-minerals interfaces. The enthalpy changes (ΔH ads ) from endothermic (6.14 kJ mol -1 ) to slightly exothermic (-0.78 kJ mol -1 ) suggested that Cu(II) is complexed with the anionic oxygen ligands on the surface of bacteria-mineral composites. Large entropies (32.96-58.89 J mol -1 K -1 ) of Cu(II) adsorption onto bacteria-mineral composites demonstrated the formation of inner-sphere complexes in the presence of bacteria. The thermodynamic data implied that Cu(II) mainly bound to the carboxyl and phosphoryl groups as inner-sphere complexes on bacteria and mineral-bacteria composites.

  10. Microcalorimetric and potentiometric titration studies on the adsorption of copper by P. putida and B. thuringiensis and their composites with minerals

    Energy Technology Data Exchange (ETDEWEB)

    Fang Linchuan [State Key Laboratory of Agricultural Microbiology, Huazhong Agricultural University, Wuhan 430070 (China); Key Laboratory of Subtropical Agriculture and Environment, Ministry of Agriculture, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070 (China); Cai Peng; Li Pengxiang; Wu Huayong; Liang Wei; Rong Xingmin [Key Laboratory of Subtropical Agriculture and Environment, Ministry of Agriculture, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070 (China); Chen Wenli [State Key Laboratory of Agricultural Microbiology, Huazhong Agricultural University, Wuhan 430070 (China); Huang Qiaoyun, E-mail: qyhuang@mail.hzau.edu.cn [State Key Laboratory of Agricultural Microbiology, Huazhong Agricultural University, Wuhan 430070 (China); Key Laboratory of Subtropical Agriculture and Environment, Ministry of Agriculture, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070 (China)

    2010-09-15

    In order to have a better understanding of the interactions of heavy metals with bacteria and minerals in soil and associated environments, isothermal titration calorimetry (ITC), potentiometric titration and equilibrium sorption experiments were conducted to investigate the adsorption behavior of Cu(II) by Bacillus thuringiensis, Pseudomonas putida and their composites with minerals. The interaction of montmorillonite with bacteria increased the reactive sites and resulted in greater adsorption for Cu(II) on their composites, while decreased adsorption sites and capacities for Cu(II) were observed on goethite-bacteria composites. A gram-positive bacterium B. thuringiensis played a more important role than a gram-negative bacterium P. putida in determining the properties of the bacteria-minerals interfaces. The enthalpy changes ({Delta}H{sub ads}) from endothermic (6.14 kJ mol{sup -1}) to slightly exothermic (-0.78 kJ mol{sup -1}) suggested that Cu(II) is complexed with the anionic oxygen ligands on the surface of bacteria-mineral composites. Large entropies (32.96-58.89 J mol{sup -1} K{sup -1}) of Cu(II) adsorption onto bacteria-mineral composites demonstrated the formation of inner-sphere complexes in the presence of bacteria. The thermodynamic data implied that Cu(II) mainly bound to the carboxyl and phosphoryl groups as inner-sphere complexes on bacteria and mineral-bacteria composites.

  11. Microcalorimetric and potentiometric titration studies on the adsorption of copper by P. putida and B. thuringiensis and their composites with minerals.

    Science.gov (United States)

    Fang, Linchuan; Cai, Peng; Li, Pengxiang; Wu, Huayong; Liang, Wei; Rong, Xingmin; Chen, Wenli; Huang, Qiaoyun

    2010-09-15

    In order to have a better understanding of the interactions of heavy metals with bacteria and minerals in soil and associated environments, isothermal titration calorimetry (ITC), potentiometric titration and equilibrium sorption experiments were conducted to investigate the adsorption behavior of Cu(II) by Bacillus thuringiensis, Pseudomonas putida and their composites with minerals. The interaction of montmorillonite with bacteria increased the reactive sites and resulted in greater adsorption for Cu(II) on their composites, while decreased adsorption sites and capacities for Cu(II) were observed on goethite-bacteria composites. A gram-positive bacterium B. thuringiensis played a more important role than a gram-negative bacterium P. putida in determining the properties of the bacteria-minerals interfaces. The enthalpy changes (DeltaH(ads)) from endothermic (6.14 kJ mol(-1)) to slightly exothermic (-0.78 kJ mol(-1)) suggested that Cu(II) is complexed with the anionic oxygen ligands on the surface of bacteria-mineral composites. Large entropies (32.96-58.89 J mol(-1) K(-1)) of Cu(II) adsorption onto bacteria-mineral composites demonstrated the formation of inner-sphere complexes in the presence of bacteria. The thermodynamic data implied that Cu(II) mainly bound to the carboxyl and phosphoryl groups as inner-sphere complexes on bacteria and mineral-bacteria composites. Copyright 2010 Elsevier B.V. All rights reserved.

  12. Oxygen Therapy

    Directory of Open Access Journals (Sweden)

    Bonnie Solmes

    2000-01-01

    Full Text Available LTOT is prescribed for people with chronic lung disease in whom there is a decrease in the ability of the lungs to supply enough oxygen to the body. The heart is obliged to pump faster to meet the body's oxygen requirements. This may place undue stress on the heart, resulting in palpitations, dizziness and fatigue. A low oxygen level in arterial blood is also harmful to the heart, the brain and the pulmonary blood vessels. Oxygen therapy is used to break this cycle. A person with low blood oxygen will often be able to accomplish more with less fatigue with the help of supplemental oxygen therapy. Shortness of breath is a mechanical problem resulting from the effects of chronic obstructive pulmonary disease. Oxygen therapy may or may not reduce shortness of breath, but it will help the lungs and heart to function with less stress.

  13. RECENT PROGRESS OF OXYGEN/NITROGEN SEPARATION USING MEMBRANE TECHNOLOGY

    OpenAIRE

    K. C. CHONG; S. O. LAI; H. S. THIAM; H. C. TEOH; S. L. HENG

    2016-01-01

    The oxygen-enriched air is highly demanded for various industrial applications such as medical, chemical and enhanced combustion processes. The conventional oxygen/nitrogen production is either cryogenic distillation or pressure swing adsorption (PSA). Both of these techniques possess the production capability of 20 to 300 tonnes of oxygen per day and oxygen purity of more than 95%. However, these techniques are energy intensive. Alternatively, membrane technology is an emerging technology...

  14. A DFT and QTAIM study of the adsorption of organic molecules over the copper-doped coronene and circumcoronene

    Science.gov (United States)

    Malček, Michal; Cordeiro, M. Natalia D. S.

    2018-01-01

    Graphene based materials are nowadays extensively studied because of their potential applications as gas sensors, biosensors or adsorbents. Doping the graphene surface with heteroatoms or transition metals can improve its electronic properties and chemical reactivity. Polyaromatic hydrocarbons coronene and circumcoronene can be used as models of tiny graphene quantum dots. The adsorption of a set of organic molecules (water, hydrogen peroxide, hydrogen sulfide, methanol, ethanol and oxygen molecule) over the copper-doped coronene and circumcoronene was theoretically studied using density functional theory (DFT) and quantum theory of atoms in molecules (QTAIM). In the case of coronene, only one site was considered for the Cu-doping, whereas in the case of circumcoronene being a polyaromatic hydrocarbon composed of 54 carbon atoms, three different sites for Cu-doping were considered. For the systems under study, the adsorption of O2 was found energetically the most favorable, with energetic outcome ranging from -3.1 to -3.7 eV related to the position of dopant Cu atom. Changes in the topology of charge densities at Cu and in its vicinity after the adsorption of studied molecules were investigated in the framework of QTAIM. In addition, QTAIM analysis of bond critical points (BCP) was employed to study the character of the newly formed chemical bonds. The results of this study point out the suitability of Cu-doped graphene materials as sensors and/or adsorbents in practical applications.

  15. Adsorption of uranium on halloysite

    International Nuclear Information System (INIS)

    Kilislioglu, A.; Bilgin, B.

    2002-01-01

    Adsorption of uranium (U(VI)) from aqueous solutions on halloysite type clay was studied as a function of amount of adsorbent, initial concentration and pH. The values of adsorption data were fitted to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) adsorption isotherms. The mean energy of adsorption was calculated as 5.91 kJ/mol from D-R adsorption isotherm. Lagergren and Bangham equation has been used for dynamic modelling of process and the rate constants of adsorption of uranium on halloysite type clay were calculated at 293, 313 and 333 K. In order to explain the mechanism of adsorption reaction, the rate constants were calculated at high and low uranium concentrations. Adsorption reaction was studied at 293, 303, 313, 323 and 333 K for halloysite type clay and also thermodynamic constants have been calculated. The results show that the adsorption reaction was endothermic and more spontaneous at high temperature. (orig.)

  16. Adsorption of uranium on halloysite

    Energy Technology Data Exchange (ETDEWEB)

    Kilislioglu, A.; Bilgin, B. [Istanbul Univ. (Turkey). Faculty of Engineering

    2002-07-01

    Adsorption of uranium (U(VI)) from aqueous solutions on halloysite type clay was studied as a function of amount of adsorbent, initial concentration and pH. The values of adsorption data were fitted to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) adsorption isotherms. The mean energy of adsorption was calculated as 5.91 kJ/mol from D-R adsorption isotherm. Lagergren and Bangham equation has been used for dynamic modelling of process and the rate constants of adsorption of uranium on halloysite type clay were calculated at 293, 313 and 333 K. In order to explain the mechanism of adsorption reaction, the rate constants were calculated at high and low uranium concentrations. Adsorption reaction was studied at 293, 303, 313, 323 and 333 K for halloysite type clay and also thermodynamic constants have been calculated. The results show that the adsorption reaction was endothermic and more spontaneous at high temperature. (orig.)

  17. AIR SEPARATION BY PRESSURE SWING ADSORPTION USING SUPERIOR ADSORBENTS; FINAL

    International Nuclear Information System (INIS)

    Ralph T Yang

    2001-01-01

    Li-X zeolite (Si/Al= 1.0) is currently the best sorbent for use in the separation of air by adsorption processes. In particular, pressure swing adsorption (PSA) using zeolite sorbents is being increasingly used for air separation. Silver is also known to strongly affect the adsorptive properties of zeolites; and it is known that thermal vacuum dehydration of silver zeolites leads to the formation of silver clusters within the zeolite. In this work we have synthesized type X zeolites containing Ag and also varying mixtures of Li and Ag. In this project, we developed the Ag-containing zeolite as the best sorbent for air separation. We have also studied Co-ligand compounds as oxygen-selective sorbents. Syntheses, structural characterization and adsorption properties have been performed on all sorbents. The results are described in detail in 5 chapters

  18. AIR SEPARATION BY PRESSURE SWING ADSORPTION USING SUPERIOR ADSORBENTS

    Energy Technology Data Exchange (ETDEWEB)

    Ralph T. Yang

    2001-08-31

    Li-X zeolite (Si/Al = 1.0) is currently the best sorbent for use in the separation of air by adsorption processes. In particular, pressure swing adsorption (PSA) using zeolite sorbents is being increasingly used for air separation. Silver is also known to strongly affect the adsorptive properties of zeolites; and it is known that thermal vacuum dehydration of silver zeolites leads to the formation of silver clusters within the zeolite. In this work we have synthesized type X zeolites containing Ag and also varying mixtures of Li and Ag. In this project, we developed the Ag-containing zeolite as the best sorbent for air separation. We have also studied Co-ligand compounds as oxygen-selective sorbents. Syntheses, structural characterization and adsorption properties have been performed on all sorbents. The results are described in detail in 5 chapters.

  19. Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide

    Science.gov (United States)

    Balistrieri, L.S.; Chao, T.T.

    1990-01-01

    This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites

  20. Pressure Swing Adsorption in the Unit Operations Laboratory

    Science.gov (United States)

    Ganley, Jason

    2018-01-01

    This paper describes a student laboratory in the Unit Operations Laboratory at the Colorado School of Mines: air separation by pressure swing adsorption. The flexibility of the system enables students to study the production of enriched nitrogen or oxygen streams. Automatic data acquisition permits the study of cycle steps and performance.…

  1. Adsorption behavior of strontium on binary mineral mixtures of Montmorillonite and Kaolinite

    Energy Technology Data Exchange (ETDEWEB)

    Bascetin, Elvan [Cekmece Nuclear Research and Training Center, P.K.1 34149, Atatuerk Airport, Istanbul (Turkey); Atun, Guelten [Engineering Faculty, Chemistry Department, Istanbul University, 34850 Avcilar, Istanbul (Turkey)]. E-mail: gultena@istanbul.edu.tr

    2006-08-15

    The adsorption behavior of kaolinite and montmorillonite minerals and their mixtures in respect of Sr ion were studied by means of a batch method using {sup 90}Sr as a radio tracer. The effect of several parameters such as temperature, pH, Sr concentration and supporting electrolyte were investigated. Experimentally measured distribution coefficients showed a good agreement to within 98.5-99.7% with theoretically calculated values. The values of adsorption capacity of adsorbents and mean adsorption energy of adsorption were calculated by fitting the adsorption data to Dubinin-Radushkevich isotherm. The adsorption capacity of clay mixtures decreased as kaolinite fractions increased. The mean adsorption energy values of 8.0-9.5 kJ mol{sup -1} showed that adsorption was governed by ion exchange. The Freundlich parameters were used to characterize a site distribution function for binary exchange between Sr and Na.

  2. Adsorption behavior of strontium on binary mineral mixtures of Montmorillonite and Kaolinite

    International Nuclear Information System (INIS)

    Bascetin, Elvan; Atun, Guelten

    2006-01-01

    The adsorption behavior of kaolinite and montmorillonite minerals and their mixtures in respect of Sr ion were studied by means of a batch method using 90 Sr as a radio tracer. The effect of several parameters such as temperature, pH, Sr concentration and supporting electrolyte were investigated. Experimentally measured distribution coefficients showed a good agreement to within 98.5-99.7% with theoretically calculated values. The values of adsorption capacity of adsorbents and mean adsorption energy of adsorption were calculated by fitting the adsorption data to Dubinin-Radushkevich isotherm. The adsorption capacity of clay mixtures decreased as kaolinite fractions increased. The mean adsorption energy values of 8.0-9.5 kJ mol -1 showed that adsorption was governed by ion exchange. The Freundlich parameters were used to characterize a site distribution function for binary exchange between Sr and Na

  3. Defective graphene supported MPd12 (M = Fe, Co, Ni, Cu, Zn, Pd) nanoparticles as potential oxygen reduction electrocatalysts: A first-principles study

    KAUST Repository

    Liu, Xin

    2013-01-24

    We studied the electronic structure of MPd12 (M = Fe, Co, Ni, Cu, Zn, Pd) nanoparticles deposited on graphene substrates and their reactivity toward O adsorption, which are directly related to the catalytic performance of these composites in oxygen reduction reaction, by first-principles-based calculations. We found that the alloying between M and Pd can enhance the stability of nanoparticles and promote their oxygen reduction activity to be comparable with that of Pt(111). The defective graphene substrate can provide anchoring sites for these nanoparticles by forming strong metal-substrate interaction. The interfacial interaction can contribute to additional stability and further tune the averaged d-band center of the deposited alloy nanoparticles, resulting in strong interference on the O adsorption. As the O adsorption on these composites is weakened, the oxygen reduction reaction kinetics over these composites will also be promoted. These composites are thus expected to exhibit both high stability and superior catalytic performance in oxygen reduction reaction. © 2013 American Chemical Society.

  4. Repeated assessment of orthotopic glioma pO2 by multi-site EPR oximetry: A technique with the potential to guide therapeutic optimization by repeated measurements of oxygen

    Science.gov (United States)

    Khan, Nadeem; Mupparaju, Sriram; Hou, Huagang; Williams, Benjamin B.; Swartz, Harold

    2011-01-01

    Tumor hypoxia plays a vital role in therapeutic resistance. Consequently, measurements of tumor pO2 could be used to optimize the outcome of oxygen-dependent therapies, such as, chemoradiation. However, the potential optimizations are restricted by the lack of methods to repeatedly and quantitatively assess tumor pO2 during therapies, particularly in gliomas. We describe the procedures for repeated measurements of orthotopic glioma pO2 by multi-site electron paramagnetic resonance (EPR) oximetry. This oximetry approach provides simultaneous measurements of pO2 at more than one site in the glioma and contralateral cerebral tissue. The pO2 of intracerebral 9L, C6, F98 and U251 tumors, as well as contralateral brain, were measured repeatedly for five consecutive days. The 9L glioma was well oxygenated with pO2 of 27 - 36 mm Hg, while C6, F98 and U251 glioma were hypoxic with pO2 of 7 - 12 mm Hg. The potential of multi-site EPR oximetry to assess temporal changes in tissue pO2 was investigated in rats breathing 100% O2. A significant increase in F98 tumor and contralateral brain pO2 was observed on day 1 and day 2, however, glioma oxygenation declined on subsequent days. In conclusion, EPR oximetry provides the capability to repeatedly assess temporal changes in orthotopic glioma pO2. This information could be used to test and optimize the methods being developed to modulate tumor hypoxia. Furthermore, EPR oximetry could be potentially used to enhance the outcome of chemoradiation by scheduling treatments at times of increase in glioma pO2. PMID:22079559

  5. Sub-ambient carbon dioxide adsorption properties of nitrogen doped graphene

    Energy Technology Data Exchange (ETDEWEB)

    Tamilarasan, P.; Ramaprabhu, Sundara, E-mail: ramp@iitm.ac.in [Alternative Energy and Nanotechnology Laboratory (AENL), Nano Functional Materials Technology Centre (NFMTC), Department of Physics, Indian Institute of Technology Madras, Chennai 600036 (India)

    2015-04-14

    Carbon dioxide adsorption on carbon surface can be enhanced by doping the surface with heterogeneous atoms, which can increase local surface affinity. This study presents the carbon dioxide adsorption properties of nitrogen doped graphene at low pressures (<100 kPa). Graphene was exposed to nitrogen plasma, which dopes nitrogen atoms into carbon hexagonal lattice, mainly in pyridinic and pyrrolic forms. It is found that nitrogen doping significantly improves the CO{sub 2} adsorption capacity at all temperatures, due to the enrichment of local Lewis basic sites. In general, isotherm and thermodynamic parameters suggest that doped nitrogen sites have nearly same adsorption energy of surface defects and residual functional groups. The isosteric heat of adsorption remains in physisorption range, which falls with surface coverage, suggesting the distribution of magnitude of adsorption energy. The absolute values of isosteric heat and entropy of adsorption are slightly increased upon nitrogen doping.

  6. Simulating multi-component liquid phase adsorption systems: ethanol and residual sugar

    Energy Technology Data Exchange (ETDEWEB)

    Jones, R.; Tezel, F.H.; Thibault, J. [Department of Chemical and Biological Engineering, University of Ottawa (Canada)], email: Jules.Thibault@uottawa.ca

    2011-07-01

    A series of multi-component adsorption studies was performed to determine the relative advantages of producing ethanol which is to be blended with gasoline. These studies developed a model to describe the competition for adsorption sites between ethanol and sugar molecules on the surface of the adsorbent. Three competitive adsorption models established by batch systems were examined to evaluate the suitability of the experiment data across different ethanol and sugar concentrations and determine their isotherm parameters. Multi-component packed bed adsorption experiments were then performed. The results show that ethanol capacity was decreased only slightly from that obtained in single component adsorption studies. There is significant evidence to indicate that sugar displacement from adsorption sites occurs because adsorption of ethanol is preferred. So the capacity of sugars will be greatly reduced if there are appreciable ethanol concentrations.

  7. Adsorption of chloroacetanilide herbicides on soil and its components. III. Influence of clay acidity, humic acid coating and herbicide structure on acetanilide herbicide adsorption on homoionic clays.

    Science.gov (United States)

    Liu, Wei-ping; Fang, Zhuo; Liu, Hui-jun; Yang, Wei-chun

    2002-04-01

    Adsorption of chloroacetanilide herbicides on homoionic montmorillonite, soil humic acid, and their mixtures was studied by coupling batch equilibration and FT-IR analysis. Adsorption isotherms of acetochlor, alachlor, metolachlor and propachlor on Ca(2+)-, Mg(2+)-, Al(3+)- and Fe(3+)-saturated clays were well described by the Freundlich equation. Regardless of the type of exchange cations, Kf decreased in the order of metolachlor > acetolachlor > alachlor > propachlor on the same clay. FT-IR spectra showed that the carbonyl group of the herbicide molecule was involved in binding, probably via H-bond with water molecules in the clay interlayer. The type and position of substitutions around the carbonyl group may have affected the electronegativity of oxygen, thus influencing the relative adsorption of these herbicides. For the same herbicide, adsorption on clay increased in the order of Mg2+ < Ca2+ < Al3+ < or = Fe3+ which coincided with the increasing acidity of homoionic clays. Acidity of cations may have affected the protonation of water, and thus the strength of H-bond between the clay water and herbicide. Complexation of clay and humic acid resulted in less adsorption than that expected from independent adsorption by the individual constituents. The effect varied with herbicides, but the greatest decrease in adsorption occurred at a 60:40 clay-to-humic acid ratio for all the herbicides. Causes for the decreased adsorption need to be characterized to better understand adsorption mechanisms and predict adsorption from soil compositions.

  8. Regenerative adsorption distillation system

    KAUST Repository

    Ng, Kim Choon

    2013-12-26

    There is provided a regenerative adsorption distillation system comprising a train of distillation effects in fluid communication with each other. The train of distillation effects comprises at least one intermediate effect between the first and last distillation effects of the train, each effect comprising a vessel and a condensing tube for flow of a fluid therein. The system further comprises a pair of adsorption-desorption beds in vapour communication with the last effect and at least one intermediate effect, wherein the beds contain an adsorbent that adsorbs vapour from the last effect and transmits desorbed vapour into at least one of the intermediate effect.

  9. Regenerative adsorption distillation system

    KAUST Repository

    Ng, Kim Choon; Thu, Kyaw; Amy, Gary; Chunggaze, Mohammed; Al-Ghasham, Tawfiq

    2013-01-01

    There is provided a regenerative adsorption distillation system comprising a train of distillation effects in fluid communication with each other. The train of distillation effects comprises at least one intermediate effect between the first and last distillation effects of the train, each effect comprising a vessel and a condensing tube for flow of a fluid therein. The system further comprises a pair of adsorption-desorption beds in vapour communication with the last effect and at least one intermediate effect, wherein the beds contain an adsorbent that adsorbs vapour from the last effect and transmits desorbed vapour into at least one of the intermediate effect.

  10. Mechanism of adsorption of gold and silver species on activated carbons

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Y.F.; Steele, C.J.; Hayward, I.P.; Thomas, K.M. [University of Newcastle-upon-Tyne, Newcastle-upon-Tyne (United Kingdom). Northern Carbon Research Labs., Dept. of Chemistry

    1998-12-31

    The adsorption characteristics of gold and silver cyanide anionic species on a suite of active carbons derived from coal, coconut shell and polyacrylonitrile was investigated. The gold and silver cyanide adsorption capacities for both coconut shell and coal derived carbons correlated with total pore volume. Nitric acid treatment of the carbon was detrimental to gold adsorption in spite of the incorporation of oxygen into the carbon through oxidation. The influence of nitrogen functional groups in the carbon structure on gold and silver adsorption was investigated using carbons with very high nitrogen contents derived from polyacrylonitrile.

  11. Theoretical investigation of CO adsorption on Rhn (n = 3-13) clusters

    NARCIS (Netherlands)

    Shetty, S.G.; Strych, S.; Jansen, A.P.J.; Santen, van R.A.

    2009-01-01

    The adsorption of CO onto Rhn (n = 3–13) clusters has been investigated using the density functional approach. Stable active sites for CO adsorption such as top, bridge, and hollow have been identified on these clusters. Our results show that CO mostly prefers the bridge or top site, except on the

  12. Distinct site- and state-selective dissociation of methyl-trifluoroacetate observed in core-electron excitation at the oxygen K-edge region

    Science.gov (United States)

    Yamanaka, T.; Tabayashi, K.; Maruyama, T.; Harada, C.; Yoshida, H.

    2009-11-01

    Distinct site- and state-selective dissociation following the O1s core-excitation has been found in the gaseous molecules of methyl trifluoroacetate (MTFA). The site- and state-selective dissociation was examined by measuring the branching ratios of dominant CH3+ and CHO+ fragments. The branching ratios from MTFA showed that site-selective dissociation takes place via the excitation from the different atomic sites to the same π*CO resonance state, (O1sCO-1π*CO) and (O1sOMe-1π*CO). A pronounced O1sOMe site-selectivity was identified by a significant increment of CHO+ formation at the (O1sOMe→π*CO) band. The site-selectivity was also justified by an equivalent core approximation using the density functional theory calculation. State-selective dissociation was identified among the (O1sOMe-1π*CO), (O1sOMe-1σ*O-Me) and (O1sOMe-1σ*C-OMe) transitions originated from the same OMe core. State-selective production of CH3+ could be found at the (O1sOMe→σ*O-Me) band, whereas state-selective formation of CHO+ was observed at the (O1sOMe→π*CO) and (O1sOMe→σ*C-OMe) bands.

  13. The investigation of adsorption and dissociation of H2O on Li2O (111) by ab initio theory

    International Nuclear Information System (INIS)

    Kong, Xianggang; Yu, You; Ma, Shenggui; Gao, Tao; Lu, Tiecheng; Xiao, Chengjian; Chen, Xiaojun; Zhang, Chuanyu

    2017-01-01

    Highlights: • The adsorption structures of H 2 O on Li 2 O (111) are obtained by calculations. • By Bader charge analysis, the charge translation from slab to adsorbate is found. • The vibrational frequencies of adsorbate are in line with the experimental values. - Abstract: The adsorption and dissociation mechanism of H 2 O molecule on the Li 2 O (111) surface have been systematically studied by using the density functional theory calculations. The parallel and vertical configurations of H 2 O at six different symmetry adsorption sites on the Li 2 O (111) surface are considered. In our calculations, it is suggested that H 2 O can dissociate on the perfect Li 2 O surface, of which the corresponding adsorption energy is 1.118 eV. And the adsorption energy decrease to be 0.241 eV when oxygen atom of H 2 O bonds to lithium atom of the slab. The final configurations are sensitive to the initial molecular orientation. By Bader charge analysis, the charge transfer from slab to adsorbed H 2 O/OH can be found due to the downward shift of lowest-unoccupied molecular orbital. We also analyze the vibrational frequencies at the Brillouin Zone centre for H 2 O molecule adsorbed on the stoichiometric surface. Due to the slightly different structure parameters, the calculated values of the vibrational frequencies of hydroxyl group range from 3824 to 3767 cm −1 . Our results agree well with experimental results performed in FT-IR spectrum, which showed that an absorption peak of OH group appeared at 3677 cm −1 at room temperature.

  14. Physical adsorption and molecular dynamics

    International Nuclear Information System (INIS)

    Cohan, N.V.

    1981-01-01

    Some aspects of noble gases adsorption (except He) on graphite substracts are reviewed. Experimental results from this adsorption are analyzed and compared with molecular dynamics calculations. (L.C.) [pt

  15. Adsorption of poly(ethylene oxide) on smectite: Effect of layer charge.

    Science.gov (United States)

    Su, Chia-Chi; Shen, Yun-Hwei

    2009-04-01

    The adsorption of polymers on clay is important in many applications. However the mechanisms of poly(ethylene oxide) (PEO) adsorption on smectite is not well elucidated at present. The aim of this study was to investigate the effect of layer charge density on the adsorption of PEO by smectite. The results indicated that both the hydrophobic interaction (between CH(2)CH(2) groups and siloxane surface) and the hydrogen bonding (between ether oxygen of PEO and structure OH of smectite) lead to PEO preferential adsorption on the surface of low-charge smectite. In addition, the delamination of low-charge smectite in water is enhanced upon PEO adsorption presumably due to the hydrophilic ether oxygen of adsorbed PEO.

  16. Adsorption and reduction of NO2 over activated carbon at low temperature

    International Nuclear Information System (INIS)

    Gao, Xiang; Liu, Shaojun; Zhang, Yang; Luo, Zhongyang; Ni, Mingjiang; Cen, Kefa

    2011-01-01

    The reactive adsorption of NO 2 over activated carbon (AC) was investigated at 50 C. Both the NO 2 adsorption and its reduction to NO were observed during the exposure of AC to NO 2 . Temperature programmed desorption (TPD) was then performed to evaluate the nature and thermal stability of the adsorbed species. Adsorption and desorption processes have been proposed based on the nitrogen and oxygen balance data. The micropores in AC act as a nano-reactor for the formation of -C(ONO 2 ) complexes, which is composed by NO 2 adsorption on existing -C(O) complexes and the disproportionation of adsorbed NO 2 . The generated -C(ONO 2 ) complexes are decomposed to NO and NO 2 in the desorption step. The remaining oxygen complexes can be desorbed as CO and CO 2 to recover the adsorptive and reductive capacity of AC. (author)

  17. Adsorption heats of olefins on supported MoO3/Al2O3 catalists

    International Nuclear Information System (INIS)

    Grinev, V.E.; Madden, M.; Khalit, V.A.; Aptekar', E.L.; Aldag, A.; Krylov, O.V.

    1983-01-01

    Adsorption heats of C 2 H 4 , C 3 H 6 and C 4 H 8 on supported MoO 3 /Al 2 O 3 catalysts containing 6, 10 and 15 wt. % of MoO 3 at 25, 77 and 195 deg are determimed. Adsorption heat of an olefin increases with a growing length of its carbonic chain. The number of adsorbed olefin molecules grows with an increase in the MoO 3 concentration, while initial adsorption heats decrease. The number of adsorbed olefins is proportional to mean rate of molybdenum reduction in catalysts. Adsorption heats of oxygen on the surface of the catalysts with preliminarily adsorbed olefins are determined. It is shown that adsorption of oxygen and olefins proceeeds both on the same and on different centres of the surface. Mechanisms of surface interactions are discussed

  18. Adsorption of elemental mercury vapors from synthetic exhaust combustion gas onto HGR carbon.

    Science.gov (United States)

    Musmarra, D; Karatza, D; Lancia, A; Prisciandaro, M; Mazziotti di Celso, G

    2016-07-01

    An activated carbon commercially available named HGR, produced by Calgon-Carbon Group, was used to adsorbe metallic mercury. The work is part of a wider research activity by the same group focused on the removal of metallic and divalent mercury from combustion flue gas. With respect to previously published papers, this one is aimed at studying in depth thermodynamic equilibria of metallic mercury adsorption onto a commercial activated carbon. The innovativeness lies in the wider operative conditions explored (temperature and mercury concentrations) and in the evaluation of kinetic and thermodynamic data for a commercially available adsorbing material. In detail, experimental runs were carried out on a laboratory-scale plant, in which Hg° vapors were supplied in a nitrogen gas stream at different temperature and mercury concentration. The gas phase was flowed through a fixed bed of adsorbent material. Adsorbate loading curves for different Hg° concentrations together with adsorption isotherms were achieved as a function of temperature (120, 150, 200°C) and Hg° concentrations (1.0-7.0 mg/m(3)). Experimental runs demonstrated satisfying results of the adsorption process, while Langmuir parameters were evaluated with gas-solid equilibrium data. Especially, they confirmed that adsorption capacity is a favored process in case of lower temperature and they showed that the adsorption heat was -20 kJ/mol. Furthermore, a numerical integration of differential equations that model the adsorption process was proposed. Scanning electron microscopy (SEM) investigation was an useful tool to investigate about fresh and saturated carbon areas. The comparison between them allowed identification of surface sites where mercury is adsorbed; these spots correspond to carbon areas where sulfur concentration is greater. Mercury compounds can cause severe harm to human health and to the ecosystem. There are a lot of sources that emit mercury species to the atmosphere; the main ones are

  19. Adsorption and Gas Separation of Molecules by Carbon Nanohorns.

    Science.gov (United States)

    Gatica, Silvina M; Nekhai, Anton; Scrivener, Adam

    2016-05-19

    In this paper, we report the results of Monte Carlo simulations of the adsorption of neon, argon, methane and carbon dioxide in carbon nanohorns. We model the nanohorns as an array of carbon cones and obtained adsorption isotherms and isosteric heats. The main sites of adsorption are inside the cones and in the interstices between three cones. We also calculated the selectivity of carbon dioxide/methane, finding that nanohorns are a suitable substrate for gas separation. Our simulations are compared to available experimental data.

  20. A Combined Probe-Molecule, Mössbauer, Nuclear Resonance Vibrational Spectroscopy, and Density Functional Theory Approach for Evaluation of Potential Iron Active Sites in an Oxygen Reduction Reaction Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kneebone, Jared L. [Univ. of Rochester, Rochester, NY (United States); Daifuku, Stephanie L. [Univ. of Rochester, Rochester, NY (United States); Kehl, Jeffrey A. [Univ. of Rochester, Rochester, NY (United States); Wu, Gang [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Chung, Hoon T. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Hu, Michael Y. [Argonne National Lab. (ANL), Argonne, IL (United States); Alp, E. Ercan [Argonne National Lab. (ANL), Argonne, IL (United States); More, Karren L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Zelenay, Piotr [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Holby, Edward F. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Neidig, Michael L. [Univ. of Rochester, Rochester, NY (United States)

    2017-07-06

    While non-precious metal M-N-C (M = Fe or Co) catalysts have been developed that are effective for the oxygen reduction reaction in polymer electrolyte fuel cells, no consensus has yet been reached regarding the nature of the M sites in these heterogeneous catalysts that are responsible for reaction with dioxygen (O2). While multiple studies have developed correlations between Fe distributions in as-prepared catalysts and ORR activity, the direct identification of sites reactive towards O2 or O2-analog molecules remains a significant challenge. In the present study, we demonstrate a new approach to identifying and characterizing potential Fe active sites in complex ORR catalysts that combines an effective probe molecule (NO(g)) Mössbauer spectroscopy and nuclear resonance vibrational spectroscopy (NRVS) with density functional theory (DFT) calculations. Mössbauer spectroscopic studies demonstrate that NO(g) treatment of electrochemically reduced PANI-57Fe-C leads to selective reaction with only a sub-set of the Fe species present. Nuclear resonance vibrational spectroscopic studies identified new Fe-ligand vibrations associated with the site reactive towards NO(g). DFT calculations of vibrational properties of a small selection of previously proposed active site structures suggest that graphene zig-zag edge hosted Fe-N structures may be responsible for the observed vibrational behavior with NO(g) probe molecules. Moreover, such sites are likely also reactive to O2, possibly serving as the ORR active sites in the synthesized materials.

  1. Sulfate adsorption on goethite

    Energy Technology Data Exchange (ETDEWEB)

    Rietra, R P.J.J.; Hiemstra, T; Riemsdijk, W.H. van

    1999-10-15

    Recent spectroscopic work has suggested that only one surface species of sulfate is dominant on hematite. Sulfate is therefore a very suitable anion to test and develop adsorption models for variable charge minerals. The authors have studied sulfate adsorption on goethite covering a large range of sulfate concentrations, surface coverages, pH values, and electrolyte concentrations. Four different techniques were used to cover the entire range of conditions. For characterization at low sulfate concentrations, below the detection limit of sulfate with ICP-AES, the authors used proton-sulfate titrations at constant pH. Adsorption isotherms were studied for the intermediate sulfate concentration range. Acid-base titrations in sodium sulfate and electromobility were used for high sulfate concentrations. All the data can be modeled with one adsorbed species if it is assumed that the charge of adsorbed sulfate is spatially distributed in the interface. The charge distribution of sulfate follows directly from modeling the proton-sulfate adsorption stoichoimemtry sine this stoichiometry is independent of the intrinsic affinity constant of sulfate. The charge distribution can be related to the structure of the surface complex by use of the Pauling bond valence concept and is in accordance with the microscopic structure found by spectroscopy. The intrinsic affinity constant follows from the other measurements. Modeling of the proton-ion stoichoimetry with the commonly used 2-pK models, where adsorbed ions are treated as point charges, is possible only if at least two surface species for sulfate are used.

  2. Adsorption property of volatile molecules on ZnO nanowires ...

    Indian Academy of Sciences (India)

    2018-02-02

    Feb 2, 2018 ... 2Centre for Fire Explosive and Environment Safety, Defence Research and Development Organisation, Ministry ... present work, Zn site was chosen as an adsorption site for a ... Virtual NanoLab [18] software was utilized to construct the ..... In reality, there will be plenty of vapour molecules that interact over.

  3. Investigation of the adsorption of amino acids on Pd(1 1 1): A density functional theory study

    International Nuclear Information System (INIS)

    James, Joanna N.; Han, Jeong Woo; Sholl, David S.

    2014-01-01

    Graphical abstract: - Highlights: • Density functional theory calculations have been performed to study the adsorption of glycine, alanine, norvaline, valine, proline, cysteine, and serine on Pd(1 1 1). • The common structural framework for the adsorption of most amino acids onto Pd(1 1 1) is in a tridentate fashion via a nitrogen atom and two oxygen atoms. • The shifts in vibrational frequencies associated with NHH and COO support the adsorption patterns of amino acids we examined. • The adsorption strength of amino acids depends on how much the molecules deform during the adsorption process. - Abstract: Density functional theory calculations have been used to study the adsorption of glycine, alanine, norvaline, valine, proline, cysteine, and serine on Pd(1 1 1). Most amino acids except cysteine adsorb onto the surface in a tridentate fashion through a nitrogen atom and both oxygen atoms. For cysteine, an additional bond is formed with the surface due to the strong affinity of the sulfur atom, resulting in a significantly larger adsorption energy. The adsorption patterns of amino acids we examined are supported by the shifts in vibrational frequencies associated with NHH and COO. The adsorption strength of amino acids depends on how much the molecules deform during the adsorption process. Understanding the adsorption of amino acids on Pd(1 1 1) provides fundamental information for future consideration of the interactions between their derivatives or more complicated biomolecules and metal surfaces

  4. Behaviors and kinetics of toluene adsorption-desorption on activated carbons with varying pore structure.

    Science.gov (United States)

    Yang, Xi; Yi, Honghong; Tang, Xiaolong; Zhao, Shunzheng; Yang, Zhongyu; Ma, Yueqiang; Feng, Tiecheng; Cui, Xiaoxu

    2018-05-01

    This work was undertaken to investigate the behaviors and kinetics of toluene adsorption and desorption on activated carbons with varying pore structure. Five kinds of activated carbon from different raw materials were selected. Adsorption isotherms and breakthrough curves for toluene were measured. Langmuir and Freundlich equations were fitted to the equilibrium data, and the Freundlich equation was more suitable for simulating toluene adsorption. The process consisted of monolayer, multilayer and partial active site adsorption types. The effect of the pore structure of the activated carbons on toluene adsorption capacity was investigated. The quasi-first-order model was more suitable for describing the process than the quasi-second-order model. The adsorption data was also modeled by the internal particle diffusion model and it was found that the adsorption process could be divided into three stages. In the external surface adsorption process, the rate depended on the specific surface area. During the particle diffusion stage, pore structure and volume were the main factors affecting adsorption rate. In the final equilibrium stage, the rate was determined by the ratio of meso- and macro-pores to total pore volume. The rate over the whole adsorption process was dominated by the toluene concentration. The desorption behavior of toluene on activated carbons was investigated, and the process was divided into heat and mass transfer parts corresponding to emission and diffusion mechanisms, respectively. Physical adsorption played the main role during the adsorption process. Copyright © 2017. Published by Elsevier B.V.

  5. Fundamentals of high pressure adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Y.P.; Zhou, L. [Tianjin University, Tianjin (China). High Pressure Adsorption Laboratory

    2009-12-15

    High-pressure adsorption attracts research interests following the world's attention to alternative fuels, and it exerts essential effect on the study of hydrogen/methane storage and the development of novel materials addressing to the storage. However, theoretical puzzles in high-pressure adsorption hindered the progress of application studies. Therefore, the present paper addresses the major theoretical problems that challenged researchers: i.e., how to model the isotherms with maximum observed in high-pressure adsorption; what is the adsorption mechanism at high pressures; how do we determine the quantity of absolute adsorption based on experimental data. Ideology and methods to tackle these problems are elucidated, which lead to new insights into the nature of high-pressure adsorption and progress in application studies, for example, in modeling multicomponent adsorption, hydrogen storage, natural gas storage, and coalbed methane enrichment, was achieved.

  6. Adsorption of SO{sub 2} on Li atoms deposited on MgO (1 0 0) surface: DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Eid, Kh.M., E-mail: Kheid98@hotmail.com [Physics Department, Faculty of Education, Ain Shams University, Cairo 11757 (Egypt); Ammar, H.Y. [Department of Physics, Faculty of Science, Najran University, Najran 1988 (Saudi Arabia)

    2011-05-01

    The adsorption of sulfur dioxide molecule (SO{sub 2}) on Li atom deposited on the surfaces of metal oxide MgO (1 0 0) on both anionic and defect (F{sub s}-center) sites located on various geometrical defects (terrace, edge and corner) has been studied using density functional theory (DFT) in combination with embedded cluster model. The adsorption energy (E{sub ads}) of SO{sub 2} molecule (S-atom down as well as O-atom down) in different positions on both of O{sup -2} and F{sub s} sites is considered. The spin density (SD) distribution due to the presence of Li atom is discussed. The geometrical optimizations have been done for the additive materials and MgO substrate surfaces (terrace, edge and corner). The oxygen vacancy formation energies have been evaluated for MgO substrate surfaces. The ionization potential (IP) for defect free and defect containing of the MgO surfaces has been calculated. The adsorption properties of SO{sub 2} are analyzed in terms of the E{sub ads}, the electron donation (basicity), the elongation of S-O bond length and the atomic charges on adsorbed materials. The presence of the Li atom increases the catalytic effect of the anionic O{sup -2} site of MgO substrate surfaces (converted from physisorption to chemisorption). On the other hand, the presence of the Li atom decreases the catalytic effect of the F{sub s}-site of MgO substrate surfaces. Generally, the SO{sub 2} molecule is strongly adsorbed (chemisorption) on the MgO substrate surfaces containing F{sub s}-center.

  7. Nickel adsorption by sodium polyacrylate-grafted activated carbon

    Energy Technology Data Exchange (ETDEWEB)

    Ewecharoen, A. [Division of Biotechnology, School of Bioresources and Technology, King Mongkut' s University of Technology Thonburi, 83 Moo 8 Thakham, Bangkhuntien, Bangkok 10150 (Thailand); Thiravetyan, P., E-mail: paitip@hotmail.com [Division of Biotechnology, School of Bioresources and Technology, King Mongkut' s University of Technology Thonburi, 83 Moo 8 Thakham, Bangkhuntien, Bangkok 10150 (Thailand); Wendel, E.; Bertagnolli, H. [Institut fuer Physikalische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany)

    2009-11-15

    A novel sodium polyacrylate grafted activated carbon was produced by using gamma radiation to increase the number of functional groups on the surface. After irradiation the capacity for nickel adsorption was studied and found to have increased from 44.1 to 55.7 mg g{sup -1}. X-ray absorption spectroscopy showed that the adsorbed nickel on activated carbon and irradiation-grafted activated carbon was coordinated with 6 oxygen atoms at 2.04-2.06 A. It is proposed that this grafting technique could be applied to other adsorbents to increase the efficiency of metal adsorption.

  8. Water Adsorption and Dissociation on Ceria-Supported Single-Atom Catalysts: A First-Principles DFT+U Investigation.

    Science.gov (United States)

    Han, Zhong-Kang; Gao, Yi

    2016-02-01

    Single-atom catalysts have attracted wide attention owing to their extremely high atom efficiency and activities. In this paper, we applied density functional theory with the inclusion of the on-site Coulomb interaction (DFT+U) to investigate water adsorption and dissociation on clean CeO 2 (111) surfaces and single transition metal atoms (STMAs) adsorbed on the CeO 2 (111) surface. It is found that the most stable water configuration is molecular adsorption on the clean CeO 2 (111) surface and dissociative adsorption on STMA/CeO 2 (111) surfaces, respectively. In addition, our results indicate that the more the electrons that transfer from STMA to the ceria substrate, the stronger the binding energies between the STMA and ceria surfaces. A linear relationship is identified between the water dissociation barriers and the d band centers of STMA, known as the generalized Brønsted-Evans-Polanyi principle. By combining the oxygen spillovers, single-atom dispersion stabilities, and water dissociation barriers, Zn, Cr, and V are identified as potential candidates for the future design of ceria-supported single-atom catalysts for reactions in which the dissociation of water plays an important role, such as the water-gas shift reaction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Intraportal islet oxygenation.

    Science.gov (United States)

    Suszynski, Thomas M; Avgoustiniatos, Efstathios S; Papas, Klearchos K

    2014-05-01

    Islet transplantation (IT) is a promising therapy for the treatment of diabetes. The large number of islets required to achieve insulin independence limit its cost-effectiveness and the number of patients who can be treated. It is believed that >50% of islets are lost in the immediate post-IT period. Poor oxygenation in the early post-IT period is recognized as a possible reason for islet loss and dysfunction but has not been extensively studied. Several key variables affect oxygenation in this setting, including (1) local oxygen partial pressure (pO(2)), (2) islet oxygen consumption, (3) islet size (diameter, D), and (4) presence or absence of thrombosis on the islet surface. We discuss implications of oxygen-limiting conditions on intraportal islet viability and function. Of the 4 key variables, the islet size appears to be the most important determinant of the anoxic and nonfunctional islet volume fractions. Similarly, the effect of thrombus formation on the islet surface may be substantial. At the University of Minnesota, average size distribution data from clinical alloislet preparations (n = 10) indicate that >150-µm D islets account for only ~30% of the total islet number, but >85% of the total islet volume. This suggests that improved oxygen supply to the islets may have a profound impact on islet survivability and function since most of the β-cell volume is within large islets which are most susceptible to oxygen-limiting conditions. The assumption that the liver is a suitable islet transplant site from the standpoint of oxygenation should be reconsidered. © 2014 Diabetes Technology Society.

  10. Screening of active metals for reactive adsorption desulfurization adsorbent using density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Lei; Zhao, Liang, E-mail: liangzhao@cup.edu.cn; Xu, Chunming; Wang, Yuxian; Gao, Jinsen

    2017-03-31

    Highlights: • Electronic characteristics determined adsorption characteristics of transition metals. • Cobalt has the similar adsorption ability of thiophene as nickel. • Adsorption capacity of Cr and Mo was extremely fierce, while Cu has the potential ability for adsorbing thiophene. • The preference adsorption site for thiophene was hollow site on all the seven surface. - Abstract: To explore characteristics of active metals for reactive adsorption desulfurization (RADS) technology, the adsorption of thiophene on M (100) (M = Cr, Mo, Co, Ni, Cu, Au, and Ag) surfaces was systematically studied by density functional theory with vdW correction (DFT + D3). We found that, in all case, the most stable molecular adsorption site was the hollow site and adsorptive capabilities of thiophene followed the order: Cr > Mo > Co ≈ Ni > Cu > Au ≈ Ag. By analyzing the nature of binding between thiophene and corresponding metals and the electronic structure of metals, the excessive activities of Cr and Mo were found to have a negative regeneration, the passive activities of Au and Ag were found to have an inactive adsorption for RADS adsorbent alone, while Ni and Co have appropriate characteristics as the active metals for RADS, followed by Cu.

  11. Traps for phosphorus adsorption

    International Nuclear Information System (INIS)

    Montoya, Nawer D; Villegas, Wilson E; Rodriguez, Lino M; Taborda, Nelson; Montes de C, Consuelo

    2001-01-01

    Several AL 2 O 3 supported oxides such as: NiO, CuO, Co 2 O 3 BaO, CeO 2 and ZnO were investigated for phosphorus adsorption. Zno/y-Al 2 O 3 exhibited the highest phosphorus adsorption capacity. However, since it diminishes the activity of to the reaction mixture it should be located upstream of the NoX catalyst, i.e. 0,3% Pd-H-MOR, in order to protect it against p poisoning. The treatment procedure with citric acid was effective for the removal of more than 70% phosphorus from the adsorbent, ZnO/y-Al 2 O 3

  12. Water Adsorption on Clean and Defective Anatase TiO2 (001) Nanotube Surfaces: A Surface Science Approach.

    Science.gov (United States)

    Kenmoe, Stephane; Lisovski, Oleg; Piskunov, Sergei; Bocharov, Dmitry; Zhukovskii, Yuri F; Spohr, Eckhard

    2018-04-11

    We use ab initio molecular dynamics simulations to study the adsorption of thin water films with 1 and 2 ML coverage on anatase TiO 2 (001) nanotubes. The nanotubes are modeled as 2D slabs, which consist of partially constrained and partially relaxed structural motifs from nanotubes. The effect of anion doping on the adsorption is investigated by substituting O atoms with N and S impurities on the nanotube slab surface. Due to strain-induced curvature effects, water adsorbs molecularly on defect-free surfaces via weak bonds on Ti sites and H bonds to surface oxygens. While the introduction of an S atom weakens the interaction of the surface with water, which adsorbs molecularly, the presence of an N impurity renders the surface more reactive to water, with a proton transfer from the water film and the formation of an NH group at the N site. At 2 ML coverage, a further surface-assisted proton transfer takes place in the water film, resulting in the formation of an OH - group and an NH 2 + cationic site on the surface.

  13. Diffusion Influenced Adsorption Kinetics.

    Science.gov (United States)

    Miura, Toshiaki; Seki, Kazuhiko

    2015-08-27

    When the kinetics of adsorption is influenced by the diffusive flow of solutes, the solute concentration at the surface is influenced by the surface coverage of solutes, which is given by the Langmuir-Hinshelwood adsorption equation. The diffusion equation with the boundary condition given by the Langmuir-Hinshelwood adsorption equation leads to the nonlinear integro-differential equation for the surface coverage. In this paper, we solved the nonlinear integro-differential equation using the Grünwald-Letnikov formula developed to solve fractional kinetics. Guided by the numerical results, analytical expressions for the upper and lower bounds of the exact numerical results were obtained. The upper and lower bounds were close to the exact numerical results in the diffusion- and reaction-controlled limits, respectively. We examined the validity of the two simple analytical expressions obtained in the diffusion-controlled limit. The results were generalized to include the effect of dispersive diffusion. We also investigated the effect of molecular rearrangement of anisotropic molecules on surface coverage.

  14. Oxygen exchange between C18O2 and ''acidic'' oxide and zeolite catalysts

    International Nuclear Information System (INIS)

    Peri, J.B.

    1975-01-01

    The exchange of oxygen between C 18 O 2 and several high-area oxides, including silica, γ-alumina, silica--alumina, and zeolite catalysts, was studied. Infrared spectra of adsorbed CO 2 and of surface ''carbonates'' were used to follow the rate of oxygen exchange and investigate the nature of unusually exchangeable surface oxide ions, present at low concentrations. Interaction of CO 2 with the surface typically produced initial exchange of one oxygen atom, as expected from interaction with a single oxide ion (CO 2 + O 2- reversible CO 3 2- ), and the number of exchangeable ions increased with increasing temperature. The rate of oxygen exchange did not correlate with chemisorption to form stable surface carbonates or with the extent of strong physical adsorption of CO 2 . With dry silica, exchange was insignificant below 600 0 ; with catalytically active zeolites and dry γ-alumina, it was detectable at 200 0 and fairly rapid at 300--400 0 . Silica--alumina required 100--150 0 higher temperature for exchange than did an active zeolite. Activity for cracking and other hydrocarbon reactions may be related to the ease of exchange of some surface oxide ions with CO 2 . Active zeolites have reactive oxide sites resembling those on dry γ-alumina, but such sites on zeolites are probably less-readily eliminated by chemisorption of H 2 O or other compounds. (U.S.)

  15. Reduced step edges on rutile TiO (110) as competing defects to oxygen vacancies on the terraces and reactive sites for ethanol dissociation

    DEFF Research Database (Denmark)

    Martinez, U.; Hansen, Jonas Ørbæk; Salazar, Estephania Lira

    2012-01-01

    microscopy studies, we here present experimental evidence for the existence of O vacancies along the ⟨11̅ 1⟩R step edges (OS vac.’s) on rutile TiO2(110). Both the distribution of bridging O vacancies on the terraces and temperature-programed reaction experiments of ethanol-covered TiO2(110) point...... to the existence of the OS vac.’s. Based on experiments and density functional theory calculations, we show that OS vac.’s are reactive sites for ethanol dissociation via O-H bond scission. Implications of these findings are discussed...

  16. Density functional study of carbon monoxide adsorption on small cationic, neutral, and anionic aluminum nitride clusters

    Science.gov (United States)

    Guo, Ling

    CO adsorption on small cationic, neutral, and anionic (AlN)n (n = 1-6) clusters has been investigated using density functional theory in the generalized gradient approximation. Among various possible CO adsorption sites, an N on-top (onefold coordinated) site is found to be the most favorable one, irrespective of the charge state of the clusters. The adsorption energies of CO on the anionic (AlN)nCO (n = 2-4) clusters are greater than those on the neutral and cationic complexes. The adsorption energies on the cationic and neutral complexes reflect the odd-even oscillations, and the adsorption energies of CO on the cationic (AlN)nCO (n = 5, 6) clusters are greater than those on the neutral and anionic complexes. The adsorption energies for the different charge states decrease with increasing cluster size.

  17. Chirality in adsorption on solid surfaces.

    Science.gov (United States)

    Zaera, Francisco

    2017-12-07

    In the present review we survey the main advances made in recent years on the understanding of chemical chirality at solid surfaces. Chirality is an important topic, made particularly relevant by the homochiral nature of the biochemistry of life on Earth, and many chiral chemical reactions involve solid surfaces. Here we start our discussion with a description of surface chirality and of the different ways that chirality can be bestowed on solid surfaces. We then expand on the studies carried out to date to understand the adsorption of chiral compounds at a molecular level. We summarize the work published on the adsorption of pure enantiomers, of enantiomeric mixtures, and of prochiral molecules on chiral and achiral model surfaces, especially on well-defined metal single crystals but also on other flat substrates such as highly ordered pyrolytic graphite. Several phenomena are identified, including surface reconstruction and chiral imprinting upon adsorption of chiral agents, and the enhancement or suppression of enantioselectivity seen in some cases upon adsorption of enantiomixtures of chiral compounds. The possibility of enhancing the enantiopurity of adsorbed layers upon the addition of chiral seeds and the so-called "sergeants and soldiers" phenomenon are presented. Examples are provided where the chiral behavior has been associated with either thermodynamic or kinetic driving forces. Two main approaches to the creation of enantioselective surface sites are discussed, namely, via the formation of supramolecular chiral ensembles made out of small chiral adsorbates, and by adsorption of more complex chiral molecules capable of providing suitable chiral environments for reactants by themselves, via the formation of individual adsorbate:modifier adducts on the surface. Finally, a discussion is offered on the additional effects generated by the presence of the liquid phase often required in practical applications such as enantioselective crystallization, chiral

  18. Adsorption isotherm special study. Final report

    International Nuclear Information System (INIS)

    1993-05-01

    The study was designed to identify methods to determine adsorption applicable to Uranium Mill Tailings Remedial Action (UMTRA) Project sites, and to determine how changes in aquifer conditions affect metal adsorption, resulting retardation factors, and estimated contaminant migration rates. EPA and ASTM procedures were used to estimate sediment sorption of U, As, and Mo under varying groundwater geochemical conditions. Aquifer matrix materials from three distinct locations at the DOE UMTRA Project site in Rifle, CO, were used as the adsorbents under different pH conditions; these conditions stimulated geochemical environments under the tailings, near the tailings, and downgradient from the tailings. Grain size, total surface area, bulk and clay mineralogy, and petrography of the sediments were characterized. U and Mo yielded linear isotherms, while As had nonlinear ones. U and Mo were adsorbed strongly on sediments acidified to levels similar to tailings leachate. Changes in pH had much less effect on As adsorption. Mo was adsorbed very little at pH 7-7.3, U was weakly sorbed, and As was moderately sorbed. Velocities were estimated for metal transport at different pHs. Results show that the aquifer materials must be characterized to estimate metal transport velocities in aquifers and to develop groundwater restoration strategies for the UMTRA project

  19. Mercury adsorption properties of sulfur-impregnated adsorbents

    Science.gov (United States)

    Hsi, N.-C.; Rood, M.J.; Rostam-Abadi, M.; Chen, S.; Chang, R.

    2002-01-01

    Carbonaceous and noncarbonaceous adsorbents were impregnated with elemental sulfur to evaluate the chemical and physical properties of the adsorbents and their equilibrium mercury adsorption capacities. Simulated coal combustion flue gas conditions were used to determine the equilibrium adsorption capacities for Hg0 and HgCl2 gases to better understand how to remove mercury from gas streams generated by coal-fired utility power plants. Sulfur was deposited onto the adsorbents by monolayer surface deposition or volume pore filling. Sulfur impregnation increased the total sulfur content and decreased the total and micropore surface areas and pore volumes for all of the adsorbents tested. Adsorbents with sufficient amounts of active adsorption sites and sufficient microporous structure had mercury adsorption capacities up to 4,509 ??g Hg/g adsorbent. Elemental sulfur, organic sulfur, and sulfate were formed on the adsorbents during sulfur impregnation. Correlations were established with R2>0.92 between the equilibrium Hg0/HgCl2 adsorption capacities and the mass concentrations of elemental and organic sulfur. This result indicates that elemental and organic sulfur are important active adsorption sites for Hg0 and HgCl2.

  20. First-principles study of H, O, and N adsorption on metal embedded carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Li, Detian [Science and Technology on Vacuum Technology and Physics Laboratory, Lanzhou Institute of Physics, Lanzhou, Gansu 730000 (China); Institute of Micro-nano Structures & Optoelectronics, Wenzhou University, Wenzhou, Zhejiang 325035 (China); Luo, Haijun, E-mail: luohaijun@wzu.edu.cn [Institute of Micro-nano Structures & Optoelectronics, Wenzhou University, Wenzhou, Zhejiang 325035 (China); Cai, Jianqiu [Institute of Micro-nano Structures & Optoelectronics, Wenzhou University, Wenzhou, Zhejiang 325035 (China); Cheng, Yongjun [Science and Technology on Vacuum Technology and Physics Laboratory, Lanzhou Institute of Physics, Lanzhou, Gansu 730000 (China); Shao, Xiji [Institute of Micro-nano Structures & Optoelectronics, Wenzhou University, Wenzhou, Zhejiang 325035 (China); Dong, Changkun, E-mail: dck@wzu.edu.cn [Science and Technology on Vacuum Technology and Physics Laboratory, Lanzhou Institute of Physics, Lanzhou, Gansu 730000 (China); Institute of Micro-nano Structures & Optoelectronics, Wenzhou University, Wenzhou, Zhejiang 325035 (China)

    2017-05-01

    Highlights: • Ni or Fe embedment and high atomic adsorption coverage benefit applications like hydrogen storage and field emission. • Ni or Fe embedment could help tune the catalytic properties. • Ni or Fe embedment enhances the adatom-SWNT interaction significantly. - Abstract: The density functional theory calculation has been conducted to investigate the structural and electronic properties, including the adsorption energies, bond structures, work functions, charge transfer behaviors, and density of states for pristine, Ni-, and Fe-embedded capped (5, 5) single-walled carbon nanotubes (SWNTs) with different coverage of atomic hydrogen, oxygen, and nitrogen adsorptions. Ni or Fe embedment enhances the adatom-SWNT interactions significantly for three kinds of gas atoms with the increases of the adsorption energies. The SWNT work function drops with H adsorption, while Ni or Fe embedment assists further the reduction. When increasing the coverage, the adsorption energy decreases and the work function climbs for O adsorption, but the nitrogen adsorption energy increases. The Bader charge transfer analysis implies that the cap possesses higher oxygen reduction activities than the tube, and the density of states analysis shows that Ni or Fe embedment deepens the C-adatom hybridizations.

  1. Inter-row Adsorption Configuration and Stability of Threonine Adsorbed on the Ge(100) Surfaces

    International Nuclear Information System (INIS)

    Lee, Myungjin; Park, Youngchan; Jeong, Hyuk; Lee, Hangil

    2013-01-01

    The adsorption structures of threonine on the Ge(100) surface were investigated using core-level photoemission spectroscopy (CLPES) in conjunction with density functional theory (DFT) calculations. CLPES measurements were performed to identify the experimentally preferred adsorption structure. The preferred structure indicated the relative reactivities of the carboxyl and hydroxymethyl groups as electron donors to the Ge(100) surface during adsorption. The core-level C 1s, N 1s, and O 1s CLPES spectra indicated that the carboxyl oxygen competed more strongly with the hydroxymethyl oxygen during the adsorption reaction. Three among six possible adsorption structures were identified as energetically favorable using DFT calculation methods that considered the inter- and intra-bonding configurations upon adsorption onto the Ge(100) surface. These structures were O-H dissociated N dative inter bonding, O-H dissociated N dative intra bonding, O-H dissociation bonding. One of the adsorption structures: O-H dissociated N dative inter bonding was predicted to be stable in light of the transition state energies. We thus confirmed that the most favorable adsorption structure is the O-H dissociated N dative-inter bonding structure using CLPES and DFT calculation

  2. Application of Nanosize Zeolite Molecular Sieves for Medical Oxygen Concentration

    Directory of Open Access Journals (Sweden)

    Mingfei Pan

    2017-07-01

    Full Text Available The development of a portable oxygen concentrator is of prime significance for patients with respiratory problems. This paper presents a portable concentrator prototype design using the pressure/vacuum swing adsorption (PVSA cycle with a deep evacuation step (−0.82 barg instead of desorption with purge flow to simplify the oxygen production process. The output of the oxygen concentrator is a ~90 vol % enriched oxygen stream in a continuous adsorption and desorption cycle (cycle time ~90 s. The size of the adsorption column is 3 cm in diameter and 20 cm in length. A Li+ exchanged 13X nanosize zeolite is used as the adsorbent to selectively adsorb nitrogen from air. A dynamic model of the pressure and vacuum swing adsorption units was developed to study the pressurization and depressurization process inside the microporous area of nanosized zeolites. The describing equations were solved using COMSOL Multiphysics Chemical Engineering module. The output flow rate and oxygen concentration results from the simulation model were compared with the experimental data. Velocity and concentration profiles were obtained to study the adsorption process and optimize the operational parameters.

  3. Ion adsorption properties of molybdenum (II) bromide

    International Nuclear Information System (INIS)

    Ganzerli-Valentini, M.T.; Meloni, S.; Caramella-Crespi, V.; Borroni, P.A.

    1976-01-01

    The adsorption of about 50 ions on molybdenum dibromide, (Mo 6 Br 8 )Br 4 .2H 2 O in nitric acid was investigated. The behaviour of the investigated elements on MDB in nitric acid, in the concentration range 10 -2 -8M is presented, where the distribution coefficients are given against the HNO 3 molarity. In some cases the elements were investigated in different oxidation states. Most of the elements are not adsorbed or poorly adsorbed, among these the stable anions, thus indicating that bromide ions substitution with other anions is not competitive. The preparation of the adsorber and its characterization is presented and discussed. Adsorption mechanism studies were carried out for some noble metals and chromium. Sorption cannot be ascribed to ion exchange mechanism but to formation of insoluble species, and to settlement of few ions into surface sorption sites or into a limited number of cavitites in the cluster crystal structure of the adsorber. (T.G.)

  4. Appearance of enhancement effect in adsorption of binary gas mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Sakano, T. [Ajinomoto General Foods, Inc., Tokyo (Japan); Tamon, H.; Okazaki, M. [Kyoto University, Kyoto (Japan)

    1997-10-20

    The properties of adsorbents and adsorbates contributing to the enhancement in adsorption of binary gas mixtures were experimentally investigated. It is found that adsorbent is required to maintain the phenolic hydroxyl group and the carbonyl group as acidic surface oxides on the carbon surface, and to have a microporous structure for the main adsorption sites. Each gas component is required to be chemisorbed on the phenolic hydroxyl group or the carbonyl group on the adsorbent, and that both components are adsorbed in the micropores together. From the characterization of adsorbents after adsorption-desorption runs, it is demonstrated that the adsorbates in the micropores exist at a higher density than in the bulk state through the promotion of micropore filling when adsorption enhancement appears. 17 refs., 7 figs., 5 tabs.

  5. Study of adsorption properties on lithium doped activated carbon materials

    International Nuclear Information System (INIS)

    Los, S.; Daclaux, L.; Letellier, M.; Azais, P.

    2005-01-01

    A volumetric method was applied to study an adsorption coefficient of hydrogen molecules in a gas phase on super activated carbon surface. The investigations were focused on getting the best possible materials for the energy storage. Several treatments on raw samples were used to improve adsorption properties. The biggest capacities were obtain after high temperature treatment at reduced atmosphere. The adsorption coefficient at 77 K and 2 MPa amounts to 3.158 wt.%. The charge transfer between lithium and carbon surface groups via the doping reaction enhanced the energy of adsorption. It was also found that is a gradual decrease in the adsorbed amount of H 2 molecules due to occupation active sites by lithium ions. (author)

  6. Purification and site-directed mutagenesis of linoleate 9S-dioxygenase-allene oxide synthase of Fusarium oxysporum confirms the oxygenation mechanism.

    Science.gov (United States)

    Chen, Yang; Jernerén, Fredrik; Oliw, Ernst H

    2017-07-01

    Plants and fungi form jasmonic acid from α-linolenic acid. The first two steps of biosynthesis in plants occur by sequential transformation by 13S-lipoxygenase and allene oxide synthase (AOS). The biosynthesis in fungi may follow this classical scheme, but the only fungal AOS discovered so far are cytochromes P450 (CYP) fused to 8- and 9-dioxygenases (DOX). In the present report, we purified recombinant 9S-DOX-AOS of Fusarium oxysporum from cell lysate by cobalt affinity chromatography to near homogeneity and studied key residues by site-directed mutagenesis. Sequence homology with 8R-DOX-linoleate diol synthases (8R-DOX-LDS) suggested that Tyr414 catalyzes hydrogen abstraction and that Cys1051 forms the heme thiolate ligand. Site-directed mutagenesis (Tyr414Phe; Cys1051Ser) led to loss of 9S-DOX and 9S-AOS activities, respectively, but other important residues in the CYP parts of 5,8- and 7,8-LDS or 9R-AOS were not conserved. The UV-visible spectrum of 9S-DOX-AOS showed a Soret band at 409 nm, which shifted to 413 nm in the Cys1051Ser mutant. The 9S-AOS of the Tyr414Phe mutant transformed 9S-hydroperoxides of α-linolenic and linoleic acids to allene oxides/α-ketols, but it did not transform 13-hydroperoxides. We conclude that 9S- and 8R-DOX catalyze hydrogen abstraction at C-11 and C-8, respectively, by homologous Tyr residues. Copyright © 2017 Elsevier Inc. All rights reserved.

  7. A new 0.9 Ma oxygen isotope stratigraphy for a shallow-water sedimentary transect across three IODP 317 sites in the Canterbury Bight of southwest Pacific Ocean

    Science.gov (United States)

    Ding, Xuan; Wu, YingYing

    2016-04-01

    Sedimentary records in shallow-water environment provide unique opportunity to further our understanding on the regional relative sea level changes in relation to global climate change. Here we present a new 0.9 Ma oxygen isotope stratigraphy for a shallow-water sedimentary transect across three IODP 317 sites in the Canterbury Bight of southwest Pacific Ocean. The three sites are located on the eastern margin of the South Island of New Zealand, including a continental slope site, IODP317-U1352 and two continental shelf sites, IODP317-U1354 and IODP317-U1351. We first generated high resolution benthic foraminifers (Nonionella flemingi) δ18O records for the three sites and a planktonic (Globigerina bulloides) record for the U1352B. An initial chronological framework for the benthic δ18O record of the U1352B was constructed using 8 accelerator mass spectrometry (AMS) radiocarbon dates and 4 biostratigraphic events. Then a refined age model was established by correlating the U1352B benthic δ18O record with the EDC δD record on the AICC2012 time-scale, and the LR04 benthic δ18O stack. Although the U1354B and U1351B have lower sedimentation rates, their benthic δ18O records correlate well with that of U1352B. In order to ensure the accuracy of the chronostratigraphic framework established, we also analyzed the characteristics of sedimentary grain size and the planktonic and benthic δ18O values. In accord with the adjacent sites, the results show that the melt of Southern Alps glaciers due to the warming climate during MIS 11 and 5.5 led to the increased fresh water delivery, with massive terrigenous deposit; and the warm SST during the MIS7 is related with the STF migration, which led to strong current activity, with coarser grain size. Meanwhile, records of benthic δ18O, sedimentation rate and content of >63μm coarse fraction of site U1352 all indicate the MIS 20 was indeed a colder interval compared to subsequent glacial times.

  8. Study of Adsorption Mechanism of Congo Red on Graphene Oxide/PAMAM Nanocomposite

    Science.gov (United States)

    Rafi, Mohammad; Samiey, Babak; Cheng, Chil-Hung

    2018-01-01

    Graphene oxide/poly(amidoamine) (GO/PAMAM) nanocomposite adsorbed high quantities of congo red (CR) anionic dye in 0.1 M NaCl solution, with the maximum adsorption capacity of 198 mg·g−1. The kinetics and thermodynamics of adsorption were investigated to elucidate the effects of pH, temperature, shaking rate, ionic strength, and contact time. Kinetic data were analyzed by the KASRA model and the KASRA, ISO, and pore-diffusion equations. Adsorption adsorption isotherms were studied by the ARIAN model and the Henry, Langmuir, and Temkin equations. It was shown that adsorption sites of GO/PAMAM at experimental conditions were phenolic hydroxyl groups of GO sheets and terminal amine groups of PAMAM dendrimer. Analysis of kinetic data indicated that amine sites were located on the surface, and that hydroxyl sites were placed in the pores of adsorbent. CR molecules interacted with the adsorption sites via hydrogen bonds. The molecules were adsorbed firstly on the amine sites, and then on the internal hydroxyl sites. Adsorption kinetic parameters indicated that the interaction of CR to the –NH3+ sites was the rate-controlling step of adsorption of CR on this site and adsorption activation energies calculated for different parts of this step. On the other hand, kinetic parameters showed that the intraparticle diffusion was the rate-controlling step during the interaction of CR molecules to –OH sites and activation energy of this step was not calculable. Finally, the used GO/PAMAM was completely regenerated by using ethylenediamine. PMID:29587463

  9. Study of Adsorption Mechanism of Congo Red on Graphene Oxide/PAMAM Nanocomposite

    Directory of Open Access Journals (Sweden)

    Mohammad Rafi

    2018-03-01

    Full Text Available Graphene oxide/poly(amidoamine (GO/PAMAM nanocomposite adsorbed high quantities of congo red (CR anionic dye in 0.1 M NaCl solution, with the maximum adsorption capacity of 198 mg·g−1. The kinetics and thermodynamics of adsorption were investigated to elucidate the effects of pH, temperature, shaking rate, ionic strength, and contact time. Kinetic data were analyzed by the KASRA model and the KASRA, ISO, and pore-diffusion equations. Adsorption adsorption isotherms were studied by the ARIAN model and the Henry, Langmuir, and Temkin equations. It was shown that adsorption sites of GO/PAMAM at experimental conditions were phenolic hydroxyl groups of GO sheets and terminal amine groups of PAMAM dendrimer. Analysis of kinetic data indicated that amine sites were located on the surface, and that hydroxyl sites were placed in the pores of adsorbent. CR molecules interacted with the adsorption sites via hydrogen bonds. The molecules were adsorbed firstly on the amine sites, and then on the internal hydroxyl sites. Adsorption kinetic parameters indicated that the interaction of CR to the –NH3+ sites was the rate-controlling step of adsorption of CR on this site and adsorption activation energies calculated for different parts of this step. On the other hand, kinetic parameters showed that the intraparticle diffusion was the rate-controlling step during the interaction of CR molecules to –OH sites and activation energy of this step was not calculable. Finally, the used GO/PAMAM was completely regenerated by using ethylenediamine.

  10. Oxygen safety

    Science.gov (United States)

    ... sure you have working smoke detectors and a working fire extinguisher in your home. If you move around the house with your oxygen, you may need more than one fire extinguisher in different locations. Smoking can be very dangerous. No one should smoke ...

  11. Adsorption and collective paramagnetism

    CERN Document Server

    Selwood, Pierce W

    1962-01-01

    Adsorption and Collective Paramagnetism describes a novel method for studying chemisorption. The method is based on the change in the number of unpaired electrons in the adsorbent as chemisorption occurs. The method is applicable to almost all adsorbates, but it is restricted to ferromagnetic adsorbents such as nickel, which may be obtained in the form of very small particles, that is to say, to ferromagnetic adsorbents with a high specific surface. While almost all the data used illustratively have been published elsewhere this is the first complete review of the subject. The book is addresse

  12. Probing Gas Adsorption in Zeolites by Variable-Temperature IR Spectroscopy: An Overview of Current Research.

    Science.gov (United States)

    Garrone, Edoardo; Delgado, Montserrat R; Bonelli, Barbara; Arean, Carlos O

    2017-09-15

    The current state of the art in the application of variable-temperature IR (VTIR) spectroscopy to the study of (i) adsorption sites in zeolites, including dual cation sites; (ii) the structure of adsorption complexes and (iii) gas-solid interaction energy is reviewed. The main focus is placed on the potential use of zeolites for gas separation, purification and transport, but possible extension to the field of heterogeneous catalysis is also envisaged. A critical comparison with classical IR spectroscopy and adsorption calorimetry shows that the main merits of VTIR spectroscopy are (i) its ability to provide simultaneously the spectroscopic signature of the adsorption complex and the standard enthalpy change involved in the adsorption process; and (ii) the enhanced potential of VTIR to be site specific in favorable cases.

  13. Parameterization and evaluation of sulfate adsorption in a dynamic soil chemistry model

    International Nuclear Information System (INIS)

    Martinson, Liisa; Alveteg, Mattias; Warfvinge, Per

    2003-01-01

    Including sulfate adsorption improves the dynamic behavior of the SAFE model. - Sulfate adsorption was implemented in the dynamic, multi-layer soil chemistry model SAFE. The process is modeled by an isotherm in which sulfate adsorption is considered to be fully reversible and dependent on sulfate concentration as well as pH in soil solution. The isotherm was parameterized by a site-specific series of simple batch experiments at different pH (3.8-5.0) and sulfate concentration (10-260 μmol l -1 ) levels. Application of the model to the Lake Gaardsjoen roof covered site shows that including sulfate adsorption improves the dynamic behavior of the model and sulfate adsorption and desorption delay acidification and recovery of the soil. The modeled adsorbed pool of sulfate at the site reached a maximum level of 700 mmol/m 2 in the late 1980s, well in line with experimental data

  14. Adsorption of diclofenac and nimesulide on activated carbon: Statistical physics modeling and effect of adsorbate size

    Science.gov (United States)

    Sellaoui, Lotfi; Mechi, Nesrine; Lima, Éder Cláudio; Dotto, Guilherme Luiz; Ben Lamine, Abdelmottaleb

    2017-10-01

    Based on statistical physics elements, the equilibrium adsorption of diclofenac (DFC) and nimesulide (NM) on activated carbon was analyzed by a multilayer model with saturation. The paper aimed to describe experimentally and theoretically the adsorption process and study the effect of adsorbate size using the model parameters. From numerical simulation, the number of molecules per site showed that the adsorbate molecules (DFC and NM) were mostly anchored in both sides of the pore walls. The receptor sites density increase suggested that additional sites appeared during the process, to participate in DFC and NM adsorption. The description of the adsorption energy behavior indicated that the process was physisorption. Finally, by a model parameters correlation, the size effect of the adsorbate was deduced indicating that the molecule dimension has a negligible effect on the DFC and NM adsorption.

  15. Oxygen Deficit: The Bio-energetic Pathophysiology

    Directory of Open Access Journals (Sweden)

    ABHAY KUMAR PANDEY

    2014-09-01

    Full Text Available Scarcity of oxygen in humans arises via three modes. The environment may have low oxygen to breath. There can be disease in respiratory system causing hindrance to uptake of oxygen from environment and the circulatory system may be sluggish to supply to body parts that starve for oxygen. Thirdly the chemico-cellular components of blood which carry oxygen may be lowered or defective. In reference to body cells several limiting sites and mechanisms affect the amount of oxygen delivered to them, and these are under regulatory control of several functional and metabolic systems.

  16. Oxygen therapy - infants

    Science.gov (United States)

    ... breathe increased amounts of oxygen to get normal levels of oxygen in their blood. Oxygen therapy provides babies with the extra oxygen. Information Oxygen is a gas that the cells in your body need to work properly. The ...

  17. A Cabin Air Separator for EVA Oxygen

    Science.gov (United States)

    Graf, John C.

    2011-01-01

    Presently, the Extra-Vehicular Activities (EVAs) conducted from the Quest Joint Airlock on the International Space Station use high pressure, high purity oxygen that is delivered to the Space Station by the Space Shuttle. When the Space Shuttle retires, a new method of delivering high pressure, high purity oxygen to the High Pressure Gas Tanks (HPGTs) is needed. One method is to use a cabin air separator to sweep oxygen from the cabin air, generate a low pressure/high purity oxygen stream, and compress the oxygen with a multistage mechanical compressor. A main advantage to this type of system is that the existing low pressure oxygen supply infrastructure can be used as the source of cabin oxygen. ISS has two water electrolysis systems that deliver low pressure oxygen to the cabin, as well as chlorate candles and compressed gas tanks on cargo vehicles. Each of these systems can feed low pressure oxygen into the cabin, and any low pressure oxygen source can be used as an on-board source of oxygen. Three different oxygen separator systems were evaluated, and a two stage Pressure Swing Adsorption system was selected for reasons of technical maturity. Two different compressor designs were subjected to long term testing, and the compressor with better life performance and more favorable oxygen safety characteristics was selected. These technologies have been used as the basis of a design for a flight system located in Equipment Lock, and taken to Preliminary Design Review level of maturity. This paper describes the Cabin Air Separator for EVA Oxygen (CASEO) concept, describes the separator and compressor technology trades, highlights key technology risks, and describes the flight hardware concept as presented at Preliminary Design Review (PDR)

  18. Metal adsorption on monolayer blue phosphorene: A first principles study

    Science.gov (United States)

    Khan, Imran; Son, Jicheol; Hong, Jisang

    2018-01-01

    We investigated the electronic structure, adsorption energies, magnetic properties, dipole moment and work function of metal adatoms (Mg, Cr, Mo, Pd, Pt, and Au) adsorption on a blue phosphorene monolayer. For Mg, Pt and Au metals, the most stable state was found in hollow site while for Cr, Mo and Pd metals we found an adsorption in valley site. We suggest that the Pd and Pt atoms prefer 2D growth mode while the Mg, Cr, Mo and Au atoms prefer 3D island growth mode on monolayer phosphorene. The electronic band structures and magnetic properties were dependent on the doping site and dopant materials. For instance, the semiconducting features were preserved in Mg, Pd, Pt, and Au doped systems. However, the Cr and Mo doped systems displayed half-metallic band structures. The total magnetic moment of 4.05, 2.0 and 0.77 μB /impurity atom were obtained in Cr, Mo and Au doped systems whereas the Mg, Pd and Pt doped systems remained nonmagnetic. We also investigated the magnetic interaction between two transition metal impurities. We observed ferromagnetic coupling between two transition metal impurities in Cr and Mo doped systems while the Au doped system displayed almost degenerated magnetic state. For Mg, Cr, and Mo adsorptions, we found relatively large values of dipole moments compared to those in the Pd, Pt and Au adsorptions. This resulted in a significant suppression of the work function in Mg, Cr and Mo adsorptions. Overall, adsorption can tune the physical and magnetic properties of phosphorene monolayer.

  19. Studies of surface adsorption on LiAlO2

    International Nuclear Information System (INIS)

    Fischer, A.K.; Johnson, C.E.; McDaniel, J.A.

    1986-01-01

    Computational and experimental approaches are being taken to understanding surface adsorption/desorption effects on tritium inventory and release. The computational survey integrates a thermodynamic treatment of surface adsorption and bulk phase effects such as solubility and gas phase composition. The system T 2 O:T 2 :LiAlO 2 was examined. The calculations indicate that surface adsorption can be expected to contribute most to tritium inventory under the conditions of lower temperatures and higher oxygen activities. Higher temperature and lower oxygen activity favor lower surface inventory. In the experimental work, a high temperature gas chromatograph was constructed in order to measure the H 2 O:H 2 surface adsorption isotherms and the solubility of hydroxide in LiAlO 2 . Preliminary data indicate that at 478 K approximately 15% of the surface is coverred for a partial pressure of H 2 O of approximately 52 Pa. Calculated values can be obtained that are in reasonable agreement with this. (orig.)

  20. Studies of surface adsorption on LiAlO2

    International Nuclear Information System (INIS)

    Fischer, A.K.; McDaniel, J.A.; Johnson, C.E.

    1986-01-01

    Computational and experimental approaches are being taken to understanding surface adsorption/desorption effects on tritium inventory and release. The computational survey integrates a thermodynamic treatment of surface adsorption and bulk phase effects such as solubility and gas phase composition. The system T 2 O:T 2 :LiAlO 2 was examined. The calculations indicate that surface adsorption can be expected to contribute most to tritium inventory under the conditions of lower temperatures and higher oxygen activities. Higher temperature and lower oxygen activity favor lower surface inventory. In the experimental work, a high temperature gas chromatograph was constructed in order to measure the H 2 O:H 2 surface adsorption isotherms and the solubility of hydroxide in LiAlO 2 . Preliminary data indicate that at 478K approximately 15% of the surface is covered for a partial pressure of H 2 O of approximately 52 Pa. Calculated values can be obtained that are in reasonable agreement with this

  1. Study on Shale Adsorption Equation Based on Monolayer Adsorption, Multilayer Adsorption, and Capillary Condensation

    OpenAIRE

    Chen, Qing; Tian, Yuanyuan; Li, Peng; Yan, Changhui; Pang, Yu; Zheng, Li; Deng, Hucheng; Zhou, Wen; Meng, Xianghao

    2017-01-01

    Shale gas is an effective gas resource all over the world. The evaluation of pore structure plays a critical role in exploring shale gas efficiently. Nitrogen adsorption experiment is one of the significant approaches to analyze pore size structure of shale. Shale is extremely heterogeneous due to component diversity and structure complexity. Therefore, adsorption isotherms for homogeneous adsorbents and empirical isotherms may not apply to shale. The shape of adsorption-desorption curve indi...

  2. First-principles calculation of adsorption of shale gas on CaCO3 (100) surfaces.

    Science.gov (United States)

    Luo, Qiang; Pan, Yikun; Guo, Ping; Wang, Zhouhua; Wei, Na; Sun, Pengfei; Liu, Yuxiao

    2017-06-16

    To demonstrate the adsorption strength of shale gas to calcium carbonate in shale matrix, the adsorption of shale gas on CaCO3 (100) surfaces was studied using the first-principles method, which is based on the density functional theory (DFT). The structures and electronic properties of CH4, C2H6, CO2 and N2 molecules were calculated by the generalized gradient approximation (GGA), for a coverage of 1 monolayer (ML). Under the same conditions, the density of states (DOS) of CaCO3 (100) surfaces before and after the adsorption of shale gas molecules at high-symmetry adsorption sites were compared. The results showed that the adsorption energies of CH4, C2H6, CO2 and N2 on CaCO3 (100) surfaces were between 0.2683 eV and -0.7388 eV. When a CH4 molecule was adsorbed at a hollow site and its 2 hydrogen atoms were parallel to the long diagonal (H3) on the CaCO3 (100) surface, it had the most stable adsorption, and the adsorption energy was only -0.4160 eV. The change of adsorption energy of CH4 was no more than 0.0535 eV. Compared with the DOS distribution of CH4 before adsorption, it shifted to the left overall after adsorption. At the same time, the partial density of states (PDOS) curves of CaCO3 (100) surfaces before and after adsorption basically overlapped. This work showed that the adsorption effect of shale gas on calcium carbonate is very weak, and the adsorption is physisorption at the molecular level.

  3. Effect of active zinc oxide dispersion on reduced graphite oxide for hydrogen sulfide adsorption at mid-temperature

    Energy Technology Data Exchange (ETDEWEB)

    Song, Hoon Sub [Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L3G1 (Canada); Greenhouse Gas Department, Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon, 305-343 (Korea, Republic of); Park, Moon Gyu [Department of Chemical Engineering Education, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 305-764 (Korea, Republic of); Croiset, Eric, E-mail: ecroiset@uwaterloo.ca [Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L3G1 (Canada); Chen, Zhongwei [Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L3G1 (Canada); Nam, Sung Chan; Ryu, Ho-Jung [Greenhouse Gas Department, Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon, 305-343 (Korea, Republic of); Yi, Kwang Bok, E-mail: cosy32@cnu.ac.kr [Department of Chemical Engineering Education, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 305-764 (Korea, Republic of)

    2013-09-01

    Composites of Zinc oxide (ZnO) with reduced graphite oxide (rGO) were synthesized and used as adsorbents for hydrogen sulfide (H{sub 2}S) at 300 °C. Various characterization methods (TGA, XRD, FT-IR, TEM and XPS) were performed in order to link their H{sub 2}S adsorption performance to the properties of the adsorbent's surface. Microwave-assisted reduction process of graphite oxide (GO) provided mild reduction environment, allowing oxygen-containing functional groups to remain on the rGO surface. It was confirmed that for the ZnO/rGO synthesize using the microwave-assisted reduction method, the ZnO particle size and the degree of ZnO dispersion remained stable over time at 300 °C, which was not the case for only the ZnO particles themselves. This stable highly dispersed feature allows for sustained high surface area over time. This was confirmed through breakthrough experiments for H{sub 2}S adsorption where it was found that the ZnO/rGO composite showed almost four times higher ZnO utilization efficiency than ZnO itself. The effect of the H{sub 2} and CO{sub 2} on H{sub 2}S adsorption was also investigated. The presence of hydrogen in the H{sub 2}S stream had a positive effect on the removal of H{sub 2}S since it allows a reducing environment for Zn-O and Zn-S bonds, leading to more active sites (Zn{sup 2+}) to sulfur molecules. On the other hand, the presence of carbon dioxide (CO{sub 2}) showed the opposite trend, likely due to the oxidation environment and also due to possible competitive adsorption between H{sub 2}S and CO{sub 2}.

  4. Effect of active zinc oxide dispersion on reduced graphite oxide for hydrogen sulfide adsorption at mid-temperature

    Science.gov (United States)

    Song, Hoon Sub; Park, Moon Gyu; Croiset, Eric; Chen, Zhongwei; Nam, Sung Chan; Ryu, Ho-Jung; Yi, Kwang Bok

    2013-09-01

    Composites of Zinc oxide (ZnO) with reduced graphite oxide (rGO) were synthesized and used as adsorbents for hydrogen sulfide (H2S) at 300 °C. Various characterization methods (TGA, XRD, FT-IR, TEM and XPS) were performed in order to link their H2S adsorption performance to the properties of the adsorbent's surface. Microwave-assisted reduction process of graphite oxide (GO) provided mild reduction environment, allowing oxygen-containing functional groups to remain on the rGO surface. It was confirmed that for the ZnO/rGO synthesize using the microwave-assisted reduction method, the ZnO particle size and the degree of ZnO dispersion remained stable over time at 300 °C, which was not the case for only the ZnO particles themselves. This stable highly dispersed feature allows for sustained high surface area over time. This was confirmed through breakthrough experiments for H2S adsorption where it was found that the ZnO/rGO composite showed almost four times higher ZnO utilization efficiency than ZnO itself. The effect of the H2 and CO2 on H2S adsorption was also investigated. The presence of hydrogen in the H2S stream had a positive effect on the removal of H2S since it allows a reducing environment for Znsbnd O and Znsbnd S bonds, leading to more active sites (Zn2+) to sulfur molecules. On the other hand, the presence of carbon dioxide (CO2) showed the opposite trend, likely due to the oxidation environment and also due to possible competitive adsorption between H2S and CO2.

  5. Effect of active zinc oxide dispersion on reduced graphite oxide for hydrogen sulfide adsorption at mid-temperature

    International Nuclear Information System (INIS)

    Song, Hoon Sub; Park, Moon Gyu; Croiset, Eric; Chen, Zhongwei; Nam, Sung Chan; Ryu, Ho-Jung; Yi, Kwang Bok

    2013-01-01

    Composites of Zinc oxide (ZnO) with reduced graphite oxide (rGO) were synthesized and used as adsorbents for hydrogen sulfide (H 2 S) at 300 °C. Various characterization methods (TGA, XRD, FT-IR, TEM and XPS) were performed in order to link their H 2 S adsorption performance to the properties of the adsorbent's surface. Microwave-assisted reduction process of graphite oxide (GO) provided mild reduction environment, allowing oxygen-containing functional groups to remain on the rGO surface. It was confirmed that for the ZnO/rGO synthesize using the microwave-assisted reduction method, the ZnO particle size and the degree of ZnO dispersion remained stable over time at 300 °C, which was not the case for only the ZnO particles themselves. This stable highly dispersed feature allows for sustained high surface area over time. This was confirmed through breakthrough experiments for H 2 S adsorption where it was found that the ZnO/rGO composite showed almost four times higher ZnO utilization efficiency than ZnO itself. The effect of the H 2 and CO 2 on H 2 S adsorption was also investigated. The presence of hydrogen in the H 2 S stream had a positive effect on the removal of H 2 S since it allows a reducing environment for Zn-O and Zn-S bonds, leading to more active sites (Zn 2+ ) to sulfur molecules. On the other hand, the presence of carbon dioxide (CO 2 ) showed the opposite trend, likely due to the oxidation environment and also due to possible competitive adsorption between H 2 S and CO 2 .

  6. Adsorption of sulfur dioxide on ammonia-treated activated carbon fibers

    Science.gov (United States)

    Mangun, C.L.; DeBarr, J.A.; Economy, J.

    2001-01-01

    A series of activated carbon fibers (ACFs) and ammonia-treated ACFs prepared from phenolic fiber precursors have been studied to elucidate the role of pore size, pore volume, and pore surface chemistry on adsorption of sulfur dioxide and its catalytic conversion to sulfuric acid. As expected, the incorporation of basic functional groups into the ACFs was shown as an effective method for increasing adsorption of sulfur dioxide. The adsorption capacity for dry SO2 did not follow specific trends; however the adsorption energies calculated from the DR equation were found to increase linearly with nitrogen content for each series of ACFs. Much higher adsorption capacities were achieved for SO2 in the presence of oxygen and water due to its catalytic conversion to H2SO4. The dominant factor for increasing adsorption of SO2 from simulated flue gas for each series of fibers studied was the weight percent of basic nitrogen groups present. In addition, the adsorption energies calculated for dry SO2 were shown to be linearly related to the adsorption capacity of H2SO4 from this flue gas for all fibers. It was shown that optimization of this parameter along with the pore volume results in higher adsorption capacities for removal of SO2 from flue gases. ?? 2001 Elsevier Science Ltd. All rights reserved.

  7. Adsorption of ammonia on vanadium-antimony mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, Hernan; German, Estefania [Departamento e Instituto de Fisica del Sur, Universidad Nacional del Sur-CONICET, Avda. Alem 1253, (8000) Bahia Blanca (Argentina); Juan, Alfredo, E-mail: cajuan@uns.edu.ar [Departamento e Instituto de Fisica del Sur, Universidad Nacional del Sur-CONICET, Avda. Alem 1253, (8000) Bahia Blanca (Argentina); Irigoyen, Beatriz [Departamento de Ingenieria Quimica, Facultad de Ingenieria, Universidad de Buenos Aires, Pabellon de Industrias, Ciudad Universitaria, (1428) Ciudad Autonoma de Buenos Aires (Argentina)

    2012-02-01

    We analyzed the adsorption of ammonia (NH{sub 3}) on the VSbO{sub 4}(1 1 0) catalyst surface using density functional theory (DFT) calculations. We followed the evolution of the chemical bonds between different atoms of the resulting NH{sub 3}/VSbO{sub 4} system and the changes in the electronic structure of the catalyst. NH{sub 3} preferential adsorption geometries were analyzed through the crystal orbital overlap population (COOP) concept and the density of states (DOS) curves. The VSbO{sub 4}(1 1 0) surface exhibits Lewis and Bronsted acid sites on which the ammonia molecule can interact. On the Lewis acid site, NH{sub 3} adsorption resulted in the interaction between the N and a surface V-isolated cation. On Bronsted acid site, N interacted with a surface H coming from the chemical dissociation of water. The COOP analysis indicate that NH{sub 3} interaction on the VSbO{sub 4}(1 1 0) surface is weak. In addition, the DOS curves show more developed electronic interactions for NH{sub 3} adsorption on Lewis acid site than over Bronsted acid site.

  8. Photochemical characterization of water samples from Minnesota and Vermont sites with malformed frogs: potential influence of photosensitization by singlet molecular oxygen (1O2) and free radicals on aquatic toxicity

    International Nuclear Information System (INIS)

    Bilski, P.; Burkhart, J.G.; Chignell, C.F.

    2003-01-01

    Environmental pollutants activated by UV sunlight may have contributed to the recent decline in frog populations and the concomitant increase in malformations in the USA and abroad. UV radiation is able to mutate DNA and to initiate photosensitization processes that generate mutagenic and biologically disruptive oxygen transients. We have examined water from selected sites in Minnesota and Vermont using singlet molecular oxygen ( 1 O 2 ), detected by its phosphorescence and free radicals detected by spin trapping, as markers for photosensitization. Water from a pond in Minnesota with malformed frogs, which also causes malformations in the laboratory, photosensitized more 1 O 2 , even though it absorbed less UV light compared to water from a site that did not cause malformations. This suggested that unknown natural or pollutant agents were present, and that photosensitization may be involved. Although UV irradiation of the two Minnesota water samples in the presence of the spin trap 5,5-dimethyl-1-pyrroline N-oxide (DMPO) revealed the presence of the DMPO/·OH, DMPO/·H(e aq - ) and DMPO/·C(unknown) adducts there were no qualitative or quantitative differences between them. We also examined water samples from several sites in Vermont, and compared them by measuring the quantum yield of 1 O 2 photosensitization. While all the Vermont samples produced a small amount of 1 O 2 , there was no clear correlation with the incidence of frog malformations. However, the samples differed strongly in absorption spectra and the ability to quench 1 O 2 . These factors may determine how much UV light is absorbed and converted into chemical reactions. Our results show that photochemical characterization of 1 O 2 photosensitization is possible in untreated natural water samples. Photosensitization falls into the category of global factors that may be closely associated with the effects of UV irradiation of the Earth's environments. Thus, photosensitization might be an important

  9. Photochemical characterization of water samples from Minnesota and Vermont sites with malformed frogs: potential influence of photosensitization by singlet molecular oxygen ({sup 1}O{sub 2}) and free radicals on aquatic toxicity

    Energy Technology Data Exchange (ETDEWEB)

    Bilski, P.; Burkhart, J.G.; Chignell, C.F

    2003-11-19

    Environmental pollutants activated by UV sunlight may have contributed to the recent decline in frog populations and the concomitant increase in malformations in the USA and abroad. UV radiation is able to mutate DNA and to initiate photosensitization processes that generate mutagenic and biologically disruptive oxygen transients. We have examined water from selected sites in Minnesota and Vermont using singlet molecular oxygen ({sup 1}O{sub 2}), detected by its phosphorescence and free radicals detected by spin trapping, as markers for photosensitization. Water from a pond in Minnesota with malformed frogs, which also causes malformations in the laboratory, photosensitized more {sup 1}O{sub 2}, even though it absorbed less UV light compared to water from a site that did not cause malformations. This suggested that unknown natural or pollutant agents were present, and that photosensitization may be involved. Although UV irradiation of the two Minnesota water samples in the presence of the spin trap 5,5-dimethyl-1-pyrroline N-oxide (DMPO) revealed the presence of the DMPO/{center_dot}OH, DMPO/{center_dot}H(e{sub aq}{sup -}) and DMPO/{center_dot}C(unknown) adducts there were no qualitative or quantitative differences between them. We also examined water samples from several sites in Vermont, and compared them by measuring the quantum yield of {sup 1}O{sub 2} photosensitization. While all the Vermont samples produced a small amount of {sup 1}O{sub 2}, there was no clear correlation with the incidence of frog malformations. However, the samples differed strongly in absorption spectra and the ability to quench {sup 1}O{sub 2}. These factors may determine how much UV light is absorbed and converted into chemical reactions. Our results show that photochemical characterization of {sup 1}O{sub 2} photosensitization is possible in untreated natural water samples. Photosensitization falls into the category of global factors that may be closely associated with the effects of

  10. Joint absorption of lithium and oxygen on the tungsten (100) face

    International Nuclear Information System (INIS)

    Gupalo, M.S.; Smereka, T.P.; Babkin, G.V.; Palyukh, B.M.

    1981-01-01

    The paper deals with studying the effect of oxygen on emission-adsorption properties of metal-film Li-W system. Data on work of phi yield and adsorption heat q of lithium on tungsten face (100), preliminarily coated with different quantity of oxygen, are obtained. The method of contact potential difference was used. Strong decrease of yield work with the increase of oxygen coatings, as well as essential growth of initial adsorption heat are observed. Temperature dependence of phi is not practically observed. The data obtained point out, that oxygen presence on the surface causes increase of dipole momentum of lithium adatoms, which results in bond energy growth and reduction phi minimal value of lithium in the presence of oxygen phi=2 eV, q=2.2 eV is obtained at optimal compositions of oxygen-lithium layers on W (100) [ru

  11. Characteristics of Alcian-blue Dye Adsorption of Natural Biofilm Matrix

    Science.gov (United States)

    Kurniawan, A.; Yamamoto, T.; Sukandar; Guntur

    2018-01-01

    In this study, natural biofilm matrices formed on stones have been used for the adsorption of Alcian blue dye. Alcian blue is a member of polyvalent basic dyes that largely used from laboratory until industrial dying purposes. The adsorption of the dye onto the biofilm matrix has been carried out at different experimental conditions such as adsorption isotherm and kinetic of adsorption. The electric charge properties of biofilm matrix and its changes related to the adsorption of Alcian blue have been also investigated. Moreover, the results of Alcian blue adsorption to the biofilm were compared to those onto the acidic and neutral resin. The kinetics of adsorption result showed that the adsorption of the Alcian blue dye reached to a maximum adsorption amount within 60 minutes. The adsorption amount of Alcian blue to biofilm increased monotonously, and the maximum adsorption amount was greater compared to the resins. On the contrary, Alcian blue did not attach to the neutral resin having no electric charge. It seems that Alcian blue attached to the acidic resins due to electrostatic attractive force, and the same seems to be the case for adsorption of Alcian blue to biofilm. The adsorption of Alcian blue to the biofilm and acidic resins fitted to Langmuir type indicates that the binding of Alcian blue to the biofilm and acidic resins occurred in a monolayer like form. The maximum adsorption amount of Alcian blue on the biofilm (0.24 mmol/dry-g) was greater than those of acidic resin (0.025 mmol/dry-g). This indicates that the biofilm has many more sites for Alcian blue attachment than acidic resins. According to the result of this study, the biofilm matrix can be a good adsorbent for dye such as Alcian blue or other dyes that causing hazards in nature.

  12. Influence of different carbon monolith preparation parameters on pesticide adsorption

    Directory of Open Access Journals (Sweden)

    Vukčević Marija

    2013-01-01

    Full Text Available The capacity of carbon monolith for pesticide removal from water, and the mechanism of pesticide interaction with carbon surface were examined. Different carbon monolith samples were obtained by varying the carbonization and activation parameters. In order to examine the role of surface oxygen groups in pesticide adsorption, carbon monolith surface was functionalized by chemical treatment in HNO3, H2O2 and KOH. The surface properties of the obtained samples were investigated by BET surface area, pore size distribution and temperature-programmed desorption. Adsorption of pesticides from aqueous solution onto activated carbon monolith samples was studied by using five pesticides belonging to different chemical groups (acetamiprid, dimethoate, nicosulfuron, carbofuran and atrazine. Presented results show that higher temperature of carbonization and the amount of activating agent allow obtaining microporous carbon monolith with higher amount of surface functional groups. Adsorption properties of the activated carbon monolith were more readily affected by the amount of the surface functional groups than by specific surface area. Results obtained by carbon monolith functionalisation showed that π-π interactions were the main force for adsorption of pesticides with aromatic structure, while acidic groups play an important role in adsorption of pesticides with no aromatic ring in the chemical structure.

  13. Chemical Tuning of Adsorption Properties of Titanate Nanotubes

    Directory of Open Access Journals (Sweden)

    Anastasia V. Grigorieva

    2012-01-01

    Full Text Available A conventional hydrothermal method widely used for the preparation of titania-based nanotubes still generates many unsolved questions. One of them is definitely connected with the influence of a posthydrothermal treatment of titania nanotubes on their micromorphology, structure, and adsorption characteristics. Here, it was analyzed systematically by a group of methods including nitrogen adsorption and temperature-programmed desorption of ammonia and carbon dioxide. It is proved that adsorption characteristics and the surface state of titania nanotubes correlate with a sodium content, since sodium ions act as Lewis acid sites and shield Ti4+ acid sites of the nanotubes. To obey a balance between chemical and heat treatments of the nanotubes to design their functional properties has been suggested.

  14. Nitrogen adsorption on Fe(111), (100), and (110) surfaces

    DEFF Research Database (Denmark)

    Mortensen, Jens Jørgen; Ganduglia-Pirovano, Veronica; Hansen, Lars Bruno

    1999-01-01

    Adsorption energies and structures for N atoms on three low-index surfaces of Fe have been calculated using density functional theory (DFT) and the generalized gradient approximation (GGA). At low N coverage the adsorption energy on Fe(100) is found to be similar to 0.7 eV higher than on the (111......) and (110) surfaces - particularly the c(2 x 2)-N/Fe(100) structure with the N atoms in four-fold sites is very stable. We attribute the differences in adsorption energy to the lack of four-fold sites on the (111) and (110) surfaces, We suggest that at higher N coverages, islands with a structure similar...

  15. First-principle study of Mg adsorption on Si(111) surfaces

    International Nuclear Information System (INIS)

    Min-Ju, Ying; Ping, Zhang; Xiao-Long, Du

    2009-01-01

    We have carried out first-principle calculations of Mg adsorption on Si(111) surfaces. Different adsorption sites and coverage effects have been considered. We found that the threefold hollow adsorption is energy-favoured in each coverage considered, while for the clean Si(111) surface of metallic feature, we found that 0.25 and 0.5 ML Mg adsorption leads to a semiconducting surface. The results for the electronic behaviour suggest a polarized covalent bonding between the Mg adatom and Si(111) surface. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  16. Synergetic effects in CO adsorption on Cu-Pd(111) alloys

    DEFF Research Database (Denmark)

    Lopez, Nuria; Nørskov, Jens Kehlet

    2001-01-01

    We present density functional calculations for the interaction of CO on different Cu-Pd(111) bulk and surface alloys. The modification of the adsorption properties with respect to hose of the adsorption on pure Cu(111) and Pd(111) is described in terms of changes in the adsorption sites...... and the change of the electronic structure occurring upon alloying. The presence of cooperative, synergetic. effects is found to be important specially for Cu-rich bulk alloys. In this case. a larger adsorption energy is found for the inactive component than for the pure inactive system. This activation induces...

  17. Plant residues: short term effect on sulphate, borate, zinc and copper adsorption by an acid oxisol

    Directory of Open Access Journals (Sweden)

    Dias Ana Cristi Basile

    2003-01-01

    Full Text Available Laboratory experiments were carried out to examine the effects of plant residues on Cu, Zn, B and S adsorption by an acidic oxisol. The plant residues were: black oats (Avena strigosa, oil seed radish(Raphanus sativus, velvet beans (Stizolobium cinereum, and pigeon pea (Cajanus cajan collected at flowering stage. Plant residues increased Cu and Zn adsorptions and decreased B and S adsorptions. The results indicated that for short term effect plant residues decreased the availabilities of Cu and Zn through metal organic complex reactions and increased availabilities of S and B through competition with organic anions by the adsorption sites on soil.

  18. Adsorption of gas molecules on graphene-like InN monolayer: A first-principle study

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Xiang; Yang, Qun [Faculty of Mechanical and Electrical Engineering, Guilin University of Electronic Technology, 541004 Guilin (China); Key Laboratory of Optoelectronic Technology & Systems, Education Ministry of China, Chongqing University and College of Optoelectronic Engineering, Chongqing University, 400044 Chongqing (China); Meng, Ruishen [Faculty of Mechanical and Electrical Engineering, Guilin University of Electronic Technology, 541004 Guilin (China); Tan, Chunjian [Key Laboratory of Optoelectronic Technology & Systems, Education Ministry of China, Chongqing University and College of Optoelectronic Engineering, Chongqing University, 400044 Chongqing (China); Liang, Qiuhua [Faculty of Mechanical and Electrical Engineering, Guilin University of Electronic Technology, 541004 Guilin (China); Jiang, Junke [Faculty of Mechanical and Electrical Engineering, Guilin University of Electronic Technology, 541004 Guilin (China); Key Laboratory of Optoelectronic Technology & Systems, Education Ministry of China, Chongqing University and College of Optoelectronic Engineering, Chongqing University, 400044 Chongqing (China); Ye, Huaiyu [Key Laboratory of Optoelectronic Technology & Systems, Education Ministry of China, Chongqing University and College of Optoelectronic Engineering, Chongqing University, 400044 Chongqing (China); Chen, Xianping, E-mail: xianpingchen@cqu.edu.cn [Faculty of Mechanical and Electrical Engineering, Guilin University of Electronic Technology, 541004 Guilin (China); Key Laboratory of Optoelectronic Technology & Systems, Education Ministry of China, Chongqing University and College of Optoelectronic Engineering, Chongqing University, 400044 Chongqing (China)

    2017-05-15

    Highlights: • A comprehensive adsorption mechanism of InN monolayer is theoretical studied to distinguish the physic/chemi-sorption. • Different adsorption sites for different gases are systematically discussed. • The influence (enhanced or weakened) of external electric field to InN-gas system is well investigated. • The influences of gas adsorption to the optical properties (work function and light adsorption ability) of InN monolayer are also researched. - Abstract: Using first-principles calculation within density functional theory (DFT), we study the gas (CO, NH{sub 3}, H{sub 2}S, NO{sub 2}, NO, SO{sub 2}) adsorption properties on the surface of single-layer indium nitride (InN). Four different adsorption sites (Bridge, In, N, Hollow) are chosen to explore the most sensitive adsorption site. On the basis of the adsorption energy, band gap and charge transfer, we find that the most energetic favourable site is changeable between In site and N site for different gases. Moreover, our results reveal that InN is sensitive to NH{sub 3}, SO{sub 2}, H{sub 2}S and NO{sub 2}, by a physisorption or a chemisorption nature. We also perform a perpendicular electric field to the system and find that the applied electric field has a significant effect for the adsorption process. Besides, we also observed the desorption effects on NH{sub 3} adsorbed at the hollow site of InN when the electric field applied. In addition, the optical properties of InN monolayer affected by different gases are also discussed. Most of the gas adsorptions will cause the inhibition of light adsorption while the others can reduce the work function or enhance the adsorption ability in visible region. Our theoretical results indicate that monolayer InN is a promising candidate for gas sensing applications.

  19. The investigation of adsorption and dissociation of H{sub 2}O on Li{sub 2}O (111) by ab initio theory

    Energy Technology Data Exchange (ETDEWEB)

    Kong, Xianggang [Institute of Atom and Molecular physics, Sichuan University, Chengdu, 610065 (China); Yu, You [College of Optoelectronic Technology, Chengdu University of Information Technology, Chengdu, 610225 (China); Ma, Shenggui [Institute of Atom and Molecular physics, Sichuan University, Chengdu, 610065 (China); Gao, Tao, E-mail: gaotao@scu.edu.cn [Institute of Atom and Molecular physics, Sichuan University, Chengdu, 610065 (China); Lu, Tiecheng [Department of Physics and Key Laboratory for Radiation Physics & Technology of Ministry of Education, Sichuan University, Chengdu, 610065 (China); Xiao, Chengjian; Chen, Xiaojun [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, 621900 (China); Zhang, Chuanyu [College of Geophysics, Chengdu University of Technology, Chengdu, 610059 (China)

    2017-06-15

    Highlights: • The adsorption structures of H{sub 2}O on Li{sub 2}O (111) are obtained by calculations. • By Bader charge analysis, the charge translation from slab to adsorbate is found. • The vibrational frequencies of adsorbate are in line with the experimental values. - Abstract: The adsorption and dissociation mechanism of H{sub 2}O molecule on the Li{sub 2}O (111) surface have been systematically studied by using the density functional theory calculations. The parallel and vertical configurations of H{sub 2}O at six different symmetry adsorption sites on the Li{sub 2}O (111) surface are considered. In our calculations, it is suggested that H{sub 2}O can dissociate on the perfect Li{sub 2}O surface, of which the corresponding adsorption energy is 1.118 eV. And the adsorption energy decrease to be 0.241 eV when oxygen atom of H{sub 2}O bonds to lithium atom of the slab. The final configurations are sensitive to the initial molecular orientation. By Bader charge analysis, the charge transfer from slab to adsorbed H{sub 2}O/OH can be found due to the downward shift of lowest-unoccupied molecular orbital. We also analyze the vibrational frequencies at the Brillouin Zone centre for H{sub 2}O molecule adsorbed on the stoichiometric surface. Due to the slightly different structure parameters, the calculated values of the vibrational frequencies of hydroxyl group range from 3824 to 3767 cm{sup −1}. Our results agree well with experimental results performed in FT-IR spectrum, which showed that an absorption peak of OH group appeared at 3677 cm{sup −1} at room temperature.

  20. Adsorption mechanism and kinetics of azo dye chemicals on oxide nanotubes: a case study using porous CeO{sub 2} nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Junshu; Wang, Jinshu, E-mail: wangjsh@bjut.edu.cn; Du, Yucheng; Li, Hongyi; Jia, Xinjian [Beijing University of Technology, School of Materials Science and Engineering (China)

    2016-07-15

    Metal oxide nanotubes are believed to be promising materials with adsorption functionality for water purification due to their synergistic effect of the overall microscale morphology for easy separation and nanoscale surface characters providing enough surface active absorption sites. This work shows the synthesis of uniform hierarchical porous CeO{sub 2} nanotubes via nanowire-directed templating method and describes the adsorption behavior of CeO{sub 2} nanotubes for a typical azo dye Congo red which has resistance to oxidation and decoloration in natural conditions. Fourier transform infrared spectroscopy spectra provided the evidence that Congo red was successfully coated on the surface of CeO{sub 2} nanotubes by both bidentate-type bridge link of Ce{sup 4+} cations from sulfonate SO{sub 3}{sup −} groups and the electrostatic attraction between the protonated surface generated by oxygen vacancies and dissociated sulfonate groups. The adsorption kinetic data fitted well to the pseudo-second-order kinetic equation, whereas the Langmuir isotherm equation exhibited better correlation with the experimental data. The calculated maximum adsorption capacity from the isothermal model was 362.32 mg/g. In addition, the prepared CeO{sub 2} nanotubes exhibited good recyclability and reusability as highly efficient adsorbents for Congo red removal after regeneration. These favorable performances enable the obtained CeO{sub 2} nanotubes to be promising materials for dye removal from aqueous solution.Graphical AbstractCeO{sub 2} nanotubes composed of crystallized nanoparticles exhibit well adsorption ability for a typical azo dye Congo red.

  1. In situ DRIFTS study of O{sub 3} adsorption on CaO, γ-Al{sub 2}O{sub 3}, CuO, α-Fe{sub 2}O{sub 3} and ZnO at room temperature for the catalytic ozonation of cinnamaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Jianfeng; Su, Tongming; Jiang, Yuexiu; Xie, Xinling [School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Qin, Zuzeng, E-mail: qinzuzeng@gmail.com [School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Ji, Hongbing, E-mail: jihb@mail.sysu.edu.cn [School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); School of Chemistry, Sun Yat-sen University, Guangzhou 510275 (China)

    2017-08-01

    Highlights: • In situ DRIFTS study of O{sub 3} adsorption on metal oxides at room temperature. • Using acidic probe molecules (DRIFTS) characterization of surface basicity. • Correlation between basic strength of metal oxides and O{sub 3} adsorption. • Study on the competitive adsorption of O{sub 3} and CO{sub 2}. • DRIFTS study of cinnamaldehyde ozonation and benzaldehyde excessive oxidation. - Abstract: In situ DRIFTS were conducted to identify adsorbed ozone and/or adsorbed oxygen species on CaO, ZnO, γ-Al{sub 2}O{sub 3}, CuO and α-Fe{sub 2}O{sub 3} surfaces at room temperature. Samples were characterized by means of TG, XRD, N{sub 2} adsorption–desorption, pyridine-IR, nitrobenzene-IR, chloroform-IR, and CO{sub 2}-TPD. Pyridine-DRIFTS measurements evidence two kinds of acid sites in all the samples. Nitrobenzene, chloroform-DRIFTS, and CO{sub 2}-TPD reveal that there are large amounts of medium-strength base sites on all the metal oxides, and only CaO, ZnO, and γ-Al{sub 2}O{sub 3} have strong base sites. And the benzaldehyde selectivity was increased in the same order of the alkalinity of the metal oxides. With weaker sites, ozone molecules form coordinative complexes bound via the terminal oxygen atom, observed by vibrational frequencies at 2095–2122 and 1026–1054 cm{sup −1}. The formation of ozonide O{sub 3}{sup −} at 790 cm{sup −1}, atomic oxygen at 1317 cm{sup −1}, and superoxide O{sub 2}{sup −} at 1124 cm{sup −1} was detected; these species are believed to be intermediates of O{sub 3} decomposition on strong acid/base sites. The adsorption of ozone on metal oxides is a weak adsorption, and other gases, such as CO{sub 2}, will compete with O{sub 3} adsorption. The mechanism of cinnamaldehyde ozonation at room temperature over CaO shows that cinnamaldehyde can not only be oxidized into cinnamic acid, but also be further oxidized into benzaldehyde, benzoic acid, maleic anhydride, and ultimately mineralized to CO{sub 2} in the

  2. Adsorption behavior of NH3 and NO2 molecules on stanene and stanane nanosheets - A density functional theory study

    Science.gov (United States)

    Nagarajan, V.; Chandiramouli, R.

    2018-03-01

    Using density functional theory method, we investigate the adsorption properties of NH3 and NO2 molecules on stanene and stanane nanosheets. The adsorption of molecules is explored based on the charge transfer, energetics, energy band gap and average energy gap variation. Moreover, the optimal adsorption sites of NH3 and NO2 molecules are identified on stanene and stanane nanosheets. Besides, the state-of-the-art provides the key features for the development of chemi-resistive nanosensor based on stanene and stanane nanosheets upon adsorption of NH3 and NO2 molecules. Furthermore, the study shows that adsorption of NO2 molecules is more prominent rather than NH3 molecules.

  3. Effective adsorption and collection of cesium from aqueous solution using graphene oxide grown on porous alumina

    Science.gov (United States)

    Entani, Shiro; Honda, Mitsunori; Shimoyama, Iwao; Li, Songtian; Naramoto, Hiroshi; Yaita, Tsuyoshi; Sakai, Seiji

    2018-04-01

    Graphene oxide (GO) with a large surface area was synthesized by the direct growth of GO on porous alumina using chemical vapor deposition to study the Cs adsorption mechanism in aqueous solutions. Electronic structure analysis employing in situ near-edge X-ray absorption fine structure spectroscopy and X-ray photoelectron spectroscopy measurements clarifies the Cs atoms bond via oxygen functional groups on GO in the aqueous solution. The Cs adsorption capacity was found to be as high as 650-850 mg g-1, which indicates that the GO/porous alumina acts as an effective adsorbent with high adsorption efficiency for radioactive nuclides in aqueous solutions.

  4. Oxygen influence on ceramics wettability by liquid metals: Ag/{alpha}-Al{sub 2}O{sub 3}-Experiments and modelling

    Energy Technology Data Exchange (ETDEWEB)

    Muolo, M.L.; Valenza, F. [Institute for Energetics and Interphases - IENI CNR, via de Marini 6, 16149 Genova (Italy); Passerone, A. [Institute for Energetics and Interphases - IENI CNR, via de Marini 6, 16149 Genova (Italy)], E-mail: a.passerone@ge.ieni.cnr.it; Passerone, D. [Swiss Federal Lab. for Mater. Testing and Res. (EMPA) - Uberlandstrasse 129, 8600 Duebendorf (Switzerland)

    2008-11-15

    A renewed interest in the effects of oxygen on the wetting of solid oxides has recently risen in connection to the development of the technique of 'air brazing' which makes use of the strong effect of oxygen to increase the wettability of oxides by means of processes running in air or in atmospheres with high oxygen content. Adsorption of oxygen not only at the liquid-vapour surface but also at the solid-liquid interface has been postulated by many previous researches, mainly on the basis of thermodynamic considerations. Along the same line, new results of the wetting behaviour in the system Ag/{alpha}-Al{sub 2}O{sub 3} as a function of oxygen partial pressure are presented, with the simultaneous measurement of the liquid surface tension. These results are compared with the existing ones, and discussed on the basis of thermodynamic principles. The resulting work of adhesion is compared with the 'work of separation' computed by the density functional theory (DFT) approach. DFT calculations are also employed, at variance with previous models, to investigate the structures that are formed at the interface upon addition of oxygen in different sites energetics, atomic and electronic properties of this oxygen-rich interface are discussed together with the connection with experiments.

  5. Synergistically enhanced activity of nitrogen-doped carbon dots/graphene composites for oxygen reduction reaction

    Science.gov (United States)

    Liu, Hui; Zhao, Qingshan; Liu, Jingyan; Ma, Xiao; Rao, Yuan; Shao, Xiaodong; Li, Zhongtao; Wu, Wenting; Ning, Hui; Wu, Mingbo

    2017-11-01

    With rapid dissociative adsorption of oxygen, nitrogen-doped carbon nanomaterials have been demonstrated to be efficient alternative catalysts for oxygen reduction reaction (ORR) in fuel cells. Herein, we developed a mild hydrothermal strategy to construct nitrogen-doped carbon dots/graphene (NCDs-NG) composites towards ORR. Carbon dots (CDs) were derived from petroleum coke via acid oxidation while graphene oxide (GO) was obtained from graphite by modified Hummer's method. Graphene was employed as a conductive substrate to disperse CDs during hydrothermal reducing reaction while ammonia was utilized as N source to dope both graphene and CDs. The synergistic effects, i.e. CDs as pillars for graphene and catalytic sites for ORR, the high conductivity of graphene, the quick O2 adsorption on doped pyridinic nitrogen endow the NCDs-NG composites with enhanced ORR catalytic performance in alkaline electrolyte. The onset potential of -95 mV and kinetic current density of 12.7 mA cm-2 at -0.7 V (vs. Ag/AgCl) can be compared to those of the commercial 20 wt% Pt/C catalyst. The electron transfer number is about 3.9, revealing a four-electron pathway for ORR. The optimal NCDs-NG catalyst shows superior durability and methanol tolerance than 20 wt% Pt/C. This work demonstrates a feasible and effective strategy to prepare metal-free efficient ORR electrocatalysts for fuel cell applications.

  6. Influences of salt concentration, loading and pH on strontium adsorption

    International Nuclear Information System (INIS)

    Atun, G.; Kaplan, Z.

    1996-01-01

    The adsorption of Sr on clay with contains zeolites and montmorillonite mixtures was investigated in solutions of NaCl by means of a batch technique. Sr retention was reduced with increasing NaCl concentration from 5*10 -4 to 5*10 -1 M. Distribution coefficients (K d ) linearly increased with pH in the acidic region but they were almost independent of pH in neutral and alkaline solutions. By fitting the data of the Dubinin-Radushkevich (D-R) isotherm, the mean energies of adsorption and adsorption capacities of Sr at different pH values were calculated. The results showed that the mode of adsorption below pH 4.5 is ion exchange, while above that value a multilayer adsorption occurs. Adsorption data were fitted to the Freundlich isotherm and from empirical Freundlich parameters a site distribution function was calculated. (author)

  7. Effects of humic acid on adsorption of actinide elements on rocks and others

    Energy Technology Data Exchange (ETDEWEB)

    Ohashi, Masakazu; Sato, Seichi; Ohashi, Hiroshi [Hokkaido Univ., Sapporo (Japan). Faculty of Engineering; Sakamoto, Yoshiaki; Nagao, Seiya; Onuki, Toshihiko; Senoo, Muneaki

    1996-01-01

    Since the transfer rates of radionuclides are reduced by their adsorption to rocks and soils, it is essential to elucidate the adsorption process for safety assessment of their geological disposal. In this study, adsorption of Np(V) to goethite, one of the widely distributed minerals was investigated as functions of pH and humic acid concentration. The surface charge density of goethite was determined and the zero charge point was 6.2 for synthesized and 6.4 for natural goethite. Since the point for humic acid was 4.5, adsorption sites for humic acid were reduced as the increase of negative charge density above pH6, resulting in a decrease in its adsorption rate. Np(V) adsorption to goethite was raised by the presence of humic acid in the range of 0-10ppm because the surface charge on the rock was shifted to negative by the adsorption of humic acid, resulting in easy adsorption of NpO{sub 2}{sup +}, which is stable in the condition below pH 9.5. On the other hand, humic acid adsorption was saturated at a concentration higher than 50 ppm, but its content in the solution would increase. Thus, it was thought that Np(V)-humic acid complex becomes more stable, resulting in the decrease in Np(V) adsorption rate. (M.N.)

  8. On the Adsorption of DNA Origami Nanostructures in Nanohole Arrays.

    Science.gov (United States)

    Brassat, Katharina; Ramakrishnan, Saminathan; Bürger, Julius; Hanke, Marcel; Doostdar, Mahnaz; Lindner, Jörg K N; Grundmeier, Guido; Keller, Adrian

    2018-05-22

    DNA origami nanostructures are versatile substrates for the controlled arrangement of molecular capture sites with nanometer precision and thus have many promising applications in single-molecule bioanalysis. Here, we investigate the adsorption of DNA origami nanostructures in nanohole arrays which represent an important class of biosensors and may benefit from the incorporation of DNA origami-based molecular probes. Nanoholes with well-defined diameter that enable the adsorption of single DNA origami triangles are fabricated in Au films on Si wafers by nanosphere lithography. The efficiency of directed DNA origami adsorption on the exposed SiO 2 areas at the bottoms of the nanoholes is evaluated in dependence of various parameters, i.e., Mg 2+ and DNA origami concentrations, buffer strength, adsorption time, and nanohole diameter. We observe that the buffer strength has a surprisingly strong effect on DNA origami adsorption in the nanoholes and that multiple DNA origami triangles with 120 nm edge length can adsorb in nanoholes as small as 120 nm in diameter. We attribute the latter observation to the low lateral mobility of once adsorbed DNA origami on the SiO 2 surface, in combination with parasitic adsorption to the Au film. Although parasitic adsorption can be suppressed by modifying the Au film with a hydrophobic self-assembled monolayer, the limited surface mobility of the adsorbed DNA origami still leads to poor localization accuracy in the nanoholes and results in many DNA origami crossing the boundary to the Au film even under optimized conditions. We discuss possible ways to minimize this effect by varying the composition of the adsorption buffer, employing different fabrication conditions, or using other substrate materials for nanohole array fabrication.

  9. Adsorption of heavy metal from landfill leachate by wasted biosolids ...

    African Journals Online (AJOL)

    However, the concentration of Cd, Cu and Zn was not detected in the leachate but Fe was found to be in high concentration (184 mg/L) in raw leachate collected from a municipal landfill site. Therefore, the effects of biomass dosage, contact time, pH and agitation speed were observed for optimal adsorption of iron from ...

  10. Rare gases adsorption and separation on silver doped adsorbent

    International Nuclear Information System (INIS)

    Deliere, Ludovic

    2015-01-01

    The Comprehensive Nuclear-Test-Ban Treaty (CTBT) implements means for detecting nuclear tests in an International Monitoring System (IMS). The Commissariat a l'Energie Atomique et aux Energies Alternatives (CEA) has developed in the mid-90's, the SPALAX system (Systeme de Prelevement d'Air en Ligne avec l'Analyse des radioXenons). Xenon analysis, including radioactive isotopes from the fission reaction during the explosion, requires the development of highly efficient process for xenon concentration. In this work, the adsorption and diffusion phenomena of noble gases are studied in silver exchanged ZSM-5 zeolite. The 'experience/Monte Carlo simulation' coupling is used to determine the essential thermodynamic data on the adsorption of noble gases and to characterize the adsorption sites. The presence of a strong adsorption site, identified as silver nanoparticles and intervening at low concentration of noble gases (including xenon and radon) in some silver exchanged zeolites, achieves adsorption and selectivity performance to date unrivaled. These results allow considering their use in many critical applications in the field of capture and separation of rare gases: rare gas industrial production, reprocessing of spent fuel from gas, radon in air pollution control. (author) [fr

  11. The indium-oxygen system, ch. 5

    International Nuclear Information System (INIS)

    Dillen, A.J. van

    1977-01-01

    This chapter is divided into three sections: 1) a survey of the literature concerning the indiumoxygen system, 2) the adsorption of oxygen at pure and partially oxidized indium surfaces in the temperature range 20-180degC, and 3) the oxidation of indium at temperatures above 180degC. The oxygen uptake is determined volumetrically and gravimetrically. The influence of the melting point is considered and the results are compared with data from the literature. The oxide layer is amorphous at lower temperatures but above 350degC, crystallisation of In 2 O 3 takes place

  12. Preparation and evaluation of molecularly imprinted polymer for selective recognition and adsorption of gossypol.

    Science.gov (United States)

    Zhi, Keke; Wang, Lulu; Zhang, Yagang; Zhang, Xuemin; Zhang, Letao; Liu, Li; Yao, Jun; Xiang, Wei

    2018-03-01

    Molecularly imprinted polymers (MIPs) were designed and prepared via bulk thermal polymerization with gossypol as the template molecule and dimethylaminoethyl methacrylate as the functional monomer. The morphology and microstructures of MIPs were characterized by scanning electron microscope and Brunauer-Emmett-Teller surface areas. Static adsorption tests were performed to evaluate adsorption behavior of gossypol by the MIPs. It was found that adsorption kinetics and adsorption isotherms data of MIPs for gossypol were fit well with the pseudo-second-order model and Freundlich model, respectively. Scatchard analysis showed that heterogeneous binding sites were formed in the MIPs, including lower-affinity binding sites with the maximum adsorption of 252 mg/g and higher-affinity binding sites with the maximum adsorption of 632 mg/g. Binding studies also revealed that MIPs had favorable selectivity towards gossypol compared with non-imprinted polymers. Furthermore, adsorption capacity of MIPs maintained above 90% after 5 regeneration cycles, indicating MIPs were recyclable and could be used multiple times. These results demonstrated that prepared MIPs could be a promising functional material for selective adsorption of gossypol. Copyright © 2017 John Wiley & Sons, Ltd.

  13. Adsorption Desalination: A Novel Method

    KAUST Repository

    Ng, Kim Choon

    2010-11-15

    The search for potable water for quenching global thirst remains a pressing concern throughout many regions of the world. The demand for new and sustainable sources and the associated technologies for producing fresh water are intrinsically linked to the solving of potable water availability and hitherto, innovative and energy efficient desalination methods seems to be the practical solutions. Quenching global thirst by adsorption desalination is a practical and inexpensive method of desalinating the saline and brackish water to produce fresh water for agriculture irrigation, industrial, and building applications. This chapter provides a general overview of the adsorption fundamentals in terms of adsorption isotherms, kinetics, and heat of adsorption. It is then being more focused on the principles of thermally driven adsorption desalination methods. The recent developments of adsorption desalination plants and the effect of operating conditions on the system performance in terms of specific daily water production and performance ratio are presented. Design of a large commercial adsorption desalination plant is also discussed herein.

  14. Ti atoms in Ru0.3Ti0.7O2 mixed oxides form active and selective sites for electrochemical chlorine evolution

    DEFF Research Database (Denmark)

    Karlsson, Rasmus K. B.; Hansen, Heine Anton; Bligaard, Thomas

    2014-01-01

    affected by the presence of small amounts of Ru dopant, whereas oxygen adsorption is relatively unaffected by Ti dopants in RuO2. The calculations also indicate that coordinatively unsaturated Ti sites on Ru-doped TiO2 and on Ru0.3Ti0.7O2 could form active and selective sites for Cl2 evolution....... These results suggest a reason for why DSA shows a higher chlorine selectivity than RuO2 and propose an experimental test of the hypothesis....

  15. Methyl Butanoate Adsorption on MoS2 Surface: A Density Functional Theory Investigation

    Directory of Open Access Journals (Sweden)

    Prabowo Wahyu Aji Eko

    2018-01-01

    Full Text Available Methyl butanoate is one of the compound which is obtained from triglyceride molecule. It has hydrocarbon components and hence may produce hydrocarbon through hydrodeoxygenation (HDO or decarbonylation (DCO processes. The first step to uncover the underlying mechanism of HDO or DCO is to find the active site of methyl butanoate adsorption over the catalyst. This study attempts to investigate the active site of methyl butanoate adsorption on MoS2 surface. Stable bonding configuration for methyl butanoate adsorption on MoS2 is investigated by using density functional theory (DFT. This investigation consists of geometry optimisation and adsorption energy calculations. The stable configuration of methyl butanoate adsorption on MoS2 surface is found to be on top of Mo atom in Mo-edge surface.

  16. First principles study of the adsorption of a NO molecule on N-doped anatase nanoparticles

    International Nuclear Information System (INIS)

    Liu Juan; Liu Qin; Fang Pengfei; Pan Chunxu; Xiao Wei

    2012-01-01

    The adsorption of a NO molecule on 72 atom N-doped TiO 2 nanoparticles has been studied by first principles calculations. Two types of adsorption are considered in the calculations. In one type of the adsorption, the NO molecule forms one bond with the particle, while in the other type of adsorption, the NO molecule forms two bonds with the particle. The second type of adsorption is more energetic favorable. The adsorption energies, bond lengths, density of the states (DOSs), and the difference of the charge density are calculated to investigate the adsorption. In the adsorption process, the unpaired electron of the NO molecule transfers to the empty state of the particle, making the Fermi levels lower. As a result, the electrons of the N-doped system occupy lower energy states, making the system energy lower than that of the undoped particle. Since the adsorption of a NO molecule on N-doped nanoparticles is stronger than that on undoped particles, N-doped particles can adsorb more NO molecules on their surfaces than the undoped particles do. Meanwhile, there are more adsorption sites on the N-doped particles, on which the adsorption energies are much higher than that of the undoped particle, some of them are even higher than the highest adsorption energy of the undoped particle. It suggests that N-doped particles are more active and they can adsorb more small toxic gas molecules in the air. So, the doping method can be used to remove NO molecules for the air pollution control through the surface adsorption strategy.

  17. Heavy metal ion adsorption behavior in nitrogen-doped magnetic carbon nanoparticles: Isotherms and kinetic study

    International Nuclear Information System (INIS)

    Shin, Keun-Young; Hong, Jin-Yong; Jang, Jyongsik

    2011-01-01

    Graphical abstract: Display Omitted Research highlights: → The monodisperse and multigram-scale N-MCNPs are fabricated by carbonization of polypyrrole as a carbon precursor. → The synthesized N-MCNPs provide an enhanced adsorption uptake for various heavy metal ions. → The N-MCNPs can be applied to the Langmuir model and pseudo-second-order kinetics. → The iron-impregnated N-MCNPs are reused up to 5 times with no loss of removal efficiency. - Abstract: To clarify the heavy metal adsorption mechanism of nitrogen-doped magnetic carbon nanoparticles (N-MCNPs), adsorption capacity was investigated from the adsorption isotherms, kinetics and thermodynamics points of view. The obtained results showed that the equilibrium adsorption behavior of Cr 3+ ion onto the N-MCNPs can be applied to the Langmuir model and pseudo-second-order kinetics. It indicated that the fabricated N-MCNPs had the homogenous surface for adsorption and all adsorption sites had equal adsorption energies. Furthermore, the adsorption onto N-MCNPs taken place through a chemical process involving the valence forces. According to the thermodynamics, the adsorption process is spontaneous and endothermic in nature which means that the adsorption capacity increases with increasing temperature due to the enhanced mobility of adsorbate molecules. The effects of the solution pH and the species of heavy metal ion on the adsorption uptake were also studied. The synthesized N-MCNPs exhibited an enhanced adsorption capacity for the heavy metal ions due to the high surface area and large amount of nitrogen contents.

  18. Adsorption of benzene and toluene from aqueous solutions onto activated carbon and its acid and heat treated forms: influence of surface chemistry on adsorption.

    Science.gov (United States)

    Wibowo, N; Setyadhi, L; Wibowo, D; Setiawan, J; Ismadji, S

    2007-07-19

    The influence of surface chemistry and solution pH on the adsorption of benzene and toluene on activated carbon and its acid and heat treated forms were studied. A commercial coal-based activated carbon F-400 was chosen as carbon parent. The carbon samples were obtained by modification of F-400 by means of chemical treatment with HNO3 and thermal treatment under nitrogen flow. The treatment with nitric acid caused the introduction of a significant number of oxygenated acidic surface groups onto the carbon surface, while the heat treatment increases the basicity of carbon. The pore characteristics were not significantly changed after these modifications. The dispersive interactions are the most important factor in this adsorption process. Activated carbon with low oxygenated acidic surface groups (F-400Tox) has the best adsorption capacity.

  19. Surface and adsorptive properties of Moringa oleifera bark for removal of V(V) from aqueous solutions.

    Science.gov (United States)

    Mnisi, Robert Londi; Ndibewu, Peter Papoh

    2017-11-04

    The bark of Moringa oleifera, a cheap and readily available natural biopolymeric resource material, found to significantly reduce coliform load and turbidity in contaminated water is investigated in this paper. Its surface and adsorptive properties are investigated to explore its adsorptive potential in removing V(V) from aqueous solutions. Surface properties were investigated using FTIR, HRSEM/EDS, IC, and BET-N 2 adsorption techniques. Adsorptive properties were investigated by optimizing adsorption parameters such as pH, temperature, initial metal concentration, and adsorbent dosage, using V(V) as an adsorbate. The adsorption-desorption isotherms are typical of type II with a H3 hysteresis loop and is characteristic of a largely macroporous material. Bottle ink pores are observed, which can provide good accessibility of the active sites, even though the internal BET surface area is typically low (1.79 g/m 2 ). Solution pH significantly influences the adsorptive potential of the material. The low surface area negatively impacts on the adsorption capacity, but is compensated for by the exchangeable anions (Cl - , F - , PO 4 3- , NO 3 - , and SO 4 2- ) and cations (Ca 2+ , K + , Mg 2+ , and Al 3+ ) at the surface and the accessibility of the active sites. Adsorption isotherm modeling show that the surface is largely heterogeneous with complex multiple sites and adsorption is not limited to monolayer.

  20. Processes of H{sub 2} adsorption on Fe(1 1 0) surface: A density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Weiwei; Peng, Liang; Peng, Daoling [Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Gu, Feng Long, E-mail: gu@scnu.edu.cn [Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Liu, Jun [Material Design and Simulation Technology Co. Ltd., Room 1716, V-Faction, 10 Vanke, 2 Ring Road of North Section, Chengdu (China)

    2014-03-01

    Highlights: • The hydrogen coverages for H{sub 2} adsorption on Fe(1 1 0) surface ranging from 0.125 to 1.000 are prepared by using different surface supercells. • With the reduction of coverage, the average iron atomic energy is increased and the adsorption energy is decreased, leading to the system more stable; while coverage has little effect on the Fe(1 1 0) surface structure and the hydrogen adsorption process. • The most stable absorption site is found to be the on-top site. • DFT calculations show that it is a weak adsorption and the adsorption energy barriers under 4.4 kcal/mol. • The final state is H{sub 2} molecule dissociated into two hydrogen atoms interacting with surface iron atoms to form stable Fe-H bonds. - Abstract: Processes of H{sub 2} adsorption on Fe(1 1 0) surface have been studied by the density functional theory, properties such as surface structure, adsorption position, and adsorption energies are discussed as well. To investigate the atomic geometries and stability under different hydrogen coverages for this adsorption, the hydrogen coverages ranging from 0.125 to 1.000 are prepared by using different surface supercells. It is found that with the reduction of coverage, the average iron atomic energy and the adsorption energy are increased, leading to the system more stable; while coverage has little effect on the Fe(1 1 0) surface structure and the hydrogen adsorption process. The most stable absorption site is found to be the on-top site. Our calculations show that it is a weak adsorption and the adsorption energy barriers under 4.4 kcal/mol. The final state is H{sub 2} molecule dissociated into two hydrogen atoms and interacting with surface iron atoms to form stable Fe-H bonds.

  1. Adsorption facility and adsorption vessel for radioactive carbon dioxide

    International Nuclear Information System (INIS)

    Harashina, Heihachi; Miwa, Keiichi; Kobayashi, Takeo.

    1992-01-01

    If 14 CO 2 gas-containing gases to be adsorbed are pressurized and sent to a packaging adsorption means, CO 2 ingredient in the gases to be adsorbed is adsorbed or absorbed, and remaining gases are passed through and sent out to downstream. CO 2 adsorption or absorption of the packaging adsorption means is judged by monitoring the state of the remaining gases, and if it is normal, remaining gases are sent further to downstream and processed. If abnormality is found, a gas feedback system is operated, and CO 2 removing gas is sent again to the packaging adsorption means, in which CO 2 gases are adsorbed or absorbed again repeatingly. With such procedures, in a case where C 14 nuclides having a long half decay time are supplied in the form of 14 CO 2 gas, they are efficiently adsorbed or absorbed in the packaging system to improve removing and storing property of 14 C nuclides. (T.M.)

  2. Carbon nanomaterials for gas adsorption

    CERN Document Server

    Terranova, Maria Letizia

    2012-01-01

    Research in adsorption of gases by carbon nanomaterials has experienced considerable growth in recent years, with increasing interest for practical applications. Many research groups are now producing or using such materials for gas adsorption, storage, purification, and sensing. This book provides a selected overview of some of the most interesting scientific results regarding the outstanding properties of carbon nanomaterials for gas adsorption and of interest both for basic research and technological applications. Topics receiving special attention in this book include storage of H, purific

  3. Hydrogen purification by periodic adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Barg, Christian; Secchi, Argimiro R.; Trierweiler, Jorge O. [Rio Grande do Sul Univ., Porto Alegre, RS (Brazil). Dept. de Engenharia Quimica]. E-mail: cbarg@enq.ufrgs.br; arge@enq.ufrgs.br; jorge@enq.ufrgs.br

    2000-07-01

    The periodic adsorption processes have been widely used for industrial applications, mainly because it spends less energy than the usual gas separation processes, like the cryogenic distillation. The largest commercial application of periodic adsorption processes is the pressure swing adsorption (PSA) applied to hydrogen purification. Although its wide use in the chemical and petrochemical industry, there are no reports in the open literature about complete modeling studies of a complex commercial unit, with multiple adsorbents and multiple beds and several feed components. This study has as objective the modeling, optimization and dynamical analysis of an industrial PSA unit for hydrogen purification. (author)

  4. Protein Adsorption in Three Dimensions

    Science.gov (United States)

    Vogler, Erwin A.

    2011-01-01

    Recent experimental and theoretical work clarifying the physical chemistry of blood-protein adsorption from aqueous-buffer solution to various kinds of surfaces is reviewed and interpreted within the context of biomaterial applications, especially toward development of cardiovascular biomaterials. The importance of this subject in biomaterials surface science is emphasized by reducing the “protein-adsorption problem” to three core questions that require quantitative answer. An overview of the protein-adsorption literature identifies some of the sources of inconsistency among many investigators participating in more than five decades of focused research. A tutorial on the fundamental biophysical chemistry of protein adsorption sets the stage for a detailed discussion of the kinetics and thermodynamics of protein adsorption, including adsorption competition between two proteins for the same adsorbent immersed in a binary-protein mixture. Both kinetics and steady-state adsorption can be rationalized using a single interpretive paradigm asserting that protein molecules partition from solution into a three-dimensional (3D) interphase separating bulk solution from the physical-adsorbent surface. Adsorbed protein collects in one-or-more adsorbed layers, depending on protein size, solution concentration, and adsorbent surface energy (water wettability). The adsorption process begins with the hydration of an adsorbent surface brought into contact with an aqueous-protein solution. Surface hydration reactions instantaneously form a thin, pseudo-2D interface between the adsorbent and protein solution. Protein molecules rapidly diffuse into this newly-formed interface, creating a truly 3D interphase that inflates with arriving proteins and fills to capacity within milliseconds at mg/mL bulk-solution concentrations CB. This inflated interphase subsequently undergoes time-dependent (minutes-to-hours) decrease in volume VI by expulsion of either-or-both interphase water and

  5. Hydrogen adsorption in doped porous carbons

    International Nuclear Information System (INIS)

    L Balan; L Duclaux; S Los

    2005-01-01

    properties of doped microporous carbons (SWNTs and activated carbons). The raw nano-structured carbon materials are microporous activated carbons (BET specific surface area: 1600 m 2 /g), electric-arc closed-end single-walled carbon nano-tubes (SWNTs), and HiPCO SWNTs. They have been doped in the vapour phase by K, and Li (in order to obtain KC 7 , KC 10 , LiC 18 SWNTs and LiC 6 , LiC 18 , KC 24 activated carbons). The hydrogen adsorption-desorption isotherms of the doped activated carbons were obtained at room temperature and at 77 K, up to 3 MPa, by a volumetric method. The adsorption of D 2 was studied in situ on doped nano-tubes and nano-filaments by neutron diffraction on D1B experiment (ILL), at λ=2.52 Angstroms, as a function of temperature [300 - 20 K] and pressure. Simultaneously the adsorption isotherms were recorded in the range 0 - 0.1 MPa [13]. Doping of microporous carbon by Li or K leads to an increase in the energy of adsorption of H 2 or D 2 Molecules. Thus, the room temperature sorption capacities (al P≤3 MPa) can be higher than that of the raw materials after slight doping. However, the maximum H 2 (or D 2 ) storage measured at T ≤ 77 K is lower than the one of pristine Materials as the sites of adsorption are occupied by alkali ions inserted in the micropores [14]. The microporous adsorption sites of doped single-walled carbon nano-tubes, identified by neutron diffraction, are both the interstitial voids (in electric-arc or HiPCO tubes) in between the tubes and the central canals of the tubes (only in HiPCO tubes) [15]. We have also prepared nano-structured porous doped carbons by ball-milling carbon host materials with some dopant, such as alkali or alkaline earth metal. The new nano-porous carbons obtained by this method have been characterised and tested for their hydrogen-adsorption properties. References: [1]A. Chambers et al, J. Phys. Chem. B, 102, 4253,1998. [2]A. C. Dillon et al, Nature, 386, 377,1997. [3]J. Conard, Ann. Chim. Sci. Mat 26

  6. Hydrogen adsorption in doped porous carbons

    International Nuclear Information System (INIS)

    Balan, L.; Duchaux, L.; Los, S.

    2005-01-01

    properties of doped microporous carbons (SWNTs and activated carbons). The raw nano-structured carbon materials are microporous activated carbons (BET specific surface area: 1600 m 2 /g), electric-arc closed-end single-walled carbon nano-tubes (SWNTs), and HiPCO SWNTs. They have been doped in the vapor phase by K, and Li (in order to obtain KC 7 , KC 10 , LiC 18 SWNTs and LiC 6 , LiC 18 , KC 24 activated carbons). The hydrogen adsorption-desorption isotherms of the doped activated carbons were obtained at room temperature and at 77 K, up to 3 MPa, by a volumetric method. The adsorption of D 2 was studied in situ on doped nano-tubes and filaments by neutron diffraction on DIB experiment (ILL), at λ = 2.52 Angstroms, as a function of temperature [300-20 K] and pressure. Simultaneously the adsorption isotherms were recorded in the range 0-0.1 MPa [13]. Doping of microporous carbon by Li or K leads to an increase in the energy of adsorption of H 2 or D 2 molecules. Thus, the room temperature sorption capacities (at P≤3 MPa) can be higher than that of the raw materials after slight doping. However, the maximum H 2 (or D 2 ) storage measured at T≤ 77 K is lower than the one of pristine materials as the sites of adsorption are occupied by alkali ions inserted in the micropores [14]. The microporous adsorption sites of doped single-walled carbon nano-tubes, identified by neutron diffraction, are both the interstitial voids (in electric-arc or HiPCO tubes) in between the tubes and the central canals of the tubes (only in HiPCO tubes) [15]. We have also prepared nano-structured porous doped carbons by ball-milling carbon host materials with some dopant, such as alkali or alkaline earth metal. The new nano-porous carbons obtained by this method have been characterised and tested for their hydrogen-adsorption properties. [1] A. Chambers et al, J. Phys. Chem. B, 102, 4253, 1998; [2] A. C. Dillon et al, Nature, 386, 377, 1997; [3] J. Conard, Ann. Chim. Sci. Mat 26, 107, 2001; [4] A

  7. Surface reactivity of mercury on the oxygen-terminated hematite(0001) surface: a first-principle study

    Science.gov (United States)

    Jung, J. E.; Wilcox, J.

    2016-12-01

    Hematite (α-Fe2O3) is a common mineral found in Earth's near-surface environment. Due to its nontoxicity, corrosion-resistance, and high thermal stability, α-Fe2O3 has attracted attentions as materials for various applications such as photocatalysts, gas sensors, as well as for the removal of heavy metals. In this study, α-Fe2O3 is chosen for potential mercury (Hg) sorbent in order to remove Hg from coal-fired power plants. Specifically, theoretical approaches using density functional theory (DFT) is used to understand surface reactivity of Hg on oxygen (O) terminated α-Fe2O3(0001) surface. The most probable adsorption sites of Hg, chlorine (Cl), and mercury chloride (HgCl) on the α-Fe2O3 surface are found based on adsorption energy calculations, and the oxidation states of the adsorbates are determined by Bader charge analysis. Additionally, projected density of states (PDOS) analysis characterizes the surface-adsorbate bonding mechanism. The results of adsorption energy calculation proposes that Hg physisorbs to the α-Fe2O3(0001) surface with adsorption energy of -0.278 eV, and the subsequent Bader charge analysis confirms that Hg is slightly oxidized. In addition, Cl introduced to the Hg-adsorbed surface strengthens Hg stability on the α-Fe2O3(0001) surface as evidenced by a shortened Hg-surface equilibrium distance. The PDOS analysis also suggests that Cl enhances the chemical bonding between the surface and the adsorbate, thereby increasing adsorption strength. In summary, α-Fe2O3 has ability to adsorb and oxidize Hg, and this reactivity is enhanced in the presence of Cl.

  8. Aqueous complexation, precipitation, and adsorption reactions of cadmium in the geologic environment

    International Nuclear Information System (INIS)

    Zachara, J.M.; Rai, D.; Felmy, A.R.; Cowan, C.E.; Smith, S.C.; Moore, D.A.; Resch, C.T.

    1992-06-01

    This report contains new laboratory data and equilibrium constants for important solubility and adsorption reactions of Cd that occur in soil and groundwater and attenuate Cd migration. In addition, extensive interaction experiments with Cd and soils from electric utility sites are described. These experiments show the importance of precipitation and adsorption reactions in soil and demonstrate how such reactions can be modeled to predict Cd attenuation near utility sites

  9. Greatly enhanced adsorption of platinum on periodic graphene nanobuds: A first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Ashrafian, S.; Jahanshahi, M. [Nanoscale Simulation Group, Nanotechnology Research Institute, School of Chemical Engineering, Babol University of Technology, Babol (Iran, Islamic Republic of); Ganji, M. Darvish, E-mail: ganji_md@yahoo.com [Young Researchers and Elite club, Central Tehran Branch, Islamic Azad University, Tehran (Iran, Islamic Republic of); Agheb, R. [Faculty of Mechanical Engineering, Khaje Nasir Toosi University of Technology, P.O. Box 16315-1355, Tehran (Iran, Islamic Republic of)

    2015-10-01

    Graphical abstract: - Highlights: • Pt adsorption on periodic graphene nanobuds (PGNBs) was investigated applying DFT. • We have been performed full structural relaxation for all the possible interaction sites. • Binding energies and electronics analysis were calculated for the considered systems. • Type II PGNB captured Pt atom, stronger than the other countrparts. • Ab initio MD simulation was performed for the energetically favorable configurations. - Abstract: The structural and electronic properties of platinum atom adsorbed on periodic graphene nanobuds (PGNBs) have been investigated and compared with graphene by means of density functional theory (DFT) calculations. Our result based on the generalized gradient approximation has been validated by the state-of-the-art B3LYP level of theory for Pt adsorption on the graphene surface. We demonstrate that the bridge site over the C–C bond center intervening between two hexagonal rings of type I PGNB and the hollow site over the nonagonal ring center of type II PGNB serve as the most thermodynamically favorable states amongst several considering starting configurations. The binding energies of about −3.34 and −3.78 eV were obtained for I PGNB and II PGNB, respectively, within the BSSE corrections, which are more stronger than the Pt binding energy of −2.12 eV for a pure graphene. The electronic structures for the most favorite configurations of Pt atom adsorbed on the systems of interest, in terms of the Mulliken population, the electronic density of states (DOS), and the projected density of states (PDOS) analysis have been discussed. The stability of the Pt–PGNBs and Pt–graphene complexes was confirmed within ab initio molecular dynamics simulation carrying out at ambient temperature. We also indicate that oxygen binding energies at the most energetically favorable configurations on the Pt–PGNB I and Pt–PGNB II complexes are weaker than the O{sub 2} binding energy on a Pt

  10. Study on adsorption properties and mechanism of Pb2+ with different carbon based adsorbents.

    Science.gov (United States)

    Song, Min; Wei, Yuexing; Cai, Shipan; Yu, Lei; Zhong, Zhaoping; Jin, Baosheng

    2018-03-15

    Different activated carbon materials are prepared from a series of solid wastes (sawdust, acrylic fabric, tire powder and rice husk) by combination of the KOH activation method and steam activation method. The influences of several parameters such as pH, contact time, adsorbent dosage and temperature on adsorption performance of Pb 2+ with those different carbon adsorbents are investigated. The results demonstrate that C rice husk performance well in the adsorption process. In the following, the C rice husk is used to explain the adsorption mechanism of Pb 2+ by SEM-EDS, FT-IR and XPS. The results illustrate that the surface oxygen-containing functional groups such as carboxyl, lactone group, phenolic hydroxyl and other alkaline metal ions like Na + and K + have significant effect on the adsorption process. A reasonable mechanism of Pb 2+ adsorption is proposed that the ion exchange play key roles in the adsorption process. In addition, the effects of Cu 2+ , Zn 2+ on the Pb 2+ adsorption capacity with the four carbon adsorbents are also studied and the results demonstrate that other heavy metals play positive effects on the adsorption of Pb 2+ . Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Acetate and phosphate anion adsorption linear sweep voltammograms simulated using density functional theory

    KAUST Repository

    Savizi, Iman Shahidi Pour

    2011-04-01

    Specific adsorption of anions to electrode surfaces may alter the rates of electrocatalytic reactions. Density functional theory (DFT) methods are used to predict the adsorption free energy of acetate and phosphate anions as a function of Pt(1 1 1) electrode potential. Four models of the electrode potential are used including a simple vacuum slab model, an applied electric field model with and without the inclusion of a solvating water bi-layer, and the double reference model. The linear sweep voltammogram (LSV) due to anion adsorption is simulated using the DFT results. The inclusion of solvation at the electrochemical interface is necessary for accurately predicting the adsorption peak position. The Langmuir model is sufficient for predicting the adsorption peak shape, indicating coverage effects are minor in altering the LSV for acetate and phosphate adsorption. Anion adsorption peak positions are determined for solution phase anion concentrations present in microbial fuel cells and microbial electrolysis cells and discussion is provided as to the impact of anion adsorption on oxygen reduction and hydrogen evolution reaction rates in these devices. © 2011 Elsevier Ltd. All rights reserved.

  12. Metal-polymer interfaces studied with adsorption microcalorimetry and photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Bebensee, Fabian

    2010-06-21

    The interface formation between calcium and two different semiconducting, ?-conjugated polymers, namely poly(3-hexylthiophene) (P3HT) and poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-(1-cyanovilylene)phenylene] (CN-MEH-PPV), was investigated using adsorption microcalorimetry, low energy ion scattering spectroscopy (LEIS), atomic beam scattering and X-ray photoelectron spectroscopy. In addition to the interface formation on pristine, i.e., untreated polymer surfaces, the influence of electron irradiation prior to calcium deposition and the effect of dosing calcium at a low substrate temperature was studied. The reactive site for the interaction of calcium atoms impinging on a pristine P3HT surface appears to be the sulfur in the thiophene ring, as is concluded from a combination of XPS, adsorption calorimetry and theory results. The interaction, in fact, is strong enough that the sulfur atoms abstracted from the thiophene ring under formation of calcium sulfide with an overall reaction energy of this process of 405 kJ per mol. Quantitative evaluation of XPS data reveal that the depth up to which Ca atoms react with sulfur in the polymer is 3 nm, irrespective of increasing the amount of Ca dosed onto the substrate. A closed layer of Ca is only formed at a Ca coverage exceeding 11 ML, as suggested by LEIS. Irradiation of P3HT with electrons with a kinetic energy of 100 eV results in dehydrogenation of the hexyl side chains and formation of new C=C double bonds. This in turn results in a higher initial sticking probability of 0.63 for Ca, while no other significant changes could be observed: XPS indicates that the thiophene rings remain intact and the measured heat of adsorption is the same as observed for the deposition of Ca on pristine P3HT. Dosing Ca onto P3HT held at low temperature (130 K) is found to result in a very low saturation thickness of the reacted layer of approximately 0.3 nm. Upon warming the sample up to room temperature, the thickness of the reacted layer

  13. Water adsorption on goethite: Application of multilayer adsorption models

    Science.gov (United States)

    Hatch, C. D.; Tumminello, R.; Meredith, R.

    2016-12-01

    Adsorbed water on the surface of atmospheric mineral dust has recently been shown to significantly affect the ability of mineral dust aerosol to act as cloud condensation nuclei. We have studied water adsorption as a function of relative humidity (RH) on goethite (α-FeO(OH)), a common component of atmospheric mineral dust. The goethite surface area and particle size was determined using BET analysis and with N2 as an adsorbate and scanning electron microscopy, respectively. Water adsorption on the sample was monitored using horizontal attenuated total reflectance Fourier transform infrared (HATR-FTIR) spectroscopy equipped with a flow cell. Water content was determined using Beer's law and the optical constants for bulk water. The results were analyzed using Type II adsorption isotherms to model multilayer adsorption, including BET (Brunauer, Emmet and Teller), FHH (Frenkel, Halsey and Hill) and Freundlich. BET fits to experimental data provide parameters of monolayer coverage, while the FHH and Freundlich isotherms provide insights into multilayer adsorption mechanisms. Results indicate that goethite contains 5% H2O by mass at 50% RH, which increases to 12% by mass at 90% RH. Adsorption parameters and experimental results will be presented.

  14. MONTE CARLO SIMULATIONS OF THE ADSORPTION OF DIMERS ON STRUCTURED HETEROGENEOUS SURFACES

    Directory of Open Access Journals (Sweden)

    Abreu C.R.A.

    2001-01-01

    Full Text Available The effect of surface topography upon the adsorption of dimer molecules is analyzed by means of grand canonical ensemble Monte Carlo simulations. Heterogeneous surfaces were assumed to consist of a square lattice containing active sites with two different energies. These were distributed in three different configurations: a random distribution of isolated sites; a random distribution of grains with four high-energy sites; and a random distribution of grains with nine high-energy sites. For the random distribution of isolated sites, the results are in good agreement with the molecular simulations performed by Nitta et al. (1997. In general, the comparison with theoretical models shows that the Nitta et al. (1984 isotherm presents good predictions of dimer adsorption both on homogeneous and heterogeneous surfaces with sites having small differences in characteristic energies. The molecular simulation results also show that the energy topology of the solid surfaces plays an important role in the adsorption of dimers on solids with large differences in site energies. For these cases, the Nitta et al. model does not describe well the data on dimer adsorption on random heterogeneous surfaces (grains with one acid site, but does describe reasonably well the adsorption of dimers on more patchwise heterogeneous surfaces (grains with nine acid sites.

  15. Theoretical study of heavy metal Cd, Cu, Hg, and Ni(II) adsorption on the kaolinite(0 0 1) surface

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Jian, E-mail: zhaojian0209@aliyun.com [Institute of Applied Physics and Computational Mathematics, PO Box 8009, Beijing 100088 (China); State Key Laboratory of Geomechanics and Deep Underground Engineering, China University of Mining and Technology, Beijing 100083 (China); He, Man-Chao [State Key Laboratory of Geomechanics and Deep Underground Engineering, China University of Mining and Technology, Beijing 100083 (China)

    2014-10-30

    Highlights: • We investigated the adsorption of Cd, Cu, Hg, and Ni(II) on kaolinite(0 0 1) surface. • The adsorption capabilities of the kaolinite for HM atoms were Ni > Cu > Cd > Hg(II). • The adsorption energy increases with the coverage for Cd, Cu, and Hg(II) atoms. • The adsorption energy decreases with the coverage for Ni(II) atoms. - Abstract: Heavy metal pollution is currently of great concern because it has been recognized as a potential threat to air, water, and soil. Adsorption was one of the most popular methods for the removal of heavy metal. The adsorption of heavy metal Cd, Cu, Hg, and Ni(II) atoms on the hydroxylated (0 0 1) surface of kaolinite was investigated using density-functional theory within the generalized gradient approximation and a supercell approach. The coverage dependence of the adsorption structures and energetics were systematically studied for a wide range of coverage Θ [from 0.11 to 1.0 monolayers (ML)] and adsorption sites. The most stable among all possible adsorption sites for Cd(II) atom was the two-fold bridge site followed by the one-fold top site, and the top site was the most favorite adsorption site for Cu and Ni(II) atoms, while the three-fold hollow site was the most stable adsorption site for Hg(II) atom followed by the two-fold bridge site. The adsorption energy increases with the coverage for Cd, Cu, and Hg(II) atoms, thus indicating the higher stability of surface adsorption and a tendency to the formation of adsorbate islands (clusters) with increasing the coverage. However, the adsorption energy of Ni(II) atoms decreases when increasing the coverage. The adsorption capabilities of the kaolinite clay for the heavy metal atoms were in the order of Ni > Cu > Cd > Hg(II). The other properties of the Cd, Cu, Hg, and Ni(II)/kaolinite(0 0 1) system including the different charge distribution, the lattice relaxation, and the electronic density of states were also studied and discussed in detail.

  16. Theoretical study of heavy metal Cd, Cu, Hg, and Ni(II) adsorption on the kaolinite(0 0 1) surface

    International Nuclear Information System (INIS)

    Zhao, Jian; He, Man-Chao

    2014-01-01

    Highlights: • We investigated the adsorption of Cd, Cu, Hg, and Ni(II) on kaolinite(0 0 1) surface. • The adsorption capabilities of the kaolinite for HM atoms were Ni > Cu > Cd > Hg(II). • The adsorption energy increases with the coverage for Cd, Cu, and Hg(II) atoms. • The adsorption energy decreases with the coverage for Ni(II) atoms. - Abstract: Heavy metal pollution is currently of great concern because it has been recognized as a potential threat to air, water, and soil. Adsorption was one of the most popular methods for the removal of heavy metal. The adsorption of heavy metal Cd, Cu, Hg, and Ni(II) atoms on the hydroxylated (0 0 1) surface of kaolinite was investigated using density-functional theory within the generalized gradient approximation and a supercell approach. The coverage dependence of the adsorption structures and energetics were systematically studied for a wide range of coverage Θ [from 0.11 to 1.0 monolayers (ML)] and adsorption sites. The most stable among all possible adsorption sites for Cd(II) atom was the two-fold bridge site followed by the one-fold top site, and the top site was the most favorite adsorption site for Cu and Ni(II) atoms, while the three-fold hollow site was the most stable adsorption site for Hg(II) atom followed by the two-fold bridge site. The adsorption energy increases with the coverage for Cd, Cu, and Hg(II) atoms, thus indicating the higher stability of surface adsorption and a tendency to the formation of adsorbate islands (clusters) with increasing the coverage. However, the adsorption energy of Ni(II) atoms decreases when increasing the coverage. The adsorption capabilities of the kaolinite clay for the heavy metal atoms were in the order of Ni > Cu > Cd > Hg(II). The other properties of the Cd, Cu, Hg, and Ni(II)/kaolinite(0 0 1) system including the different charge distribution, the lattice relaxation, and the electronic density of states were also studied and discussed in detail

  17. Low-Temperature Pd/Zeolite Passive NO x Adsorbers: Structure, Performance, and Adsorption Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Yang [Institute for Integrated; Kovarik, Libor [Institute for Integrated; Engelhard, Mark H. [Institute for Integrated; Wang, Yilin [Institute for Integrated; Wang, Yong [Institute for Integrated; Gao, Feng [Institute for Integrated; Szanyi, János [Institute for Integrated

    2017-07-14

    Pd/zeolite passive NOx adsorber (PNA) materials were prepared with solution ion-exchange between NH4/zeolites (Beta, ZSM-5 and SSZ-13) and PdCl2 solutions. The nature of Pd (dispersion, distribution and oxidation states) in these materials was characterized with Na+ ion-exchange, TEM imaging, CO titration with FTIR and in situ XPS. The NOx trapping and release properties were tested using feeds with different compositions. It is concluded that multiple Pd species coexist in these materials: atomically dispersed Pd in the cationic sites of zeolites, and PdO2 and PdO particles on the external surfaces. While Pd is largely atomically dispersed in ZSM-5, the small pore opening for SSZ-13 inhibits Pd diffusion such that the majority of Pd stays as external surface PdO2 clusters. NOx trapping and release are not simple chemisorption and desorption events, but involve rather complex chemical reactions. In the absence of CO in the feed, cationic Pd(II) sites with oxygen ligands and PdO2 clusters are reduced by NO to Pd(I) and PdO clusters. These reduced sites are the primary NO adsorption sites. In the presence of H2O, the as-formed NO2 desorb immediately. In the presence of CO in the feed, metallic Pd, “naked” Pd2+, and Pd+ sites are responsible for NO adsorption. For Pd adsorption sites with the same oxidation states but in different zeolite frameworks, NO binding energies are not expected to vary greatly. However, NO release temperatures do vary substantially with different zeolite structures. This indicates that NO transport within these materials play an important role in determining release temperatures. Finally, some rational design principles on efficient PNA materials are suggested. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a

  18. Prediction of Pure Component Adsorption Equilibria Using an Adsorption Isotherm Equation Based on Vacancy Solution Theory

    DEFF Research Database (Denmark)

    Marcussen, Lis; Aasberg-Petersen, K.; Krøll, Annette Elisabeth

    2000-01-01

    An adsorption isotherm equation for nonideal pure component adsorption based on vacancy solution theory and the Non-Random-Two-Liquid (NRTL) equation is found to be useful for predicting pure component adsorption equilibria at a variety of conditions. The isotherm equation is evaluated successfully...... adsorption systems, spreading pressure and isosteric heat of adsorption are also calculated....

  19. Ultra Low Concentration Adsorption Equilibria

    National Research Council Canada - National Science Library

    Mahle, John J; Buettner, Leonard C; LeVan, M. D; Schindler, Bryan J

    2006-01-01

    .... Specifically this work focuses on novel experimental and modeling methods to characterize and predict at ultra-low chemical vapor concentrations the protection afforded by adsorption-based vapor filtration systems...

  20. Potential Theory of Multicomponent Adsorption

    DEFF Research Database (Denmark)

    Shapiro, Alexander; Stenby, Erling Halfdan

    1998-01-01

    We developed a theory of multicomponent adsorption on the basis of the potential concept originally suggested by Polanyi. The mixture is considered as a heterogeneous substance segregated in the external field emitted by the adsorbent. The same standard equation of state, with no additional fitting...... parameters, is used for the segregated and for the bulk phases. With this approach, few parameters are needed to correlate pure component adsorption isotherms. These parameters may be used to predict adsorption equilibria of multicomponent mixtures without additional adjustment. A connection between...... the potential theory and the spreading pressure concept is established, and problems of the theory consistency are studied. Numerical algorithms are suggested for evaluation of the segregated state of the mixture in the potential field of adsorption forces. Comparison with experimental data shows good agreement...

  1. Adsorption kinetics of surfactants on activated carbon

    Science.gov (United States)

    Arnelli; Aditama, WP; Fikriani, Z.; Astuti, Y.

    2018-04-01

    A study on the adsorption of both cationic and anionic surfactants using activated carbon as well as the investigation of the adsorption isotherms and adsorption kinetics has been conducted. The results showed that the adsorption of sodium lauryl sulfate (SLS) by activated carbon was Langmuir’s adsorption isotherm while its adsorption kinetics showed pseudo-second order with an adsorption rate constant of 2.23 x 103 g mg-1 hour-1. Meanwhile, the adsorption of HDTMA-Br by activated carbon showed that the isotherm adsorption tended to follow Freundlich’s isotherm and was pseudo-second order with an adsorption rate constant of 89.39 g mg-1 hour-1.

  2. Adsorption of amylase enzyme on ultrafiltration membranes

    DEFF Research Database (Denmark)

    Beier, Søren; Enevoldsen, Ann Dorrit; Kontogeorgis, Georgios

    2007-01-01

    A method to measure the static adsorption on membrane surfaces has been developed and described. The static adsorption of an amylase-F has been measured on two different ultrafiltration membranes, both with a cut-off value of 10 kDa (a PES membrane and the ETNA10PP membrane, which is a surface......-modified PVDF membrane). The adsorption follows the Langmuir adsorption theory. Thus, the static adsorption consists of monolayer coverage. The static adsorption is expressed both as a permeability drop and an adsorption resistance. From the adsorption isotherms the maximum static permeability drops...... and the maximum static adsorption resistances are determined. The maximum static permeability drop for the hydrophobic PES membrane is 75 % and the maximum static adsorption resistance is 0.014 m2hbar/L. The maximum static permeability drop for the hydrophilic surface-modified PVDF membrane (ETNA10PP) is 23...

  3. Adsorption of metalorganic molecules on metal-semiconductor systems

    Energy Technology Data Exchange (ETDEWEB)

    Brand, Christian; Schmeidel, Jedrzej; Chen, Wei; Tegenkamp, Christoph; Pfnuer, Herbert [Institut fuer Festkoerperphysik, Leibniz Universitaet Hannover (Germany)

    2011-07-01

    The controlled implementation of single molecules in appropriate contact assemblies is the ultimate realization of an ultra-small device structure. Besides extremely high integration densities the functionalities of the devices are adjustable by chemical synthesis. However, the interaction of the molecule with its environment is decisive. The adsorption of ferrocene-1,1'-dithiol (FDT) on Ag-{radical}(3) reconstructions on nominally flat and vicinal Si(111) substrates has been studied. The FDT was chosen because of its large conductance and high structural flexibility with respect to rotation of the two cyclopentadienyl (Cp) rings. The reconstruction is a prototype of a highly conductive low dimensional electron gas on a technologically relevant substrate. The adsorption of intact molecules takes place predominantly at defect sites, e.g. vacancy and step structures. Submolecular resolution showing the Cp-ring structure was obtained at perfect terrace sites. Due to chemisorption of the S-atoms at hollow sites the molecule axis is oriented parallel to the substrate. The initial rotational flexibility is frozen and only tow different rotated configurations were found. The adsorption geometry is confirmed by VASP calculations. Recently, Ag reconstructions on Si(557) substrates have been used. The effect of the uniaxial step configuration towards the adsorption of the FDT molecules is discussed.

  4. Adsorption of antibiotics on microplastics.

    Science.gov (United States)

    Li, Jia; Zhang, Kaina; Zhang, Hua

    2018-06-01

    Microplastics and antibiotics are two classes of emerging contaminants with proposed negative impacts to aqueous ecosystems. Adsorption of antibiotics on microplastics may result in their long-range transport and may cause compound combination effects. In this study, we investigated the adsorption of 5 antibiotics [sulfadiazine (SDZ), amoxicillin (AMX), tetracycline (TC), ciprofloxacin (CIP), and trimethoprim (TMP)] on 5 types of microplastics [polyethylene (PE), polystyrene (PS), polypropylene (PP), polyamide (PA), and polyvinyl chloride (PVC)] in the freshwater and seawater systems. Scanning Electron Microscope (SEM) and X-ray diffractometer (XRD) analysis revealed that microplastics have different surface characterizes and various degrees of crystalline. Adsorption isotherms demonstrated that PA had the strongest adsorption capacity for antibiotics with distribution coefficient (K d ) values ranged from 7.36 ± 0.257 to 756 ± 48.0 L kg -1 in the freshwater system, which can be attributed to its porous structure and hydrogen bonding. Relatively low adsorption capacity was observed on other four microplastics. The adsorption amounts of 5 antibiotics on PS, PE, PP, and PVC decreased in the order of CIP > AMX > TMP > SDZ > TC with K f correlated positively with octanol-water partition coefficients (Log K ow ). Comparing to freshwater system, adsorption capacity in seawater decreased significantly and no adsorption was observed for CIP and AMX. Our results indicated that commonly observed polyamide particles can serve as a carrier of antibiotics in the aquatic environment. Copyright © 2018 Elsevier Ltd. All rights reserved.

  5. Density functional theory investigation of oxygen interaction with boron-doped graphite

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Juan; Wang, Chen [State Key Lab of New Ceramic and Fine Processing, Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Liang, Tongxiang, E-mail: txliang@tsinghua.edu.cn [State Key Lab of New Ceramic and Fine Processing, Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Lai, Wensheng [Advanced Material Laboratory, School of Materials Science & Engineering, Tsinghua University, Beijing, 100084 (China)

    2016-12-30

    Highlights: • Density-functional approach is applied to study the interaction of oxygen with boron-doped graphite. • Adsorption and diffusion of oxygen atoms on boron doped graphite surfaces are studied. • Recombination of oxygen is investigated by ER and LH mechanisms. • Low boron concentration facilitates O{sub 2} forma