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Sample records for chemisorption

  1. Chemisorption And Precipitation Reactions

    Science.gov (United States)

    The transport and bioavailability of chemical components within soils is, in part, controlled by partitioning between solids and solution. General terms used to describe these partitioning reactions include chemisorption and precipitation. Chemisorption is inclusive of the suit...

  2. The chemisorptive bond basic concepts

    CERN Document Server

    Clark, Alfred

    1974-01-01

    The Chemisorptive Bond: Basic Concepts describes the basic concepts of the chemisorptive bond on solid surfaces from the simple analogies with ordinary chemical bonds to the quantum-mechanical approaches.This book is composed of 10 chapters and begins with discussions of simple formulas for correlating measurable quantities in chemisorptions and catalysis. The succeeding chapters deal with theories based on quantum-mechanical principles that describe the mutual interactions of atoms of the solid and foreign atoms on the surface. The remaining chapters consider the possible arrangements

  3. CO Chemisorption at Metal Surfaces and Overlayers

    DEFF Research Database (Denmark)

    Hammer, Bjørk; Morikawa, Y.; Nørskov, Jens Kehlet

    1996-01-01

    A database of ab initio calculations of the chemisorption energy of CO over Ni(111), Cu(111), Ru(0001), Pd(111), Ag(111), Pt(111), Au(111), Cu3Pt(111), and some metallic overlayer structures is presented. The trends can be reproduced with a simple model describing the interaction between the meta...... d states and the CO 2 pi* and 5 sigma states, renormalized by the metal sp continuum. Our model rationalizes the results by Rodriguez and Goodman [Science 257, 897 (1992)] showing a strong correlation between the CO chemisorption energy and the surface core level shift.......A database of ab initio calculations of the chemisorption energy of CO over Ni(111), Cu(111), Ru(0001), Pd(111), Ag(111), Pt(111), Au(111), Cu3Pt(111), and some metallic overlayer structures is presented. The trends can be reproduced with a simple model describing the interaction between the metal...

  4. Quantitative evaluation of chemisorption processes on semiconductors

    Science.gov (United States)

    Rothschild, A.; Komem, Y.; Ashkenasy, N.

    2002-12-01

    This article presents a method for numerical computation of the degree of coverage of chemisorbates and the resultant surface band bending as a function of the ambient gas pressure, temperature, and semiconductor doping level. This method enables quantitative evaluation of the effect of chemisorption on the electronic properties of semiconductor surfaces, such as the work function and surface conductivity, which is of great importance for many applications such as solid- state chemical sensors and electro-optical devices. The method is applied for simulating the chemisorption behavior of oxygen on n-type CdS, a process that has been investigated extensively due to its impact on the photoconductive properties of CdS photodetectors. The simulation demonstrates that the chemisorption of adions saturates when the Fermi level becomes aligned with the chemisorption-induced surface states, limiting their coverage to a small fraction of a monolayer. The degree of coverage of chemisorbed adions is proportional to the square root of the doping level, while neutral adsorbates are independent of the doping level. It is shown that the chemisorption of neutral adsorbates behaves according to the well-known Langmuir model, regardless of the existence of charged species on the surface, while charged adions do not obey Langmuir's isotherm. In addition, it is found that in depletive chemisorption processes the resultant surface band bending increases by 2.3kT (where k is the Boltzmann constant and T is the temperature) when the gas pressure increases by one order of magnitude or when the doping level increases by two orders of magnitude.

  5. Chemisorption of chlorine and sulfur dioxide on zinc oxide

    Energy Technology Data Exchange (ETDEWEB)

    Vinokurov, A.A.; Derlyukova, L.E.; Evdokimov, V.I.

    1987-03-10

    The chemisorption of sulfur dioxide and chlorine on the surface of zinc oxide and the change in the electric conductivity of ZnO during the chemisorption process were studied. It was shown that both gases induce a negative charging of the surface of zinc oxide. The kinetics of the chemisorption of Cl/sub 2/ and SO/sub 2/ is described by the Zel'dovich-Roginskii equation. The mutual influence of sulfur dioxide and chlorine during successive chemisorption was investigated. It was shown that the nature of the mutual influence depends on the temperature and the sequence of action of the gases. The results obtained were analyzed from the standpoint of the electronic theory of chemisorption on semiconductors.

  6. Chemisorption of Au on Si(001) surface

    Institute of Scientific and Technical Information of China (English)

    Wei Shu-Yi; Wang Jian-Guang; Ma Li

    2004-01-01

    @@ The chemisorption of one monolayer of Au atoms on an ideal Si(001) surface is studied by using the self-consistent tight binding linear muffin-tin orbital method. Energies of the adsorption system of a Au atom on different sites are calculated. It is found that the most stable position is A site (top site) for the adsorbed Au atoms above the Si(001)surface. It is possible for the adsorbed Au atoms to sit below the Si(001) surface at the B1 site(bridge site), resulting in a Au-Si mixed layer. This is in agreement with the experiment results. The layer projected density of states is calculated and compared with that of the clean surface. The charge transfer is also investigated.

  7. Chemisorption effects on the thin-film conductivity

    Science.gov (United States)

    Geistlinger, H.

    1992-10-01

    An investigation of chemisorption effects on the electrical conductivity of thin, wide bandgap semiconductors is presented in the framework of the Volkenstein model. The controversially discussed problem of a neutral, weak-chemisorbed state is reconsidered on the basis of the one-electron theory of chemisorption (considered by Einstein and Schrieffer). An analytically tractable variational method is developed for the ground state in lattice space. It turns out that in case of atop-anion binding a stable, weak-chemisorbed state can arise. For the case of acceptor-like chemisorption the pressure dependence of the thin-film conductivity is derived, solving selfconsistently the one-dimensional Poisson equation. In a wide pressure region the conductivity shows a power-law behaviour. It is found that the power is determined by different, fundamental parameters and cannot be expressed by only one parameter, e.g., the constant, stochiometric exponent in the mass-action law. Furthermore, the theoretical values of the power vary between 0 and 1 in agreement with the variety of experimental results.

  8. Model study in chemisorption: atomic hydrogen on beryllium clusters

    Energy Technology Data Exchange (ETDEWEB)

    Bauschlicher, C.W. Jr.

    1976-08-01

    The interaction between atomic hydrogen and the (0001) surface of Be metal has been studied by ab initio electronic structure theory. Self-consistent-field (SCF) calculations have been performed using minimum, optimized minimum, double zeta and mixed basis sets for clusters as large as 22 Be atoms. The binding energy and equilibrium geometry (the distance to the surface) were determined for 4 sites. Both spatially restricted (the wavefunction was constrained to transform as one of the irreducible representations of the molecular point group) and unrestricted SCF calculations were performed. Using only the optimized minimum basis set, clusters containing as many as 22 beryllium atoms have been investigated. From a variety of considerations, this cluster is seen to be nearly converged within the model used, providing the most reliable results for chemisorption. The site dependence of the frequency is shown to be a geometrical effect depending on the number and angle of the bonds. The diffusion of atomic hydrogen through a perfect beryllium crystal is predicted to be energetically unfavorable. The cohesive energy, the ionization energy and the singlet-triplet separation were computed for the clusters without hydrogen. These quantities can be seen as a measure of the total amount of edge effects. The chemisorptive properties are not related to the total amount of edge effects, but rather the edge effects felt by the adsorbate bonding berylliums. This lack of correlation with the total edge effects illustrates the local nature of the bonding, further strengthening the cluster model for chemisorption. A detailed discussion of the bonding and electronic structure is included. The remaining edge effects for the Be/sub 22/ cluster are discussed.

  9. Chemisorption and Reactions of Small Molecules on Small Gold Particles

    Directory of Open Access Journals (Sweden)

    Geoffrey C. Bond

    2012-02-01

    Full Text Available The activity of supported gold particles for a number of oxidations and hydrogenations starts to increase dramatically as the size falls below ~3 nm. This is accompanied by an increased propensity to chemisorption, especially of oxygen and hydrogen. The explanation for these phenomena has to be sought in kinetic analysis that connects catalytic activity with the strength and extent of chemisorption of the reactants, the latter depending on the electronic structure of the gold atoms constituting the active centre. Examination of the changes to the utilisation of electrons as particle size is decreased points to loss of metallic character at about 3 nm, as energy bands are replaced by levels, and a band gap appears. Detailed consideration of the Arrhenius parameters (E and ln A for CO oxidation points clearly to a step-change in activity at the point where metallic character is lost, as opposed to there being a monotonic dependence of rate on a physical property such as the fraction of atoms at corners or edges of particles. The deplorable scarcity of kinetic information on other reactions makes extension of this analysis difficult, but non-metallic behaviour is an unavoidable property of very small gold particles, and therefore cannot be ignored when seeking to explain their exceptional activity.

  10. Influence of chemisorption on the magnetic properties of metallic iron nanoparticles

    DEFF Research Database (Denmark)

    Bødker, F.; Mørup, S.; Linderoth, Søren

    1995-01-01

    Nano-sized alpha-Fe particles on a carbon support have been studied by Mossbauer spectroscopy. It is found that chemisorption of CO results in formation of a diamagnetic surface component. The magnetic anisotropy energy constant is only slightly affected by chemisorption of carbon monoxide and hy...

  11. Molecular N-2 chemisorption-specific adsorption on step defect sites on Pt surfaces

    DEFF Research Database (Denmark)

    Tripa, C. Emil; Zubkov, T.S.; Yates, John T.

    1999-01-01

    Infrared reflection-absorption spectroscopy and density functional theory, within the generalized gradient approximation, were used to investigate both experimentally and theoretically N-2 chemisorption on stepped and smooth Pt surfaces. N-2 chemisorption was observed to occur only on the edge...

  12. Dissociative chemisorption dynamics of small molecules on metal surfaces

    Institute of Scientific and Technical Information of China (English)

    JIANG Bin; XIE DaiQian

    2014-01-01

    Much progress has been achieved for both experimental and theoretical studies on the dissociative chemisorption of molecules on surfaces.Quantum state-resolved experimental data has provided unprecedented details for these fundamental steps in heterogeneous catalysis,while the quantitative dynamics is still not fully understood in theory.An in-depth understanding of experimental observations relies on accurate dynamical calculations,in which the potential energy surface and adequate quantum mechanical implementation are desired.This article summarizes the current methodologies on the construction of potential energy surfaces and the quantum mechanical treatments,some of which are promising for future applications.The challenges in this field are also addressed.

  13. Communication: Enhanced dissociative chemisorption of CO2 via vibrational excitation

    Science.gov (United States)

    Jiang, Bin; Guo, Hua

    2016-03-01

    A fully coupled global nine-dimensional potential energy surface for the dissociative chemisorption of CO2 on Ni(100) is constructed from ˜18 000 density functional points. It reveals a complex reaction pathway dominated by two near iso-energetic transition states. The dissociation probabilities obtained by quasi-classical trajectories on the potential energy surface reproduced experimental trends, and indicate that vibrational excitations of CO2 significantly promote the dissociation. Using the sudden vector projection model, the behavior of the reactivity is rationalized by couplings with the reaction coordinate at each transition state. These results offer plausible rationalization for the observed enhancement of CO2 dissociation in non-thermal plasmas by metal surfaces.

  14. Nanocatalysis: size- and shape-dependent chemisorption and catalytic reactivity

    Science.gov (United States)

    Roldan Cuenya, Beatriz; Behafarid, Farzad

    2015-06-01

    In recent years, the field of catalysis has experienced an astonishing transformation, driven in part by more demanding environmental standards and critical societal and industrial needs such as the search for alternative energy sources. Thanks to the advent of nanotechnology, major steps have been made towards the rational design of novel catalysts. Striking new catalytic properties, including greatly enhanced reactivities and selectivities, have been reported for nanoparticle (NP) catalysts as compared to their bulk counterparts. However, in order to harness the power of these nanocatalysts, a detailed understanding of the origin of their enhanced performance is needed. The present review focuses on the role of the NP size and shape on chemisorption and catalytic performance. Since homogeneity in NP size and shape is a prerequisite for the understanding of structure-reactivity correlations, we first review different synthesis methods that result in narrow NP size distributions and shape controlled NPs. Next, size-dependent phenomena which influence the chemical reactivity of NPs, including quantum size-effects and the presence of under-coordinated surface atoms are examined. The effect of the NP shape on catalytic performance is discussed and explained based on the existence of different atomic structures on the NP surface with distinct chemisorption properties. The influence of additional factors, such as the oxidation state of the NPs and NP-support interactions, is also considered in the frame of the size- and shape-dependency that these phenomena present. Ultimately, our review highlights the importance of achieving a systematic understanding of the factors that control the activity and selectivity of a catalyst in order to avoid trial and error methods in the rational design of the new generation of nanocatalysts with properties tunable at the atomic level.

  15. Cluster Studies of Chemisorption Using Total Energy Techniques.

    Science.gov (United States)

    Wander, Adrian

    Available from UMI in association with The British Library. Requires signed TDF. Chapter 1 introduces the topic. Chapter 2 contains a discussion of ab initio quantum chemistry techniques and in particular the self consistent Hartree-Fock equations. Section 2.2 discusses the Hartree -Fock equations and their matrix form the Roothaan-Hall equations. Section 2.3 deals with the important question of the choice of a basis set for molecular calculations and in section 2.4 we move on to present a brief review of the GAMESS SCF MO package. Finally, section 2.5 deals with methods of moving beyond HF theory by including electron -electron correlation effects. Chapters 3, 4 and 5 deal with applications of the ab initio method to real systems. Chapter 3 details calculations performed on the formate and methoxy radicals on the Cu(100) surface, while chapter 4 looks at the controversial topic of the low temperature structure of oxygen on Cu(110). Finally, chapter 5 considers the effects of atomic oxygen chemisorption on the Si(100)(2 times 1) reconstructed surface. While the preceding three chapters highlight the virtues of ab initio methods, chapter 6 points out some of their vices and in particular the severe demands they make on computational resources. Alternative semi-empirical techniques are then introduced in the form of the extended Huckel and ASED methods. In particular, we discuss the role of charge self consistency in semi-empirical techniques and show that in contrast to other methods, it has little effect on the quality of results produced using the ASED method. Finally, we conclude in chapter 7 by reviewing the thesis and suggesting possible future developments to this work, both in terms of interesting systems to investigate and new directions in which the theory could be developed. (Abstract shortened with permission of author.).

  16. Chemisorption-facilitated dislocation emission and motion, and induced nucleation of brittle nanocrack

    Institute of Scientific and Technical Information of China (English)

    宿彦京; 王燕斌; 褚武扬

    1997-01-01

    Using a special TEM constant deflection device, the change in dislocation configuration ahead of a loaded crack tip before and after adsorption of Hg atoms and the initiation of liquid metal-induced nanocracks (LMIC) have been observed. The results show that chemisorption of Hg atoms can facilitate dislocation emission, multiplication and motion. Nanocracks will be initiated in the dislocation-free zone (DFZ) or at the crack tip when chemisorption-facilitated dislocation emission, multiplication and motion reach a critical condition. On the basis of the available experimental evidence concerning liquid metal embnttlement (LME), a new mechanism for this phenomenon is considered. This involves the fact that the decrease in surface energy induced by chemisorption of Hg atoms results in a reduction in the critical stress intensity factors for dislocation emission and the resistance for dislocation motion. On the other hand, the plastic work and KIC will decrease with the decrease in the surface energy.

  17. The Ab Initio Studies of NO Chemisorption on TiO2(110) Surface

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    The studies of NO chemisorption on TiO2(110) surface are the base of research to NO decomposed to N2O on TiO2 surface. In this paper, 12 kinds of possible models of NO adsorbed on TiO2 perfect and defect surface were calculated by use of ab initio cluster method. We carried out optimization of the geometry, calculation of the chemisorption energy and analysis of the Mulliken population to those adsorption models. According to the calculation results, it can be got that the adsorbed decomposition of NO on defect surface is more advantageous and M6 and M12 are the important models to NO chemisorption and decomposition on TiO2 surface.

  18. Raman and computational study of solvation and chemisorption of thiazole in silver hydrosol.

    Science.gov (United States)

    Muniz-Miranda, Maurizio; Pagliai, Marco; Muniz-Miranda, Francesco; Schettino, Vincenzo

    2011-03-21

    A SERS investigation combined with ab initio computational analysis involving Car-Parrinello molecular dynamics simulations and Density Functional Theory approach allows fundamental information to be obtained on the behaviour of thiazole in silver aqueous suspension where solvation and chemisorption processes competitively occur.

  19. Chemisorption-induced n-doping of MoS{sub 2} by oxygen

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Long; Wang, Ying; Wu, Yihong, E-mail: elewuyh@nus.edu.sg [Department of Electrical and Computer Engineering, National University of Singapore, 4 Engineering Drive 3, Singapore, Singapore 117583 (Singapore); Shen, Lei, E-mail: shenlei@nus.edu.sg [Engineering Science Program, Faculty of Engineering, National University of Singapore, Singapore, Singapore 117579 (Singapore)

    2016-02-08

    Both chemisorption and physisorption affect the electronic properties of two-dimensional materials, such as MoS{sub 2}, but it remains a challenge to probe their respective roles experimentally. Through repeated in-situ electrical measurements of few-layer MoS{sub 2} field-effect transistors in an ultrahigh vacuum system with well-controlled oxygen partial pressure (6 × 10{sup −8} mbar–3 × 10{sup −7} mbar), we were able to study the effect of chemisorption on surface defects separately from physically adsorbed oxygen molecules. It is found that chemisorption of oxygen results in n-doping in the channel but negligible effect on mobility and on/off ratio of the MoS{sub 2} transistors. These results are in disagreement with the previous reports on p-doping and degradation of the device's performance when both chemisorption and physisorption are present. Through the analysis of adsorption-desorption kinetics and the first-principles calculations of electronic properties, we show that the experimentally observed n-doping effect originates from dissociative adsorption of oxygen at the surface defects of MoS{sub 2}, which lowers the conduction band edge locally and makes the MoS{sub 2} channel more n-type-like as compared to the as-fabricated devices.

  20. Texture effect of layered double hydroxides on chemisorption of Orange II

    Science.gov (United States)

    Géraud, Erwan; Bouhent, Mustapha; Derriche, Zoubir; Leroux, Fabrice; Prévot, Vanessa; Forano, Claude

    2007-05-01

    The chemisorption properties of hydrotalcite (HT) with novel macroporous properties have been investigated for azo dye, Orange II (O-II), and compared to coprecipitated HT and their calcined derivatives. Adsorption isotherms satisfactorily fit the Langmuir model. Adsorption capacities of the layered double hydroxides (LDH) macroporous structures are very high, particularly for the calcined materials (4.34 mmol/g) compared to standard HT (0.504 mmol/g), showing that accessibility to the LDH layer surface insures better sorptive properties. For both synthetic materials, the calcination/reconstruction process gives rise to highest concentrations of adsorbed O-II and a partial intercalation of O-II molecules in the structure as shown by the expansion of the basal spacing (d=2.4nm). Conversely, the uncalcined HT phases mainly display a surface exchange chemisorption process.

  1. Experimental investigation of the influence of Mo contained in stainless steel on Cs chemisorption behavior

    Science.gov (United States)

    Di Lemma, F. G.; Nakajima, K.; Yamashita, S.; Osaka, M.

    2017-02-01

    Chemisorption phenomena can affect fission products (FP) retention in a nuclear reactor vessel during a severe accident (SA). Detailed information on the FP chemisorbed deposits, especially for Cs, are important for a rational decommissioning of the reactor following a SA, as for the Fukushima Daiichi Power Station. Moreover the retention of Cs will influence the source term assessment and thus improved models for this phenomenon are needed in SA codes. This paper describes the influence on Cs chemisorption of molybdenum contained in stainless steel (SS) type 316. In our experiments it was observed that Cs-Mo deposits (CsFe(MoO4)3, Cs2MoO4) were formed together with CsFeSiO4, which is the predominant compound formed by chemisorption. The Cs-Mo deposits were found to revaporize from the SS sample at 1000 °C, and thus could contribute to the source term. On the other hand, CsFeSiO4 will be probably retained in the reactor during a SA due to its stability.

  2. Chemisorption and catalytic reactivity of cobalt and sulfur monolayers on ordered molybdenum surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Knight, C.C.

    1992-03-01

    Complex Co/Mo sulfide catalysts are modelled by the chemisorption of layers on Mo single crystal surfaces. Growth and structure of overlayers on flat, stepped and kinked surfaces were investigated. Growth of Co overlayers on clean and S covered Mo surfaces was studied using AES and CO chemisorption; results reveal that Co grows as a flat monolayer on clean Mo surfaces. Co multilayers then form 3-D islands. When Co is deposited on S covered surfaces, the S overlayer migrates to the top; this topmost overlayer reduces CO adsorption capacity. While growth mode of Co overlayers are similar on flat and stepped surfaces, the number and type of ordered Co and S structures on flat and stepped surfaces are different. In the case of Co, an ordered (3 {times} 1) structure is formed on Mo(910) and (28,4,1) surfaces; this structure does not develop on clean (100) surface. Only one of two possible (3 {times} 1) Co domains are formed on Mo(910) and Mo(28,4,1) surfaces. These domains have one side of (3 {times} 1) unit cell parallel to the step edges, suggesting that Co adsorbs at the step edges. The (3 {times} 1) structure does not form on Mo(911) surface, indicating that step orientation can restrict formation of ordered overlayers. For chemisorbed S, only a subset of ordered overlayers on flat (100) surface nucleate on (910) and (911) and (28,4,1) surfaces. Ordered S overlayers also form domains that maximize the number of sulfur-step atom bonds. The adsorption and ordering of S overlayers on stepped and kinked Mo surfaces lead to doubling of step height and terrace width. Thiophene hydrodesulfurization (HDS) reactions were performed over Mo crystal surfaces modified by chemisorption of S, Co, C, and S + Co. The stepped and kinked Mo surfaces have reactivities greater than low Miller index (100) surface. Chemisorption of adsorbates decreased the thiophene HDS reactivity. Deposition of Co on Mo single crystal surfaces did not lead to increased HDS activity.

  3. The Role of Gas-Silicate Chemisorption Reactions in Modifying Planetary Crusts and Surfaces

    Science.gov (United States)

    King, P. L.; Henley, R. W.; Wykes, J. L.; Renggli, C.; Troitzsch, U.; Clark, D.; O'Neill, H. S.

    2014-12-01

    Evidence for gas-solid reactions is found throughout the solar system: for example, sulfidation reactions in some meteorites and secondary phases coating lunar pyroclastic glasses. On Earth, the products of gas-solid reactions are documented in volcanic systems, metalliferous mineral deposits, impact craters, and on dust or meteorites after passage through the atmosphere - such reactions are also likely on the surfaces of Mars and Venus. To understand the chemical dynamics of such gas-solid reactions, we are undertaking systematic experiments and thermochemical modelling. Experiments were conducted in a vertical gas-mixing furnace at 600 - 800 °C and 1 bar, using SO2and a range of Ca-bearing materials: labradorite, feldspar glass and anorthosite (rock). In each case, anhydrite formed rapidly. In shorter experiments with labradorite, isolated anhydrite is observed surrounded by 'moats' of Ca-depleted silicate. In longer experiments, anhydrite is found as clusters of crystals that, in some cases, extend from the substrate forming precarious 'towers' (Figure). Anhydrite fills cracks in porous samples. We propose that the nucleation and rapid growth of anhydrite on the surface of these Ca-rich phases occurs by chemisorption of SO2(g) molecules with slightly negatively charged oxygen onto available near-surface calcium with slight positive charge. Anhydrite growth is sustained by SO2(g) chemisorption and Ca migration through the reacting silicate lattice, accelerated by increased bond lengths at high temperature. Significantly, the chemisorption reaction indicates that SO2 disproportionates to form both oxidized sulfur (as anhydrite) and a reduced sulfur species (e.g., an S* radical ion). On Earth, in the presence of H2O, the predominant reduced sulfur species is H2S, through an overall reaction: 3CaAl2Si2O8 + 4 SO2(g)+ H2O(g) → 3CaSO4 + 3Al2SiO5 + 3SiO2 + H2S(g)The reduced sulfur may react with gas phase Fe, Ni, Zn and Cu cluster compounds to form metal sulfides

  4. Ab initio investigation of the SCN{sup -} chemisorption of single-walled boron nitride nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Soltani, Alireza, E-mail: alireza.soltani46@yahoo.com [Young Researchers Club, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of); Ahmadian, Nasim [Department of Chemistry, Qaemshahr Branch, Islamic Azad University, Qaemshahr (Iran, Islamic Republic of); Kanani, Yaser [Department of Chemistry, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of); Dehnokhalaji, Aliakbar; Mighani, Hossein [Department of Chemistry, Faculty of Science, Golestan University, Gorgan (Iran, Islamic Republic of)

    2012-10-01

    Highlights: Black-Right-Pointing-Pointer We explored the adsorption behavior of the SCN{sup -} on outer surface BNNTs via DFT. Black-Right-Pointing-Pointer We reported the NBO charge distribution of SCN{sup -} on BNNTs surface. Black-Right-Pointing-Pointer Chemisorptions are observed for SCN{sup -} on Al- and Ga-doped BNNTs. Black-Right-Pointing-Pointer Notable changes are observed in the electronic properties of BNNT after doping. - Abstract: The thiocyanate anion (SCN{sup -}) adsorption capacity of zigzag single-walled boron nitride nanotubes (SWBNNTs) is studied via first-principles theory. Binding energy corresponding to the most stable configuration of SCN{sup -}/BNNT is found to be -148.42 kJ mol{sup -1}, which is typical for the chemisorptions. Our results indicate that both aluminum and gallium doping can significantly enhance the adsorption energy of SCN{sup -}/BNNTs complexes. Our electronic results reveal that there is a significant orbital hybridization between two species in adsorption process being an evidence of strong interaction. Thus, we arrive at the prediction that the BNNTs nanocage can be implemented as suitable sensor for practical applications.

  5. The dissociative chemisorption of CO2 on Ni(100): A quantum dynamics study

    Science.gov (United States)

    Farjamnia, Azar; Jackson, Bret

    2017-02-01

    A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of CO2 on Ni(100). The largest barrier to reaction corresponds to the formation of a bent anionic molecular precursor, bound to the surface by about 0.24 eV. The barrier to dissociation from this state is small. Our computed dissociative sticking probabilities on Ni(100) for molecules in the ground state are in very good agreement with available experimental data, reasonably reproducing the variation in reactivity with collision energy. Vibrational excitation of the incident CO2 can enhance reactivity, particularly for incident energies at or below threshold, and there is clear mode specific behavior. Both the vibrational enhancement and the increase in dissociative sticking with surface temperature are much weaker than that found in recent studies of methane and water dissociative chemisorption. The energetics for CO2 adsorption and dissociation on the stepped Ni(711) surface are found to be similar to that on Ni(100), except that the barrier to dissociation from the anionic precursor is even smaller on Ni(711). We predict that the dissociative sticking behavior is similar on the two surfaces.

  6. First principles analysis of hydrogen chemisorption on Pd-Re alloyed overlayers and alloyed surfaces

    DEFF Research Database (Denmark)

    Pallassana, Venkataraman; Neurock, Matthew; Hansen, Lars Bruno;

    2000-01-01

    Gradient corrected periodic density functional theory (DFT-GGA) slab calculations were used to examine the chemisorption of atomic hydrogen on various Pd-Re alloyed overlayers and uniformly alloyed surfaces. Adsorption was examined at 33% surface coverage, where atomic hydrogen preferred the three......-fold fcc sites. The binding energy of atomic hydrogen is observed to vary by as much as 0.7 eV due to Pd-Re interactions. The computed adsorption energies were found to be between -2.35 eV [for monolayer Pd-on-Re, i.e., Pd-ML/Re(0001)] and -3.05 eV [for Pd-33 Re-66/Pd(111)]. A d-band weighting scheme...... was developed to extend the Hammer-Norskov surface reactivity model [Surf. Sci. 343, 211 (1995)] to the analysis of bimetallic Pd-Re alloyed systems. The hydrogen chemisorption energies are correlated linearly to the surface d-band center, which is weighted appropriately by the d-band coupling matrix elements...

  7. The influence of chemisorption on the defect equilibrium of metal oxide thin films

    Science.gov (United States)

    Geistlinger, H.

    1996-08-01

    Using the exact charge density of intrinsic point defects of metal oxides (MOs), the phenomenological electron theory of chemisorption, developed by Volkenstein, is applied to acceptorlike and donorlike chemisorption on MO thin films for the whole ξ region (where ξ=D/LD, D is the film thickness, and LD is Debye length). The experimental temperature and oxygen partial pressure dependence of the averaged electron concentration (pO2,T)∝e-EA/kTpO2-m(T) for polycrystalline ZnO films are discussed on the bases of three different models: the Schottky-defect model, the Volkenstein model for electronic equilibrium, and the comprehensive model for complete equilibrium. It turns out that a Schottky-defect model that uses single-crystal-mass action constants will not yield the experimental high temperature limit (T=1000 K: EA=1.6 eV, m=0.26). This limit is obtained using a higher averaged concentration of oxygen vacancies for polycrystalline films (due to the presence of grain boundaries). The comparison between the electronic and complete equilibrium shows that the screening of the surface charge through mobile positively charged oxygen vacancies has a tremendous reducing effect of about 30% of the surface potential in the temperature range considered.

  8. Microcanonical unimolecular rate theory at surfaces. I. Dissociative chemisorption of methane on Pt(111)

    Science.gov (United States)

    Bukoski, A.; Blumling, D.; Harrison, I.

    2003-01-01

    A model of gas-surface reactivity is developed based on the ideas that (a) adsorbate chemistry is a local phenomenon, (b) the active system energy of an adsorbed molecule and a few immediately adjacent surface atoms suffices to fix microcanonical rate constants for surface kinetic processes such as desorption and dissociation, and (c) energy exchange between the local adsorbate-surface complexes and the surrounding substrate can be modeled via a Master equation to describe the system/heat reservoir coupling. The resulting microcanonical unimolecular rate theory (MURT) for analyzing and predicting both thermal equilibrium and nonequilibrium kinetics for surface reactions is applied to the dissociative chemisorption of methane on Pt(111). Energy exchange due to phonon-mediated energy transfer between the local adsorbate-surface complexes and the surface is explored and estimated to be insignificant for the reactive experimental conditions investigated here. Simulations of experimental molecular beam data indicate that the apparent threshold energy for CH4 dissociative chemisorption on Pt(111) is E0=0.61 eV (over a C-H stretch reaction coordinate), the local adsorbate-surface complex includes three surface oscillators, and the pooled energy from 16 active degrees of freedom is available to help surmount the dissociation barrier. For nonequilibrium molecular beam experiments, predictions are made for the initial methane dissociative sticking coefficient as a function of isotope, normal translational energy, molecular beam nozzle temperature, and surface temperature. MURT analysis of the thermal programmed desorption of CH4 physisorbed on Pt(111) finds the physisorption well depth is 0.16 eV. Thermal equilibrium dissociative sticking coefficients for methane on Pt(111) are predicted for the temperature range from 250-2000 K. Tolman relations for the activation energy under thermal equilibrium conditions and for a variety of "effective activation energies" under

  9. DFT-GGA errors in NO chemisorption energies on (111) transition metal surfaces: Possible origins and correction schemes

    CERN Document Server

    Huang, Xu

    2013-01-01

    Here we investigate whether well-known DFT-GGA errors in predicting the chemisorption energy ($E_{\\rm chem}$) of CO on transition metal surfaces manifest in analogous NO chemisorption systems. To verify the occurrence of DFT-GGA overestimation of the back-donation mechanism in NO Chemisorption, we use electronic structure analysis to show that the partially filled molecular NO 2$\\pi^{*}$ orbital rehybridizes with the transition metal $d$-band to form new bonding and anti-bonding states. We relate the back-donation charge transfer associated with chemisorption to the promotion of an electron from the 5$\\sigma$ orbital to the 2$\\pi^{*}$ orbital in the gas-phase NO G$^{2}\\Sigma^{-}\\leftarrow \\rm{X}^{2}\\Pi$ excitation. We establish linear relationships between $E_{\\rm chem}$ and $\\Delta E_{\\rm G\\leftarrow X}$ and go on to formulate an $E_{\\rm chem}$ correction scheme in the style of Mason {\\it et al.}, {[Physical Review B {\\bf 69}, 161401(R)]}. We apply the NO $E_{\\rm chem}$ correction method to the (111) surface...

  10. DFT study of the coverage-dependent chemisorption of molecular H2 on neutral cobalt dimers

    Science.gov (United States)

    Zeinalipour-Yazdi, Constantinos D.

    2017-02-01

    We have studied the coverage-dependent chemisorption of H2 on neutral cobalt dimers and found at θ magnetic moment Δμ = 4.9 μB and a linear weakening of the metal-metal bond strength, given by calculated oscillator frequencies. An approximate equation is derived that can be implemented in kinetic models to take account of the coverage-dependent decrease of the adsorption energy of H2 on cobalt clusters. We show that sub-nanometer cobalt clusters when exposed to H2 have strong coverage-dependent properties useful for the development of very sensitive H2-trace gas sensors in the sub-ppm range.

  11. Communication: Chemisorption of muonium on gold nanoparticles: A sensitive new probe of surface magnetism and reactivity

    Science.gov (United States)

    Dehn, M. H.; Arseneau, D. J.; Böni, P.; Bridges, M. D.; Buck, T.; Cortie, D. L.; Fleming, D. G.; Kelly, J. A.; MacFarlane, W. A.; MacLachlan, M. J.; McFadden, R. M. L.; Morris, G. D.; Wang, P.-X.; Xiao, J.; Zamarion, V. M.; Kiefl, R. F.

    2016-11-01

    Chemisorption of muonium onto the surface of gold nanoparticles has been observed. Muonium (μ+e- ), a light hydrogen-like atom, reacts chemically with uncapped 7 nm gold nanoparticles embedded in mesoporous silica (SBA-15) with a strong temperature-dependent rate. The addition rate is fast enough to allow coherent spin transfer into a diamagnetic muon state on the nanoparticle surface. The muon is well established as a sensitive probe of static or slowly fluctuating magnetic fields in bulk matter. These results represent the first muon spin rotation signal on a nanoparticle surface or any metallic surface. Only weak magnetic effects are seen on the surface of these Au nanoparticles consistent with Pauli paramagnetism.

  12. Chemisorption of NO on Pt-decorated graphene as modified nanostructure media: A first principles study

    Science.gov (United States)

    Rad, Ali Shokuhi; Abedini, Ehsan

    2016-01-01

    We used density functional theory calculations (DFT) to search the potential of pristine as well as Pt-decorated graphene sheets as adsorbent/gas sensors for NO by considering the electronic properties of NO on these two surfaces. We found much higher adsorption energy, higher charge transfer, lower connecting distance, and higher orbital hybridizing of NO gas molecule on Pt-decorated graphene than pristine graphene. We used orbital analysis including density of states as well as frontier molecular orbital study for NO-surface systems because of more understanding of the kind of interaction. Our results reveal physisorption of NO on pristine graphene with adsorption energy of -24 kJ mol-1while in contrast much higher adsorption energy of -199 kJ mol-1 is achieved upon adsorption of NO on Pt-decorated graphene which is in the range of chemisorption.

  13. Study on Chemisorption and Desorption of Hydrogen and Nitrogen on Ru-based Ammonia Synthesis Catalyst

    Institute of Scientific and Technical Information of China (English)

    祝一锋; 李小年

    2003-01-01

    The effects of promoters K,Ba,Sm,on the chemisorption and desorption of hydrogen and nitrogen,dispersion of metallic Ru and catalytic activity of active carbon(AC) supported ruthenium catalyst for ammonia synthesis have been studied by means of pulse chromatography,temperature-programmed desorption,and activity test,Promoters K,Ba and Sm increased the activity of Ru/AC catalysts for ammonia synthesis significantly,and particularly,potassium exhibited the best promotion on the activity because of the strong electronic donation to metallic Ru.Much higher activity can be obtained for Ru/AC catalyst with binary or triple promoters.The activity of Ru/AC catalyst is dependent on the adsorption of hydrogen and nitrogen.The high activity of catalyst could be ascribed to strong dissociation of nitrogen on the catalyst surface.Strong adsorption of hydrogen would inhibit the adsorption of nitrogen,resulted in decrease of the catalytic activity.Ru/AC catalyst promoted by Sm2O3 shows the best dispersion of metallic Ru,since the partly reduced SmO2 on the surface modifies the morphology of active sites and favors the dispersion of metallic Ru.The activity of Ru/AC catalysts is in accordance to the corresponding amount of nitrogen chemisorption and the desorption activation enery of nitrogen.The desorption activation energy for nitrogen decreases in the order of Ru>Ru-Ba>Ru-Sm>Ru-Bs-Sm>Ru-K>Ru-K-Bm>Ru-K-Ba>Ru-K-Ba-Sm,just opposite to the order or catalytic activity,suggesting that the ammonia synthesis over Ru-based catalyst is controlled by the step of dissociation of nitrogen.

  14. Effect of van der Waals interactions on the chemisorption and physisorption of phenol and phenoxy on metal surfaces

    Science.gov (United States)

    Peköz, Rengin; Donadio, Davide

    2016-09-01

    The adsorption of phenol and phenoxy on the (111) surface of Au and Pt has been investigated by density functional theory calculations with the conventional PBE functional and three different non-local van der Waals (vdW) exchange and correlation functionals. It is found that both phenol and phenoxy on Au(111) are physisorbed. In contrast, phenol on Pt(111) presents an adsorption energy profile with a stable chemisorption state and a weakly metastable physisorbed precursor. While the use of vdW functionals is essential to determine the correct binding energy of both chemisorption and physisorption states, the relative stability and existence of an energy barrier between them depend on the semi-local approximations in the functionals. The first dissociation mechanism of phenol, yielding phenoxy and atomic hydrogen, has been also investigated, and the reaction and activation energies of the resulting phenoxy on the flat surfaces of Au and Pt were discussed.

  15. Relaxation of the chemical bond skin chemisorption size matter ZTP mechanics H2O myths

    CERN Document Server

    Sun, Chang Q

    2014-01-01

    The aim of this book is to explore the detectable properties of a material to the parameters of bond and non-bond involved and to clarify the interdependence of various properties. This book is composed of four parts; Part I deals with the formation and relaxation dynamics of bond and non-bond during chemisorptions with uncovering of the correlation among the chemical bond, energy band, and surface potential barrier (3B) during reactions; Part II is focused on the relaxation of bonds between atoms with fewer neighbors than the ideal in bulk with unraveling of the bond order-length-strength (BOLS) correlation mechanism, which clarifies the nature difference between nanostructures and bulk of the same substance; Part III deals with the relaxation dynamics of bond under heating and compressing with revealing of rules on the temperature-resolved elastic and plastic properties of low-dimensional materials; Part IV is focused on the asymmetric relaxation dynamics of the hydrogen bond (O:H-O) and the anomalous behav...

  16. Cooperative Chemisorption-Induced Physisorption of CO2 Molecules by Metal-Organic Chains.

    Science.gov (United States)

    Feng, Min; Petek, Hrvoje; Shi, Yongliang; Sun, Hao; Zhao, Jin; Calaza, Florencia; Sterrer, Martin; Freund, Hans-Joachim

    2015-12-22

    Effective CO2 capture and reduction can be achieved through a molecular scale understanding of interaction of CO2 molecules with chemically active sites and the cooperative effects they induce in functional materials. Self-assembled arrays of parallel chains composed of Au adatoms connected by 1,4-phenylene diisocyanide (PDI) linkers decorating Au surfaces exhibit self-catalyzed CO2 capture leading to large scale surface restructuring at 77 K (ACS Nano 2014, 8, 8644-8652). We explore the cooperative interactions among CO2 molecules, Au-PDI chains and Au substrates that are responsible for the self-catalyzed capture by low temperature scanning tunneling microscopy (LT-STM), X-ray photoelectron spectroscopy (XPS), infrared reflection absorption spectroscopy (IRAS), temperature-programmed desorption (TPD), and dispersion corrected density functional theory (DFT). Decorating Au surfaces with Au-PDI chains gives the interfacial metal-organic polymer characteristics of both a homogeneous and heterogeneous catalyst. Au-PDI chains activate the normally inert Au surfaces by promoting CO2 chemisorption at the Au adatom sites even at surface supported Au-PDI chains provide a platform for investigating the physical and chemical interactions involved in CO2 capture and reduction.

  17. Electrophilic surface sites as precondition for the chemisorption of pyrrole on GaAs(001) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Bruhn, Thomas [Institut für Festkörperphysik, Technische Universität Berlin, Hardenbergstr.36, D-10623 Berlin (Germany); Leibniz-Institut für Analytische Wissenschaften - ISAS - e.V., Albert-Einstein-Str.9, 12489 Berlin (Germany); Fimland, Bjørn-Ove [Department of Electronics and Telecommunications, Norwegian University of Science and Technology, NO-7491 Trondheim (Norway); Vogt, Patrick, E-mail: patrick.vogt@tu-berlin.de [Institut für Festkörperphysik, Technische Universität Berlin, Hardenbergstr.36, D-10623 Berlin (Germany)

    2015-03-14

    We report how the presence of electrophilic surface sites influences the adsorption mechanism of pyrrole on GaAs(001) surfaces. For this purpose, we have investigated the adsorption behavior of pyrrole on different GaAs(001) reconstructions with different stoichiometries and thus different surface chemistries. The interfaces were characterized by x-ray photoelectron spectroscopy, scanning tunneling microscopy, and by reflectance anisotropy spectroscopy in a spectral range between 1.5 and 5 eV. On the As-rich c(4 × 4) reconstruction that exhibits only nucleophilic surface sites, pyrrole was found to physisorb on the surface without any significant modification of the structural and electronic properties of the surface. On the Ga-rich GaAs(001)-(4 × 2)/(6 × 6) reconstructions which exhibit nucleophilic as well as electrophilic surface sites, pyrrole was found to form stable covalent bonds mainly to the electrophilic (charge deficient) Ga atoms of the surface. These results clearly demonstrate that the existence of electrophilic surface sites is a crucial precondition for the chemisorption of pyrrole on GaAs(001) surfaces.

  18. Calorimetry, activity, and micro-FTIR analysis of CO chemisorption, titration, and oxidation on supported Pt

    Science.gov (United States)

    Sermon, Paul A.; Self, Valerie A.; Vong, Mariana S. W.; Wurie, Alpha T.

    1990-01-01

    The value of in situ analysis on CO chemisorption, titration and oxidation over supported Pt catalysts using calorimetry, catalytic and micro-FTIR methods is illustrated using silica- and titania-supported samples. Isothermal CO-O and O2-CO titrations have not been widely used on metal surfaces and may be complicated if some oxide supports are reduced by CO titrant. However, they can illuminate the kinetics of CO oxidation on metal/oxide catalysts since during such titrations all O and CO coverages are scanned as a function of time. There are clear advantages in following the rates of the catalyzed CO oxidation via calorimetry and gc-ms simultaneously. At lower temperatures the evidence they provide is complementary. CO oxidation and its catalysis of CO oxidation have been extensively studied with hysteresis and oscillations apparent, and the present results suggest the benefits of a combined approach. Silica support porosity may be important in defining activity-temperature hysteresis. FTIR microspectroscopy reveals the chemical heterogeneity of the catalytic surfaces used; it is interesting that the evidence with regard to the dominant CO surface species and their reactivities with regard to surface oxygen for present oxide-supported Pt are different from those seen on graphite-supported Pt.

  19. Sequential oxygen chemisorption on Fe13 clusters: from first-principles to practical insights

    Science.gov (United States)

    Mejía-López, Ana; Mazo-Zuluaga, Johan; Mejía-López, José

    2016-12-01

    With the advent of more precise technologies allowing manipulation of matter at nanoscopic scales and novel characterization techniques, a growing field of research is focused on magnetic materials of technical interest—such as Fe clusters—and their related physical-chemical processes. In this study, we present the results of the sequential oxidation process of the Fe13 cluster by considering the physical-chemistry properties of the ground state configurations of Fe13O n (n=0-19 ) clusters. We develop an exhaustive ab initio study into the GGA approach and explore the effect of the chemisorption of oxygen on the structural properties, the chemical stability, the magnetization and the magnetic anisotropy energy (MAE) of the systems. Our results clearly indicate that: (i) one of the studied clusters, Fe13O17, presents the biggest electrophilicity index and the lowest chemical hardness, being the most reactive among the systems studied; (ii) the Fe13O10 exhibits a much more enhanced magnetization than other related clusters intended for health and technology applications (Sun et al 2007 J. Phys. Chem. C 111 4159-63), so that it might be a better candidate for those purposes; and (iii) the MAE presents a complex and intriguing landscape that encourages thinking about the plausible control of magnetic states focused on technical applications.

  20. Surface Complexation at the TiO(2) (anatase)/Aqueous Solution Interface: Chemisorption of Catechol.

    Science.gov (United States)

    Rodríguez; Blesa; Regazzoni

    1996-01-15

    Catechol adsorbs at the TiO(2) (anatase)/aqueous solution interface forming inner-sphere surface complexes. The UV-visible differential reflectance spectrum of surface titanium-catecholate complexes presents a band centered at 420 nm which corresponds to the ligand to metal charge transfer transition within the surface complexes. At pH values below pK(a1), the surface excess of catechol is almost insensitive toward pH and presents a Langmuirian dependence with the concentration of uncomplexed catechol. The ratio Gamma(max):N(S) (N(S) being the measured density of available OH surface groups) indicates a prevailing 1 to 2 ligand exchange adsorption stoichiometry. In the range pH >/= pK(a1), the catechol surface excess decreases markedly with increasing pH. Formation of 1 to 1 surface complexes produces an excess of negative surface charge that is revealed by the shift of the iep to lower pH values. The reported data, which are supplemented with information on the charging behavior of TiO(2) suspended in indifferent electrolyte solutions, are interpreted in terms of the multi-site surface complexation model. In this model, two types of surface OH groups are considered: identical withTiOH(1/3-) and identical withOH(1/3+). Although both surface groups undergo protonation-deprotonation reactions, only identical withTiOH(1/3-) are prone to chemisorption.

  1. Single-crystal adsorption calorimetry and density functional theory of CO chemisorption on fcc Co{110}.

    Science.gov (United States)

    Liao, Kristine; Fiorin, Vittorio; Gunn, David S D; Jenkins, Stephen J; King, David A

    2013-03-21

    Using single-crystal adsorption calorimetry (SCAC) and density functional theory (DFT), the interaction of carbon monoxide on fcc Co{110} is reported for the first time. The results indicate that adsorption is consistent with molecular chemisorption at all coverages. The initial heat of adsorption of 140 kJ mol(-1) is found in the range of heat values calorimetrically measured on other ferromagnetic metal surfaces, such as nickel and iron. DFT adsorption energies are in good agreement with the experimental results, and comparison between SCAC and DFT for CO on other ferromagnetic surfaces is made. The calculated dissociation barrier of 2.03 eV implies that dissociation at 300 K is unlikely even at the lowest coverage. At high coverages during the adsorption-desorption steady state regime, a pre-exponential factor for CO desorption of 1.2 × 10(17) s(-1) is found, implying a localised molecular adsorbed state prior to desorption in contrast to what we found with Ni surfaces. This result highlights the importance of the choice of the pre-exponential factor in evaluating the activation energy for desorption.

  2. Internal stress induced natural self-chemisorption of ZnO nanostructured films

    Science.gov (United States)

    Chi, Po-Wei; Su, Chih-Wei; Wei, Da-Hua

    2017-01-01

    The energetic particles bombardment can produce large internal stress in the zinc oxide (ZnO) thin film, and it can be used to intentionally modify the surface characteristics of ZnO films. In this article, we observed that the internal stress increased from −1.62 GPa to −0.33 GPa, and the naturally wettability of the textured ZnO nanostructured films changed from hydrophobicity to hydrophilicity. According to analysis of surface chemical states, the naturally controllable wetting behavior can be attributed to hydrocarbon adsorbates on the nanostructured film surface, which is caused by tunable internal stress. On the other hand, the interfacial water molecules near the surface of ZnO nanostructured films have been identified as hydrophobic hydrogen structure by Fourier transform infrared/attenuated total reflection. Moreover, a remarkable near-band-edge emission peak shifting also can be observed in PL spectra due to the transition of internal stress state. Furthermore, our present ZnO nanostructured films also exhibited excellent transparency over 80% with a wise surface wetting switched from hydrophobic to hydrophilic states after exposing in ultraviolet (UV) surroundings. Our work demonstrated that the internal stress of the thin film not only induced natural wettability transition of ZnO nanostructured films, but also in turn affected the surface properties such as surface chemisorption. PMID:28233827

  3. Measurement of Total Free Iron in Soils by H2S Chemisorption and Comparison with the Citrate Bicarbonate Dithionite Method

    Directory of Open Access Journals (Sweden)

    Shui-Sheng Fan

    2016-01-01

    Full Text Available Free iron is one of the major analytical items for soil basic properties. It is also an important indicator for understanding the genesis of soil, soil classification, and soil distribution behavior. In this study, an alternative analytical method (chemisorption based on thermodynamic knowledge was proposed for measurement of total free iron oxides in soils. Several representative soil samples belonging to alfisols, ultisols, inceptisols, and entisols were collected from Taiwan and tested by the chemisorption, and the estimated total free iron oxides were compared with those measured from the traditional citrate bicarbonate dithionite (CBD method. Experimental results showed that the optimal operating temperature was found to be at 773 K and the carbon monoxide (CO is the best gaseous reagent to promote the formation of FeS. The estimated total free iron oxides for soil samples determined from the chemisorption in the presence of CO were very close to those from the CBD technique. The result of regression indicates that the estimated total free iron is strongly correlated with the CBD-Fe content (R2=0.999 in the presence of CO.

  4. A Computational NMR Study for Chemisorption of Oxygen-doped on the Surface of Single-Walled Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    A. Ghasemi

    2012-08-01

    Full Text Available In this study computational Nuclear Magnetic Resonance (NMR study and chemisorptions are performed to investigate the electronic structure properties of arm-chair (4, 4 and zig-zag (5, 0 Single-Wall Carbon Nanotubes (SWCNTs. First-principles of Density Function Theory (DFT have applied in calculations on properties of molecular oxygen-doped (O-doped SWCNTs. The results show dramatic differences between two types, (5, 0 zigzag and (4, 4 arm chair, of carbon nano-tubes. Structural models are optimized and chemisorption energies are obtained to investigate the Nuclear Magnetic Resonance (NMR parameters for Odoped (5, 0 zigzag and (4, 4 armchair single-walled carbon nanotubes based on calculations using DFT. The chemical-shielding (σιι tensors were converted to isotropic chemical-shielding (iso and anisotropic chemicalshielding (Δσ and asymmetric (μj parameters of 17O and 13C atom for the optimized structures. We found that introduction oxygen does significantly change the structure of the SWCNT and thus the bonding mode of the structure is remarkably altered. Comparing the results of the zigzag and armchair models and calculated chemical shielding, electric filed gradient tensors at the sites of carbon reveal that O2 chemisorption has a dramatic effect on the electronic structure of SWCNTs.

  5. Measurement of Total Free Iron in Soils by H2S Chemisorption and Comparison with the Citrate Bicarbonate Dithionite Method

    Science.gov (United States)

    Fan, Shui-Sheng; Chang, Feng-Hsiang

    2016-01-01

    Free iron is one of the major analytical items for soil basic properties. It is also an important indicator for understanding the genesis of soil, soil classification, and soil distribution behavior. In this study, an alternative analytical method (chemisorption) based on thermodynamic knowledge was proposed for measurement of total free iron oxides in soils. Several representative soil samples belonging to alfisols, ultisols, inceptisols, and entisols were collected from Taiwan and tested by the chemisorption, and the estimated total free iron oxides were compared with those measured from the traditional citrate bicarbonate dithionite (CBD) method. Experimental results showed that the optimal operating temperature was found to be at 773 K and the carbon monoxide (CO) is the best gaseous reagent to promote the formation of FeS. The estimated total free iron oxides for soil samples determined from the chemisorption in the presence of CO were very close to those from the CBD technique. The result of regression indicates that the estimated total free iron is strongly correlated with the CBD-Fe content (R2 = 0.999) in the presence of CO. PMID:28116218

  6. Reversible and Selective O2 Chemisorption in a Porous Metal-Organic Host Material

    Energy Technology Data Exchange (ETDEWEB)

    Southon, Peter D; Price, David J; Nielsen, Pia K; McKenzie, Christine J; Kepert, Cameron J [Sydney; (USD-Netherlands)

    2011-11-17

    The metal-organic host material [{CoIII2(bpbp)(O2)}2bdc](PF6)4 (1 ∙ 2O2; bpbp- = 2,6-bis(N,N-bis(2-pyridylmethyl)aminomethyl)-4-tert-butylphenolato; bdc2- = 1,4-benzenedicarboxylato) displays reversible chemisorptive desorption and resorption of dioxygen through conversion to the deoxygenated Co(II) form [{CoII2(bpbp)}2bdc](PF6)4 (1). Single crystal X-ray diffraction analysis indicates that the host lattice 1 ∙ 2O2, achieved through desorption of included water guests from the as-synthesized phase 1 ∙ 2O2 ∙ 3H2O, consists of an ionic lattice containing discrete tetranuclear complexes, between which lie void regions that allow the migration of dioxygen and other guests. Powder X-ray diffraction analyses indicate that the host material retains crystallinity through the dioxygen desorption/chemisorption processes. Dioxygen chemisorption measurements on 1 show near-stoichiometric uptake of dioxygen at 5 mbar and 25 °C, and this capacity is largely retained at temperatures above 100 °C. Gas adsorption isotherms of major atmospheric gases on both 1 and 1 ∙ 2O2 indicate the potential suitability of this material for air separation, with a O2/N2 selectivity factor of 38 at 1 atm. Comparison of oxygen binding in solution and in the solid state indicates a dramatic increase in binding affinity to the complex when it is incorporated in a porous solid.

  7. Quantum dynamics of dissociative chemisorption of CH(4) on Ni(111): Influence of the bending vibration.

    Science.gov (United States)

    Krishnamohan, G P; Olsen, R A; Kroes, G-J; Gatti, F; Woittequand, S

    2010-10-14

    Two-dimensional, three-dimensional, and four-dimensional quantum dynamic calculations are performed on the dissociative chemisorption of CH(4) on Ni(111) using the multiconfiguration time-dependent Hartree (MCTDH) method. The potential energy surface used for these calculations is 15-dimensional (15D) and was obtained with density functional theory for points which are concentrated in the region that is dynamically relevant to reaction. Many reduced dimensionality calculations were already performed on this system, but the molecule was generally treated as pseudodiatomic. The main improvement of our model is that we try to describe CH(4) as a polyatomic molecule by including a degree of freedom describing a bending vibration in our three-dimensional and four-dimensional models. Using a polyspherical coordinate system, a general expression for the 15D kinetic energy operator is derived, which discards all the singularities in the operator and includes rotational and Coriolis coupling. We use seven rigid constraints to fix the CH(3) umbrella of the molecule to its gas phase equilibrium geometry and to derive two-dimensional, three-dimensional, and four-dimensional Hamiltonians, which were used in the MCTDH method. Only four degrees of freedom evolve strongly along the 15D minimum energy path: the distance of the center of mass of the molecule to the surface, the dissociative C[Single Bond]H bond distance, the polar orientation of the molecule, and the bending angle between the dissociative C[Single Bond]H bond and the umbrella. A selection of these coordinates is included in each of our models. The polar rotation is found to be important in determining the mode selective behavior of the reaction. Furthermore, our calculations are in good agreement with the finding of Xiang et al. [J. Chem. Phys. 117, 7698 (2002)] in their reduced dimensional calculation that the helicopter motion of the umbrella symmetry axis is less efficient than its cartwheel motion for promoting

  8. Theoretical studies on chemisorption of oxygen on β-Mo2C catalyst and its surface oxidation

    Science.gov (United States)

    Shi, Xue-Rong; Wang, Sheng-Guang; Hu, Jia; Qin, Zhangfeng; Wang, Jianguo

    2012-08-01

    Oxygen chemisorption on β-Mo2C surface and its oxidation have been investigated by using the density functional theory with the periodic models. Two surfaces of (011) and (101) were chosen to perform the calculations and the most stable surface structures together with the energetics of oxygen stepwise adsorption were identified. Thermodynamic effect of temperature and reactant pressure on the chemisorption and surface oxidation was investigated. The results suggest that the (101) surface is more active than the (011) surface towards the oxygen adsorption. The (101) surface can be fully oxidized by O2 at PO2/P0 of 10- 21-104 and temperature of 100-700 K. For the (011) surface with O2 as the oxidant, the most stable structure is that with 1/2 ML or 7/8 ML oxygen coverage, depending on the temperature and PO2/P0 value. The increase of gaseous oxidant pressure or decrease of temperature can enhance the oxidation of β-Mo2C surface and lead a more negative reaction Gibbs free energy. High temperature and low oxidant pressure may hinder the surface oxidation process.

  9. Chemisorption of estrone in nylon microfiltration membranes: Adsorption mechanism and potential use for estrone removal from water.

    Science.gov (United States)

    Han, Jie; Qiu, Wei; Hu, Jiangyong; Gao, Wei

    2012-03-01

    Estrone is a representative steroid estrogen contaminant that has been detected in effluents from sewage treatment facilities, as well as in surface and ground waters. Our study shows that estrone can be readily removed from water via a unique chemisorption mechanism using nylon microfiltration membranes. Experiments on a laboratory in-line filtration system showed instant removal of estrone from 200 μg/l aqueous solutions by 0.45-μm nylon membranes (ca. 35 L per m(2) membrane). Comparisons with 0.45-μm PVDF, PTFE and glass microfiber membranes suggested that the significant estrone adsorption in nylon membrane should be predominately driven by a different mechanism rather than common physical adsorption. Fourier transform infrared spectroscopy study on nylon membranes and a model compound, N-methylacetamide, showed that the significant adsorption originated from the hydrogen bonding between terminal -OH groups on estrone molecules and nucleophile -C=O groups in amide groups of nylon 6,6. The saturated nylon membrane showed very low leachability in ambient water, while it could be effectively regenerated in alkaline or ethanol solutions. Preliminary reusability study showed that the membrane maintained a consistent adsorption capacity for estrone during ten cycles of reuse. The chemisorption-based polymeric adsorption may provide a new alternative approach for removing estrone and potentially other trace organic contaminants from water.

  10. Molecular simulation of CO chemisorption on Co(0001) in presence of supercritical fluid solvent: A potential of mean force study

    Science.gov (United States)

    Asiaee, Alireza; Benjamin, Kenneth M.

    2016-08-01

    For several decades, heterogeneous catalytic processes have been improved through utilizing supercritical fluids (SCFs) as solvents. While numerous experimental studies have been established across a range of chemistries, such as oxidation, pyrolysis, amination, and Fischer-Tropsch synthesis, still there is little fundamental, molecular-level information regarding the role of the SCF on elementary heterogeneous catalytic steps. In this study, the influence of hexane solvent on the adsorption of carbon monoxide on Co(0001), as the first step in the reaction mechanism of many processes involving syngas conversion, is probed. Simulations are performed at various bulk hexane densities, ranging from ideal gas conditions (no SCF hexane) to various near- and super-critical hexane densities. For this purpose, both density functional theory and molecular dynamics simulations are employed to determine the adsorption energy and free energy change during CO chemisorption. Potential of mean force calculations, utilizing umbrella sampling and the weighted histogram analysis method, provide the first commentary on SCF solvent effects on the energetic aspects of the chemisorption process. Simulation results indicate an enhanced stability of CO adsorption on the catalyst surface in the presence of supercritical hexane within the reduced pressure range of 1.0-1.5 at a constant temperature of 523 K. Furthermore, it is shown that the maximum stability of CO in the adsorbed state as a function of supercritical hexane density at 523 K nearly coincides with the maximum isothermal compressibility of bulk hexane at this temperature.

  11. First-principles quantum dynamical theory for the dissociative chemisorption of H2O on rigid Cu(111).

    Science.gov (United States)

    Zhang, Zhaojun; Liu, Tianhui; Fu, Bina; Yang, Xueming; Zhang, Dong H

    2016-06-10

    Despite significant progress made in the past decades, it remains extremely challenging to investigate the dissociative chemisorption dynamics of molecular species on surfaces at a full-dimensional quantum mechanical level, in particular for polyatomic-surface reactions. Here we report, to the best of our knowledge, the first full-dimensional quantum dynamics study for the dissociative chemisorption of H2O on rigid Cu(111) with all the nine molecular degrees of freedom fully coupled, based on an accurate full-dimensional potential energy surface. The full-dimensional quantum mechanical reactivity provides the dynamics features with the highest accuracy, revealing that the excitations in vibrational modes of H2O are more efficacious than increasing the translational energy in promoting the reaction. The enhancement of the excitation in asymmetric stretch is the largest, but that of symmetric stretch becomes comparable at very low energies. The full-dimensional characterization also allows the investigation of the validity of previous reduced-dimensional and approximate dynamical models.

  12. Theoretical studies on chemisorption of oxygen on β-Mo2C catalyst and its surface oxidation

    DEFF Research Database (Denmark)

    Shi, Xue-Rong; Wang, Shengguang; Hu, Jia

    2012-01-01

    Oxygen chemisorption on β-Mo2C surface and its oxidation have been investigated by using the density functional theory with the periodic models. Two surfaces of (011) and (101) were chosen to perform the calculations and the most stable surface structures together with the energetics of oxygen...... stepwise adsorption were identified. Thermodynamic effect of temperature and reactant pressure on the chemisorption and surface oxidation was investigated. The results suggest that the (101) surface is more active than the (011) surface towards the oxygen adsorption. The (101) surface can be fully oxidized...... by O2 at PO2/P0 of 10−21–104 and temperature of 100–700K. For the (011) surface with O2 as the oxidant, the most stable structure is that with 1/2ML or 7/8ML oxygen coverage, depending on the temperature and PO2/P0 value. The increase of gaseous oxidant pressure or decrease of temperature can enhance...

  13. Chemisorption of oxygen and subsequent reactions on low index surfaces of β-Mo2C

    DEFF Research Database (Denmark)

    Shi, Xue Rong; Wang, Shengguang; Wang, Jianguo

    2016-01-01

    Oxygen chemisorption on β-Mo2C surfaces, the subsequent CO/CO2 desorption and oxygen diffusion to the carbon vacancy have been investigated by density-functional theory. The most stable structures together with the energetics of oxygen stepwise adsorption, CO/CO2 desorption and oxygen diffusion...... to the carbon vacancy were identified. We examined the effect of oxygen coverage on the morphology of β-Mo2C by plotting the equilibrium crystal shape. Thermodynamic effect of temperature and reactant or product pressure on the CO/CO2 desorption were investigated. The CO/CO2 desorption is more favorable...... at the saturated oxygen coverage than the low oxygen coverage thermodynamically. The subsequent oxygen diffusion to the carbon vacancy after CO/CO2 desorption may happen depending on the surfaces and oxygen coverage....

  14. Six-dimensional potential energy surface of the dissociative chemisorption of HCl on Au(111) using neural networks

    Institute of Scientific and Technical Information of China (English)

    LIU TianHui; FU BiNa; ZHANG Dong H

    2014-01-01

    We constructed a six-dimensional potential energy surface(PES)for the dissociative chemisorption of HCl on Au(111)using the neural networks method based on roughly 70000 energies obtained from extensive density functional theory(DFT)calculations.The resulting PES is accurate and smooth,based on the small fitting errors and good agreement between the fitted PES and the direct DFT calculations.Time-dependent wave packet calculations show that the potential energy surface is very well converged with respect to the number of DFT data points,as well as to the fitting process.The dissociation probabilities of HCl initially in the ground rovibrational state from six-dimensional quantum dynamical calculations are quite diferent from the four-dimensional fixed-site calculations,indicating it is essential to perform full-dimensional quantum dynamical studies for the title molecule-surface interaction system.

  15. A First Principle Comparative Study on Chemisorption of H2 on C60, C80, and Sc3N@C80 in Gas Phase and Chemisorption of H2 on Solid Phase C60

    Directory of Open Access Journals (Sweden)

    Hongtao Wang

    2014-01-01

    Full Text Available The chemisorptions of H2 on fullerenes C60 and C80, endofullerene Sc3C@C80 and solid C60 were comparatively studied. A chain reaction mechanism for dissociative adsorption of H2 on solid C60 is proposed under high pressure. The breaking of H–H bond is concerted with the formation of two C–H bonds on two adjacent C60 in solid phase. The adsorption process is facilitated by the application of high pressure. The initial H2 adsorption on two adjacent C60 gives a much lower barrier 1.36 eV in comparison with the barrier of adsorption on a single C60 (about 3.0 eV. As the stereo conjugate aromaticity of C60 is destructed by the initial adsorption, some active sites are created. Hence the successive adsorption becomes easier with much low barriers (0.6 eV. In addition, further adsorption can create new active sites for the next adsorption. Thus, a chain reaction path is formed with the initial adsorption dominating the whole adsorption process.

  16. Selective chemisorption of graphene-like molecules on the Si(111) 7 x 7 surface: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Kiss, Janos; Gruhn, Thomas; Felser, Claudia [Institut fuer Anorganische Chemie und Analytische Chemie, Johannes Gutenberg-Universitaet, D-55099 Mainz (Germany)

    2011-07-01

    Graphene and porous graphene are very promising materials, which have been widely studied for electronic applications. Because of their improved properties, in the future it is expected, that graphene, porous graphene and graphene-like molecules will replace silicon. Despite its superior material properties, however, the field-effect transistors based on graphene or graphene nanoribbons build so far via top-down approaches have low on/off ratios. On the other hand, molecular nanotransistors build with precisely know atomic structures resembling graphene were synthesized only very recently. In order to pave the way towards the industrial fabrication of molecular nanotransistors, we have investigated the chemisorption of graphene-like molecules on the 7 x 7 reconstructed Si(111) surface via density functional theory (DFT) calculations. We found, that Si(111) is a very promising candidate to serve as substrate for the large-scale fabrication of coronene-based molecular transistors. Moreover, our calculations show, that various adsorbate molecules prefer specific binding sites on the Si(111) surface. By following the template of the Si(111) substrate, the molecules selectively adsorb and form a well defined two-dimensional grid with a 1 x 1 surface pattern.

  17. Theoretical analysis of hydrogen chemisorption on Pd(111), Re(0001) and PdML/Re(0001), ReML/Pd(111) pseudomorphic overlayers

    DEFF Research Database (Denmark)

    Pallassana, Venkataraman; Neurock, Matthew; Hansen, Lars Bruno;

    1999-01-01

    with the location of the d-band center of the bare metal surfaces, using a model developed by Hammer and N phi rskov. The DFT-computed adsorption energies were also analyzed on the basis of the density of states (DOS) at the Fermi level for the clean metal surfaces. The results indicate a clear correlation between...... the d-band center of the surface metal atoms and the hydrogen chemisorption energy. The further the d-band center is from the Fermi level, the weaker is the chemisorption bond of atomic hydrogen on the surface. Although the DOS at the Fermi level may be related to the location of the d-band, it does...... not appear to provide an independent parameter for assessing surface reactivity. The weak chemisorption of hydrogen on the Pd-ML/Re(0001) surface relates to substantial lowering of the d-band center of Pd, when it is pseudomorphically deposited as a monolayer on a Re substrate. [S0163-1829(99)00331-2]....

  18. Alloy formation and chemisorption at Zn/Pt(111) bimetallic surfaces using alkali ISS, XPD, and TPD.

    Science.gov (United States)

    Ho, Chih-Sung; Martono, Eddie; Banerjee, Santanu; Roszell, John; Vohs, John; Koel, Bruce E

    2013-11-21

    Alloy formation and chemisorption at bimetallic surfaces formed by vapor-depositing Zn on a Pt(111) single crystal were investigated primarily by using X-ray photoelectron diffraction (XPD), X-ray photoelectron spectroscopy (XPS), low-energy alkali ion scattering spectroscopy (ALISS), low electron energy diffraction (LEED), and temperature programmed desorption (TPD). A wide range of conditions were investigated to explore whether deposition and annealing of Zn films could produce well-defined, ordered alloy surfaces, similar to those encountered for Sn/Pt(111) surface alloys. These attempts were unsuccessful, although weak, diffuse (2 × 2) spots were observed under special conditions. The particular PtZn bimetallic alloy created by annealing one monolayer of Zn on Pt(111) at 600 K, which has a Zn composition in the surface layer of about 5 at. %, was investigated in detail by using XPD and ALISS. Only a diffuse (1 × 1) pattern was observed from this surface by LEED, suggesting that no long-range, ordered alloy structure was formed. Zn atoms were substitutionally incorporated into the Pt(111) crystal to form a near-surface alloy in which Zn atoms were found to reside primarily in the topmost and second layers. The alloyed Zn atoms in the topmost layer are coplanar with the Pt atoms in the surface layer, without any "buckling" of Zn, that is, displacement in the vertical direction. This result is expected because of the similar size of Pt and Zn, based on previous studies of bimetallic Pt alloys. Zn atoms desorb upon heating rather than diffusing deep into the bulk of the Pt crystal. Temperature programmed desorption (TPD) measurements show that both CO and NO have lower desorption energies on the PtZn alloy surface compared to that on the clean Pt(111) surface.

  19. Chemisorptive removal of carbon dioxide from process streams using a reactive bubble column with simultaneous production of usable materials

    Energy Technology Data Exchange (ETDEWEB)

    Petrov, P.; Ewert, G.; Roehm, H.J. [Department of Process and Environmental Engineering, Ruhr-University, Bochum (Germany)

    2006-09-15

    In the context of attempts to improve the protection of the environment, a novel process where the carbon dioxide reacts rapidly with almost 100 % conversion under mild conditions, is proposed. The chemisorptive process takes place in a slurry bubble column which operates with countercurrent flow, utilizing special solutions of primary long chain amines in a nonaqueous media. The product obtained is insoluble and separated by filtration. Because of its molecular structure, this product possesses tenside properties and can be used as an industrial additive. Typically the liquid phase consists of a mixture of hexadecylamine (C{sub 16}H{sub 33}NH{sub 2}) or dodecylamine (C{sub 12}H{sub 25}NH{sub 2}) in various concentrations with methanol or other alcohols as the solvent. Numerous parameters have been studied including different column heights, gas inlet compositions, gas flow rates and solvent type. Efficiencies of up to 99 % are achievable for CO{sub 2} absorption with methanol as the solvent. The second solvent examined, isopropanol, shows lower CO{sub 2} conversion rates. This can be attributed to its physical properties, mainly higher viscosity and hence, smaller mass transfer coefficient. In order to simulate real gas conditions, the influence of other sour gases, e.g., SO{sub 2} was also investigated experimentally. Because of coabsorption of the two gases, the CO{sub 2} efficiency was lower in this instance. In both solvents, the absorption efficiency with respect to SO{sub 2} is more than 99 % due to its high solubility and reactivity. A complex mathematical model has been developed and applied to describe the mass and enthalpy transport in the reactive bubble column. (Abstract Copyright [2006], Wiley Periodicals, Inc.)

  20. Ion photon-stimulated desorption as a tool to monitor the physisorption to chemisorption transition of benzene on Si(111) 7 x 7

    CERN Document Server

    Carbone, M; Casaletto, M P; Zanoni, R; Besnard-Ramage, M J; Comtet, G; Dujardin, G; Hellner, L

    2003-01-01

    We investigated the use of ion photodesorption as a tool to monitor the transition from the physisorbed to the chemisorbed state on a surface. The adsorption of benzene on Si(111) 7 x 7 in the temperature range 40-300 K is chosen as a prototype. The D sup + ion photodesorption yield was monitored as a function of temperature at various benzene exposures. Comparative measurements of the C 1s photoelectron yield in the same temperature range enable the physisorbed to chemisorbed state transition to be distinguished from that of the multilayer to the chemisorbed state. We find the onset at 110 K in the first case, and at 130-140 K in the second case. These results demonstrate that ion photodesorption is a potentially interesting method to identify physisorption to chemisorption transitions of adsorbed molecules on surfaces. (letter to the editor)

  1. Dissociative and molecular oxygen chemisorption channels on reduced rutile TiO2(110): A high-resolution STM study

    DEFF Research Database (Denmark)

    Lira, Estephania; Hansen, Jonas Ørbæk; Huo, Peipei;

    2010-01-01

    High-resolution scanning tunneling microscopy (STM) and temperature-programmed desorption (TPD) were used to study the interaction of O2 with reduced TiO2(110)–(1 × 1) crystals. STM is the technique of choice to unravel the relation between vacancy and non-vacancy assisted O2 dissociation channels...... interaction channels and the TPD data, a new comprehensive model of the O2 chemisorption on reduced TiO2(110) is proposed. The model explains the relations between the two dissociative and the molecular O2 interaction channels. The experimental data are interpreted by considering the available charge...... in the near-surface region of reduced TiO2(110) crystals, the kinetics of the two O2 dissociation channels as well as the kinetics of the diffusion and reaction of Ti interstitials....

  2. Coupled cluster and density functional theory calculations of atomic hydrogen chemisorption on pyrene and coronene as model systems for graphene hydrogenation.

    Science.gov (United States)

    Wang, Ying; Qian, Hu-Jun; Morokuma, Keiji; Irle, Stephan

    2012-07-05

    Ab initio coupled cluster and density functional theory studies of atomic hydrogen addition to the central region of pyrene and coronene as molecular models for graphene hydrogenation were performed. Fully relaxed potential energy curves (PECs) were computed at the spin-unrestricted B3LYP/cc-pVDZ level of theory for the atomic hydrogen attack of a center carbon atom (site A), the midpoint of a neighboring carbon bond (site B), and the center of a central hexagon (site C). Using the B3LYP/cc-pVDZ PEC geometries, we evaluated energies at the PBE density functional, as well as ab initio restricted open-shell ROMP2, ROCCSD, and ROCCSD(T) levels of theory, employing cc-pVDZ and cc-pVTZ basis sets, and performed a G2MS extrapolation to the ROCCSD(T)/cc-pVTZ level of theory. In agreement with earlier studies, we find that only site A attack leads to chemisorption. The G2MS entrance channel barrier heights, binding energies, and PEC profiles are found to agree well with a recent ab initio multireference wave function theory study (Bonfanti et al. J. Chem. Phys.2011, 135, 164701), indicating that single-reference open-shell methods including B3LYP are sufficient for the theoretical treatment of the interaction of graphene with a single hydrogen atom.

  3. Pentacene on Au(1 1 1), Ag(1 1 1) and Cu(1 1 1): From physisorption to chemisorption

    Science.gov (United States)

    Lu, Meng-Chao; Wang, Rong-Bin; Yang, Ao; Duhm, Steffen

    2016-03-01

    We measured the electronic and the molecular surface structure of pentacene deposited on the (1 1 1)-surfaces of coinage metals by means of ultraviolet photoelectron spectroscopy (UPS) and low-energy electron diffraction (LEED). Pentacene is almost flat-lying in monolayers on all three substrates and highly ordered on Au(1 1 1) and on Cu(1 1 1). On Ag(1 1 1), however, weak chemisorption leads to almost disordered monolayers, both, at room temperature and at 78 K. On Cu(1 1 1) pentacene is strongly chemisorbed and the lowest unoccupied molecular orbital becomes observable in UPS by a charge transfer from the substrate. On Ag(1 1 1) and Cu(1 1 1) multilayers adopt a tilted orientation and a high degree of crystallinity. On Au(1 1 1), most likely, also in multilayers the molecular short and long axes are parallel to the substrate, leading to a distinctively different electronic structure than on Ag(1 1 1) and Cu(1 1 1). Overall, it could be demonstrated that the substrate not only determines the geometric and electronic characteristics of molecular monolayer films but also plays a crucial role for multilayer film growth.

  4. Use of Hydrogen Chemisorption and Ethylene Hydrogenation as Predictors for Aqueous Phase Reforming of Lactose over Ni@Pt and Co@Pt Bimetallic Overlayer Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lai, Qinghua; Skoglund, Michael D.; Zhang, Chen; Morris, Allen R.; Holles, Joseph H.

    2016-10-20

    Overlayer Pt on Ni (Ni@Pt) or Co (Co@Pt) were synthesized and tested for H2 generation from APR of lactose. H2 chemisorption descriptor showed that Ni@Pt and Co@Pt overlayer catalysts had reduced H2 adsorption strength compared to a Pt only catalyst, which agree with computational predictions. The overlayer catalysts also demonstrated lower activity for ethylene hydrogenation than the Pt only catalyst, which likely resulted from decreased H2 binding strength decreasing the surface coverage of H2. XAS results showed that overlayer catalysts exhibited higher white line intensity than the Pt catalyst, which indicates a negative d-band shift for the Pt overlayer, further providing evidence for overlayer formation. Lactose APR studies showed that lactose can be used as feedstock to produce H2 and CO under desirable reaction conditions. The Pt active sites of Ni@Pt and Co@Pt overlayer catalysts showed significantly enhanced H2 production selectivity and activity when compared with that of a Pt only catalyst. The single deposition overlayer with the largest d-band shift showed the highest H2 activity. The results suggest that overlayer formation using directed deposition technique could modify the behavior of the surface metal and ultimately modify the APR activity.

  5. A first-principles study of the SCN{sup -} chemisorption on the surface of AlN, AlP, and BP nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Soltani, Alireza, E-mail: Alireza.soltani46@yahoo.com [Young Researchers Club, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of); Taghartapeh, Mohammad Ramezani [Young Researchers Club, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of); Mighani, Hossein [Department of Chemistry, Faculty of science, Golestan University, Gorgan (Iran, Islamic Republic of); Pahlevani, Amin Allah [Young Researchers Club, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of); Mashkoor, Reza [Department of Chemistry, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of)

    2012-10-15

    Graphical abstract: Adsorption properties of SCN{sup -} on AlN, AlP, and BP nanotubes based on density functional theory. Black-Right-Pointing-Triangle We demonstrate the most stable configurations (N-side) of SCN{sup -} on AlN, AlP, and BP nanotubes models. Highlights: Black-Right-Pointing-Pointer The SCN{sup -} Adsorption on surface of AlN, AlP, and BP nanotubes were studied via density functional theory (DFT). Black-Right-Pointing-Pointer The interaction of SCN{sup -} on the electronic properties and the NBO charge distribution of mentioned configurations are investigated. Black-Right-Pointing-Pointer The studies suggest that the adsorption energies of SCN{sup -} on AlPNT is most notable in comparison with AlNNT and BPNT. - Abstract: We have performed first-principles calculations to explore the adsorption behavior of the SCN{sup -} on electronic properties of AlN, AlP, and BP nanotubes. The adsorption value of SCN{sup -} for the most stable formation on the AlPNT is about -318.16 kJ mol{sup -1}, which is reason via the chemisorptions of SCN anion. The computed density of states (DOS) indicates that a notable orbital hybridization take place between SCN{sup -} and AlP nanotube in adsorption process. Finally, the AlP nanotube can be used to design as useful sensor for nanodevice applications.

  6. CO Oxidation and Subsequent CO2 Chemisorption on Alkaline Zirconates: Li2 ZrO3 and Na2 ZrO3

    Energy Technology Data Exchange (ETDEWEB)

    Alcántar-Vázquez, Brenda; Duan, Yuhua; Pfeiffer, Heriberto

    2016-09-21

    Here, two different alkaline zirconates (Li2ZrO3 and Na2ZrO3) were studied as possible bifunctional catalytic-captor materials for CO oxidation and the subsequent CO2 chemisorption process. Initially, CO oxidation reactions were analyzed in a catalytic reactor coupled to a gas chromatograph, using Li2ZrO3 and Na2ZrO3, under different O2 partial flows. We found results clearly showed that Na2ZrO3 possesses much better catalytic properties than Li2ZrO3. After the CO-O2 oxidation catalytic analysis, CO2 chemisorption process was analyzed by thermogravimetric analysis, only for the Na2ZrO3 ceramic. The results confirmed that Na2ZrO3 is able to work as a bifunctional material (CO oxidation and subsequent CO2 chemisorption), although the kinetic CO2 capture process was not the best one under the physicochemical condition used in this case. For Na2ZrO3, the best CO conversions were found between 445 and 580 °C (100%), while Li2ZrO3 only showed a 35% of efficiency between 460 and 503 °C. However, in the Na2ZrO3 case, at temperatures higher than 580 °C its catalytic activity gradually decreases as a result of CO2 capture process. Finally, all these experiments were compared and supported with theoretical thermodynamic data.

  7. Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

    Science.gov (United States)

    Huang, C. J.; Yeager, E.; Ogrady, W. E.

    1975-01-01

    The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.

  8. Study on Chemisorption and Desorption of Hydrogen and Nitrogen on Ru-based Ammonia Synthesis Catalyst%钌基氨合成催化剂氢氮吸附性能的研究

    Institute of Scientific and Technical Information of China (English)

    祝一锋; 李小年; 高冬梅; 周春晖; 刘化章

    2003-01-01

    The effects of promoters K, Ba, Sm on the chemisorption and desorption of hydrogen and nitrogen,dispersion of metallic Ru and catalytic activity of active carbon (AC) supported ruthenium catalyst for ammoniasynthesis have been studied by means of pulse chromatography, temperature-programmed desorption, and activitytest. Promoters K, Ba and Sm increased the activity of Ru/AC catalysts for ammonia synthesis significantly, andparticularly, potassium exhibited the best promotion on the activity because of the strong electronic donation tometallic Ru. Much higher activity can be obtained for Ru/AC catalyst with binary or triple promoters. The activityof Ru/AC catalyst is dependent on the adsorption of hydrogen and nitrogen. The high activity of catalyst could beascribed to strong dissociation of nitrogen on the catalyst surface. Strong adsorption of hydrogen would inhibit theadsorption of nitrogen, resulted in decrease of the catalytic activity. Ru/AC catalyst promoted by Sm2O3 showsthe best dispersion of metallic Ru, since the partly reduced SmOx on the surface modifies the morphology of activesites and favors the dispersion of metallic Ru. The activity of Ru/AC catalysts is in accordance to the correspondingamount of nitrogen chemisorption and the desorption activation energy of nitrogen. The desorption activation energyfor nitrogen decreases in the order of Ru>Ru-Ba>Ru-Sm>Ru-Ba-Sm>Ru-K>Ru-K-Sm>Ru-K-Ba>Ru-K-Ba-Sm,just opposite to the order of catalytic activity, suggesting that the ammonia synthesis over Ru-based catalyst iscontrolled by the step of dissociation of nitrogen.

  9. High-resolution solid-state (13)C NMR studies of chemisorbed organometallics. Chemisorptive formation of cation-like and alkylidene organotantalum complexes on high surface area inorganic oxides.

    Science.gov (United States)

    Ahn, Hongsang; Marks, Tobin J

    2002-06-19

    (13)C CPMAS NMR spectroscopy has been employed to investigate the surface chemistry of the organotantalum hydrocarbyl/alkylidene complexes, Cp'Ta((13)CH(3))(4) (1*), Cp(2)Ta((13)CH(3))(3) (2*), Cp(2)Ta((13)CH(2))((13)CH(3)) (3*), and Ta((13)CH(t)Bu)((13)CH(2)(t)Bu)(3) (4*) [Cp' = eta(5)-(CH(3))(5)C(5), Cp = eta(5)-C(5)H(5)] supported on partially dehydroxylated silica (PDS), dehydroxylated silica (DS), or dehydroxylated gamma-alumina (DA). Mono-Cp tantalum hydrocarbyl 1* undergoes chemisorption to form Cp'Ta((13)CH(3))(3)O-Si mu-oxo species on silica, and "cation-like" Cp'Ta((13)CH(3))(3)(+) and Cp'Ta((13)CH(3))(3)O-Al mu-oxo species on DA, via pathways analogous to those established for organo-group 4 and actinide complexes. When supported on DA, bis-Cp tantalum hydrocarbyl 2* follows the same chemisorption mode as 1*. However, when 2* is chemisorbed on PDS and DS, a "cation-like" Cp(2)Ta((13)CH(3))(2)(+) species is the major adsorbate product. On PDS, bis-Cp tantalum alkylidene complex 3* is converted predominantly to a stable "cation-like" Cp(2)Ta((13)CH(3))(2)(+) species, presumably via electrophilic addition of a proton from the PDS surface. In contrast to 3*, Ta alkylidene complex 4* forms predominantly a Ta((13)CH(t)Bu)((13)CH(2)(t)Bu)(2)O-Si, mu-oxo-alkylidene species on PDS.

  10. SrCl2-NH3化学吸附式制冷工质对吸附特性的研究%STUDY ON THE ADSORPTION CHARACTERISTICS OF SrCl2-NH3 CHEMISORPTION REFRIGERATION WORKING PAIR

    Institute of Scientific and Technical Information of China (English)

    陈砺; 谭盈科

    2001-01-01

    A study on the adsorption characteristics of the chemisorptionrefrigeration working pair using SrCl2 as adsorbent and NH3 as refrigerant was performed.The adsorption isotherms were obtained,the adsorpt i on isotherm equations were fit and the chemisorption mechanisms were discussed.T he results showed that SrCl2-NH3 is an excellent working pair in its larg e adsorption refrigeration capacity per unit weight of adsorbent and suitable fo r solar energy and low grade waste heat.%对以SrCl2为吸附剂、NH3为致冷剂所组成的化学吸附式制冷工质对的吸附性能进行了研究,得到了吸附等温线、回归出吸附等温方程并对化学吸附过程机理进行了探讨。研究结果表明,SrCl2-NH3工质对的吸附制冷量大,适宜太阳能或低品位余热驱动,是性能优良的工质对。

  11. The effect of additives on the reactivity of palladium surfaces for the chemisorption and hydrogenation of carbon monoxide: A surface science and catalytic study. [LaMO/sub 3/(M = Cr, Mn, Fe, Co, Rh)

    Energy Technology Data Exchange (ETDEWEB)

    Rucker, T.G.

    1987-06-01

    This research studied the role of surface additives on the catalytic activity and chemisorptive properties of Pd single crystals and foils. Effects of Na, K, Si, P, S, and Cl on the bonding of CO and H and on the cyclotrimerization of acetylene on the (111), (100) and (110) faces of Pd were investigated in addition to role of TiO/sub 2/ and SiO/sub 2/ overlayers deposited on Pd foils in the CO hydrogenation reaction. On Pd, only in the presence of oxide overlayers, are methane or methanol formed from CO and H/sub 2/. The maximum rate of methane formation is attained on Pd foil where 30% of the surface is covered with titania. Methanol formation can be achieved only if the TiO/sub x//Pd surface is pretreated in 50 psi of oxygen at 550/sup 0/C prior to the reaction. The additives (Na, K, Si, P, S, Cl) affect the bonding of CO and hydrogen and the cyclotrimerization of acetylene to benzene by structural and electronic interactions. In general, the electron donating additives increase the desorption temperature of CO and increase the rate of acetylene cyclotrimerization and the electron withdrawing additives decrease the desorption temperature of CO and decrease the rate of benzene formation from acetylene.

  12. Ammonia Chemisorption Studies on Silicon Cluster Ions

    Science.gov (United States)

    1990-07-23

    produced for these experiments without any ArF excimer laser reionization step. The ArF laser was only used for clusters larger than Si2 5 Subsequent...experiments have shown that laser excitation efficiently anneals these silicon clusters5 . Inadvertently in these experiments the ArF reionization laser...such that all the reaction data appeared to fit well to a single rate. Above 19 atoms without the ArF reionization step, and above 49 atoms even with

  13. Chemisorption of catechol on gibbsite, boehmite, and noncrystalline alumina surfaces

    Energy Technology Data Exchange (ETDEWEB)

    McBride, M.B.; Wesselink, L.G.

    1988-06-01

    The mechanism of bonding of catechol and related phenolic compounds on aluminum oxides was elucidated from sorption behavior in the presence of competing adsorbates and the nature of the infrared spectra of the surface-bound molecules. The surfaces demonstrated a high degree of selectivity toward catechol, adsorbing the molecule in the presence of a large excess of chloride. Phosphate competed effectively with catechol for sorption sites while acetate did not. Dispersive and Fourier transform infrared spectroscopy verified that catechol bound on the aluminum oxide surfaces was chemically perturbed in much the same manner as catechol chelated by Al/sup 3 +/, suggesting that the dominant sorption process involved the formation of a 1:1 bidentate complex with surface Al. The mechanisms of bonding was similar for all the aluminum oxides, but the dominant crystal surfaces of the crystalline oxides were unreactive toward catechol, and adsorption was attributed to -AlOH groups situated on edge faces. As a result, the noncrystalline oxide was more reactive per unit of surface area than the crystalline minerals boehmite and gibbsite.

  14. Electronic shell structure and chemisorption on gold nanoparticles

    DEFF Research Database (Denmark)

    Larsen, Ask Hjorth; Kleis, Jesper; Thygesen, Kristian Sommer

    2011-01-01

    We use density functional theory (DFT) to investigate the electronic structure and chemical properties of gold nanoparticles. Different structural families of clusters are compared. For up to 60 atoms we optimize structures using DFT-based simulated annealing. Cluster geometries are found to dist...

  15. Active chemisorption sites in functionalized ionic liquids for carbon capture.

    Science.gov (United States)

    Cui, Guokai; Wang, Jianji; Zhang, Suojiang

    2016-07-25

    Development of novel technologies for the efficient and reversible capture of CO2 is highly desired. In the last decade, CO2 capture using ionic liquids has attracted intensive attention from both academia and industry, and has been recognized as a very promising technology. Recently, a new approach has been developed for highly efficient capture of CO2 by site-containing ionic liquids through chemical interaction. This perspective review focuses on the recent advances in the chemical absorption of CO2 using site-containing ionic liquids, such as amino-based ionic liquids, azolate ionic liquids, phenolate ionic liquids, dual-functionalized ionic liquids, pyridine-containing ionic liquids and so on. Other site-containing liquid absorbents such as amine-based solutions, switchable solvents, and functionalized ionic liquid-amine blends are also investigated. Strategies have been discussed for how to activate the existent reactive sites and develop novel reactive sites by physical and chemical methods to enhance CO2 absorption capacity and reduce absorption enthalpy. The carbon capture mechanisms of these site-containing liquid absorbents are also presented. Particular attention has been paid to the latest progress in CO2 capture in multiple-site interactions by amino-free anion-functionalized ionic liquids. In the last section, future directions and prospects for carbon capture by site-containing ionic liquids are outlined.

  16. Dissociative chemisorption of N2 on Rhenium

    DEFF Research Database (Denmark)

    Billing, Gert D.; Guldberg, Annette; Henriksen, Niels Engholm

    1990-01-01

    mechanically using the FFT (fast Fourier transform) technique. Also normal modes of the solid are quantized using a quantum boson approach and the remaining degrees of freedom are treated classically. Full corrugation of the surface and phonon coupling to infinite order as well as rotational motion...

  17. Chemisorption of a Strained but Flexible Molecule: Cyclooctyne on Si(001).

    Science.gov (United States)

    Pecher, Josua; Schober, Christoph; Tonner, Ralf

    2017-01-24

    The adsorption characteristics of a promising system for hybrid organic-inorganic interfaces, cyclooctyne on Si(001), is analyzed using density functional theory. The chemisorbed 'on-top' configuration, where a cycloadduct is formed between the ring triple bond and a surface dimer, is shown to be most stable. Less stable are 'bridge' and 'sublayer' modes featuring two molecule-surface bonds and the 'pedestal' mode with four bonds. Investigations with our recently proposed periodic energy decomposition analysis (pEDA) reveal that the four-bond configuration is destabilized by large deformation energies needed within molecule and surface as well as rather weak molecule-surface bonds. Dispersion interactions show significant influence on energy and structure of the configurations leading to an increased bending of the rather flexible molecules. Thus, features found in previous scanning tunneling microscopy experiments are conclusively explained with bent 'on-top' configurations and the 'pedestal' mode can be ruled out. A comparison to acetylene shows that the ring structure and the resulting strain of cyclooctyne are responsible for an increased reactivity of the larger adsorbate due to a pre-forming of the ring triple bond for surface bonding. In contrast, ring strain leads only to negligible electronic effects on the adsorbate-surface bonds. The computations highlight the need for in-depth theoretical analysis to understand adsorption characteristics of large, flexible molecules.

  18. Study on Chemisorption, Catalytic Behavior, and Stability of Supported Au Catalyst for the Propylene Epoxidation Reaction

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The supported Au/TiO2 and Au/TiO2-SiO2 catalysts were prepared by deposition precipitation method. The TPD study reveals that propylene oxide competes with propylene to be adsorbed on the same adsorptive center-Tin+ site on the surface of the catalyst and that the adsorbing capacity of the catalyst for propylene oxide is larger than that for propylene. Catalytic behavior for propylene epoxidation with H2 and O2 was tested in a micro-reactor. Under typical conditions, the selectivity for propylene oxide is over 87%. The TG curves show that PO successive oxidation cause carbon deposition on the active center and deactivation of the Au catalysts. Because the amounts of Tin+ site decrease significantly, and consequently the separation between Tin+ sites increases, the Au/TiO2-SiO2 catalyst is more stable than Au/TiO2.

  19. Thermal and spatial effects in chemisorption measurements; Effetti termici e spaziali nelle misure di chemisorbimento

    Energy Technology Data Exchange (ETDEWEB)

    Marengo, S. [Stazione sperimentale per i Combustibili, S.Donato Milanese, Milano (Italy)

    1998-03-01

    A new application of infrared thermography in catalyst characterization is described, in which an experimental set-up featuring high spatial resolution and capability of revealing dynamic effects and performing real time image analysis is adopted. Some significant results obtained in the study of acid-base properties of catalysts and solid materials, metal dispersion, reaction mechanism and deactivation processes are discussed. [Italiano] Viene illustrata una nuova applicazione della tecnica di termografia infrarossa, attuata con un`apparecchiatura ed un assetto sperimentale che presentano caratteristiche peculiari quali: elevata risoluzione spaziale, descrizione accurata di fenomeni dinamici, analisi delle immagini in tempo reale. Vengono presentati alcuni esempi significativi di impiego nei seguenti campi: catatterizzazioni di catalizzatori e materiali solidi in termini di proprieta` acido-base e di dispersione dei metalli supportati; studi cinetici-meccanicistici, studio della disattivazione del letto catalitico.

  20. Self-chemisorption of azurin on functionalized oxide surfaces for the implementation of biomolecular devices

    Energy Technology Data Exchange (ETDEWEB)

    Biasco, A.; Maruccio, G.; Visconti, P.; Bramanti, A.; Calogiuri, P.; Cingolani, R.; Rinaldi, R

    2004-06-01

    In this work, we investigate the formation of redox protein Azurin (Az) monolayers on functionalized oxygen exposing surfaces. These metallo-proteins mediate electron transfer in the denitrifying chain of Pseudomonas bacteria and exhibit self-assembly properties, therefore they are good candidates for bio-electronic applications. Azurin monolayers are self-assembled onto silane functionalized surfaces and characterized by atomic force microscopy (AFM). We show also that a biomolecular field effect transistor (FET) in the solid state can be implemented by interconnecting an Azurin monolayer immobilized on SiO{sub 2} with two gold nanoelectrodes. Transport experiments, carried out at room temperature and ambient pressure, show FET behavior with conduction modulated by the gate potential.

  1. Chemisorption of CO and Mechanism of CO Oxidation on Supported Platinum Nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Allian, Ayman D.; Takanabe, Kazuhiro; Fujdala, Kyle L.; Hao, Xianghong; Truex, Timothy J.; Cai, Juan; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2011-03-30

    Kinetic, isotopic, and infrared studies on well-defined dispersed Pt clusters are combined here with first-principle theoretical methods on model cluster surfaces to probe the mechanism and structural requirements for CO oxidation catalysis at conditions typical of its industrial practice. CO oxidation turnover rates and the dynamics and thermodynamics of adsorption-desorption processes on cluster surfaces saturated with chemisorbed CO were measured on 1-20 nm Pt clusters under conditions of strict kinetic control. Turnover rates are proportional to O2 pressure and inversely proportional to CO pressure, consistent with kinetically relevant irreversible O2 activation steps on vacant sites present within saturated CO monolayers. These conclusions are consistent with the lack of isotopic scrambling in C16O-18O2-16O2 reactions, and with infrared bands for chemisorbed CO that did not change within a CO pressure range that strongly influenced CO oxidation turnover rates. Density functional theory estimates of rate and equilibrium constants show that the kinetically relevantO2 activation steps involve directO2* (or O2) reactions with CO* to form reactive O*-O-C*dO intermediates that decompose to form CO2 and chemisorbed O*, instead of unassisted activation steps involving molecular adsorption and subsequent dissociation of O2. These CO-assisted O2 dissociation pathways avoid the higher barriers imposed by the spin-forbidden transitions required for unassistedO2 dissociation on surfaces saturated with chemisorbed CO. Measured rate parameters for CO oxidation were independent of Pt cluster size; these parameters depend on the ratio of rate constants for O2 reactions with CO* and CO adsorption equilibrium constants, which reflect the respective activation barriers and reaction enthalpies for these two steps. Infrared spectra during isotopic displacement and thermal desorption with 12CO-13CO mixtures showed that the binding, dynamics, and thermodynamics of CO chemisorbed at saturation coverages do not depend on Pt cluster size in a range that strongly affects the coordination of Pt atoms exposed at cluster surfaces. These data and their theoretical and mechanistic interpretations indicate that the remarkable structure insensitivity observed for CO oxidation reactions reflects average CO binding properties that are essentially independent of cluster size. Theoretical estimates of rate and equilibriumconstants for surface reactions and CO adsorption show that both parameters increase as the coordination of exposed Pt atoms decreases in Pt201 cluster surfaces; such compensation dampens but does not eliminate coordination and cluster size effects on measured rate constants. The structural features and intrinsic non-uniformity of cluster surfaces weaken when CO forms saturated monolayers on such surfaces, apparently because surfaces and adsorbates restructure to balance CO surface binding and CO-CO interaction energies.

  2. NO Chemisorption on Cu/SSZ-13: a Comparative Study from Infrared Spectroscopy and DFT Calculations

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Renqin; McEwen, Jean-Sabin; Kollar, Marton; Gao, Feng; Wang, Yilin; Szanyi, Janos; Peden, Charles HF

    2014-11-07

    The locations and energies of Cu ions in a Cu/SSZ-13 zeolite catalyst were investigated by density functional theory (DFT) calculations. For 'naked' Cu2+ ions (i.e., Cu2+ ions with no ligands in their coordination spheres other than zeolite lattice oxygen atoms), the more energetically favorable sites are within a 6-membered ring. However, with the presence of various adsorbates, the energy difference between 6- and 8-membered ring locations greatly diminishes. Specifically, Cu2+ ions are substantially stabilized by -OH ligands (as [CuII(OH)]+), making the extra-framework sites in an 8-membered ring energetically more favorable than 6-membered ring sites. Under fully dehydrated high vacuum conditions with different Si/Al and Cu/Al ratios, three chemisorbed NO species coexist upon exposure of NO to Cu/SSZ-13: NO+, Cu2+-NO and Cu+-NO. The relative signal intensities for these bands vary greatly with Si/Al ratios. The vibrational frequency of chemisorbed NO was found to be very sensitive to the location of Cu2+ ions. On the one hand, with the aid from DFT calculations, the nature for these vibrations can be assigned in detail. On the other hand, the relative intensities for various Cu2+-NO species provide a good measure of the nature of Cu2+ ions as functions of Si/Al and Cu/Al ratios and the presence of humidity. These new findings cast doubt on the generally accepted proposal that only Cu2+ ions located in 6-membered rings are catalytically active for NH3-SCR.

  3. Scattering, Adsorption, and Langmuir-Hinshelwood Desorption Models for Physisorptive and Chemisorptive Gas-Surface Systems

    Science.gov (United States)

    2013-09-01

    during a gas-surface collision, and Rc is a critical value of Reff. For a given incident translational energy Etr , Reff is estimated from the one...dimensional (1D) approximation Etr εLJ ≈ ( r0 Reff )12 − 2 ( r0 Reff )6 , (7) where εLJ is the Lennard-Jones (LJ) well-depth parameter for the interaction...tr > Etr . This phenomenon is termed super-elastic scattering, and describes the case where the gas molecule picks up thermal energy from the surface

  4. Mechanical properties of chiral and achiral silicon carbide nanotubes under oxygen chemisorption.

    Science.gov (United States)

    Ansari, R; Mirnezhad, M; Hosseinzadeh, M

    2015-03-01

    In this paper, the mechanical properties of fully oxygenated silicon carbide nanotubes (O2-SiCNTs) are explored using a molecular mechanics model joined with the density functional theory (DFT). The closed-form analytical expressions suggested in this study can easily be adapted for nanotubes with different chiralities. The force constants of molecular mechanics model proposed herein are derived through DFT within a generalized gradient approximation. Moreover, the mechanical properties of fully oxygenated silicon carbide (O2-SiC) sheet are evaluated for the case that the oxygen atoms are adsorbed on one side of the SiC sheet. According to the results obtained for the bending stiffness of O2-SiC sheet, one can conclude that the O2-SiC sheet has isotropic characteristics.

  5. Chemisorption of aromatic molecules on Si(100)-2x1. An HREELS study

    CERN Document Server

    Alkunshalie, T

    1998-01-01

    HREELS has been used to investigate the growth of ultra-thin organic film on Si(100)-2x1 by reactive coupling of polyimide precursors. 1,4- phenylenediamine and pyromelltic dianhydride were sequentially dosed on clean Si(100)-2x1 under ultra high vacuum conditions. The interfacial imidisation was initiated by thermal curing at 200 deg C. To simplify the analysis of the vibrational data, model compounds benzoic acid, aniline and phthalic anhydride were characterised first. HREEL spectra show that the model compounds absorb through dissociation of the functional group. The spectra also show that an oligimide chain has been formed which stands upright on the surface. The oligomer chain bonds to the silicon surface via a Si-(NH)-C linkage.

  6. CO chemisorption and dissociation at high coverages during CO hydrogenation on Ru catalysts.

    Science.gov (United States)

    Loveless, Brett T; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2013-04-24

    Density functional theory (DFT) and infrared spectroscopy results are combined with mechanism-based rate equations to assess the structure and thermodynamics of chemisorbed CO (CO*) and its activation during Fischer-Tropsch synthesis (FTS). CO* binding becomes weaker with increasing coverage on Ru(0001) and Ru201 clusters, but such decreases in binding energy occur at higher coverages on Ru201 clusters than on Ru(0001) surfaces (CO*/Ru = 1.55 to 0.75); such differences appear to reflect weaker repulsive interactions on the curved surfaces prevalent on small Ru201 clusters. Ru201 clusters achieve stable supramonolayer coverages (CO*/Ru > 1) by forming geminal dicarbonyls at low-coordination corner/edge atoms. CO* infrared spectra on Ru/SiO2 (~7 nm diameter) detect mobile adlayers that anneal into denser structures at saturation. Mechanism-based FTS rate equations give activation energies that reflect the CO*-saturated surfaces prevalent during catalysis. DFT-derived barriers show that CO* predominantly reacts at (111) terraces via H-assisted reactions, consistent with measured effects of H2 and CO pressures and cluster size effects on rates and O-rejection selectivities. Barriers are much higher for unassisted CO* dissociation on (111) terraces and low-coordination atoms, including step-edge sites previously proposed as active sites for CO* dissociation during FTS. DFT-derived barriers indicate that unassisted CO* dissociation is irreversible, making such steps inconsistent with measured rates. The modest activation barriers of H-assisted CO* dissociation paths remove a requirement for special low-coordination sites for unassisted CO* activation, which is inconsistent with higher rates on larger clusters. These conclusions seem generally applicable to Co, Fe, and Ru catalysts, which show similar FTS rate equations and cluster size effects. This study also demonstrates the feasibility and relevance of DFT treatments on the curved and crowded cluster surfaces where catalysis occurs.

  7. Chemisorption of Hydroxide on 2D Materials from DFT Calculations: Graphene versus Hexagonal Boron Nitride.

    Science.gov (United States)

    Grosjean, Benoit; Pean, Clarisse; Siria, Alessandro; Bocquet, Lydéric; Vuilleumier, Rodolphe; Bocquet, Marie-Laure

    2016-11-17

    Recent nanofluidic experiments revealed strongly different surface charge measurements for boron-nitride (BN) and graphitic nanotubes when in contact with saline and alkaline water (Nature 2013, 494, 455-458; Phys. Rev. Lett. 2016, 116, 154501). These observations contrast with the similar reactivity of a graphene layer and its BN counterpart, using density functional theory (DFT) framework, for intact and dissociative adsorption of gaseous water molecules. Here we investigate, by DFT in implicit water, single and multiple adsorption of anionic hydroxide on single layers. A differential adsorption strength is found in vacuum for the first ionic adsorption on the two materials-chemisorbed on BN while physisorbed on graphene. The effect of implicit solvation reduces all adsorption values, resulting in a favorable (nonfavorable) adsorption on BN (graphene). We also calculate a pKa ≃ 6 for BN in water, in good agreement with experiments. Comparatively, the unfavorable results for graphene in water echo the weaker surface charge measurements but point to an alternative scenario.

  8. Chemisorption of CO and mechanism of CO oxidation on supported platinum nanoclusters

    KAUST Repository

    Allian, Ayman Daoud

    2011-03-30

    Kinetic, isotopic, and infrared studies on well-defined dispersed Pt clusters are combined here with first-principle theoretical methods on model cluster surfaces to probe the mechanism and structural requirements for CO oxidation catalysis at conditions typical of its industrial practice. CO oxidation turnover rates and the dynamics and thermodynamics of adsorption-desorption processes on cluster surfaces saturated with chemisorbed CO were measured on 1-20 nm Pt clusters under conditions of strict kinetic control. Turnover rates are proportional to O2 pressure and inversely proportional to CO pressure, consistent with kinetically relevant irreversible O2 activation steps on vacant sites present within saturated CO monolayers. These conclusions are consistent with the lack of isotopic scrambling in C16O-18O2-16O 2 reactions, and with infrared bands for chemisorbed CO that did not change within a CO pressure range that strongly influenced CO oxidation turnover rates. Density functional theory estimates of rate and equilibrium constants show that the kinetically relevant O2 activation steps involve direct O2* (or O2) reactions with CO* to form reactive O*-O-C*=O intermediates that decompose to form CO 2 and chemisorbed O*, instead of unassisted activation steps involving molecular adsorption and subsequent dissociation of O2. These CO-assisted O2 dissociation pathways avoid the higher barriers imposed by the spin-forbidden transitions required for unassisted O2 dissociation on surfaces saturated with chemisorbed CO. Measured rate parameters for CO oxidation were independent of Pt cluster size; these parameters depend on the ratio of rate constants for O2 reactions with CO* and CO adsorption equilibrium constants, which reflect the respective activation barriers and reaction enthalpies for these two steps. Infrared spectra during isotopic displacement and thermal desorption with 12CO- 13CO mixtures showed that the binding, dynamics, and thermodynamics of CO chemisorbed at saturation coverages do not depend on Pt cluster size in a range that strongly affects the coordination of Pt atoms exposed at cluster surfaces. These data and their theoretical and mechanistic interpretations indicate that the remarkable structure insensitivity observed for CO oxidation reactions reflects average CO binding properties that are essentially independent of cluster size. Theoretical estimates of rate and equilibrium constants for surface reactions and CO adsorption show that both parameters increase as the coordination of exposed Pt atoms decreases in Pt201 cluster surfaces; such compensation dampens but does not eliminate coordination and cluster size effects on measured rate constants. The structural features and intrinsic non-uniformity of cluster surfaces weaken when CO forms saturated monolayers on such surfaces, apparently because surfaces and adsorbates restructure to balance CO surface binding and CO-CO interaction energies. © 2011 American Chemical Society.

  9. Endohedral nitrogen storage in carbon fullerene structures: Physisorption to chemisorption transition with increasing gas pressure

    Science.gov (United States)

    Barajas-Barraza, R. E.; Guirado-López, R. A.

    2009-06-01

    We present extensive pseudopotential density functional theory (DFT) calculations in order to analyze the structural properties and chemical reactivity of nitrogen molecules confined in spheroidal (C82) and tubelike (C110) carbon fullerene structures. For a small number of encapsulated nitrogens, the N2 species exist in a nonbonded state within the cavities and form well defined molecular conformations such as linear chains, zigzag arrays, as well as both spheroidal and tubular configurations. However, with increasing the number of stored molecules, the interaction among the confined nitrogens as well as between the N2 species and the fullerene wall is not always mainly repulsive. Actually, at high densities of the encapsulated gas, we found both adsorption of N2 to the inner carbon surface together with the formation of (N2)m molecular clusters. Total energy DFT calculations reveal that the shape of the interaction potential of a test molecule moving within the carbon cavities strongly varies with the number and proximity of the coadsorbed N2 from being purely repulsive to having short-range attractive contributions close to the inner wall. In particular, the latter are always found when a group of closely spaced nitrogens is located near the carbon cage (a fact that will naturally occur at high densities of the encapsulated gas), inducing the formation of covalent bonds between the N2 and the fullerene network. Interestingly, in some cases, the previous nitrogen adsorption to the inner surface is reversible by reducing the gas pressure. The calculated average density of states of our considered carbon compounds reveals the appearance of well defined features that clearly reflect the occurring structural changes and modifications in the adsorption properties in the systems. Our results clearly underline the crucial role played by confinement effects on the reactivity of our endohedral compounds, define this kind of materials as nonideal nanocontainers for high density nitrogen storage applications, and must be taken into account when analyzing the diffusion properties of the encapsulated species.

  10. Determination of the structural and chemisorption characteristics of granulated active charcoal on the basis of coconut shell

    Directory of Open Access Journals (Sweden)

    Milenković Dragan D.

    2004-01-01

    Full Text Available Wastewater purification and the acquirement of drinking water from water streams that are in most cases recipients of various industrial plants, present a significant problem nowadays. The structural characteristics of granulated active charcoal (GAC obtained by the carbonization of coconut shells and activated by steam are presented in this paper. The established kinetics of suspending cyanide from aqueous solution using GAC impregnated with copper(II acetate were studied and a mathematical model estabkusged by a regression - correlation analysis.

  11. Correlation of Chemisorption and Electronic Effects for Metal Oxide Interfaces: Transducing Principles for Temperature Programmed Gas Microsensors

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Steve Semancik

    2002-01-03

    The spectrum of chemical monitoring problems faced by the Department of Energy at its hazardous waste sites is formidable. It is likely that a variety of existing types of instrumentation will be applied in the years ahead, with varying degrees of practicality and success. A tremendous impact could be realized, however, if instrumental methods could be supplemented by a low-cost, reliable sensing technology for continuous monitoring of a range of species, including, for example, volatile organics, chlorinated hydrocarbons, ammonia, and hydrogen. To meed the diverse gas and vapor monitoring needs at ODE hazardous waste sites, the sensing system must offer, inherently, and adaptability to match the wide variety of analytes and environmental conditions that well be encountered (in tank vapor spaces, and at locations with contaminated soil or groundwater.) The purpose of this project was to investigate scientific and technical concepts that could enable a MEMS-based chemical sensing technology (developed in its foundational form at NIST during early and mid 1990's) to be made tunable for multiple target analytes in differing types of backgrounds relevant to DOE waste storage and remediation

  12. Correlation of Chemisorption and Electronic Effects for Metal Oxide Interfaces: Transducing Principles for Temperature Programmed Gas Microsensors (Final Report)

    Energy Technology Data Exchange (ETDEWEB)

    S. Semancik; R. E. Cavicchi; D. L. DeVoe; T. J. McAvoy [National Institute of Standards and Technology (US)]|[University of Maryland (US)

    2001-12-21

    This Final Report describes efforts and results for a 3-year DoE/OST-EMSP project centered at NIST. The multidisciplinary project investigated scientific and technical concepts critical for developing tunable, MEMS-based, gas and vapor microsensors that could be applied for monitoring the types of multiple analytes (and differing backgrounds) encountered at DoE waste sites. Micromachined ''microhotplate'' arrays were used as platforms for fabricating conductometric sensor prototypes, and as microscale research tools. Efficient microarray techniques were developed for locally depositing and then performance evaluating thin oxide films, in order to correlate gas sensing characteristics with properties including composition, microstructure, thickness and surface modification. This approach produced temperature-dependent databases on the sensitivities of sensing materials to varied analytes (in air) which enable application-specific tuning of microsensor arrays. Mechanistic studies on adsorb ate transient phenomena were conducted to better understand the ways in which rapid temperature programming schedules can be used to produce unique response signatures and increase information density in microsensor signals. Chemometric and neural network analyses were also employed in our studies for recognition and quantification of target analytes.

  13. Preparation and characterization of alkylphosphonic acid self-assembled monolayers on titanium alloy by chemisorption and electrochemical deposition.

    Science.gov (United States)

    Metoki, Noah; Liu, Liang; Beilis, Edith; Eliaz, Noam; Mandler, Daniel

    2014-06-17

    Ti-6Al-4V alloy is the most commonly used alloy for dental and orthopedic implants. In order to improve osseointegration, different surface modification methods are usually employed, including self-assembled monolayers (SAMs). This study presents an investigation of both active (electroassisted) and passive (adsorption) approaches for the modification of Ti-6Al-4V using alkylphosphonic acid. The monolayers were characterized by cyclic voltammetry, double-layer capacitance, contact angle measurements, X-ray photoelectron spectroscopy, polarization modulation infrared reflection adsorption spectroscopy, electrochemical impedance spectroscopy, and corrosion potentiodynamic polarization measurements. It is shown that the electrochemically assisted monolayers, which are assembled faster, exhibit better control over surface properties, a superior degree of order, and a somewhat higher packing density. The electrosorbed SAMs also exhibit better blockage of electron transfer across the interface and thus have better corrosion resistance.

  14. Effect of substrate preparation on the structure and chemisorption properties of Pd/MgO model catalyst

    Science.gov (United States)

    Henry, C. R.; Poppa, H.

    1988-01-01

    Pd/MgO model catalysts are prepared by vapor deposition of Pd particles on MgO thin films which are deposited, at different temperatures, on UHV cleaved mica. MgO films and Pd particles are characterized in situ by Auger electron spectroscopy and energy-loss spectroscopy and ex situ by transmission electron microscopy. Succesive temperature programmed desorption (TPD) of CO shows a different evolution of the morphology of the Pd particles deposited on MgO films prepared at low and high temperature. In addition, on MgO prepared at low temperature, the smallest particles show a continuous decay of CO adsorption during TPD due to contamination by support species.

  15. The adsorption of 1,3-butadiene on Pd/Ni multilayers: The interplay between spin polarization and chemisorption strength

    Science.gov (United States)

    Gómez, Guillermina; Belelli, Patricia G.; Cabeza, Gabriela F.; Castellani, Norberto J.

    2010-12-01

    The adsorption of 1,3-butadiene (BD) on the Pd/Ni(1 1 1) multilayers has been studied using the VASP method in the framework of the density functional theory (DFT). The adsorption on two different configurations of the Pd n/Ni m(1 1 1) systems were considered. The most stable adsorption sites are dependent on the substrate composition and on the inclusion or not of spin polarization. On Pd 1Ni 3(1 1 1) surface, di-π-cis and 1,2,3,4-tetra-σ adsorption structures are the most stable for non-spin polarized (NSP) and spin polarized (SP) levels of calculation, respectively. Conversely, on Pd 3Ni 1(1 1 1) surface, the 1,2,3,4-tetra-σ adsorption structure is the most stable for both NSP and SP levels, respectively. The magnetization of the Pd atoms strongly modifies the adsorption energy of BD and its most stable adsorption mode. On the other hand, as a consequence of BD adsorption, the Pd magnetization decreases. The smaller adsorption energies of BD and 1-butene on the Pd 1Ni 3(1 1 1) surface than on Pd(1 1 1) can be associated to the strained Pd overlayer deposited on Ni(1 1 1).

  16. Protein adsorption on dopamine-melanin films: role of electrostatic interactions inferred from zeta-potential measurements versus chemisorption.

    Science.gov (United States)

    Bernsmann, Falk; Frisch, Benoît; Ringwald, Christian; Ball, Vincent

    2010-04-01

    We recently showed the possibility to build dopamine-melanin films of controlled thickness by successive immersions of a substrate in alkaline solutions of dopamine [F. Bernsmann, A. Ponche, C. Ringwald, J. Hemmerlé, J. Raya, B. Bechinger, J.-C. Voegel, P. Schaaf, V. Ball, J. Phys. Chem. C 113 (2009) 8234-8242]. In this work the structure and properties of such films are further explored. The zeta-potential of dopamine-melanin films is measured as a function of the total immersion time to build the film. It appears that the film bears a constant zeta-potential of (-39+/-3) mV after 12 immersion steps. These data are used to calculate the surface density of charged groups of the dopamine-melanin films at pH 8.5 that are mostly catechol or quinone imine chemical groups. Furthermore the zeta-potential is used to explain the adsorption of three model proteins (lysozyme, myoglobin, alpha-lactalbumin), which is monitored by quartz crystal microbalance. We come to the conclusion that protein adsorption on dopamine-melanin is not only determined by possible covalent binding between amino groups of the proteins and catechol groups of dopamine-melanin but that electrostatic interactions contribute to protein binding. Part of the adsorbed proteins can be desorbed by sodium dodecylsulfate solutions at the critical micellar concentration. The fraction of weakly bound proteins decreases with their isoelectric point. Additionally the number of available sites for covalent binding of amino groups on melanin grains is quantified.

  17. Surface Properties of Metal-Incorporated Al-Pillared Interlayered Clay Catalysts Analyzed by Chemisorption and Infrared Analysis

    OpenAIRE

    BASOĞLU, Funda Turgut; BALCI, Suna

    2010-01-01

    Al-pillared interlayered clay (Al-PILC) was synthesized using bentonite from the Hançılı region of Central Anatolia in Turkey. Samples of Al-PILC were impregnated with Cu or Ag to produce Cu@Al-PILC and Ag@Al-PILC. Cu/Al-mixed PILCs were also obtained using mixed metal sources having (Cu/(Cu+Al)) atom percents as 5 and 10. The FTIR intensities of Lewis acidity peaks decreased whereas the intensity of BrÖnsted acidity remained nearly the same for pyridine sorbed PILCs after desorption a...

  18. Highly stable chemisorption of dyes with pyridyl anchors over TiO2: application in dye-sensitized photoelectrochemical water reduction in aqueous media.

    Science.gov (United States)

    Takijiri, Kohei; Morita, Kohei; Nakazono, Takashi; Sakai, Ken; Ozawa, Hironobu

    2017-03-09

    A polypyridyl ruthenium sensitizer possessing pyridyl anchors (Ru-py) forms much stronger chemical linkages to TiO2 surfaces compared to the conventional carboxylate and phosphonate ones. A highly stable dye-sensitized photoelectrochemical cell for water reduction is successfully demonstrated using this technique.

  19. Atomic-Level Organization of Vicinal Acid-Base Pairs through the Chemisorption of Aniline and Derivatives onto Mesoporous SBA15

    KAUST Repository

    Basset, Jean-Marie

    2016-06-09

    The design of novel heterogeneous catalysts with multiple adjacent functionalities is of high interest for heterogeneous catalysis. Herein, we report a method to obtain a majority bifunctional acid-base pairs on SBA15. Aniline reacts with SBA15 by opening siloxane bridges leading to N-phenylsilanamine-silanol pairs. In contrast with ammonia treated surfaces, the material is stable under air/moisture. Advanced solid state MAS NMR: 2D ¹H-¹H double-quantum, ¹H-¹³C HETCOR experiments and dynamic nuclear polarization enhanced ²⁹Si and ¹⁵N spectra demonstrate both the close proximity between the two moieties and the formation of a covalent Si-N surface bond and confirm the design of vicinal acid-base pairs. This approach was successfully applied to the design of a series of aniline derivatives bifunctional SBA15. A correlation of the substituents effects on the aromatic ring (Hammet parameters) on the kinetics of the model reaction of Knoevenagel is observed.

  20. Direct Measuring Methods of Water Vapor Content and Air Velocity at High Temperature using ZrO2-MgO Gas Chemisorption Type Ceramic Body

    Science.gov (United States)

    Nomura, Tomohiro; Nishimura, Nobuya; Shiba, Tooru; Hyodo, Tsutomu

    The control of humidity or air velocity as well as temperature is imperative for industrial process equipment such as air conditioners, dryers. At present, much about humidity sensors has been reported, and recently, ceramic sensors have been used with improved results. However, the effective operating temperature of these sensors for a direct measurement of the humidity is about 423 K at the highest. From the various ceramic sensors so far investigated, the authors selected composite ceramics ZrO2-MgO with porous structure and n-type semiconductor for humidity sensing at high temperature. This is because, when the working temperature of the ceramic sensor is between 673 and 973K, the sensor detects the presence of water vapor and gas velocity by the variations in the electronic condition caused by the reversible of the water vapor. From the test, the sensor that use a single sensing ceramic element can detect directly both the water vapor content in a mixed gas of air and superheated vapor in the temperature range 373-773 K and the air velocity(O.5-4m/s) in the range 373-573K.

  1. Strong Lithium Polysulfide Chemisorption on Electroactive Sites of Nitrogen-Doped Carbon Composites For High-Performance Lithium–Sulfur Battery Cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Song, Jiangxuan; Gordin, Mikhail; Xu, Terrence; Chen, Shuru; Yu, Zhaoxin; Sohn, Hiesang; Lu, Jun; Ren, Yang; Duan, Yuhua; wang, Donghai

    2015-03-27

    Despite the high theoretical capacity of lithium–sulfur batteries, their practical applications are severely hindered by a fast capacity decay, stemming from the dissolution and diffusion of lithium polysulfides in the electrolyte. A novel functional carbon composite (carbon-nanotube-interpenetrated mesoporous nitrogen-doped carbon spheres, MNCS/CNT), which can strongly adsorb lithium polysulfides, is now reported to act as a sulfur host. The nitrogen functional groups of this composite enable the effective trapping of lithium polysulfides on electroactive sites within the cathode, leading to a much improved electrochemical performance (1200 mAh g-1 after 200 cycles). The enhancement in adsorption can be attributed to the chemical bonding of lithium ions by nitrogen functional groups in the MNCS/CNT framework. Furthermore, the micrometer-sized spherical structure of the material yields a high areal capacity (ca. 6 mAh cm-2) with a high sulfur loading of approximately 5 mg cm-2, which is ideal for practical applications of the lithium–sulfur batteries.

  2. Strong Lithium Polysulfide Chemisorption on Electroactive Sites of Nitrogen-Doped Carbon Composites For High-Performance Lithium-Sulfur Battery Cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Song, Jiangxuan [Pennsylvania State Univ., State College, PA (United States). Dept. of Mechanical and Nuclear Engineering; Gordin, Mikhail L. [Pennsylvania State Univ., State College, PA (United States). Dept. of Mechanical and Nuclear Engineering; Xu, Terrence [Pennsylvania State Univ., State College, PA (United States). Dept. of Mechanical and Nuclear Engineering; Chen, Shuru [Pennsylvania State Univ., State College, PA (United States). Dept. of Mechanical and Nuclear Engineering; Yu, Zhaoxin [Pennsylvania State Univ., State College, PA (United States). Dept. of Mechanical and Nuclear Engineering; Sohn, Hiesang [Pennsylvania State Univ., State College, PA (United States). Dept. of Mechanical and Nuclear Engineering; Lu, Jun [Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Div.; Ren, Yang [Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Div.; Duan, Yuhua [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Wang, Donghai [Pennsylvania State Univ., State College, PA (United States). Dept. of Mechanical and Nuclear Engineering

    2015-03-27

    Despite the high theoretical capacity of lithium–sulfur batteries, their practical applications are severely hindered by a fast capacity decay, stemming from the dissolution and diffusion of lithium polysulfides in the electrolyte. A novel functional carbon composite (carbon-nanotube-interpenetrated mesoporous nitrogen-doped carbon spheres, MNCS/CNT), which can strongly adsorb lithium polysulfides, is now reported to act as a sulfur host. The nitrogen functional groups of this composite enable the effective trapping of lithium polysulfides on electroactive sites within the cathode, leading to a much improved electrochemical performance (1200 mAhg-1after 200 cycles). The enhancement in adsorption can be attributed to the chemical bonding of lithium ions by nitrogen functional groups in the MNCS/CNT framework. Furthermore, the micrometer-sized spherical structure of the material yields a high areal capacity (ca.6 mAhcm-2) with a high sulfur loading of approximately 5 mgcm-2, which is ideal for practical applications of the lithium–sulfur batteries.

  3. Synergistically Enhanced Polysulfide Chemisorption Using a Flexible Hybrid Separator with N and S Dual-Doped Mesoporous Carbon Coating for Advanced Lithium-Sulfur Batteries.

    Science.gov (United States)

    Balach, Juan; Singh, Harish K; Gomoll, Selina; Jaumann, Tony; Klose, Markus; Oswald, Steffen; Richter, Manuel; Eckert, Jürgen; Giebeler, Lars

    2016-06-15

    Because of the outstanding high theoretical specific energy density of 2600 Wh kg(-1), the lithium-sulfur (Li-S) battery is regarded as a promising candidate for post lithium-ion battery systems eligible to meet the forthcoming market requirements. However, its commercialization on large scale is thwarted by fast capacity fading caused by the Achilles' heel of Li-S systems: the polysulfide shuttle. Here, we merge the physical features of carbon-coated separators and the unique chemical properties of N and S codoped mesoporous carbon to create a functional hybrid separator with superior polysulfide affinity and electrochemical benefits. DFT calculations revealed that carbon materials with N and S codoping possess a strong binding energy to high-order polysulfide species, which is essential to keep the active material in the cathode side. As a result of the synergistic effect of N, S dual-doping, an advanced Li-S cell with high specific capacity and ultralow capacity degradation of 0.041% per cycle is achieved. Pushing our simple-designed and scalable cathode to a highly increased sulfur loading of 5.4 mg cm(-2), the Li-S cell with the functional hybrid separator can deliver a remarkable areal capacity of 5.9 mAh cm(-2), which is highly favorable for practical applications.

  4. Chemisorption of CH2O on N-doped TiO2 anatase nanoparticle as modified nanostructure media: A DFT study

    Science.gov (United States)

    Abbasi, Amirali; Sardroodi, Jaber Jahanbin; Ebrahimzadeh, Alireza Rastkar

    2016-12-01

    The structural and electronic properties of N-doped TiO2 anatase nanoparticles and their effects on the adsorption of formaldehyde molecule have been investigated using the density functional theory computations. Given the need to better understand the behavior of the adsorbed CH2O molecule on the anatase nanoparticle, we report results of density functional theory studies of the N-doped nanoparticles, as well as complex systems consisting of the CH2O molecule bound to a TiO2 nanoparticle. N-doped nanoparticle was obtained by substitution of nitrogen atom of TiO2 instead of oxygen atom. Adsorptions of the CH2O molecule on the dangling oxygen atom, twofold coordinated oxygen atom and doped nitrogen atom sites of the pristine and N-doped anatase nanoparticles were investigated. The results presented include structural parameters such as adsorption energies, bond lengths and bond angles and electronic properties such as density of states, spin distribution densities and molecular orbitals. It was found that the adsorption of the CH2O molecule on the dangling oxygen of considered N-doped TiO2 anatase nanoparticles is energetically more favorable than the adsorption on the undoped ones. It means a more stable configuration compared to the undoped nanoparticle adsorption, but not as stable as the CH2O adsorption on the doped nitrogen site of N-doped nanoparticles.

  5. The dissociative chemisorption of methane on Ni(100) and Ni(111): classical and quantum studies based on the reaction path Hamiltonian.

    Science.gov (United States)

    Mastromatteo, Michael; Jackson, Bret

    2013-11-21

    Electronic structure methods based on density functional theory are used to construct a reaction path Hamiltonian for CH4 dissociation on the Ni(100) and Ni(111) surfaces. Both quantum and quasi-classical trajectory approaches are used to compute dissociative sticking probabilities, including all molecular degrees of freedom and the effects of lattice motion. Both approaches show a large enhancement in sticking when the incident molecule is vibrationally excited, and both can reproduce the mode specificity observed in experiments. However, the quasi-classical calculations significantly overestimate the ground state dissociative sticking at all energies, and the magnitude of the enhancement in sticking with vibrational excitation is much smaller than that computed using the quantum approach or observed in the experiments. The origin of this behavior is an unphysical flow of zero point energy from the nine normal vibrational modes into the reaction coordinate, giving large values for reaction at energies below the activation energy. Perturbative assumptions made in the quantum studies are shown to be accurate at all energies studied.

  6. Adsorption-induced restructuring of gold nanochains

    DEFF Research Database (Denmark)

    Bahn, Sune Rastad; Lopez, Nuria; Nørskov, Jens Kehlet;

    2002-01-01

    The chemical properties of single-atomic chains of gold atoms are investigated using density functional calculations. The nanochains are shown to be unusually chemically active with strong chemisorption of oxygen atoms and carbon monoxide. The chemisorption energies vary significantly...

  7. The adsorption and decomposition of methane on Fe/Cu(110)bimetallic surface

    Institute of Scientific and Technical Information of China (English)

    鲍世宁; 范朝阳; 李海洋; 徐亚伯

    1995-01-01

    The adsorption and decomposition of methane on Fe/Cu(110) bimetallic surface have been studied by HREELS and ARUPS. The results show that the activation energy of dissociative chemisorption for methane is reduced obviously by preadsorption of iron on copper surface. The chemisorption probability of methane is so high on Fe/Cu(110) bimetallic surface that chemisorption of methane can be observed at room temperature and low pressure. When the iron coverage is lower than 1 ML, the chemisorption probability increases linearly with increasing iron coverage. After the iron coverage is beyond 1 ML(<2ML) the probability continues increasing. The iron atom with disordered structure can offer the site of dissociative chemisorption to methane too. A hydroformyl species is formed through interaction between methane and the preadsorbed oxygen atoms. The reaction enhances the dissociative chemisorption of methane on the surface.

  8. CARBON DIOXIDE REDUCTION CONTACTORS IN SPACE VEHICLES AND OTHER ENCLOSED STRUCTURES,

    Science.gov (United States)

    CONTROLLED ATMOSPHERES, CARBON DIOXIDE , REMOVAL, LIFE SUPPORT SYSTEMS, SPACE ENVIRONMENTS, CONFINED ENVIRONMENTS, OXYGEN CONSUMPTION, REGENERATION(ENGINEERING), CHEMISORPTION, MASS TRANSFER, FLUID MECHANICS, CENTRIFUGES.

  9. Chemisorption characteristics of 2,4-dichlorophenol in aqueous solution onto adsorption resin modified by acetylaniline%乙酰苯胺修饰的吸附树脂对2,4-二氯苯酚的吸附研究

    Institute of Scientific and Technical Information of China (English)

    刘总堂; 张华彬; 费正皓; 柏书周; 张根成

    2006-01-01

    通过后交联反应,用乙酰苯胺修饰氯甲基化的低交联大孔聚苯乙烯-二乙烯(氯球),合成了一种超高交联吸附树脂ZH-05.用活性炭GAC和Amberlite XAD-4树脂作为参照,测试了ZH-05吸附树脂对2,4-二氯苯酚的吸附性能.讨论了静态平衡吸附行为和化学吸附特征的证实.结果表明:吸附等温线都能用Langmuir方程很好的拟合,且2,4-二氯苯酚在ZH-05吸附树脂上的吸附是一个吸热过程,吸附量随吸附温度的升高而增加,和活性炭一样,ZH-05树脂对水溶液中2,4-二氯苯酚的吸附过程中同时存在着物理吸附和化学吸附.

  10. Efficient CO2 capture and photoreduction by amine-functionalized TiO2.

    Science.gov (United States)

    Liao, Yusen; Cao, Shao-Wen; Yuan, Yupeng; Gu, Quan; Zhang, Zhenyi; Xue, Can

    2014-08-11

    Amine-functionalization of TiO2 nanoparticles, through a solvothermal approach, substantially increases the affinity of CO2 on TiO2 surfaces through chemisorption. This chemisorption allows for more effective activation of CO2 and charge transfer from excited TiO2 , and significantly enhances the photocatalytic rate of CO2 reduction into methane and CO.

  11. Effects of steps and defects on O2 dissociation on clean and modified Cu(100)

    DEFF Research Database (Denmark)

    Hirsimaki, M.; Chorkendorff, Ib

    2003-01-01

    Dissociative chemisorption of O-2 on Cu(100), S/Cu(100) and Ag/Cu(100) surface alloy has been investigated by Auger electron spectroscopy (AES). A strong reduction in the initial O-2 chemisorption probability (S-0) from 0.05 to 7.4 x 10(-3) is observed already at an Ag coverage of 0.02 ML. Further...

  12. (10, 10) Single walled carbon nanotube consisted of chemisorbed oxygen atoms as a promising supercapacitor electrode material: A first principles study

    Science.gov (United States)

    Targholi, Ehsan; Molaei, Masoumeh; Mousavi-Khoshdel, S. Morteza

    2016-11-01

    The effects of atomic oxygen chemisorption on the electronic structures and quantum capacitance of (10, 10) CNT have been studied in this article. The results indicated that the chemisorption on bonds aligned with nanotube axis is more favorable than other position. The most efficient configuration for enhancing quantum capacitance is the nanotube with oxygen atoms chemisorbed on axial bonds. Specifically, in water stability range, the quantum capacitance of (10, 10) CNT before and after chemisorption of six oxygen atoms (aligned with nanotube axis) were found to be 222.6 (anode) -117.6 (cathode) and 306.9 (anode) -217.2 (cathode) F/g, respectively.

  13. Surface photovoltage spectroscopy study of reduced and oxidized nanocrystalline TiO 2 films

    Science.gov (United States)

    Rothschild, A.; Levakov, A.; Shapira, Y.; Ashkenasy, N.; Komem, Y.

    2003-06-01

    Nanocrystalline TiO 2 films used for gas sensors have been studied by means of surface photovoltage spectroscopy and other analytical tools to investigate the oxygen chemisorption effect on the electrical properties of the films. The results show that the surface (and intergranular interface) band bending increases with oxygen exposure due to electron trapping at midgap states induced by chemisorption. The surface electronic structure is revealed by the measurements, allowing determination of the sensing mechanism of these important films. In addition, a photoinduced chemisorption of oxygen at room temperature is observed. This has important implications for low-temperature gas sensors.

  14. Surface enhanced raman spectra of biliverdine and pyrromethenone adsorbed to silver colloids

    Science.gov (United States)

    Lippitsch, Max E.

    1981-04-01

    Adsorption of certain bile pigments to silver colloids yields an enormous enhancement in Raman intensity, while fluorescence remains more or less unaffected. It is argued that this may be caused by (weak) chemisorption.

  15. Progress in surface and membrane science

    CERN Document Server

    Cadenhead, D A; Rosenberg, M D

    1975-01-01

    Progress in Surface and Membrane Science, Volume 9 covers the developments in surface and membrane science. The book discusses the physical adsorption of gases and vapors in micropores; the chemisorption theory; and the role of radioisotopes in the studies of chemisorption and catalysis. The text also describes the interaction of ions with monolayers; and the isolation and characterization of mycoplasma membranes. Chemists, physical chemists, and microbiologists will find the book useful.

  16. A New Activation Method for Electroless Metal Plating: Palladium Laden via Bonding with Self-Assembly Monolayers

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A new activation method has been developed for electroless copper plating on silicon wafer based on palladium chemisorption on SAMs of APTS without SnCl2 sensitization and roughening condition. A closely packed electroless copper film with strong adhesion is successfully fonned by AFM observation. XPS study indicates that palladium chemisorption occurred via palladium chloride bonding to the pendant amino group of the SAMs.

  17. Hydrogen interactions with polycrystalline and with deposited titanium surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Azoulay, A. [Ben-Gurion Univ. of the Negev, Beersheba (Israel); Shamir, N. [Nuclear Research Center-Negev, PO Box 9001, Beer Sheva (Israel); Fromm, E. [Max-Planck Institute fuer Metallforschung, Stuttgart (Germany); Szokefalvi-Nagy, A. [Max-Planck Institute fuer Metallforschung, Stuttgart (Germany); Mintz, M.H. [Ben-Gurion Univ. of the Negev, Beersheba (Israel)]|[Nuclear Research Center-Negev, PO Box 9001, Beer Sheva (Israel)

    1997-02-15

    The room temperature kinetics of hydrogen chemisorption and adsorption on polycrystalline and on deposited (sputter-deposited and evaporation-deposited) titanium surfaces were studied. Measurements of hydrogen surface accumulation were performed in a combined surface analyses system incorporating direct recoils spectrometry and Auger electron spectroscopy (AES). There, three different types of surface cleaning procedure were applied: heat-flashing, sputtering and sputter-deposition of titanium on a polycrystalline titanium substrate. The surface chemisorption kinetics obtained for the deposited samples were compared with the total kinetics of the gas phase consumption, performed in a volumetric Wagener system. From this comparison it was possible to distinguish between topmost surface chemisorption and subsurface (or bulk) absorption kinetics. It was concluded that, for all types of surface studied, hydrogen chemisorbed according to a Langmuir-type random two-sites chemisorption model, with high (close to unity) zero-coverage sticking probabilities. The only difference between these surfaces was in their roughness factors, which increased going from the heat-flashed, through the sputtered, to the deposited surfaces. Following the initial stage of a chemisorbed surface layer formation, constant-rate absorption of hydrogen proceeded over a very wide range of exposures (greater than 10{sup 4} Langmuirs). The accommodation probability of hydrogen during this linear stage was about 10{sup -2}. It is possible that this absorption process is controlled by the chemisorption of the H{sub 2} on the surface hydride phase, formed by the earlier hydrogen chemisorption. (orig.)

  18. Guest-Induced Two-Way Structural Transformation in a Layered Metal-Organic Framework Thin Film.

    Science.gov (United States)

    Haraguchi, Tomoyuki; Otsubo, Kazuya; Sakata, Osami; Fujiwara, Akihiko; Kitagawa, Hiroshi

    2016-12-28

    Fabrication of thin films made of metal-organic frameworks (MOFs) has been intensively pursued for practical applications that use the structural response of MOFs. However, to date, only physisorption-induced structural response has been studied in these films. Chemisorption can be expected to provide a remarkable structural response because of the formation of bonds between guest molecules and reactive metal sites in host MOFs. Here, we report that chemisorption-induced two-way structural transformation in a nanometer-sized MOF thin film. We prepared a two-dimensional layered-type MOF Fe[Pt(CN)4] thin film using a step-by-step approach. Although the as-synthesized film showed poor crystallinity, the dehydrated form of this thin film had a highly oriented crystalline nature (Film-D) as confirmed by synchrotron X-ray diffraction (XRD). Surprisingly, under water and pyridine vapors, Film-D showed chemisorption-induced dynamic structural transformations to Fe(L)2[Pt(CN)4] thin films [L = H2O (Film-H), pyridine (Film-P)], where water and pyridine coordinated to the open Fe(2+) site. Dynamic structural transformations were also confirmed by in situ XRD, sorption measurement, and infrared reflection absorption spectroscopy. This is the first report of chemisorption-induced dynamic structural response in a MOF thin film, and it provides useful insights, which would lead to future practical applications of MOFs utilizing chemisorption-induced structural responses.

  19. On adsorption of aluminium and methyl groups on silica for TMA/H2O process in atomic layer deposition of aluminium oxide nano layers

    Indian Academy of Sciences (India)

    Anu Philip; K Rajeev Kumar

    2010-04-01

    A detailed chemisorption mechanism is proposed for the atomic layer deposition (ALD) of aluminium oxide nano layers using trimethyl aluminum (TMA) and water as precursors. Six possible chemisorption mechanisms, complete ligand exchange, partial ligand exchange, simple dissociation, complete dissociation via ligand exchange, complete dissociation and association, are proposed and related parameters like ligand to metal ratio (L/M), concentrations of metal atoms and methyl groups adsorbed are calculated and compared against reported values. The maximum number of methyl groups that can get attached on the surface is calculated in a different way which yields a more realistic value of 6.25 per nm2 substrate area. The dependence of the number of metal atoms adsorbed on OH concentration is explained clearly. It is proposed that a combination of complete ligand exchange and complete dissociation is the most probable chemisorption mechanism taking place at various OH concentrations.

  20. The chemistry of simple alkene molecules on Si(100)c(4 × 2): The mechanism of cycloaddition and their selectivities

    Science.gov (United States)

    Akagi, Kazuto; Yoshinobu, Jun

    2016-10-01

    The chemistry of simple alkene molecules on the Si(100) surface is reviewed with the newly-produced visual presentation by theoretical calculations. The early pioneering studies by the Kyoto Group and Pittsburgh group reported the di-σ bond formation and the precursor-mediated chemisorption for acetylene and ethylene on Si(100), respectively. Thereafter, these studies have been stimulating various studies of organic molecules on Si surfaces. Our recent studies have observed the precursor states for alkene chemisorption and elucidated the microscopic mechanisms of the di-σ bond formation (cycloaddition) with the help of theoretical calculations; the site-, stereo- and regio-selective chemisorption of simple alkene molecules on Si(100)c(4 × 2) has been established.

  1. Some problems in adsorption and calorimetric studies of the steps of catalytic processes

    Institute of Scientific and Technical Information of China (English)

    Victor E. Ostrovskii

    2004-01-01

    Principal side factors as well as technical and procedural peculiarities capable of distorting the results of measurements of adsorbed and desorbed amounts, of falsifying the nature of the processes proceeding in the systems under study, and of promoting artifacts in calorimetric and other studies of gas chemisorption on powders are considered. Modified techniques and procedures allowing the elimination of sources of side phenomena and artifacts and freeing traditional glass static adsorption apparatuses and experimental procedures from undesirable factors and peculiarities are proposed.Some available chemisorption and calorimetric data representing artifacts and also some data that are not artifacts but,due to imperfections of chemisorption techniques, show up as artifacts are presented and discussed. Several applications of the improved techniques and procedures to calorimetric and adsorption studies of the steps of catalytic processes proceeding on the basis of natural gas and of products of its processing are presented and discussed.

  2. Chlorine-induced modifications in the electronic structure of Ag surfaces: a metastable deexcitation spectroscopy and photoemission comparative study

    CERN Document Server

    Pasquali, L; Canepa, M; Staicu-Casagrande, E M; Esaulov, V A

    2003-01-01

    Surface-sensitive spectroscopic techniques, namely metastable deexcitation spectroscopy (MDS) and ultraviolet photoemission (UPS), have been applied to investigate the effects of chlorine chemisorption on the electronic properties (surface density of states and charge density) of Ag(100), Ag(110) and Ag(111) surfaces. Initial stages of chemisorption, up to the formation of a saturated Cl overlayer, have been examined. In particular, MDS permitted us to observe at low Cl gas exposure a progressive depletion of the Ag (5s) charge due to transfer and bonding with Cl atoms. From both MDS and UPS it was possible to observe the development of Cl (3p) bonding and anti-bonding states, the amount of their splitting increasing with coverage. Differences between chemisorption at the three surfaces have been noticed and they have been justified in terms of the different adatom packing and possible formation of small AgCl clusters (especially for the Ag(111) surface).

  3. ADSORPTION OF 2,4-DICHLOROPHENOL IN AQUEOUS SOLUTION ONTO ADSORPTION RESIN MODIFIED BY N-ACETYLANILINE

    Institute of Scientific and Technical Information of China (English)

    Zheng-hao Fei; Hua-bin Zhang; Zong-tang Liu

    2007-01-01

    A hypercrosslinked adsorption resin (ZH-05) modified by N-acetylaniline in the post crosslinking process was prepared. The adsorption properties of ZH-05 toward 2,4-dichlorophenol in comparison with granular activated carbon (GAC) and Amberlite XAD-4 were observed. The present study mainly focuses on the static equilibrium adsorption behaviors, desorption profiles and the proof of chemisorption. The results show that the Langmuir equation can give a perfect fitting to experimental data, and high temperature was favorable for adsorption of 2,4-dichlorophenol on ZH-05. A related equation was used to correlate the amount of chemisorption and the suppositional chemisorption equilibrium concentration of adsorbate in aqueous solution. The adsorption capacities from different ranges of temperature and the static desorption experiment both reveal the same conclusion, i.e., the adsorption of 2,4-dichlorophenol from water on ZH-05 is a coexistent process of physical adsorption and chemical transition as on GAC.

  4. Chemical reactions on solid surfaces using molecular beam techniques

    Science.gov (United States)

    Palmer, R. L.

    1980-07-01

    Thermal energy molecular beams have been used to study chemical interactions with metal surfaces. Chemisorption of simple molecules such as H2, O2, CH4, C2Hx and CO was investigated on single and polycrystalline surfaces of Pt, Ni, Co, and Ag. Kinetic parameters and reaction mechanisms were determined for model catalytic reactions including CO and C2Hx oxidation and methanation from H2/CO mixtures. Chemical reactions of NOx with CO and D2 on Pt(111) and other surfaces have been surveyed and the kinetics of NO and O2 chemisorption have been measured. The theory of adsorption/desorption kinetics is reviewed and certain deficiencies identified.

  5. 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

  6. Pt-Rh/g Al2O3 Influence of Catalyst Preparation Methods on Metallic Particle Dispersion and Size Distribution

    Directory of Open Access Journals (Sweden)

    N.M. da Fonseca

    1998-06-01

    Full Text Available - Pt-Rh/Al2O3 catalysts were prepared by successive incipient impregnations or coimpregnation. Characterization was achieved by H2 chemisorption and transmission electron microscopy. It was verified that method of preparation, ratio of metal weights and sequence of deposition are factors that result in very distinct catalysts.

  7. Long-Range Interfacial Electrochemical Electron Transfer of Pseudomonas aeruginosa Azurin-Gold Nanoparticle Hybrid Systems

    DEFF Research Database (Denmark)

    Jensen, Palle Skovhus; Chi, Qijin; Zhang, Jingdong

    2009-01-01

    We have prepared a "hybrid" of the blue copper protein azurin (Pseudomonas aeruginosa) and a 3 nm gold nanoparticle (AuNP). The AuNP/azurin hybrid was assembled on a Au(111)-electrode surface in a two-step process. The AuNP was first attached to the Au(111) electrode via Au-S chemisorption of a 4...

  8. Atomic and molecular adsorption on Rh(111)

    DEFF Research Database (Denmark)

    Mavrikakis, Manos; Rempel, J.; Greeley, Jeffrey Philip

    2002-01-01

    A systematic study of the chemisorption of both atomic (H, O, N, S, C), molecular (N-2, CO, NO), and radical (CH3, OH) species on Rh(111) has been performed. Self-consistent, periodic, density functional theory (DFT-GGA) calculations, using both PW91 and RPBE functionals, have been employed to de...

  9. Dithiocarbamate Assembly on Gold

    OpenAIRE

    Yan ZHAO; Perez-Segarra, Waleska; Shi, Qicun; Wei, Alexander

    2005-01-01

    Metal surfaces are functionalized by stable dithiocarbamate ligands when exposed to carbon disulfide and secondary amines. The adsorbed dithiocarbamates are robust under a wide pH range and can resist displacement by other chemisorptive surfactants, providing an attractive method for conjugating sensitive molecules onto metal surfaces.

  10. An Electrochemical and Raman Spectroscopy Study of the Surface Behaviour of Mononuclear Ruthenium and Osmium Polypyridyl Complexes Based on Pyridyl- and Thiophene-Based Linkers

    NARCIS (Netherlands)

    Halpin, Yvonne; Logtenberg, Hella; Cleary, Laura; Schenk, Stephan; Schulz, Martin; Draksharapu, Apparao; Browne, Wesley R.; Vos, Johannes G.

    2013-01-01

    The utility of a thiophene anchor unit as an alternative for thiols in the immobilisation of ruthenium and osmium complexes on gold and platinum is examined with special attention focused on the relative contributions of physi- and chemisorption of the complexes and the chemical stability of the thi

  11. When Langmuir is too simple: H-2 dissociation on Pd(111) at high coverage

    DEFF Research Database (Denmark)

    Lopez, Nuria; Lodziana, Zbigniew; Illas, F.

    2004-01-01

    Recent experiments of H-2 adsorption on Pd(111) [T. Mitsui et al., Nature (London) 422, 705 (2003)] have questioned the classical Langmuir picture of second order adsorption kinetics at high surface coverage requiring pairs of empty sites for the dissociative chemisorption. Experiments find that ...

  12. Production of hydrogen from methanol over Cu/ZnO catalysts promoted by ZrO2 and Al2O3

    NARCIS (Netherlands)

    Navarro, R.M.; Melián-Cabrera, I.; Boutonnet, M.; Birgersson, H.; Agrell, J.; Fierro, J.L.G.

    2003-01-01

    Production of H2 from methanol by steam reforming, partial oxidation, or a combination thereof was studied over Cu/ZnO-based catalysts. The catalysts were characterized by a variety of techniques, including N2O chemisorption, X-ray photoelectron spectroscopy, X-ray diffraction, and temperature-progr

  13. Calcium-phosphorus interactions at a nano-structured silicate surface.

    Science.gov (United States)

    Southam, Daniel C; Lewis, Trevor W; McFarlane, Andrew J; Borrmann, T; Johnston, Jim H

    2008-03-15

    Nano-structured calcium silicate (NCS), a highly porous material synthesized by controlled precipitation from geothermal fluids or sodium silicate solution, was developed as filler for use in paper manufacture. NCS has been shown to chemisorb orthophosphate from an aqueous solution probably obeying a Freundlich isotherm with high selectivity compared to other common environmental anions. Microanalysis of the products of chemisorption indicated there was significant change from the porous and nano-structured morphology of pristine NCS to fibrous and crystalline morphologies and non-porous detritus. X-ray diffraction analysis of the crystalline products showed it to be brushite, CaHPO42H2O, while the largely X-ray amorphous component was a mixture of calcium phosphates. A two-step mechanism was proposed for the chemisorption of phosphate from an aqueous solution by NCS. The first step, which was highly dependent on pH, was thought to be desorption of hydroxide ions from the NCS surface. This was kinetically favoured at lower initial pH, where the predominant form of phosphate present was H2PO(-)4, and led to decreased phosphorus uptake with increasing pH. The second step was thought to be a continuing chemisorption process after stabilization of the pH-value. The formation of brushite as the primary chemisorption product was found to be consistent with the proposed mechanism.

  14. Interactions between acid- and base-functionalized surfaces

    NARCIS (Netherlands)

    Giesbers, M.; Kleijn, J.M.; Cohen Stuart, M.A.

    2002-01-01

    In this paper we present an AFM force study on interactions between chemically modified surfaces. Surfaces with terminal groups of either NH2 or COOH were obtained by chemisorption of a silane-based compound (3-amino-propyltriethoxysilane) on silica or a thiol compound (11-mercapto undecanoic acid)

  15. Micromachined silicon plates for sensing molecular interactions

    NARCIS (Netherlands)

    Carlen, E.T.; Weinberg, M.S.; Dube, C.E.; Zapata, A.M.; Borenstein, J.T.

    2006-01-01

    A micromachined surface stress sensor based on a thin suspended crystalline silicon circular plate measures differential surface stress changes associated with vapor phase chemisorption of an alkanethiol self-assembled monolayer. The isolated face of the suspended silicon plate serves as the sensing

  16. Unsupported PVA- and PVP-stabilized Pd nanoparticles as catalyst for nitrite hydrogenation in aqueous phase

    NARCIS (Netherlands)

    Zhao, Y.; Baeza, J.A.; Koteswara Rao, N.; Calvo, L.; Gilarranz, M.A.; Li, Y.D.; Lefferts, L.

    2014-01-01

    Pd colloids stabilized with polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) have been prepared, characterized with TEM, zeta potential measurements, CO chemisorption in aqueous phase, and ATR-IR spectroscopy using CO as a probe molecule, and finally tested for performance in nitrite hydrogena

  17. The Electronic Structure Effect in Heterogeneous Catalysis

    DEFF Research Database (Denmark)

    Nilsson, A.; Pettersson, L. G. M.; Hammer, Bjørk

    2005-01-01

    Using a combination of density functional theory calculations and X-ray emission and absorption spectroscopy for nitrogen on Cu and Ni surfaces, a detailed picture is given of the chemisorption bond. It is suggested that the adsorption bond strength and hence the activity of transition metal...... surfaces as catalysts for chemical reactions can be related to certain characteristics of the surface electronic structure....

  18. Nickel(II) oxide surface-modified titanium(IV) dioxide as a visible-light-active photocatalyst.

    Science.gov (United States)

    Jin, Qiliang; Ikeda, Takuro; Fujishima, Musashi; Tada, Hiroaki

    2011-08-21

    The electronic modification of TiO(2) with highly dispersed NiO particles smaller than ca. 2 nm by the chemisorption-calcination-cycle technique has given rise to a high level of visible-light-activity exceeding that of iron oxide-surface modified TiO(2) simultaneously with the UV-light-activity being significantly increased.

  19. Photocatalytic oxidation mechanism of alkanes in contact with titanium dioxide

    Science.gov (United States)

    Formenti, M.; Juillet, F.; Teichner, S. J.

    1977-01-01

    Isobutane was photooxidized on titanium dioxide between -16 and +180 C in tertiary butanol and acetone. The formation of tertiary butanol preceded the formation of acetone. Above 20 C the latter compound became clearly predominant. The reaction kinetics obeyed a steady state model of oxygen chemisorption with the involvement of isobutane in the physisorbed phase.

  20. Electron transfer behaviour of biological macromolecules towards the single-molecule level

    DEFF Research Database (Denmark)

    Zhang, Jingdong; Grubb, Mikala; Hansen, Allan Glargaard

    2003-01-01

    on Au(111) by chemisorption via exposed sulfur-containing residues. Voltammetric, interfacial capacitance, x-ray photoelectron spectroscopy and microcantilever sensor data, together with in situ STM with single-molecule resolution, all point to a coherent view of monolayer organization with protein...

  1. Scanning Tunneling Microscopic Observation of Adatom-Mediated Motifs on Gold-Thiol Self-assembled Monolayers at High Coverage

    DEFF Research Database (Denmark)

    Wang, Yun; Chi, Qijin; Hush, Noel S.;

    2009-01-01

    Self-assembled monolayers (SAMs) formed by chemisorption of a branched-chain alkanethiol, 2-methyl-1-propanethiol, on Au(111) surfaces were studied by in situ scanning tunneling microscopy (STM) under electrochemical potential control and analyzed using extensive density functional theory (DFT) c...

  2. Materials Down Select Decisions Made Within the Department of Energy Hydrogen Sorption Center of Excellence

    Energy Technology Data Exchange (ETDEWEB)

    Simpson, Lin [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2009-11-30

    Technical report describing DOE's Hydrogen Sorption Center of Excellence investigation into various adsorbent and chemisorption materials and progress towards meeting DOE's hydrogen storage targets. The report presents a review of the material status as related to DOE hydrogen storage targets and explains the basis for the down select decisions.

  3. Dry cleaning aluminum cell gases from Söderberg cells

    Science.gov (United States)

    Doheim, M. A.; Shafey, H. M.; Abdellatif, A. A.; Ahmed, M. S.

    2000-02-01

    This article describes dry cleaning gases from vertical Söderberg cells via a two-step process involving the combustion of tars and CO followed by the chemisorption of HF on smelter-grade alumina. Both steps take place in fluidized-bed reactors. Studied parameters include distributor design, fluidizing velocity, bed temperature, and bed height.

  4. Modeling Mechanism and Growth Reactions for New Nanofabrication Processes by Atomic Layer Deposition.

    Science.gov (United States)

    Elliott, Simon D; Dey, Gangotri; Maimaiti, Yasheng; Ablat, Hayrensa; Filatova, Ekaterina A; Fomengia, Glen N

    2016-07-01

    Recent progress in the simulation of the chemistry of atomic layer deposition (ALD) is presented for technologically important materials such as alumina, silica, and copper metal. Self-limiting chemisorption of precursors onto substrates is studied using density functional theory so as to determine reaction pathways and aid process development. The main challenges for the future of ALD modeling are outlined.

  5. Removal of hydrogen sulfide using palygorskite in a fixed bed adsorber.

    Science.gov (United States)

    Higuchi, T; Zhang, Q; Sekine, M; Imai, T; Yamamoto, K

    2012-01-01

    This work describes the use of a novel palygorskite, a type of magnesium aluminium silicate clay possessing a high specific surface area and pore surface activity, as a low cost and highly efficient adsorbent for hydrogen sulfide (H(2)S) removal. Adsorption of H(2)S on palygorskite pretreated with acid or base was investigated in a fixed bed adsorber. The samples after base pretreatment had better dynamic adsorption performances than raw material and samples pretreated with acid. The H(2)S adsorption capacity decreased with an increase in inlet H(2)S concentration. This can be interpreted by the fact that H(2)S adsorption on the surface of palygorskite is chemisorption. The adsorption capacity increased from 25 to 50 °C, then decreased from 50 to 100 °C, which indicates that chemisorption took place and its better reaction temperature was around 50 °C.

  6. Oxide Defect Engineering Enables to Couple Solar Energy into Oxygen Activation.

    Science.gov (United States)

    Zhang, Ning; Li, Xiyu; Ye, Huacheng; Chen, Shuangming; Ju, Huanxin; Liu, Daobin; Lin, Yue; Ye, Wei; Wang, Chengming; Xu, Qian; Zhu, Junfa; Song, Li; Jiang, Jun; Xiong, Yujie

    2016-07-20

    Modern development of chemical manufacturing requires a substantial reduction in energy consumption and catalyst cost. Sunlight-driven chemical transformation by metal oxides holds great promise for this goal; however, it remains a grand challenge to efficiently couple solar energy into many catalytic reactions. Here we report that defect engineering on oxide catalyst can serve as a versatile approach to bridge light harvesting with surface reactions by ensuring species chemisorption. The chemisorption not only spatially enables the transfer of photoexcited electrons to reaction species, but also alters the form of active species to lower the photon energy requirement for reactions. In a proof of concept, oxygen molecules are activated into superoxide radicals on defect-rich tungsten oxide through visible-near-infrared illumination to trigger organic aerobic couplings of amines to corresponding imines. The excellent efficiency and durability for such a highly important process in chemical transformation can otherwise be virtually impossible to attain by counterpart materials.

  7. Understanding the role of thiol and disulfide self-assembled DNA receptor monolayers for biosensing applications.

    Science.gov (United States)

    Carrascosa, Laura G; Martínez, Lidia; Huttel, Yves; Román, Elisa; Lechuga, Laura M

    2010-09-01

    A detailed study of the immobilization of three differently sulfur-modified DNA receptors for biosensing applications is presented. The three receptors are DNA-(CH)n-SH-, DNA-(CH)n-SS-(CH)n-DNA, and DNA-(CH)n-SS-DMTO. Nanomechanical and surface plasmon resonance biosensors and fluorescence and radiolabelling techniques were used for the experimental evaluation. The results highlight the critical role of sulfur linker type in DNA self-assembly, affecting the kinetic adsorption and spatial distribution of DNA chains within the monolayer and the extent of chemisorption and physisorption. A spacer (mercaptohexanol, MCH) is used to evaluate the relative efficiencies of chemisorption of the three receptors by analysing the extent to which MCH can remove physisorbed molecules from each type of monolayer. It is demonstrated that -SH derivatization is the most suitable for biosensing purposes as it results in densely packed monolayers with the lowest ratio of physisorbed probes.

  8. On the behavior of Bronsted-Evans-Polanyi Relations for Transition Metal Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Vojvodic, Aleksandra

    2011-08-22

    Versatile Broensted-Evans-Polanyi (BEP) relations are found from density functional theory for a wide range of transition metal oxides including rutiles and perovskites. For oxides, the relation depends on the type of oxide, the active site and the dissociating molecule. The slope of the BEP relation is strongly coupled to the adsorbate geometry in the transition state. If it is final state-like the dissociative chemisorption energy can be considered as a descriptor for the dissociation. If it is initial state-like, on the other hand, the dissociative chemisorption energy is not suitable as descriptor for the dissociation. Dissociation of molecules with strong intramolecular bonds belong to the former and molecules with weak intramolecular bonds to the latter group. We show, for the prototype system La-perovskites, that there is a 'cyclic' behavior in the transition state characteristics upon change of the active transition metal of the oxide.

  9. Effect of method of preparation on hydrodesulphurization activity of Co- or Ni-promoted MoS2/SBA-15 catalysts

    Indian Academy of Sciences (India)

    Shelu Garg; Kapil Soni; V V D N Prasad; Manoj Kumar; Thallada Bhaskar; J K Gupta; G Murali Dhar; C S Gopinath

    2014-03-01

    Ordered mesoporous material SBA-15 was synthesized and used as a support for the preparation of molybdenum sulphide catalysts through precipitation from homogeneous solution (PFHS) technique with the Mo content varying from 2-12 wt%. The prepared catalysts were evaluated for thiophene hydrodesulphurization catalytic activities at 400°RC. Catalysts prepared through PFHS method resulted in highly dispersed MoS2 catalysts, which were inferred from powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), low temperature oxygen chemisorptions (LTOC) and BET surface area analysis. The relationship between XPS intensity ratio, oxygen chemisorption and catalytic activities is discussed in terms of highly dispersed nano particles of MoS2 and its consequence in accommodating more promoted atoms at the edge sites.

  10. Direct Observation of Molecular Preorganization for Chirality Transfer on a Catalyst Surface

    DEFF Research Database (Denmark)

    Demers-Carpentier, Vincent; Goubert,, Guillaume; Masini, Federico

    2011-01-01

    The chemisorption of specific optically active compounds on metal surfaces can create catalytically active chirality transfer sites. However, the mechanism through which these sites bias the stereoselectivity of reactions (typically hydrogenations) is generally assumed to be so complex that conti......The chemisorption of specific optically active compounds on metal surfaces can create catalytically active chirality transfer sites. However, the mechanism through which these sites bias the stereoselectivity of reactions (typically hydrogenations) is generally assumed to be so complex...... functional theory calculations reveals the stereodirecting forces governing preorganization into precise chiral modifier-substrate bimolecular surface complexes. The study shows that the chiral modifier induces prochiral switching on the surface and that different prochiral ratios prevail at different...

  11. Optical properties of molecules chemisorbed on the Ni (111) surface

    Energy Technology Data Exchange (ETDEWEB)

    Robota, H. J. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Whitmore, P. M. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Harris, C. B. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

    1982-02-15

    The adsorption of a variety of molecules on Ni(111) is studied by UV/visible spectroscopic ellipsometry. The spectra were analyzed within a simple dielectric model. The absorption spectra of annealed, thin, condensed layers of pyrazine, pyridine, and naphthalene on the Ni(111) surface resemble bulk crystal spectra, indicating minimal perturbations due to the metal substrate. Chemisorption of molecules on the Ni(111) surface produced enhanced absorption between 2800Å and 3100Å. The wide range of adsorbate properties and surface chemistry suggest a modification of the optical response of the metal upon chemisorption. Furthermore, this enhanced optical absorption is attributed to nonvertical interband transitions made possible by loss of translational invariance at the surface.

  12. Effects of Cu over Pd based catalysts supported on silica or niobia

    Directory of Open Access Journals (Sweden)

    Roma M.N.S.C.

    2000-01-01

    Full Text Available Palladium and palladium-copper catalysts supported on silica and niobia were characterized by H2 chemisorption and H2-O2 titration. Systems over silica were also analyzed by transmission electron microscopy and EXAFS. The metallic dispersion decreased from 20% to 7% when the content of Pd was increased from 0.5wt.-% to 3wt.-% in monometallic catalysts. The addition of 3 wt.-% Cu to obtain Pd-Cu catalysts caused a remarkable capacity loss of hydrogen chemisorption. TPR analysis suggested an interaction between the two metals and EXAFS characterization of the catalyst supported on silica confirmed the formation of Pd-Cu alloy. Pd/Nb2O5 catalysts showed turnover numbers higher than those obtained with the Pd/SiO2 systems in the cyclohexane dehydrogenation. However, the bimetallic catalysts showed very low turnover numbers.

  13. Communication: Energy transfer and reaction dynamics for DCl scattering on Au(111): An ab initio molecular dynamics study

    Science.gov (United States)

    Kolb, Brian; Guo, Hua

    2016-07-01

    Scattering and dissociative chemisorption of DCl on Au(111) are investigated using ab initio molecular dynamics with a slab model, in which the top two layers of Au are mobile. Substantial kinetic energy loss in the scattered DCl is found, but the amount of energy transfer is notably smaller than that observed in the experiment. On the other hand, the dissociative chemisorption probability reproduces the experimental trend with respect to the initial kinetic energy, but is about one order of magnitude larger than the reported initial sticking probability. While the theory-experiment agreement is significantly improved from the previous rigid surface model, the remaining discrepancies are still substantial, calling for further scrutiny in both theory and experiment.

  14. Surface effects of electrode-dependent switching behavior of resistive random-access memory

    KAUST Repository

    Ke, Jr Jian

    2016-09-26

    The surface effects of ZnO-based resistive random-access memory (ReRAM) were investigated using various electrodes. Pt electrodes were found to have better performance in terms of the device\\'s switching functionality. A thermodynamic model of the oxygen chemisorption process was proposed to explain this electrode-dependent switching behavior. The temperature-dependent switching voltage demonstrates that the ReRAM devices fabricated with Pt electrodes have a lower activation energy for the chemisorption process, resulting in a better resistive switching performance. These findings provide an in-depth understanding of electrode-dependent switching behaviors and can serve as design guidelines for future ReRAM devices.

  15. Ethylene binding to Au/Cu alloy nanoparticles

    Science.gov (United States)

    Gammage, Michael D.; Stauffer, Shannon; Henkelman, Graeme; Becker, Michael F.; Keto, John W.; Kovar, Desiderio

    2016-11-01

    Weak chemisorption of ethylene has been shown to be an important characteristic in the use of metals for the separation of ethylene from ethane. Previously, density functional theory (DFT) has been used to predict the binding energies of various metals and alloys, with Ag having the lowest chemisorption energy amongst the metals and alloys studied. Here Au/Cu alloys are investigated by a combination of DFT calculations and experimental measurements. It is inferred from experiments that the binding energy between a Au/Cu alloy and ethylene is lower than to either of the pure metals, and DFT calculations confirm that this is the case when Au segregates to the particle surface. Implications of this work suggest that it may be possible to further tune the binding energy with ethylene by compositional and morphological control of films produced from Au-surface segregated alloys.

  16. Carbon 1s photoemission line analysis of C-based adsorbate on (111)In2O3 surface: The influence of reducing and oxidizing conditions

    Science.gov (United States)

    Brinzari, V.; Cho, B. K.; Korotcenkov, G.

    2016-12-01

    Synchrotron radiation photoemission study of C 1s line of (111) In2O3 surface was carried out under HV (high vacuum) doses of oxygen, carbon monoxide and water. Gas interaction with the surface was activated by heating of In2O3 monocrystalline film at temperatures of 160 or 250 °C. The study of complex structure of C 1 s line and evolution of its fine components allowed to establish their nature and to propose possible surface adsorbed species and reactions, including a direct chemisorption and dissociation of CO molecules. Reduction or oxidation of the surface determines whether the first (chemisorption) or the second (dissociation) process takes place. The latter is responsible for additional formation of ionosorbed oxygen. Both processes have not been previously reported for In2O3 and for conductive metal oxides.

  17. Bandgap Restructuring of the Layered Semiconductor Gallium Telluride in Air.

    Science.gov (United States)

    Fonseca, Jose J; Tongay, Sefaattin; Topsakal, Mehmet; Chew, Annabel R; Lin, Alan J; Ko, Changhyun; Luce, Alexander V; Salleo, Alberto; Wu, Junqiao; Dubon, Oscar D

    2016-08-01

    A giant bandgap reduction in layered GaTe is demonstrated. Chemisorption of oxygen to the Te-terminated surfaces produces significant restructuring of the conduction band resulting in a bandgap below 0.8 eV, compared to 1.65 eV for pristine GaTe. Localized partial recovery of the pristine gap is achieved by thermal annealing, demonstrating that reversible band engineering in layered semiconductors is accessible through their surfaces.

  18. Reliable structural, thermodynamic, and spectroscopic properties of organic molecules adsorbed on silicon surfaces from computational modeling: the case of glycine@Si(100).

    Science.gov (United States)

    Carnimeo, Ivan; Biczysko, Malgorzata; Bloino, Julien; Barone, Vincenzo

    2011-10-06

    Chemisorption of glycine on Si(100) has been studied by an integrated computational strategy based on perturbative anharmonic computations employing geometries and harmonic force fields evaluated by hybrid density functionals coupled to purposely tailored basis sets. It is shown that such a strategy allows the prediction of spectroscopic properties of isolated and chemisorbed molecules with comparable accuracy, paving the route toward a detailed analysis of surface-induced changes of glycine vibrational spectra.

  19. Theoretical Studies of Nanoclusters (Briefing Charts)

    Science.gov (United States)

    2015-07-23

    representation of actual NP surface? • Reaction enthalpies and barriers for – chemisorption of NH3 – fragmentation of chemisorbed NH3 – formation of H2...suspended or dissolved in ionic liquids - surface-functionalized NPs can be dispersed in variety of liquids hydrocarbons , ILs, polar solvents...distribution unlimited. • DFT calculations (M06/6-311++G(d,p)) used to identify surface species and reactions leading to their formation. • Al80

  20. Visible-light-induced water oxidation by a hybrid photocatalyst consisting of bismuth vanadate and copper(II) meso-tetra(4-carboxyphenyl)porphyrin.

    Science.gov (United States)

    Nakashima, Shu; Negishi, Ryo; Tada, Hiroaki

    2016-03-04

    Copper(II) meso-tetra(4-carboxyphenyl)porphyrin surface-modified monoclinic scheelite bismuth vanadate (CuTCPP/BiVO4) has been synthesized via a two-step route involving chemisorption of TCPP on BiVO4 and successive Cu(II) ion incorporation into the TCPP, and the surface modification drastically enhances the water oxidation to oxygen (O2) under visible-light irradiation (λ > 430 nm).

  1. Surface Modification of an Experimental Silicone Rubber Maxillofacial Material to Improve Wettability

    OpenAIRE

    2002-01-01

    OBJECTIVES: Good wettability of maxillofacial prosthetic materials is important so hat a lubricating layer is formed with supporting tissues thus reducing patient discomfort. The purpose of the study was to surface modify an experimental silicone rubber material in order to improve wettability. METHODS : Samples of experimental silicone rubber were surface modified by first argon plasma treatment followed by chemisorption of ethyleneoxy functional silanes. These were compared with the s...

  2. A DFT Structural Investigation of New Bimetallic PtSnx Surface Alloys Formed on the Pt(110) Surface and Their Interaction with Carbon Monoxide

    DEFF Research Database (Denmark)

    Zheng, Jian; Busch, Michael; Artiglia, Luca

    2016-01-01

    desorbs from the PtSnx surfaces at about 415-425 K compared to 495 K on the clean Pt(110). The energetics and geometry of the CO chemisorption sites have been studied by DFT calculations, obtaining an adsorption energy of 0.7-0.86 eV on p(3 x 1) and 0.9-1.05 eV on p(6 x 1). Overall our theoretical...

  3. Thermal Emissivity-Based Chemical Spectroscopy through Evanescent Tunneling.

    Science.gov (United States)

    Poole, Zsolt L; Ohodnicki, Paul R

    2016-04-01

    A new spectroscopic technique is presented, with which environmentalchemistry-induced thermal emissivity changes of thin films are extracted with high isolation through evanescent tunneling. With this method the hydrogen-induced emissivity changes of films of TiO2 , Pd-TiO2 , and Au-TiO2 , with properties of high conductivity, hydrogen chemisorption, and plasmonic activity, are characterized in the UV-vis and NIR wavelength ranges, at 1073 K.

  4. C2Hn Fragments on Metal Surfaces.

    Science.gov (United States)

    1985-02-22

    Roald Hoffmann Prepared for Publication in I ID Physical Review Letters Laboratory of Atomic and Solid State Physics Cornell University Ithaca, NY 14853...r6me Silvestre and Roald Hoffmann Department of Chemistry and Materials Science Center Cornell University, Ithaca, NY 14853 Abstract: -The chemisorption...Bernhardt and H. Vahrenkamp, Anqew. Chem. 96, 139 (1984). 8. P.-K. Wang , C.P. Slichter and J.H. Sinfelt, Phys. Rev. Lett. 53, 81 (1984). 9. K.Y. Yu, W.E

  5. Tuning the composition of metastable CoxNiyMg100−x−y(OH)(OCH3) nanoplates for optimizing robust methane dry reforming catalyst

    DEFF Research Database (Denmark)

    Fan, Xiaoli; Liu, Zhiting; Zhu, Yi-An;

    2015-01-01

    Finding controllable, low-cost, and scalable ways to generate Ni-based catalysts is the bottleneck for methane dry reforming catalyst design. A new method for generating trimetallic CoxNiyMg100−x−yO solid solution platelets enclosed by (111) facets has been developed from the topotactic pyrolysis...... the chemisorption of oxygen and reduces the activation energy for methane fragmentation, which is the rate-determining step for the overall reaction....

  6. Chemical Reactions of Silicon Clusters

    OpenAIRE

    Ramakrishna, Mushti V.; Pan, Jun

    1994-01-01

    Smalley and co-workers discovered that chemisorption reactivities of silicon clusters vary over three orders of magnitude as a function of cluster size. In particular, they found that \\Si{33}, \\Si{39}, and \\Si{45} clusters are least reactive towards various reagents compared to their immediate neighbors in size. We explain these observations based on our stuffed fullerene model. This structural model consists of bulk-like core of five atoms surrounded by fullerene-like surface. Reconstruction...

  7. Surface effects in metallic iron nanoparticles

    DEFF Research Database (Denmark)

    Bødker, Franz; Mørup, Steen; Linderoth, Søren

    1994-01-01

    Nanoparticles of metallic iron on carbon supports have been studied in situ by use of Mossbauer spectroscopy. The magnetic anisotropy energy constant increases with decreasing particle size, presumably because of the influence of surface anisotropy. Chemisorption of oxygen results in formation...... of a surface layer with magnetic hyperfine fields similar to those of thicker passivation layers, and with a ferromagnetic coupling to the spins in the core of the particles. In contrast, thicker passivation layers have a noncollinear spin structure....

  8. (Electronic structure and reactivities of transition metal clusters)

    Energy Technology Data Exchange (ETDEWEB)

    1992-01-01

    The following are reported: theoretical calculations (configuration interaction, relativistic effective core potentials, polyatomics, CASSCF); proposed theoretical studies (clusters of Cu, Ag, Au, Ni, Pt, Pd, Rh, Ir, Os, Ru; transition metal cluster ions; transition metal carbide clusters; bimetallic mixed transition metal clusters); reactivity studies on transition metal clusters (reactivity with H{sub 2}, C{sub 2}H{sub 4}, hydrocarbons; NO and CO chemisorption on surfaces). Computer facilities and codes to be used, are described. 192 refs, 13 figs.

  9. Uniform Li2S precipitation on N,O-codoped porous hollow carbon fibers for high-energy-density lithium-sulfur batteries with superior stability.

    Science.gov (United States)

    Qie, Long; Manthiram, Arumugam

    2016-09-21

    A lithium-polysulfide cell with superior stability is reported with N,O-codoped carbon hollow fiber (NCHF) sheets as a current collector. Due to the highly effective chemisorption and physical adsorption of lithium polysulfides on doped NCHF and a uniform Li2S precipitation during cycling, the Li2S6-impregnated NCHF electrodes exhibit high sulfur utilization and superior cycling stability even with a high areal sulfur loading of 6.2 mg cm(-2).

  10. Characterization and functionalities of Pd/hydrotalcite catalysts

    Science.gov (United States)

    Naresh, Dhachapally; Kumar, Vanama Pavan; Harisekhar, Mitta; Nagaraju, Nekkala; Putrakumar, Balla; Chary, Komandur V. R.

    2014-09-01

    A series of palladium supported on calcined hydrotalcite (CHT) catalysts with varying palladium (Pd) loadings (1.0-8.0 wt%) were prepared by impregnation method. Their catalytic performance was evaluated for the reductive amination of phenol to aniline that showed a tremendous interest in the chemical industry. The catalysts were characterized by BET surface area, XRD, TEM, XPS, TPR of H2, TPD of CO2 and CO chemisorption. BET surface area decreased continuously with increase in Pd content. XRD results confirmed the changes in the crystalline phases with altering Pd content. TEM results showed the formation of fine particles at lower loadings and agglomerates at higher loadings. TPR profiles revealed that the reducibility increases with increase of Pd loading. CO2 TPD results illustrate the catalysts basicity increases with increase of Pd loading up to 4.0 wt% and decreases at higher loadings. Pd dispersion, metal area and crystallite sizes were determined by CO chemisorption method. Pd dispersion and metal area decreases with increase of Pd content and crystallite sizes. The results demonstrated that the Pd dispersion and basic properties are depending on the Pd loading. The catalytic performance clearly showed that the increase Pd loading the conversion of phenol increased up to 2.0 wt% and level off beyond the loading. The catalytic properties are well correlated with the active Pd sites determined by CO chemisorption, dispersion and basicity.

  11. 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...

  12. Ab-initio investigation of adsorption of CO and CO2 molecules on graphene: Role of intrinsic defects on gas sensing

    Science.gov (United States)

    Tit, Nacir; Said, Khadija; Mahmoud, Nadin M.; Kouser, Summayya; Yamani, Zain H.

    2017-02-01

    We determine the chemical activity of (a) carbon site of pristine graphene (pG), (b) Stone-Wales (SW) defect site, and (c) Single-vacancy of graphene (vG) site towards the adsorption of CO and CO2 molecules, through comparative analysis based on first-principles density-functional calculations incorporating van der Waals (vdW) interactions, but excluding the heat effects (i.e., at T = 0 °K). The results show that the chemisorption of both latter molecules to possibly occur only on vG. The response (sensitivity) of vG towards detecting CO molecule was confirmed by the rise of conductance with the increasing CO gas dose. The selectivity was investigated by testing the response of vG towards detecting eight different gases (i.e., CO, CO2, N2, O2, H2O, H2S, H2, and NH3). Three gases are found to exhibit physisorption (namely: N2, H2O, and H2S) and the other five gases alter chemisorption (namely: CO, CO2, O2, H2, and NH3). The chemisorption of CO molecule is distinct by being direct and not involving dissociation. This fact made defected graphene have the highest sensitivity and selectivity towards the detection of CO molecules.

  13. Tensile properties of ADI material in water and gaseous environments

    Energy Technology Data Exchange (ETDEWEB)

    Rajnovic, Dragan, E-mail: draganr@uns.ac.rs [Faculty of Technical Sciences, University of Novi Sad, Trg D. Obradovića 6, 21000 Novi Sad (Serbia); Balos, Sebastian; Sidjanin, Leposava [Faculty of Technical Sciences, University of Novi Sad, Trg D. Obradovića 6, 21000 Novi Sad (Serbia); Eric Cekic, Olivera [Innovation Centre, Faculty of Mechanical Engineering, University of Belgrade, Kraljice Marije 16, 11120 Belgrade (Serbia); Grbovic Novakovic, Jasmina [Vinca Institute of Nuclear Sciences, University of Belgrade, P.O. Box 522, 11000 Belgrade (Serbia)

    2015-03-15

    Austempered ductile iron (ADI) is an advanced type of heat treated ductile iron, having comparable mechanical properties as forged steels. However, it was found that in contact with water the mechanical properties of austempered ductile irons decrease, especially their ductility. Despite considerable scientific attention, the cause of this phenomenon remains unclear. Some authors suggested that hydrogen or small atom chemisorption causes the weakening of the surface atomic bonds. To get additional reliable data of that phenomenon, in this paper, two different types of austempered ductile irons were tensile tested in various environments, such as: argon, helium, hydrogen gas and water. It was found that only the hydrogen gas and water gave a statistically significant decrease in mechanical properties, i.e. cause embrittlement. Furthermore, the fracture surface analysis revealed that the morphology of the embrittled zone near the specimen surface shares similarities to the fatigue micro-containing striation-like lines, which indicates that the morphology of the brittle zone may be caused by cyclic local-chemisorption, micro-embrittlement and local-fracture. - Highlights: • In contact with water and other liquids the ADI suddenly exhibits embrittlement. • The embrittlement is more pronounced in water than in the gaseous hydrogen. • The hydrogen chemisorption into ADI surface causes the formation of a brittle zone. • The ADI austempered at lower temperatures (300 °C) is more resistant to embrittlement.

  14. Theoretical Study of CO Adsorption on Ni(111), Pt(111) and Pt/Ni(111) Surfaces

    Science.gov (United States)

    Cabeza, G. F.; Castellani, N. J.; Légaré, P.

    CO adsorption on a pseudomorphic Pt overlayer supported by Ni(111) has been studied with the use of extended Huckel calculations. Experimental information on the pure Pt(111) and Ni(111) single crystals was employed to select a consistent parameter set for our bimetallic system. This gives a good description of the chemisorption bond changes between the various systems considered in our study. The CO chemisorption energy on Pt/Ni(111) was found to be lowered in comparison with Pt(111) and Ni(111), in good agreement with experimental data on Pt-rich Pt-Ni surface alloys. This observation could be justified by the electronic changes of the Pt states (valence band broadening and decreasing density at the Fermi level). Indeed, they induce, in comparison with the pure substrates, a repulsion between Pt and CO although the 2π* population of the chemisorbed molecule increases. This points to the necessity of going beyond arguments based on an analysis of the 5σ donation and 2π* backdonation for a complete description of the chemisorption bond.

  15. Removal of element mercury by medicine residue derived biochars in presence of various gas compositions

    Energy Technology Data Exchange (ETDEWEB)

    Li, Guoliang [School of Energy and Environmental Engineering, Hebei University of Technology, Tianjin 300401 (China); College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Shen, Boxiong, E-mail: shenbx@nankai.edu.cn [School of Energy and Environmental Engineering, Hebei University of Technology, Tianjin 300401 (China); College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Li, Yongwang [College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Zhao, Bin [School of Chemical Engineering, Hebei University of Technology, Tianjin 300401 (China); Wang, Fumei; He, Chuan; Wang, Yinyin; Zhang, Min [College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China)

    2015-11-15

    Highlights: • Both physisorption and chemisorption of Hg{sup 0} occurred on the surface of M6WN5. • Chemisorption process was an absolute predominant route for Hg{sup 0} removal by M6WN5. • The effect of NO, H{sub 2}O, SO{sub 2} and O{sub 2} on Hg{sup 0} removal by M6WN5 was investigated. • M6WN5 demonstrated to be a promising Hg{sup 0} sorbent in flue gas. - Abstract: Pyrolyzed biochars from an industrial medicinal residue waste were modified by microwave activation and NH{sub 4}Cl impregnation. Mercury adsorption of different modified biochars was investigated in a quartz fixed-bed reactor. The results indicated that both physisorption and chemisorption of Hg{sup 0} occurred on the surface of M6WN5 which was modified both microwave and 5 wt.% NH{sub 4}Cl loading, and exothermic chemisorption process was a dominant route for Hg{sup 0} removal. Microwave activation improved pore properties and NH{sub 4}Cl impregnation introduced good active sites for biochars. The presence of NO and O{sub 2} increased Hg{sup 0} adsorption whereas H{sub 2}O inhibited Hg{sup 0} adsorption greatly. A converse effect of SO{sub 2} was observed on Hg{sup 0} removal, namely, low concentration of SO{sub 2} promoted Hg{sup 0} removal obviously whereas high concentration of SO{sub 2} suppressed Hg{sup 0} removal. The Hg{sup 0} removal by M6WN5 was mainly due to the reaction of the C−Cl with Hg{sup 0} to form HgCl{sub 2}, and the active state of C−Cl{sup *} groups might be an intermediate group in this process. Thermodynamic analysis showed that mercury adsorption by the biochars was exothermic process and apparent adsorption energy was 43.3 kJ/mol in the range of chemisorption. In spite of low specific surface area, M6WN5 proved to be a promising Hg{sup 0} sorbent in flue gas when compared with other sorbents.

  16. Dynamics of H2 dissociation on the close-packed (111) surface of the noblest metal: H2 + Au(111)

    Science.gov (United States)

    Wijzenbroek, Mark; Helstone, Darcey; Meyer, Jörg; Kroes, Geert-Jan

    2016-10-01

    We have performed calculations on the dissociative chemisorption of H2 on un-reconstructed and reconstructed Au(111) with density functional theory, and dynamics calculations on this process on un-reconstructed Au(111). Due to a very late barrier for dissociation, H2 + Au(111) is a candidate H2-metal system for which the dissociative chemisorption could be considerably affected by the energy transfer to electron-hole pairs. Minimum barrier geometries and potential energy surfaces were computed for six density functionals. The functionals tested yield minimum barrier heights in the range of 1.15-1.6 eV, and barriers that are even later than found for the similar H2 + Cu(111) system. The potential energy surfaces have been used in quasi-classical trajectory calculations of the initial (v,J) state resolved reaction probability for several vibrational states v and rotational states J of H2 and D2. Our calculations may serve as predictions for state-resolved associative desorption experiments, from which initial state-resolved dissociative chemisorption probabilities can be extracted by invoking detailed balance. The vibrational efficacy ηv=0→1 reported for D2 dissociating on un-reconstructed Au(111) (about 0.9) is similar to that found in earlier quantum dynamics calculations on H2 + Ag(111), but larger than found for D2 + Cu(111). With the two functionals tested most extensively, the reactivity of H2 and D2 exhibits an almost monotonic increase with increasing rotational quantum number J. Test calculations suggest that, for chemical accuracy (1 kcal/mol), the herringbone reconstruction of Au(111) should be modeled.

  17. Synthesis of Ag/ZnO nanostructures by different methods and investigation of their photocatalytic efficiency for 4-nitrophenol degradation

    Energy Technology Data Exchange (ETDEWEB)

    Divband, B., E-mail: baharakdivband@yahoo.com [Inorganic Chemistry Department, Faculty of Chemistry, University of Tabriz, C.P. 51664 Tabriz (Iran, Islamic Republic of); Khatamian, M., E-mail: khatamian@tabrizu.ac.ir [Inorganic Chemistry Department, Faculty of Chemistry, University of Tabriz, C.P. 51664 Tabriz (Iran, Islamic Republic of); Eslamian, G.R. Kazemi [Food Science and Technology Department, International Aras Campus, University of Tabriz (Iran, Islamic Republic of); Darbandi, M. [Experimental Physics, Faculty of Physics, Lotharstr. 1, University of Duisburg-Essen, Duisburg (Germany)

    2013-11-01

    In this paper, Ag/ZnO photocatalysts with different Ag loadings were prepared by photo reduction, chemical reduction and polyacrylamide-gel methods. The Ag/ZnO photocatalysts were characterized by XRD, SEM, TEM, EDS and DRUV–vis methods. The results of the photocatalytic degradation of 4-NP in aqueous suspensions showed that silver ions doping greatly improved the photocatalytic efficiency of ZnO nanocrystallites. The enhancement of photocatalytic activity is due to the fact that the modification of ZnO with an appropriate amount of Ag can increase the separation efficiency of photogenerated electrons and holes in ZnO, and the improvement of photo stability of ZnO is attributed to a considerable decrease of the surface defect sites of ZnO after the Ag loading. The chemisorptions of molecular oxygen and the chemisorption of atomic oxygen on Ag in the Ag/ZnO photocatalysts were observed. It was found that the metallic Ag in the Ag/ZnO photocatalysts does play a new role of O{sub 2} chemisorption sites except for electron acceptor, by which chemisorbed molecular oxygen reacts with photogenerated electrons to form active oxygen species, and thus facilitates the trapping of photogenerated electrons and further improves the photocatalytic activity of the Ag/ZnO photocatalysts. Also the method of preparation is regarded as important factors for determining photocatalysis. The best photocatalytic performance was exhibited for Ag/ZnO prepared by polyacrylamide gel method in comparison with chemical reduction and photo reduction method and the optimum Ag content was approximately 0.5%.

  18. Propane combustion over Pt/Al{sub 2}O{sub 3} catalysts with different crystalline structures of alumina

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jung Eun; Kim, Bo Bae; Park, Eun Duck [Ajou University, Suwon (Korea, Republic of)

    2015-11-15

    The effects of the crystalline phases (α-Al{sub 2}O{sub 3}, κ-Al{sub 2}O{sub 3}, δ-Al{sub 2}O{sub 3}, θ-Al{sub 2}O{sub 3}, η-Al{sub 2}O{sub 3}, and γ-Al{sub 2}O{sub 3}) of the alumina support of Pt/Al{sub 2}O{sub 3} catalysts on the catalyst activity toward propane combustion were examined. The catalysts were characterized by N{sub 2} physisorption, CO chemisorption, temperature-programmed reduction (TPR), temperature programmed oxidation (TPO), transmission electron microscopy (TEM), and infrared spectroscopy (IR) after CO chemisorption. The Pt dispersion of the catalysts (surface Pt atoms/total Pt atoms), measured via CO chemisorption, was more dependent on the crystalline structure of alumina than on the surface area of alumina. The highest catalytic activity for propane combustion was achieved with Pt/α-Al{sub 2}O{sub 3}, which has the lowest Brunauer, Emmett, and Teller (BET) surface area and Pt dispersion. The lowest catalytic activity for propane combustion was exhibited by Pt/γ-Al{sub 2}O{sub 3}, which has the highest BET surface area and Pt dispersion. The catalytic activity was confirmed to increase with increasing Pt particle size in Pt/δ-Al{sub 2}O{sub 3}. The apparent activation energies for propane combustion over Pt/α-Al{sub 2}O{sub 3}, Pt/κ- Al{sub 2}O{sub 3}, Pt/δ-Al{sub 2}O{sub 3}, Pt/θ-Al{sub 2}O{sub 3}, Pt/η-Al{sub 2}O{sub 3}, and Pt/γ-Al{sub 2}O{sub 3} were determined to be 24.7, 21.4, 24.3, 22.1, 24.0, and 19.1 kcal/mol, respectively.

  19. Pt-Rh/g Al2O3 Benzene Hydrogenation Reaction as a Characterization Technique

    Directory of Open Access Journals (Sweden)

    Fonseca N.M. da

    1998-01-01

    Full Text Available Pt-Rh/Al2O3 catalysts prepared by successive incipient impregnations and coimpregnation were characterized by H2 chemisorption, temperature programmed reduction and benzene hydrogenation reaction in the vapor phase. The results showed that Rh plays the role of Pt reducting agent, which is very different from the effects of metal-metal interaction which appear mainly in solids with the highest metal contents. The most important parameter that results in bimetallic particles in the catalyst prepared by successive impregnation is the sequence of metal addition.

  20. Influence of alumina binder content on catalytic performance of Ni/HZSM-5 for hydrodeoxygenation of cyclohexanone.

    Directory of Open Access Journals (Sweden)

    Xiangjin Kong

    Full Text Available The influence of the amount of alumina binders on the catalytic performance of Ni/HZSM-5 for hydrodeoxygenation of cyclohexanone was investigated in a fixed-bed reactor. N2 sorption, X-ray diffraction, H2-chemisorption and temperature-programmed desorption of ammonia were used to characterize the catalysts. It can be observed that the Ni/HZSM-5 catalyst bound with 30 wt.% alumina binder exhibited the best catalytic performance. The high catalytic performance may be due to relatively good Ni metal dispersion, moderate mesoporosity, and proper acidity of the catalyst.

  1. Interaction of atomic hydrogen with anthracene and polyacene from density functional theory

    Science.gov (United States)

    Ferullo, Ricardo M.; Castellani, Norberto J.; Belelli, Patricia G.

    2016-03-01

    The interaction of atomic hydrogen with two linear polycyclic aromatic hydrocarbons (PAHs), anthracene and polyacene (the polymer of benzene), was studied within the density functional theory (DFT). Using a proper dispersion-corrected method (DFT-D) the preferential physisorption sites were explored. The activation barrier for the bond formation between a peripheral C and the incoming H was calculated to be 58.5 and 34.1 meV with pure DFT on anthracene and polyacene at its antiferromagnetic ground state, respectively. DFT-D, although improves the description of the physisorbed state, tends to underestimate the chemisorption barriers due an artifact arising from the dispersion correction.

  2. Tendências em modificação de eletrodos amperométricos para aplicações eletroanalíticas Trends in amperometric electrodes modification for electroanalytical applications

    Directory of Open Access Journals (Sweden)

    Arnaldo César Pereira

    2002-11-01

    Full Text Available The most relevant advances on the analytical applications of chemically modified electrodes (CME are presented. CME have received great attention due to the possibility of electrode surface modification including chemisorption, composite generation and polymer coating. In recent years, the interest in CME has increased overall to improve the sensitivity and selectivity of the electroanalytical probes, considering the electron mediator incorporation and the new conducting polymers development. The general procedures employed for the electrode modification and the operational characteristics of some electrochemical sensors are discussed.

  3. Enhancement of Nitrite Reduction Kinetics on Electrospun Pd-Carbon Nanomaterial Catalysts for Water Purification.

    Science.gov (United States)

    Ye, Tao; Durkin, David P; Hu, Maocong; Wang, Xianqin; Banek, Nathan A; Wagner, Michael J; Shuai, Danmeng

    2016-07-20

    We report a facile synthesis method for carbon nanofiber (CNF) supported Pd catalysts via one-pot electrospinning and their application for nitrite hydrogenation. A mixture of Pd acetylacetonate (Pd(acac)2), polyacrylonitrile (PAN), and nonfunctionalized multiwalled carbon nanotubes (MWCNTs) was electrospun and thermally treated to produce Pd/CNF-MWCNT catalysts. The addition of MWCNTs with a mass loading of 1.0-2.5 wt % (to PAN) significantly improved nitrite reduction activity compared to the catalyst without MWCNT addition. The results of CO chemisorption confirmed that the addition of MWCNTs increased Pd exposure on CNFs and hence improved catalytic activity.

  4. The Role of the Coprecipitation Sequence of Salt Precursors on the Genesis of Cu-ZnO-Al2O3 Catalysts: Synthesis, Characterization and Activity for Low Temperature Shift Reaction

    Directory of Open Access Journals (Sweden)

    R.T. Figueiredo

    1998-06-01

    Full Text Available Cu-ZnO-Al2O3 catalysts for the low-temperature water-gas shift reaction were prepared using methods of direct and reverse coprecipitation. The catalysts obtained were characterized by DRX, TPR, XPS, N2O chemisorption, Hg-Porosimetry and BET surface area. It was observed that the precipitation sequence of the precursors led to significant differences in values of copper dispersion and consequently in the activity of the catalyst for the water-gas shift reaction.

  5. Electric propulsion and its applications to space missions

    Science.gov (United States)

    Finke, R. C.

    1981-01-01

    Consideration is given the NASA, Air Force and European electric propulsion programs, the characteristics of primary electric propulsion systems, nuclear electric orbit transfer vehicles, and such topics in the fundamental processes of electrostatic thrusters as sputtering in mercury ion thrusters, the screen hole plasma sheath of an ion accelerator system, and the modelling of ion beam neutralization and nitrogen chemisorption. Also considered are electrostatic thruster components and systems, electromagnetic thrusters such as MPD and RIT systems, electric rail guns and mass drivers, power sources which include solar and nuclear alternatives, power conversion systems and their cooling apparatus, and the environmental interactions between spacecraft and their electric propulsion systems.

  6. DFT Investigations About Pyrazine Molecules on Si(100)-2×1 Surface

    Institute of Scientific and Technical Information of China (English)

    YU Ang-yang; QU Yong-quan; HAN Ke-li; HE Guo-zhong

    2007-01-01

    It is important to understand the interface of aromatic molecules on semiconductor surfaces because of the rich functionality of such molecules on semiconductor surfaces. The chemisorption of pyrazine molecules on the Si( 100)-2×1 surface has been investigated using the B3LYP density functional theory with Si9H12 one-dimer and Si15H16 twodimer cluster models. The calculated results predict that N-dative bonded-state, C2= C5 [ 4 + 2 ] and the tightbridge1, 2, 5,6 products may coexist on the Si(100)-2×1 surface.

  7. Effect of HNO{sub 3} treatment on the SO{sub 2} adsorption capacity of activated carbon prepared from Chinese low-rank coal

    Energy Technology Data Exchange (ETDEWEB)

    Hang Wenhui; Wang ling; Li Shurong [China Coal Research Institute, Beijing (China)

    1999-11-01

    SO{sub 2} removal from flue gas by activated carbon and HNO{sub 3} treated activated carbon from Chinese low-rank coal was studied. SO{sub 2} adsorption on activated carbon is mainly chemisorption. There was shown to be a correlation between adsorption capacity and the number of active sites on the carbon surface. HNO{sub 3} treatment transforms C-H bonds in activated carbon into active sites, for removal of SO{sub 2}. 2 figs., 2 tabs.

  8. Influence of alumina binder content on catalytic performance of Ni/HZSM-5 for hydrodeoxygenation of cyclohexanone.

    Science.gov (United States)

    Kong, Xiangjin; Liu, Junhai

    2014-01-01

    The influence of the amount of alumina binders on the catalytic performance of Ni/HZSM-5 for hydrodeoxygenation of cyclohexanone was investigated in a fixed-bed reactor. N2 sorption, X-ray diffraction, H2-chemisorption and temperature-programmed desorption of ammonia were used to characterize the catalysts. It can be observed that the Ni/HZSM-5 catalyst bound with 30 wt.% alumina binder exhibited the best catalytic performance. The high catalytic performance may be due to relatively good Ni metal dispersion, moderate mesoporosity, and proper acidity of the catalyst.

  9. [Equipment for biological experiments with snails aboard piloted orbital stations].

    Science.gov (United States)

    Gorgiladze, G I; Korotkova, E V; Kuznetsova, E E; Mukhamedieva, L N; Begrov, V V; Pepeliaev, Iu V

    2010-01-01

    To fly biological experiments aboard piloted orbital stations, research equipment was built up of an incubation container, filter system and automatic temperature controller. Investigations included analysis of the makeup and concentrations of gases produced by animals (snails) during biocycle, and emitted after death. Filters are chemisorption active fibrous materials (AFM) with high sorption rate and water receptivity (cation exchange fiber VION-KN-1 and anion exchange fiber VION-AS-1), and water-repellent carbon adsorbent SKLTS. AFM filters were effective in air cleaning and practically excluded ingress of chemical substances from the container into cabin atmosphere over more than 100 days.

  10. A first-principles study of functionalized clusters and carbon nanotubes or fullerenes with 5-Aminolevulinic acid as vehicles for drug delivery

    Science.gov (United States)

    Kia, Majid; Golzar, Maryam; Mahjoub, Kosar; Soltani, Alireza

    2013-10-01

    At present work, we explore the adsorption properties of the 5-Aminolevulinic acid (5ALA) interacting with SWCNTs, C60, and C24 by density functional ab initio (DFT) calculations. It was found that the electronic structure of C60 is more sensitive to the presence of 5ALA in comparison with C24, (5, 5), and (9, 0) SWCNT. Our results demonstrate that the interactions between 5ALA and the nanostructures are chemisorption. The natural bond orbital (NBO) and density of states (DOSs) analyses represent that the nature of 5ALA adsorption on the applied nanostructures is permanently electrostatic rather than covalent.

  11. Nanosecond laser micro- and nanotexturing for the design of a superhydrophobic coating robust against long-term contact with water, cavitation, and abrasion

    Science.gov (United States)

    Emelyanenko, Alexandre M.; Shagieva, Farida M.; Domantovsky, Alexandr G.; Boinovich, Ludmila B.

    2015-03-01

    Existing and emerging applications of laser-driven methods make an important contribution to advancement in nanotechnological approaches for the design of superhydrophobic surfaces. In this study, we describe a superhydrophobic coating on stainless steel, designed by nanosecond IR laser treatment with subsequent chemisorption of fluorooxysilane for use in heavily loaded hydraulic systems. Coating characterization reveals extreme water repellency, chemical stability on long-term contact with water, and excellent durability of functional properties under prolonged abrasive wear and cavitation loads. The coating also demonstrates self-healing properties after mechanical damage.

  12. Mechanochemistry, catalysis, and catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Butyagin, P.Yu.

    1987-07-01

    The physical basis of mechanochemistry and the reasons for the initiation and acceleration of chemical reactions upon the mechanical treatment of solids have been considered. The phenomenon of mechanical catalysis has been described in the example case of the oxidation of CO on oxide surfaces, and the nature of the active sites and the laws governing the mechanically activated chemisorption of gases on cleavage and friction surfaces of solids have been examined. The possibilities of the use of the methods of mechanochemistry in processes used to prepare catalysts have been analyzed in examples of decomposition reactions of inorganic compounds and solid-phase synthesis.

  13. Impact of incomplete metal coverage on the electrical properties of metal-CNT contacts: A large-scale ab initio study

    Science.gov (United States)

    Fediai, Artem; Ryndyk, Dmitry A.; Seifert, Gotthard; Mothes, Sven; Schroter, Michael; Claus, Martin; Cuniberti, Gianaurelio

    2016-09-01

    Using a dedicated combination of the non-equilibrium Green function formalism and large-scale density functional theory calculations, we investigated how incomplete metal coverage influences two of the most important electrical properties of carbon nanotube (CNT)-based transistors: contact resistance and its scaling with contact length, and maximum current. These quantities have been derived from parameter-free simulations of atomic systems that are as close as possible to experimental geometries. Physical mechanisms that govern these dependences have been identified for various metals, representing different CNT-metal interaction strengths from chemisorption to physisorption. Our results pave the way for an application-oriented design of CNT-metal contacts.

  14. On the mechanism of reactive adsorption of dibenzothiophene on organic waste derived carbons

    Science.gov (United States)

    Ania, C. O.; Parra, J. B.; Arenillas, A.; Rubiera, F.; Bandosz, T. J.; Pis, J. J.

    2007-04-01

    The mechanism of reactive adsorption of dibenzothiophene (DBT) on a series of modified carbons derived from the recycled PET was investigated. The influence of the oxygen functionalities of the adsorbent on the DBT adsorption capacity was explored. The results revealed that adsorption of DBT on activated carbons is governed by two types of contributions: physisorption on the microporous network of the carbons and chemisorption. Introduction of surface acidic groups enhanced the performance of the carbons as a result of their specific interactions with DBT. The nature of the acidic groups is a decisive factor in the selectivity of the reactive adsorption process.

  15. The effects of yttrium on the hydrogenation performance and surface properties of a ruthenium-supported catalyst

    Directory of Open Access Journals (Sweden)

    LAITAO LUO

    2005-12-01

    Full Text Available The effects of yttrium on the hydrogenation performance and surface properties of a Ru/sepiolite catalyst were studied. With CO2 methanation and CS2 poisoning as the testing reactons, TPR, TPD, XRD and CO chemisorption as the characterizations, the results showed that the presence of yttrium can increase the hydrogenation activity and anti-poisoning capacity of the Ru/sepiolite catalyst, which is due to a change of surface properties of the Ru/sepiolite. In the process of the catalytic reaction, the adjusting behavior of yttrium for the Ru/sepiolite catalyst aids in increasing the catalytic activity and anti-poisoning capacity of the catalyst.

  16. Effects of Palladium Loading on the Response of a Thick Film Flame-made ZnO Gas Sensor for Detection of Ethanol Vapor

    OpenAIRE

    Liewhiran, Chaikarn; Phanichphant, Sukon

    2007-01-01

    ZnO nanoparticles doped with 0-5 mol% Pd were successfully produced in a single step by flame spray pyrolysis (FSP) using zinc naphthenate and palladium (II) acetylacetonate dissolved in toluene-acetonitrile (80:20 vol%) as precursors. The effect of Pd loading on the ethanol gas sensing performance of the ZnO nanoparticles and the crystalline sizes were investigated. The particle properties were analyzed by XRD, BET, AFM, SEM (EDS line scan mode), TEM, STEM, EDS, and CO-pulse chemisorption me...

  17. Amine-Functionalized ZnO Nanosheets for Efficient CO2 Capture and Photoreduction

    Directory of Open Access Journals (Sweden)

    Yusen Liao

    2015-10-01

    Full Text Available Amine-functionalized ZnO nanosheets were prepared through a one-step hydrothermal method by using monoethanolamine, which has a hydroxyl group, for covalent attachment on ZnO and a primary amine group to supply the amine-functionalization. We demonstrate that the terminal amine groups on ZnO surfaces substantially increase the capability of CO2 capture via chemisorption, resulting in effective CO2 activation. As a result, the photogenerated electrons from excited ZnO can more readily reduce the surface-activated CO2, which thereby enhances the activity for photocatalytic CO2 reduction.

  18. Amine-Functionalized ZnO Nanosheets for Efficient CO2 Capture and Photoreduction

    OpenAIRE

    Yusen Liao; Zhaoning Hu; Quan Gu; Can Xue

    2015-01-01

    Amine-functionalized ZnO nanosheets were prepared through a one-step hydrothermal method by using monoethanolamine, which has a hydroxyl group, for covalent attachment on ZnO and a primary amine group to supply the amine-functionalization. We demonstrate that the terminal amine groups on ZnO surfaces substantially increase the capability of CO2 capture via chemisorption, resulting in effective CO2 activation. As a result, the photogenerated electrons from excited ZnO can more readily reduce t...

  19. Influence of reaction products of K-getter fuel additives on commercial vanadia-based SCR catalysts Part II. Simultaneous addition of KCl, Ca(OH)(2), H3PO4 and H2SO4 in a hot flue gas at a SCR pilot-scale setup

    DEFF Research Database (Denmark)

    Castellino, Francesco; Jensen, Anker Degn; Johnsson, Jan Erik

    2009-01-01

    by condensation of H3PO4, whereas the larger particles are due to P-K-Ca salts formed during evaporation of the water solution. No Cl has been found in the collected particles. During the initial 240 h of exposure, the catalyst element lost about 20% of its original activity. The deactivation then proceeded...... at slower rates, and after 1000 h the relative activity loss had increased to 25%. Different samples of the spent catalyst have been characterized after 453 h and at the end of the experiment by bulk chemical analysis, Hg-porosimetry and SEM-EDX. NH3-chemisorption tests on the spent elements and activity...

  20. Quantification of zinc atoms in a surface alloy on copper in an industrial-type methanol synthesis catalyst

    DEFF Research Database (Denmark)

    Kuld, Sebastian; Moses, Poul Georg; Sehested, Jens;

    2014-01-01

    Methanol has recently attracted renewed interest because of its potential importance as a solar fuel.1 Methanol is also an important bulk chemical that is most efficiently formed over the industrial Cu/ZnO/Al2O3 catalyst. The identity of the active site and, in particular, the role of ZnO...... as a promoter for this type of catalyst is still under intense debate.2 Structural changes that are strongly dependent on the pretreatment method have now been observed for an industrial-type methanol synthesis catalyst. A combination of chemisorption, reaction, and spectroscopic techniques provides...

  1. Quantification of zinc atoms in a surface alloy on copper in an industrial-type methanol synthesis catalyst

    DEFF Research Database (Denmark)

    Kuld, Sebastian; Moses, Poul Georg; Sehested, Jens;

    2014-01-01

    Methanol has recently attracted renewed interest because of its potential importance as a solar fuel. Methanol is also an important bulk chemical that is most efficiently formed over the industrial Cu/ZnO/Al2O3 catalyst. The identity of the active site and, in particular, the role of ZnO...... as a promoter for this type of catalyst is still under intense debate. Structural changes that are strongly dependent on the pretreatment method have now been observed for an industrial-type methanol synthesis catalyst. A combination of chemisorption, reaction, and spectroscopic techniques provides a consistent...

  2. Kondo effect in molecules with strong correlations

    Energy Technology Data Exchange (ETDEWEB)

    Kuzmenko, Tetyana [Department of Physics, Ben-Gurion University, P.O. Box 653, Beer-Sheva 84105 (Israel)]. E-mail: tetyana@bgumail.bgu.ac.il; Kikoin, Konstantin [Department of Physics, Ben-Gurion University, P.O. Box 653, Beer-Sheva 84105 (Israel); Avishai, Yshai [Department of Physics, Ben-Gurion University, P.O. Box 653, Beer-Sheva 84105 (Israel)

    2005-04-30

    A theory of Kondo tunneling through molecules adsorbed on metallic substrate is constructed and the underlying physics is exposed. It is shown that in the case of weak chemisorption the sandwich-type molecules manifest a novel type of Kondo effect that has not been observed in magnetically doped bulk metals. The exchange Hamiltonian of these molecules unveils unusual dynamical SO(n) symmetries instead of conventional SU(2) symmetry. These symmetries can be experimentally realized and the specific value of n can be controlled by gate voltage.

  3. Kondo tunneling through real and artificial molecules.

    Science.gov (United States)

    Kikoin, K; Avishai, Y

    2001-03-05

    When an asymmetric double dot is hybridized with itinerant electrons, its singlet ground state and lowly excited triplet state cross, leading to a competition between the Zhang-Rice mechanism of singlet-triplet splitting in a confined cluster and the Kondo effect (which accompanies the tunneling through quantum dot under a Coulomb blockade restriction). The rich physics of an underscreened S = 1 Kondo impurity in the presence of low-lying triplet-singlet excitations is exposed and estimates of the magnetic susceptibility and the electric conductance are presented, together with applications for molecule chemisorption on metallic substrates.

  4. Atomic arrangements and electronic properties of semiconductor surfaces and interfaces

    Science.gov (United States)

    Chadi, D. J.; Martin, R. M.

    1982-05-01

    The areas of research during the past 12 months have included: step-formation energies and domain orientation at Si(111) surfaces; the electronic structure of the Al-GaAs(110) surface chemisorption system; density-functional calculations of bulk properties of GaAs and of (100)GaAs-Ge interfaces; demonstration of the importance of correlation effects on the atomic and electronic structure of Si(111) surfaces; and derivation of an exact scaling law for the resistance of a thin wire for the one dimensional Anderson model containing Loth diagonal and off-diagonal disorder.

  5. Trends in reactivity of oxides

    DEFF Research Database (Denmark)

    Toftelund, Anja

    , and I) and OH on a wide range of rutile oxide surfaces. Furthermore, Brønsted-Evans-Polanyi (BEP) relations are found for the adsorption of a large number of molecules (including Cl, Br and I) on transition metal oxides. In these relations the activation energies scale linearly with the dissociative...... chemisorption energies. It turns out that the BEP relation for rutile oxides is almost coinciding with the dissociation line, i.e. no barrier exists for the reactive surfaces. The heterogeneous catalytic oxidation of hydrogen halides (HCl, HBr, and HI) is investigated. A micro-kinetic model is solved...

  6. Amine-Functionalized Amino Acid-based Ionic Liquids as Efficient and High-Capacity Absorbents for CO2

    DEFF Research Database (Denmark)

    Shunmugavel, Saravanamurugan; Kunov-Kruse, Andreas Jonas; Fehrmann, Rasmus;

    2014-01-01

    Ionic liquids (ILs) comprised of ammonium cations and anions of naturally occurring amino acids containing an additional amine group (e.g., lysine, histidine, asparagine, and glutamine) were examined as high-capacity absorbents for CO2. An absorption capacity of 2.1 mol CO2 per mol of IL (3.5 mol...... by chemisorption; however, the amino acid–carboxyl groups on the anion played an important—but different—catalytic role for the sorption kinetics in the two ILs. The origin of the cationic effect is speculated to be correlated with the strength of the ion interactions in the two ILs....

  7. NOM removal technologies – Norwegian experiences

    Directory of Open Access Journals (Sweden)

    H. Ødegaard

    2009-10-01

    Full Text Available The paper gives an overview of the methods for removal of natural organic matter (NOM, particularly humic substances (HS, in water with focus on the Norwegian experiences. It is demonstrated that humic substances may be removed by a variety of methods, such as; molecular sieving through nanofiltration membranes, coagulation with subsequent floc separation (including granular media or membrane filtration, oxidation followed by biofiltration and sorption processes including chemisorption (ion exchange and physical adsorption (activated carbon. All these processes are in use in Norway and the paper gives an overview of the operational experiences.

  8. NOM removal technologies – Norwegian experiences

    Directory of Open Access Journals (Sweden)

    H. Ødegaard

    2010-01-01

    Full Text Available The paper gives an overview of the methods for removal of natural organic matter (NOM in water, particularly humic substances (HS, with focus on the Norwegian experiences. It is demonstrated that humic substances may be removed by a variety of methods, such as; molecular sieving through nanofiltration membranes, coagulation with subsequent floc separation (including granular media or membrane filtration, oxidation followed by biofiltration and sorption processes including chemisorption (ion exchange and physical adsorption (activated carbon. All these processes are in use in Norway and the paper gives an overview of the operational experiences.

  9. An IR study of the Σ-CO CO-adsorption state in the system CO/H/Ni(100)

    Science.gov (United States)

    Hayden, B. E.; Klauser, R.; Bradshaw, A. M.

    The weakly bound Σ-CO co-adsorption state in the system CO/H/Ni(100) has been investigated by IR reflection-absorption spectroscopy (IRAS). Its CO stretching frequency changes from 2095 to 2115 cm -1 as a function of increasing coverage. Experiments with 12CO and 13CO mixtures show that this shift is composed of an increase in frequency of 48 cm -1 due to dipole-dipole coupling and a decrease of 24 cm -1 due to "static" or chemical effects. The negative chemical shift can be correlated with the appearance of satellites in the photoelectron spectrum as in other weak chemisorption systems.

  10. An IR-study of the -CO CO-adsorption state in the system CO/H/Ni(100)

    Science.gov (United States)

    Hayden, B. E.; Klauser, R.; Bradshaw, A. M.

    1987-04-01

    The weakly bound ω-CO co-adsorption state in the system CO/H/Ni(100) has been investigated by IR reflection-absorption spectroscopy (IRAS). Its C-O stretching frequency changes from 2095 to 2115 cm -1 as a function of increasing coverage. Experiments with 12CO and 13CO mixtures show that this shift is composed of an increase in frequency of 48 cm -1 due to dipole-dipole coupling and a decrease of 24 cm -1 due to "static" or chemical effects. The negative chemical shift can be correlated with the appearance of satellites in the photoelectron spectrum as in other weak chemisorption systems.

  11. Analysis of CuInSe2: Electron and ion beam effects

    Science.gov (United States)

    Kazmerski, L. L.; Burnham, N. A.; Swartzlander, A. B.; Nelson, A. J.; Asher, S. E.

    The effects of electron and ion beams used in the analysis of CuInSe2 surfaces are examined. Potential changes in the surface chemistry-including oxidation, desorption and preferential species removal-under a range of incident probe conditions are investigated for possible artifactural information generation. Emphasis is placed on the relationships between beam conditions and oxygen chemisorption and physisorption, since oxygen treatments of devices utilizing this semiconductor are critial to performance. Single crystals and polycrystalline thin films are analyzed and compared to establish the beam-induced phenomena.

  12. Electron beam effects in the analysis of compound semiconductors and devices

    Energy Technology Data Exchange (ETDEWEB)

    Kazmerski, L.L.; Burnham, N.A.; Swartzlander, A.B.; Nelson, A.J.; Asher, S.E.

    1987-09-01

    The effects of electron beams on the analysis of CuInSe/sub 2/ surfaces are examined in this paper. Potential changes in the surface chemistry: including oxidation and desorption: under a range of incident probe conditions, are investigated for possible artifactual information generation. Emphasis is placed on the relationships between beam conditions and oxygen chemisorption and physisorption, since oxygen treatments of devices utilizing this semiconductor are critical to performance. Single crystals and polycrystalline thin films are analyzed and compared to establish the beam-induced phenomena.

  13. On the Structure Sensitivity of Direct NO Decomposition over Low-Index Transition Metal Facets

    DEFF Research Database (Denmark)

    Falsig, Hanne; Shen, Juan; Khan, Tuhin Suvra

    2014-01-01

    for generally obtaining quantitative agreement between theory and experiments is for the simulations to address in detail the propensities of the various types of active sites. Finally, we show that the ordering of NO decomposition rates among metals and facets is essentially unaltered when using BEP......We present a study of the dissociative chemisorption of NO, O2, and N2 over close-packed, stepped, kinked, and open (fcc {111}, {211}, {311}, {532}, {100}, and {110}) transition metal facets using density functional theory (DFT). The offset of the Bronsted-Evans-Polanyi (BEP) relations suggest...

  14. Aging of the nanosized photochromic WO3 films and the role of adsorbed water in the photochromism

    Science.gov (United States)

    Gavrilyuk, A. I.

    2016-02-01

    Here it has been reported on aging of the nanosized WO3 film, which is revealed is continuous reduction of the photochromic sensitivity over time. Water molecules physically adsorbed on the film surface from ambient air form donor-acceptor and hydrogen bonds, changing gradually the adsorption state to chemisorption which prevents an access of organic molecules that serve as hydrogen donors by the photochromism. The mechanism of the process has been investigated and discussed. The role of water in the photochromism has been highlighted. The difference in the efficiency for being of a hydrogen donor in the photochromic process between water and organic molecules is discussed.

  15. Purification of ethanol for highly sensitive self-assembly experiments

    Directory of Open Access Journals (Sweden)

    Kathrin Barbe

    2014-08-01

    Full Text Available Ethanol is the preferred solvent for the formation of self-assembled monolayers (SAMs of thiolates on gold. By applying a thin film sensor system, we could demonstrate that even the best commercial qualities of ethanol contain surface-active contaminants, which can compete with the desired thiolates for surface sites. Here we present that gold nanoparticles deposited onto zeolite X can be used to remove these contaminants by chemisorption. This nanoparticle-impregnated zeolite does not only show high capacities for surface-active contaminants, such as thiols, but can be fully regenerated via a simple pyrolysis protocol.

  16. Characterization of recycled rubber media for hydrogen sulphide (H2S) control.

    Science.gov (United States)

    Wang, Ning; Park, Jaeyoung; Evans, Eric A; Ellis, Timothy G

    2014-01-01

    Hydrogen sulphide (H2S) adsorption capacities on recycled rubber media, tyre-derived rubber particle (TDRP), and other rubber material (ORM) have been evaluated. As part of the research, densities, moisture contents, and surface properties of TDRP and ORM have been determined. The research team findings show that TDRP and ORM are more particulate in nature and not highly porous-like activated carbon. The characteristics of surface area, pore size, and moisture content support chemisorption on the macrosurface rather than physical adsorption in micropores. For example, moisture content is essential for H2S adsorption on ORM, and an increase in moisture content results in an increase in adsorption capacity.

  17. Superoxide Complex [W4O12(O2')]:A Theoretical Study

    Institute of Scientific and Technical Information of China (English)

    WANG Bin; ZHANG Xian-Hui; HUANG Xin; ZHANG Yong-Fan

    2008-01-01

    Extensive DFT calculations are performed to optimize the geometric structures of O-rich tungsten oxide clusters, to simulate the PES spectra, and to analyze the chemical bonding. The ground-state structure of W4O14- is best considered as W4O12(O2-), containing a side-on bound superoxide ligand. The current study indicates that the extra electron in W4O12- is capable of activating dioxygen by non-dissociative electron transfer (W 5d→O2 π*), and the anionic clusters can be viewed as models for reduced defect sites on tungsten oxide surfaces for the chemisorption of O2.

  18. Fischer-Tropsch Synthesis: Development of a Micro kinetic Model for Metal Catalysis; La synthese Fischer-Tropsch: developpement d'un modele microcinetique pour la catalyse sur metaux

    Energy Technology Data Exchange (ETDEWEB)

    Lozano-Blanco, G.; Thybaut, J.W.; Marin, G.B. [Ghent Univ., Lab. voor Petrochemische Techniek (Belgium); Surla, K.; Galtier, P. [Institut Francais du Petrole, 69 - Vernaison (France)

    2006-07-01

    The construction of a single-event micro-kinetic (SEMK) model for metal catalysis using Fischer-Tropsch synthesis as example reaction is addressed. SEMK's describe the full product distribution with a limited number of kinetic parameters. A computer algorithm is required to generate all the elementary steps and species of the reaction network. Reacting and intermediate species are represented with Boolean matrices and standardized labels. The adjustable model parameters are the atomic chemisorption enthalpies of carbon, oxygen and hydrogen on the metal surface and the single-event kinetic coefficients of the kinetically relevant reaction families. (authors)

  19. Electronic Properties of Hydrogen Storage Materials with Photon-in/Photon-out Soft-X-Ray Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Jinghua

    2008-09-22

    The applications of resonant soft X-ray emission spectroscopy on a variety of carbon systems have yielded characteristic fingerprints. With high-resolution monochromatized synchrotron radiation excitation, resonant inelastic X-ray scattering has emerged as a new source of information about electronic structure and excitation dynamics. Photon-in/photon-out soft-X-ray spectroscopy is used to study the electronic properties of fundamental materials, nanostructure, and complex hydrides and will offer potential in-depth understanding of chemisorption and/or physisorption mechanisms of hydrogen adsorption/desorption capacity and kinetics.

  20. Trends in the exchange current for hydrogen evolution

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Bligaard, Thomas; Logadottir, Ashildur;

    2005-01-01

    A density functional theory database of hydrogen chemisorption energies on close packed surfaces of a number of transition and noble metals is presented. The bond energies are used to understand the trends in the exchange current for hydrogen evolution. A volcano curve is obtained when measured...... exchange currents are plotted as a function of the calculated hydrogen adsorption energies and a simple kinetic model is developed to understand the origin of the volcano. The volcano curve is also consistent with Pt being the most efficient electrocatalyst for hydrogen evolution. (c) 2005...

  1. Outstanding inhibitive effect of colchicine on aluminium alloy 6061 corrosion

    Directory of Open Access Journals (Sweden)

    Mudigere Krishnegowda Pavithra

    2015-12-01

    Full Text Available The corrosion protection ability of colchicine (CC on Aluminium alloy 6061 (AA6061 in 3.5% NaCl medium was examined by potentiodynamic polarization, electrochemical impedance, and chronoamperometric techniques. About 99 % of protection efficiency was achieved by 2 mM concentration of CC in 3.5% NaCl solution.The adsorption of CC on AA6061 surface obeys Langmuir isotherm by following both physisorption and chemisorption mechanism. Variation in the surface morphology of inhibited and uninhibited metal samples was examined by scanning electron microscopy. 

  2. Cobalt-based layered double hydroxides as oxygen evolving electrocatalysts in neutral electrolyte

    Science.gov (United States)

    Lin, Hong; Zhang, Ye; Wang, Gang; Li, Jian-Bao

    2012-06-01

    Co-M (M= Co, Ni, Fe, Mn) layered double hydroxides (LDHs) were successfully fabricated by a hexamethylenetetramine (HMT) pyrolysis method. Composite electrodes were made using a self-assembly fashion at inorganic/organic surface binder-free and were used to catalyze oxygen evolution reaction. Water oxidation can take place in neutral electrolyte operating with modest overpotential. The doping of other transitional metal cations affords mix valences and thus more intimate electronic interactions for reversible chemisorption of dioxygen molecules. The application of employing LDH materials in water oxidation process bodes well to facilitate future hydrogen utilization.

  3. 3RD Symposium on Applied Surface Analysis.

    Science.gov (United States)

    1982-03-01

    by Solution-Deposited Mixed Oxide Films" 10:20 COFFEE BREAK E-5 10:50 E. A. Podoba, S. P. Kodali , and R. C. Curley, "Adhesive Bond Durability with...will be shown that various methods of studying the vibrational spectrum of an adsorbed species have allowed us to see relationships between diverse areas...chemisorption of CO on Pd(210) will be discussed in some detail, and it will be shown that modern methods can actually locate the exact CO bonding site on

  4. Materials for carbon dioxide separation

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Qingqing

    2014-10-01

    The CO{sub 2} adsorption capacities at room temperature have been investigated by comparing carbon nanotubes, fullerene, graphenes, graphite and granular activated carbons. It turned out that the amount of the micropore surface area was dominating the CO{sub 2} adsorption ability. Another promising class of materials for CO{sub 2} capture and separation are CaO derived from the eggshells. Two aspects were studied in present work: a new hybrid materials synthesized by doping the CaTiO{sub 3} and the relationship between physisorption and chemisorption properties of CaO-based materials.

  5. Adsorptive removal of 2-chlorophenol by low-cost coir pith carbon.

    Science.gov (United States)

    Namasivayam, C; Kavitha, D

    2003-03-17

    Adsorption of 2-chlorophenol (2-CP) by coir pith carbon was carried out by varying the parameters such as agitation time, 2-CP concentration, adsorbent dose, pH and temperature. Adsorption equilibrium reached at 40, 60, 80 and 100 min for 2-CP concentration of 10, 20, 30 and 40 mg/l, respectively. Adsorption followed second-order kinetics. The adsorption equilibrium data obeyed Freundlich isotherm. Acidic pH was favorable for the adsorption of 2-CP. Desorption studies showed that chemisorption plays a major role in the adsorption process.

  6. Point Defects in Carbon Nanotubes: ab initio and Force-Fields Based Simulations

    Science.gov (United States)

    Kroes, Jaap; Pietrucci, Fabio; Curioni, Alessandro; Andreoni, Wanda

    2014-03-01

    We present an extended investigation of point defects in carbon nanotubes (CNTs) and their effects on mechanical and electronic properties. This study is based on large-scale calculations using DFT with exchange and correlation functionals of the GGA - including empirical corrections for van-der-Waals interactions - and of the hybrid type. Additional simulations using classical interatomic potentials allow us to obtain a critical comparison between the outcome of DFT and force-fields. The CNT models adopted have a range of sizes and chiralities. In particular, (i) our simulations of oxygen chemisorption revealed a tendency to clustering and the existence of kinetic traps (epoxides), which explain STS data; (ii) the extension to oxygen isovalent species on CNTs and other graphitic surfaces has suggested a simple predictive model for the chemisorption pattern. Moreover, (iii) our analysis shows an intrinsic difficulty of available force fields to account for the energetics of vacancies and adsorption site preferences. Additional results aiming at characterizing the interaction of nitrogen oxides (NOx) with the CNT surface will also be presented. Work supported by SNSF Nano-Tera.ch and CSCS.

  7. Meso-macroporous Al2O3 supported Ru catalysts for CO preferential oxidation in hydrogen-rich gases

    Institute of Scientific and Technical Information of China (English)

    Limiao Shen; Cheng Zhang; Yuan Liu

    2012-01-01

    Series of meso-macroporous Al2O3 supported Ru catalysts with different loadings were prepared by incipient wetness method and applied to preferential oxidation of CO in hydrogen-rich gases.N2 adsorption-desorption,SEM,XRD,TEM,CO chemisorption and H2-TPR techniques were employed to characterize the catalysts.The results indicate that Ru/Al2O3 catalysts have meso-macroporous structure,high surface area and high metal dispersion.The characterization results of XRD and CO chemisorption indicate the entry of Ru ions into Al2O3 lattice.The results of catalytic performance tests indicate that the meso-macroporous Al2O3 supported Ru catalysts for CO preferential oxidation showed good activity under high space velocity.It is proposed that the macropores in the Ru/Al2O3 catalyst favor mass transfer and mesopores help to improve the dispersion of metal,resulting in the excellent catalytic performance.

  8. Combined in situ PM-IRRAS/QCM studies of water adsorption on plasma modified aluminum oxide/aluminum substrates

    Science.gov (United States)

    Giner, Ignacio; Maxisch, Michael; Kunze, Christian; Grundmeier, Guido

    2013-10-01

    Water adsorption on plasma modified oxyhydroxide covered aluminum surfaces was analyzed by means of a set-up combining in situ photoelastic modulated infrared reflection absorption spectroscopy (PM-IRRAS) and quartz crystal microbalance (QCM) in a low-temperature plasma cell. The chemical structure of the surface before and after the plasma treatment was moreover characterized by means of X-ray photoelectron spectroscopy (XPS) analysis. The surface chemistry of oxide covered aluminum was modified by oxidative and reductive low-temperature plasma pre-treatments. The Ar-plasma treatment reduced the surface hydroxyl density and effectively removed adsorbed organic contaminations. Surface modification by means of a water plasma treatment led to an increased surface hydroxyl density as well as an increase of the thickness of the native oxide film. The adsorption of water at atmospheric pressures on plasma modified aluminum surfaces led to a superimposition of reversible water layer adsorption and a simultaneous increase of the oxyhydroxide film thickness as a result of a chemisorption process. The amount of physisorbed water increased with the surface hydroxyl density whereas the chemisorption process was most significant for the surface after Ar-plasma treatment and almost negligible for the already water plasma treated surface.

  9. Photoemission study of the adsorption of benzotriazole on copper

    Energy Technology Data Exchange (ETDEWEB)

    Fang, B.S.

    1985-01-01

    A photoemission study was performed on the chemisorption of benzotriazole (BTA) on polycrystalline copper (clean and oxidized) surfaces to understand the corrosion inhibition mechanism. The energy distribution curves indicate benzotriazole bonding to copper through nitrogen lone pair orbitals. They also disagree with the models which suggest that the benzotriazole molecular plane is oriented parallel to the copper surface by showing a lack of ..pi..-d interaction. The observed chemisorption of benzotriazole on atomically clean copper surfaces at room temperature suggests that an oxide layer is not necessary for the adsorption of benzotriazole. No structural difference was observed in the photoemission studies on BTA-clean copper and BTA-cuprous oxide surface film. This result demonstrates the major role of the copper atom upon benzotriazole adsorption. A new model of the CuBTA chemisorbed structure is presented. The Cu-BTA polymer is formed by strong charge-transfer interactions between benzotriazole molecules instead of by BTA-Cu-BTA connections. It successfully interprets the experimental results from solubility and tarnish resistance tests on adsorbed films on copper surfaces. It also gives a reasonable explanation for the different inhibition coefficients among BTA-treated copper single crystal surfaces. Mechanisms are suggested for the benzotriazole inhibition mechanisms.

  10. Importance of the oxygen bond strength for catalytic activity in soot oxidation

    DEFF Research Database (Denmark)

    Christensen, Jakob M.; Grunwaldt, Jan-Dierk; Jensen, Anker D.

    2016-01-01

    energies for soot oxidation follow linear Brønsted-Evans-Polanyi relationships with the heat of oxygen chemisorption. Among the tested metal or metal oxide catalysts Co3O4 and CeO2 were nearest to the optimal bond strength in tight contact oxidation, while Cr2O3 was nearest to the optimum in loose contact......The oxygen bond strength on a catalyst, as measured by the heat of oxygen chemisorption, is observed to be a very important parameter for the activity of the catalyst in soot oxidation. With both intimate contact between soot and catalyst (tight contact) and with the solids stirred loosely together...... oxidation. The optimum of the volcano curve in loose contact is estimated to occur between the bond strengths of α-Fe2O3 and α-Cr2O3. Guided by an interpolation principle FeaCrbOx binary oxides were tested, and the activity of these oxides was observed to pass through an optimum for an FeCr2Ox binary oxide...

  11. Improved sulfur-resistant ability on CO oxidation of Pd/Ce0.75Zr0.25O2 over Pd/CeO2-TiO2 and Pd/CeO2

    Institute of Scientific and Technical Information of China (English)

    沈美庆; 林放; 魏光曦; 王建强; 朱少春

    2015-01-01

    The influence of sulfation on Pd/Ce0.75Zr0.25O2, Pd/CeO2-TiO2 and Pd/CeO2 was investigated. Physical structure and chemical properties of different catalysts were characterized by N2 adsorption, X-ray diffraction (XRD), CO chemisorption, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR) and X-ray fluorescence (XRF). After 10 h SO2 sulfation, it was found that the decrement on CO oxidation catalytic activity was limited on Pd/Ce0.75Zr0.25O2 compared to Pd/CeO2-TiO2 and Pd/CeO2. It demonstrated that Pd/Ce0.75Zr0.25O2 was more sulfur resistant compared to the other two catalysts. Af-ter sulfur exposure, catalyst texture was not much influenced as shown by N2 adsorption and XRD, and surface Pd atoms were poi-soned indicated by CO chemisorption results. Pd/Ce0.75Zr0.25O2 and Pd/CeO2-TiO2 exhibited less sulfur accumulation compared to Pd/CeO2 in the sulfation process. Furthermore, XPS results clarified that surface sulfur amount, especially surface sulfates amount on the sulfated catalysts was more crucial for the deactivation in sulfur containing environment.

  12. Adsorption of Lead Ions from Aqueous Solutions Using Gamma Irradiated Minerals

    Directory of Open Access Journals (Sweden)

    Julián Cruz-Olivares

    2016-01-01

    Full Text Available For the first time, an irradiated mineral was used as a novel modified adsorbent for lead removal of aqueous solutions. The effects of gamma radiation doses and temperature on the lead adsorption capacity of an unknown mineral were evaluated. The results show that, in the chemisorption process, the highest adsorption capacity (9.91 mg/g and the maximum percentage of lead removal (99.1% were reached at 40°C when using an irradiated mineral at 150 kGy. The improvement on the lead adsorption speed was the most important feature of the irradiated mineral. The experimental results were successfully correlated with the pseudo second-order kinetic model. For all results, the average absolute relative deviations (AARD were less than 13.20%, and the correlation factor (r2 was higher than 0.998. Moreover, the average values of the thermodynamic parameters (ΔG0=-10612 J/mol, ΔH0=-12360 J/mol, and ΔS0=171 J/mol K suggest the feasibility of the proposed process, in terms of the endothermic and irreversible chemisorption results; moreover, ion exchange was evaluated through the EDS results. The X-ray diffraction analysis showed that the unknown irradiated mineral is mainly composed of quartz (SiO2, calcite (CaCO3, and calcium magnesium silicate (Ca0.15Mg0.85 Mg (SiO6.

  13. Temperature-responsive self-assembled monolayers of oligo(ethylene glycol): control of biomolecular recognition.

    Science.gov (United States)

    Zareie, Hadi M; Boyer, Cyrille; Bulmus, Volga; Nateghi, Ebrahim; Davis, Thomas P

    2008-04-01

    Self-assembled monolayers (SAMs) of oligo(ethylene glycol) (OEG)-tethered molecules on gold are important for various biorelevant applications ranging from biomaterials to bioanalytical devices, where surface resistance to nonspecific protein adsorption is needed. Incorporation of a stimuli-responsive character to the OEG SAMs enables the creation of nonfouling surfaces with switchable functionality. Here we present an OEG-derived structure that is highly responsive to temperature changes in the vicinity of the physiological temperature, 37 degrees C. The temperature-responsive solution behavior of this new compound was demonstrated by UV-vis and nuclear magnetic resonance spectroscopy. Its chemisorption onto gold(111), and the retention of responsive behavior after chemisorption have been demonstrated by surface plasmon resonance (SPR), X-ray photoelectron spectroscopy (XPS), and atomic force and scanning tunneling microscopy. The OEG-derived SAMs have been shown to reversibly switch the wettability of the surface, as determined by contact angle measurements. More importantly, SPR and AFM studies showed that the OEG SAMs can be utilized to control the affinity binding of streptavidin to the biotin-tethered surface in a temperature-dependent manner while still offering the nonspecific protein-resistance to the surface.

  14. Nanocrystalline MgO supported nickel-based bimetallic catalysts for carbon dioxide reforming of methane

    Energy Technology Data Exchange (ETDEWEB)

    Meshkani, Fereshteh [Catalyst and Advanced Materials Research Laboratory, Chemical Engineering Department, Faculty of Engineering, University of Kashan, Kashan (Iran); Rezaei, Mehran [Catalyst and Advanced Materials Research Laboratory, Chemical Engineering Department, Faculty of Engineering, University of Kashan, Kashan (Iran); Institute of Nanoscience and Nanotechnology, University of Kashan, Kashan (Iran)

    2010-10-15

    Nanocrystalline magnesium oxide with high surface area and plate-like shape was employed as catalyst support for preparation of nickel-based bimetallic catalysts in methane reforming with carbon dioxide. The prepared samples were characterized by X-ray diffraction (XRD), N{sub 2} adsorption (BET), Temperature programmed oxidation and desorption (TPO-TPD), Thermal gravimetric and differential thermal gravimetric (TGA-DTG), H{sub 2} chemisorption and Transmission and electron microscopies (TEM and SEM) analyses. CO{sub 2}-TPD data showed the high CO{sub 2} adsorption capacity of catalysts which improves the resistance of catalysts against the carbon formation. The H{sub 2} chemisorption results also indicated that the addition of Pt to nickel catalyst improved the nickel dispersion. The obtained results revealed that the prepared catalysts showed a high activity and stability during the reaction with a low amount of deposited carbon. Addition of Pt to nickel catalyst improved both the activity and resistivity against carbon formation. (author)

  15. The electrooxidation mechanism of formic acid on platinum and on lead ad-atoms modified platinum studied with the kinetic isotope effect

    Science.gov (United States)

    Bełtowska-Brzezinska, M.; Łuczak, T.; Stelmach, J.; Holze, R.

    2014-04-01

    Kinetics and mechanism of formic acid (FA) oxidation on platinum and upd-lead ad-atoms modified platinum electrodes have been studied using unlabelled and deuterated compounds. Poisoning of the electrode surface by CO-like species was prevented by suppression of dissociative chemisorption of FA due to a fast competitive underpotential deposition of lead ad-atoms on the Pt surface from an acidic solution containing Pb2+ cations. Modification of the Pt electrode with upd lead induced a catalytic effect in the direct electrooxidation of physisorbed FA to CO2. With increasing degree of H/D substitution, the rate of this reaction decreased in the order: HCOOH > DCOOH ≥ HCOOD > DCOOD. HCOOH was oxidized 8.5-times faster on a Pt/Pb electrode than DCOOD. This primary kinetic isotope effect proves that the C-H- and O-H-bonds are simultaneously cleaved in the rate determining step. A secondary kinetic isotope effect was found in the dissociative chemisorption of FA in the hydrogen adsorption-desorption range on a bare Pt electrode after H/D exchange in the C-H bond, wherein the influence of deuterium substitution in the O-H group was negligibly small. Thus the C-H bond cleavage is accompanied by the C-OH and not the O-H bond split in the FA decomposition, producing CO-like species on the Pt surface sites.

  16. Identifying Enclosed Chemical Reaction and Dynamics at the Molecular Level Using Shell-Isolated Miniaturized Plasmonic Liquid Marble.

    Science.gov (United States)

    Han, Xuemei; Lee, Hiang Kwee; Lee, Yih Hong; Hao, Wei; Liu, Yejing; Phang, In Yee; Li, Shuzhou; Ling, Xing Yi

    2016-04-21

    Current microscale tracking of chemical kinetics is limited to destructive ex situ methods. Here we utilize Ag nanocube-based plasmonic liquid marble (PLM) microreactor for in situ molecular-level identification of reaction dynamics. We exploit the ultrasensitive surface-enhanced Raman scattering (SERS) capability imparted by the plasmonic shell to unravel the mechanism and kinetics of aryl-diazonium surface grafting reaction in situ, using just a 2-μL reaction droplet. This reaction is a robust approach to generate covalently functionalized metallic surfaces, yet its kinetics remain unknown to date. Experiments and simulations jointly uncover a two-step sequential grafting process. An initial Langmuir chemisorption of sulfonicbenzene diazonium (dSB) salt onto Ag surfaces forms an intermediate sulfonicbenzene monolayer (Ag-SB), followed by subsequent autocatalytic multilayer growth of Ag-SB3. Kinetic rate constants reveal 19-fold faster chemisorption than multilayer growth. Our ability to precisely decipher molecular-level reaction dynamics creates opportunities to develop more efficient processes in synthetic chemistry and nanotechnology.

  17. Highly Dispersed Gold Nanoparticles Supported on SBA-15 for Vapor Phase Aerobic Oxidation of Benzyl Alcohol.

    Science.gov (United States)

    Kumar, Ashish; Sreedhar, Bojja; Chary, Komandur V R

    2015-02-01

    Gold nanoparticles supported on SBA-15 are prepared by homogenous deposition-precipitation method (HDP) using urea as the precipitating agent. The structural features of the synthesized catalysts were characterized by various techniques such as X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption-desorption (BET), pore size distribution (PSD), CO chemisorption and X-ray photoelectron spectroscopy (XPS). The catalytic activity and stability of the Au/SBA-15 catalysts are investigated during the vapor phase aerobic oxidation of benzyl alcohol. The BJH pore size distribution results of SBA-15 support and Au/SBA-15 catalysts reveals that the formation of mesoporous structure in all the samples. TEM results suggest that Au nanoparticles are highly dispersed over SBA-15 and long range order of hexagonal mesopores of SBA-15 is well retained even after the deposition of Au metallic nanoparticles. XPS study reveals the formation of Au (0) after chemical reduction by NaBH4. The particle size measured from CO-chemisorption and TEM analysis are well correlated with the TOF values of the reaction. Au/SBA-1 5 catalysts are found to show higher activity compare to Au/TiO2 and Au/MgO catalysts during the vapor phase oxidation of benzyl alcohol. The catalytic functionality are well substantiated with particle size measured from TEM. The crystallite size of Au in both fresh and spent catalysts were measured from X-ray diffraction.

  18. Preparation and Characterization of Niobium Carbide and Carbonitride

    Science.gov (United States)

    Kim, Hak Soo; Bugli, Guy; Djéga-Mariadassou, Gérald

    1999-01-01

    Unsupported niobium carbide powders of NbC were prepared by carburization of commercial niobium pentoxide in flowing CH4-H2mixtures. Several routes of synthesis were investigated, leading to final carbides with specific surface areas ranging from 10 to 50 m2g-1. During direct carburization, after the first step of reduction of Nb2O5to NbO2, a long induction period which was succeeded by an acceleratory period, was observed for the reduction/carburization to NbC. In the presence of a catalyst of methane decomposition, this induction period was eliminated but the superficial carbon free contamination of the final carbide was increased. However, this contamination can be removed by a reducing treatment and CO chemisorption can be observed. The preparations through niobium oxynitride lead to face-centered cubic carbonitrides with specific surface areas ranging from 27 to 49 m2g-1. Chemical composition and cell parameter of these cabonitrides vary slightly with the synthesis conditions. After a reducing treatment, as for NbC, CO chemisorption was also observed.

  19. Density Functional Theory with Modified Dispersion Correction for Metals Applied to Self-Assembled Monolayers of Thiols on Au(111

    Directory of Open Access Journals (Sweden)

    M. P. Andersson

    2013-01-01

    Full Text Available Using sound physical principles we modify the DFT-D2 atom pairwise semiempirical dispersion correction to density functional theory to work for metallic systems and in particular self-assembled monolayers of thiols on gold surfaces. We test our approximation for two functionals PBE-D and revPBE-D for lattice parameters and cohesive energies for Ni, Pd, Pt, Cu, Ag, and Au, adsorption energies of CO on (111 surfaces of Pd, Pt, Cu, Ag, and Au, and adsorption energy of benzene on Ag(111 and Au(111. Agreement with experimental data is substantially improved. We apply the method to self-assembled monolayers of alkanethiols on Au(111 and find reasonable agreement for PBE-D and revPBE-D for both physisorption of n-alkanethiols as well as dissociative chemisorption of dimethyl disulfide as an Au-adatom-dithiolate complex. By modifying the C6 coefficient for Au, we obtain quantitative agreement for physisorption and chemisorption for both PBE-D and revPBE-D using the same set of parameters. Our results confirm that inclusion of dispersion forces is crucial for any quantitative analysis of the thiol and thiolate bonds to the gold surface using quantum chemical calculations.

  20. Low-energy electron irradiation of preheated and gas-exposed single-wall carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Ecton, P.A. [Department of Physics, University of North Texas, Denton, TX 76203 (United States); Beatty, J.; Verbeck, G. [Department of Chemistry, University of North Texas, Denton, TX 76203 (United States); Lakshantha, W.; Rout, B. [Department of Physics, University of North Texas, Denton, TX 76203 (United States); Perez, J.M., E-mail: jperez@unt.edu [Department of Physics, University of North Texas, Denton, TX 76203 (United States)

    2016-11-30

    Highlights: • Preheating SWCNTs in situ before irradiation prevents an increase in the D peak. • Preheated SWCNTs exposed to air or gases before irradiation show an increase in D peak. • The increase in D peak is not due to irradiation-induced chemisorption of adsorbates. • The effects are more significant for small diameter SWCNTs. • The increase in D peak is attributed to defects that increase inter-tube interactions. - Abstract: We investigate the conditions under which electron irradiation at 2 keV of single-wall carbon nanotube (SWCNT) bundles produces an increase in the Raman D peak. We find that irradiation of SWCNTs that are preheated in situ at 600 °C for 1 h in ultrahigh vacuum before irradiation does not result in an increase in the D peak. Irradiation of SWCNTs that are preheated in vacuum and then exposed to air or gases results in an increase in the D peak, suggesting that adsorbates play a role in the increase in the D peak. Small diameter SWCNTs that are not preheated or preheated and then exposed to air show a significant increase in the D and G bands after irradiation. X-ray photoelectron spectroscopy shows no chemical shifts in the C 1s peak of SWCNTs that have been irradiated versus SWCNTs that have not been irradiated, suggesting that chemisorption of adsorbates is not responsible for the increase in the D peak.

  1. Nano-tribological characteristics of TiO2 films on 3-mercaptopropyl trimethoxysilane sulfonated self-assembled monolayer

    Indian Academy of Sciences (India)

    J Li; X H Sheng

    2009-10-01

    Silane coupling reagent (3-mercaptopropyl trimethoxysilane (MPTS)) was used to prepare twodimensional self-assembled monolayer (SAM) on silicon substrate. The terminal –SH group was in situ oxidized to –SO3H group to endow the film with good chemisorption ability. Then TiO2 thin films were deposited on the oxidized MPTS–SAM to form composite thin films, making use of the chemisorption ability of the –SO3H group. Atomic force microscope (AFM) and contact angle measurements were used to characterize TiO2 films. Adhesive force and friction force of TiO2 thin films and silicon substrate were measured under various applied normal loads and scanning speed of AFM tip. Results showed that the friction force increased with applied normal loads and scanning speed of AFM tip. In order to study the effect of capillary force, tests were performed in various relative humidities. Results showed that the adhesive force of silicon substrate increases with relative humidities and the adhesive force of TiO2 thin films only increases slightly with relative humidity. Research showed that surfaces with more hydrophobic property revealed the lower adhesive and friction forces.

  2. Hydrogen diffusion on Fe surface and into subsurface from first principles

    Science.gov (United States)

    Shen, Xiangjian; Chen, Jun; Sun, Y. M.; Liang, Tianshui

    2016-12-01

    The chemisorption of atomic hydrogen on metal surface and into subsurface is of great importance to understand the fundamental diffusion mechanism in heterogenous catalysis and hydrogen-induced embrittlement. Using spin-polarized density functional theory, we show that hydrogen prefers the quasi four-fold hollow site near typical Hollow site on Fe(110) and that four-fold hollow site on Fe(100). A very weak surface reconstruction effect induced by hydrogen coverage is reported. Two three-dimensional (3D) potential energy surfaces (PESs) are constructed for modelling hydrogen diffusion on Fe surface and into subsurface by interpolating ab initio energy points (∼1200 for each surface). We appraise the accuracy of PES and plot some contours of potential energies at different adsorption heights including the important subsurface regions. Furthermore, possible minimum energy pathways for hydrogen diffusion on Fe surface and into subsurface are searched out based on these 3D PESs using a mesh method. These pathways are in good agreement with those obtained from the nudged elastic band method. Some trapping regions into subsurface for hydrogen chemisorption are shown and the diffusion coefficient is estimated by classical transition state theory.

  3. Enhancing the Properties of Carbon and Gold Substrates by Surface Modification

    Energy Technology Data Exchange (ETDEWEB)

    Jennifer Anne Harnisch

    2002-06-27

    The properties of both carbon and gold substrates are easily affected by the judicious choice of a surface modification protocol. Several such processes for altering surface composition have been published in literature. The research presented in this thesis primarily focuses on the development of on-column methods to modify carbon stationary phases used in electrochemically modulated liquid chromatography (EMLC). To this end, both porous graphitic carbon (PGC) and glassy carbon (GC) particles have been modified on-column by the electroreduction of arenediazonium salts and the oxidation of arylacetate anions (the Kolbe reaction). Once modified, the carbon stationary phases show enhanced chromatographic performance both in conventional liquid chromatographic columns and EMLC columns. Additionally, one may also exploit the creation of aryl films to by electroreduction of arenediazonium salts in the creation of nanostructured materials. The formation of mercaptobenzene film on the surface of a GC electrode provides a linking platform for the chemisorption of gold nanoparticles. After deposition of nanoparticles, the surface chemistry of the gold can be further altered by self-assembled monolayer (SAM) formation via the chemisorption of a second thiol species. Finally, the properties of gold films can be altered such that they display carbon-like behavior through the formation of benzenehexathiol (BHT) SAMs. BHT chemisorbs to the gold surface in a previously unprecedented planar fashion. Carbon and gold substrates can be chemically altered by several methodologies resulting in new surface properties. The development of modification protocols and their application in the analytical arena is considered herein.

  4. A quantitative method to discriminate between non-specific and specific lectin-glycan interactions on silicon-modified surfaces.

    Science.gov (United States)

    Yang, Jie; Siriwardena, Aloysius; Boukherroub, Rabah; Ozanam, François; Szunerits, Sabine; Gouget-Laemmel, Anne Chantal

    2016-02-15

    Essential to the success of any surface-based carbohydrate biochip technology is that interactions of the particular interface with the target protein be reliable and reproducible and not susceptible to unwanted nonspecific adsorption events. This condition is particularly important when the technology is intended for the evaluation of low-affinity interactions such as those typically encountered between lectins and their monomeric glycan ligands. In this paper, we describe the fabrication of glycan (mannoside and lactoside) monolayers immobilized on hydrogenated crystalline silicon (111) surfaces. An efficient conjugation protocol featuring a key "click"-based coupling step has been developed which ensures the obtention of interfaces with controlled glycan density. The adsorption behavior of these newly developed interfaces with the lectins, Lens culinaris and Peanut agglutinin, has been probed using quantitative IR-ATR and the data interpreted using various isothermal models. The analysis reveals that protein physisorption to the interface is more prevalent than specific chemisorption for the majority of washing protocols investigated. Physisorption can be greatly suppressed through application of a strong surfactinated rinse. The coexistence of chemisorption and physisorption processes is further demonstrated by quantification of the amounts of adsorbed proteins distributed on the surface, in correlation with the results obtained by atomic force microscopy (AFM). Taken together, the data demonstrates that the nonspecific adsorption of proteins to these glycan-terminated surfaces can be effectively eliminated through the proper control of the chemical structure of the surface monolayer combined with the implementation of an appropriate surface-rinse protocol.

  5. Modified energetics and growth kinetics on H-terminated GaAs (110)

    Energy Technology Data Exchange (ETDEWEB)

    Galiana, B. [Instituto de Ciencia de Materiales de Madrid, CSIC, Sor Juana Inés de la Cruz 3, 28049 Madrid (Spain); Departamento de Física, Universidad Carlos III de Madrid, Avenida de la Universidad 30, 28911 Madrid (Spain); Benedicto, M.; Díez-Merino, L.; Tejedor, P. [Instituto de Ciencia de Materiales de Madrid, CSIC, Sor Juana Inés de la Cruz 3, 28049 Madrid (Spain); Lorbek, S.; Hlawacek, G.; Teichert, C. [Institut für Physik, Montanuniversität Leoben, Franz Josef St., 18A-8700 Leoben (Austria)

    2013-10-28

    Atomic hydrogen modification of the surface energy of GaAs (110) epilayers, grown at high temperatures from molecular beams of Ga and As{sub 4}, has been investigated by friction force microscopy (FFM). The reduction of the friction force observed with longer exposures to the H beam has been correlated with the lowering of the surface energy originated by the progressive de-relaxation of the GaAs (110) surface occurring upon H chemisorption. Our results indicate that the H-terminated GaAs (110) epilayers are more stable than the As-stabilized ones, with the minimum surface energy value of 31 meV/Å{sup 2} measured for the fully hydrogenated surface. A significant reduction of the Ga diffusion length on the H-terminated surface irrespective of H coverage has been calculated from the FFM data, consistent with the layer-by-layer growth mode and the greater As incorporation coefficient determined from real-time reflection high-energy electron diffraction studies. Arsenic incorporation through direct dissociative chemisorption of single As{sub 4} molecules mediated by H on the GaAs (110) surface has been proposed as the most likely explanation for the changes in surface kinetics observed.

  6. Self-suspended permanent magnetic FePt ferrofluids

    KAUST Repository

    Dallas, Panagiotis

    2013-10-01

    We present the synthesis and characterization of a new class of self-suspended ferrofluids that exhibit remanent magnetization at room temperature. Our system relies on the chemisorption of a thiol-terminated ionic liquid with very low melting point on the surface of L10 FePt nanoparticles. In contrast, all types of ferrofluids previously reported employ either volatile solvents as the suspending media or superparamagnetic iron oxide nanoparticles (that lacks permanent magnetization) as the inorganic component. The ferrofluids do not show any sign of flocculation or phase separation, despite the strong interactions between the magnetic nanoparticles due to the strong chemisorption of the ionic liquid as evidenced by Raman spectroscopy and thermal analysis. Composites with high FePt loading (40 and 70. wt%) exhibit a pseudo solid-like rheological behavior and high remanent magnetization values (10.1 and 12.8. emu/g respectively). At lower FePt loading (12. wt%) a liquid like behavior is observed and the remanent and saturation magnetization values are 3.5 and 6.2. emu/g, respectively. The magnetic and flow properties of the materials can be easily fine tuned by controlling the type and amount of FePt nanoparticles used. © 2013 Elsevier Inc.

  7. Interaction Between Graphene Oxide Nanoparticles and Quartz Sand.

    Science.gov (United States)

    Sotirelis, Nikolaos P; Chrysikopoulos, Constantinos V

    2015-11-17

    In this study, the influence of pH, ionic strength (IS), and temperature on graphene oxide (GO) nanoparticles attachment onto quartz sand were investigated. Batch experiments were conducted at three controlled temperatures (4, 12, and 25 °C) in solutions with different pH values (pH 4, 7, and 10), and ionic strengths (IS = 1.4, 6.4, and 21.4 mM), under static and dynamic conditions. The surface properties of GO nanoparticles and quartz sand were evaluated by electrophoretic mobility measurements. Derjaguin-Landau-Verwey-Overbeek (DLVO) potential energy profiles were constructed for the experimental conditions, using measured zeta potentials. The experimental results showed that GO nanoparticles were very stable under the experimental conditions. Both temperature and pH did not play a significant role in the attachment of GO nanoparticles onto quartz sand. In contrast, IS was shown to influence attachment. The attachment of GO particles onto quartz sand increased significantly with increasing IS. The experimental data were fitted nicely with a Freundlich isotherm, and the attachment kinetics were satisfactorily described with a pseudo-second-order model, which implies that the quartz sand exhibited substantial surface heterogeneity and that GO retention was governed by chemisorption. Furthermore, thermodynamic analysis revealed that the attachment process was nonspontaneous and endothermic, which may be associated with structural changes of the sand surfaces due to chemisorption. Therefore, secondary minimum interaction may not be the dominant mechanism for GO attachment onto the quartz sand under the experimental conditions.

  8. Interaction of hydrogen with palladium clusters deposited on graphene

    Energy Technology Data Exchange (ETDEWEB)

    Alonso, Julio A.; Granja, Alejandra; Cabria, Iván; López, María J. [Departamento de Física Teórica, Atómica y Optica, Universidad de Valladolid, 47011 Valladolid (Spain)

    2015-12-31

    Hydrogen adsorption on nanoporous carbon materials is a promising technology for hydrogen storage. However, pure carbon materials do not meet the technological requirements due to the week binding of hydrogen to the pore walls. Experimental work has shown that doping with Pd atoms and clusters enhances the storage capacity of porous carbons. Therefore, we have investigated the role played by the Pd dopant on the enhancement mechanisms. By performing density functional calculations, we have found that hydrogen adsorbs on Pd clusters deposited on graphene following two channels, molecular adsorption and dissociative chemisorption. However, desorption of Pd-H complexes competes with desorption of hydrogen, and consequently desorption of Pd-H complexes would spoil the beneficial effect of the dopant. As a way to overcome this difficulty, Pd atoms and clusters can be anchored to defects of the graphene layer, like graphene vacancies. The competition between molecular adsorption and dissociative chemisorption of H{sub 2} on Pd{sub 6} anchored on a graphene vacancy has been studied in detail.

  9. Novel self-assembled films of La-based phosphonate 3-aminopropyltriethoxysilane

    Institute of Scientific and Technical Information of China (English)

    GU Qinlin; CHENG Xianhua; QI Yong

    2009-01-01

    Silane coupling reagent (3-aminopropyltriethoxysilane (APTES)) was prepared on single-crystal silicon substrates to form two-dimensional self-assembled monolayer (SAM). The terminal-NH_2 groups in the film were in situ phosphorylated to-PO(OH)_2 group to endow the film with good chemisorption ability. Then La-based thin films were deposited on phosphorylated APTES-SAM in order to make good use of the chemisorption ability of-PO(OH)_2 groups. The thickness of the film was determined with ellipsometer, while phase trans-formation and surface morphology, surface energy, phase composition were analyzed by means of atomic force microscope (AFM), contact angle measurements and X-ray photoelectron spectroscopy (XPS). The results indicated that the terminal -NH_2 groups could be completely transformed into desirable-PO(OH)_2 groups after phosphorylation of APTES-SAM. Detailed XPS analysis of the La3+ peaks revealed that lanthanum element existed in the films in different states. As a result, conclusion could be made that lanthanum reacted with-PO(OH)_2 groups on the surface of the substrate by chemical bond which would improve the bonding strength between the film and silicon substrate.Since the La-based thin films were well adhered to the silicon substrate, it might find promising application in the surface-modification of single-crystal Si and SiC in microelectromechanical systems (MEMS).

  10. Nano-tribological characteristics of lanthanum-based thin films on sulfonated self-assembled monolayer of 3-mercaptopropyl trimethoxysilane

    Institute of Scientific and Technical Information of China (English)

    BAI Tao; CHENG Xianhua

    2008-01-01

    Silane coupling reagent (3-mercaptopropyl trimethoxysilane (MPTS)) was prepared on silicon substrate to form two-dimensional Self-Assembled Monolayer (SAM) and the terminal -SH group in the film was in situ oxidized to -SO3H group to endow the film with good chemisorption ability. Thus, lanthanum-based thin films were deposited on oxidized MPTS-SAM to form rare earth composite thin films (RE thin films), making use of the chemisorption ability of the --SO3H group. Atomic Force Microscope (AFM), X-ray Photoelectron Spectrometry (XPS), and contact angle measurements were used to characterize the RE thin films. Adhesive force and friction force of the RE thin films and silicon substrate were measured under various applied normal loads and scanning speed of AFM tip. The results showed that the friction force increased with applied normal loads and scanning speed of AFM tip. To study the effect of capillary force, tests were performed in various relative humidities. The results showed that the adhesive force of silicon substrate increased with relative humidity and the adhesive force of RE thin films only increased slightly with relative humidity. Research showed that surfaces with higher hydrophobic property reveal lowered adhesive and friction forces.

  11. Novel self-assembled films of La-based phosphonate 3-aminopropyltriethoxysilane

    Institute of Scientific and Technical Information of China (English)

    GU; Qinlin; CHENG; Xianhua; QI; Yong

    2009-01-01

    Silane coupling reagent (3-aminopropyltriethoxysilane (APTES)) was prepared on single-crystal silicon substrates to form two-dimensional self-assembled monolayer (SAM). The terminal-NH2 groups in the film were in situ phosphorylated to-PO(OH)2 group to endow the film with good chemisorption ability. Then La-based thin films were deposited on phosphorylated APTES-SAM in order to make good use of the chemisorption ability of-PO(OH)2 groups. The thickness of the film was determined with ellipsometer, while phase trans-formation and surface morphology, surface energy, phase composition were analyzed by means of atomic force microscope (AFM), contact angle measurements and X-ray photoelectron spectroscopy (XPS). The results indicated that the terminal -NH2 groups could be completely transformed into desirable-PO(OH)2 groups after phosphorylation of APTES-SAM. Detailed XPS analysis of the La3+ peaks revealed that lanthanum element existed in the films in different states. As a result, conclusion could be made that lanthanum reacted with-PO(OH)2 groups on the surface of the substrate by chemical bond which would improve the bonding strength between the film and silicon substrate.Since the La-based thin films were well adhered to the silicon substrate, it might find promising application in the surface-modification of single-crystal Si and SiC in microelectromechanical systems (MEMS).

  12. Chemical Reactions of Silicon Clusters

    CERN Document Server

    Ramakrishna, M V; Ramakrishna, Mushti V.; Pan, Jun

    1994-01-01

    Smalley and co-workers discovered that chemisorption reactivities of silicon clusters vary over three orders of magnitude as a function of cluster size. In particular, they found that \\Si{33}, \\Si{39}, and \\Si{45} clusters are least reactive towards various reagents compared to their immediate neighbors in size. We explain these observations based on our stuffed fullerene model. This structural model consists of bulk-like core of five atoms surrounded by fullerene-like surface. Reconstruction of the ideal fullerene geometry gives rise to four-fold coordinated crown atoms and $\\pi$-bonded dimer pairs. This model yields unique structures for \\Si{33}, \\Si{39}, and \\Si{45} clusters without any dangling bonds and thus explains their lowest reactivity towards chemisorption of closed shell reagents. This model is also consistent with the experimental finding of Jarrold and Constant that silicon clusters undergo a transition from prolate to spherical shapes at \\Si{27}. We justify our model based on an in depth analys...

  13. Preparation, characterization and mechanical properties of Y 2O 3 thin film deposited on sulfonated self-assembled monolayer of 3-mercaptopropyl trimethoxysilane

    Science.gov (United States)

    Wang, Jinqing; Liu, Xiaohong; Guan, Fei; Wang, Bo; Yang, Shengrong

    2004-08-01

    Silane coupling reagent (3-mercaptopropyl)trimethoxysilane was self-assembled on a single-crystal Si substrate to form a two-dimensional organic monoalyer (MPTS-SAM) and the terminal -SH group in the film was in-situ oxidized to -SO 3H group to endow the film with good chemisorption ability. Thus Y 2O 3 thin film were deposited on the oxidized MPTS-SAM, by enhanced hydrolysis of yttrium nitrate (Y(NO 3) 3 · 6H 2O) solution in the presence of urea (CO(NH 2) 2) at 80 °C, making use of the chemisorption ability of the -SO 3H group. The thickness and refractive index of the films were determined with an ellipsometer. The morphologies of the films were observed on an atomic force microscope. The adhesion strength and friction behavior of the films on the silicon substrate sliding against a steel ball was examined on a UMT-2MT friction and wear test system. It was found that the Y 2O 3-600 thin film was well adhered to the substrate with a critical load ( Lc) of 2.8 N and had excellent antiwear and friction-reduction performance under a low load of 0.2 N. Thus the Y 2O 3 film might find promising application in the surface-protection of single crystal Si and SiC in microelectromechanical systems (MEMS).

  14. Enhancing the Properties of Carbon and Gold Substrates by Surface Modification

    Energy Technology Data Exchange (ETDEWEB)

    Harnisch, Jennifer Anne [Iowa State Univ., Ames, IA (United States)

    2001-01-01

    The properties of both carbon and gold substrates are easily affected by the judicious choice of a surface modification protocol. Several such processes for altering surface composition have been published in literature. The research presented in this thesis primarily focuses on the development of on-column methods to modify carbon stationary phases used in electrochemically modulated liquid chromatography (EMLC). To this end, both porous graphitic carbon (PGC) and glassy carbon (GC) particles have been modified on-column by the electroreduction of arenediazonium salts and the oxidation of arylacetate anions (the Kolbe reaction). Once modified, the carbon stationary phases show enhanced chromatographic performance both in conventional liquid chromatographic columns and EMLC columns. Additionally, one may also exploit the creation of aryl films to by electroreduction of arenediazonium salts in the creation of nanostructured materials. The formation of mercaptobenzene film on the surface of a GC electrode provides a linking platform for the chemisorption of gold nanoparticles. After deposition of nanoparticles, the surface chemistry of the gold can be further altered by self-assembled monolayer (SAM) formation via the chemisorption of a second thiol species. Finally, the properties of gold films can be altered such that they display carbon-like behavior through the formation of benzenehexathiol (BHT) SAMs. BHT chemisorbs to the gold surface in a previously unprecedented planar fashion. Carbon and gold substrates can be chemically altered by several methodologies resulting in new surface properties. The development of modification protocols and their application in the analytical arena is considered herein.

  15. Ultramicro molybdenum nitride powder prepared using high-energy mechanochemical method

    Institute of Scientific and Technical Information of China (English)

    AN Geng; LIU Gaojie

    2008-01-01

    Using the specially designed mechanochemical ball-mill equipment, ultramicro molybdenum nitride powders were prepared from pure molybdenum powders in ammonia atmosphere at room temperature by high-energy ball milling. The structure and the particle size of the powders were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results show that the mass ratio of grinding media to powder was 8:1, after milling for 30h the Mo2N of fcc structure was obtained, and the average particle size of the powders was around 100 nm. It is found that the chemisorption of ammonia onto the fresh molybdenum surfaces created by milling was the predominant process during solid-gas reaction, and the energy input due to introduction of highly dense grain boundaries and lattice defects offered the activation energy for the transition from Mo-N chemisorption to molybdenum nitride. In addition, the change of Mo electronic undersaturation induced by the grain refining accelerated the bonding between Mo and N. The mechanism model of whole nitriding reaction was given. During the high-energy ball milling processing, the rotational speed of milling played a critical role in determining the overall reaction speed.

  16. Kinetic models for irreversible processes on a lattice

    Energy Technology Data Exchange (ETDEWEB)

    Wolf, N.O.

    1979-04-01

    The development and application of kinetic lattice models are considered. For the most part, the discussions are restricted to lattices in one-dimension. In Chapter 1, a brief overview of kinetic lattice model formalisms and an extensive literature survey are presented. A review of the kinetic models for non-cooperative lattice events is presented in Chapter 2. The development of cooperative lattice models and solution of the resulting kinetic equations for an infinite and a semi-infinite lattice are thoroughly discussed in Chapters 3 and 4. The cooperative models are then applied to the problem of theoretically dtermining the sticking coefficient for molecular chemisorption in Chapter 5. In Chapter 6, other possible applications of these models and several model generalizations are considered. Finally, in Chapter 7, an experimental study directed toward elucidating the mechanistic factors influencing the chemisorption of methane on single crystal tungsten is reported. In this it differs from the rest of the thesis which deals with the statistical distributions resulting from a given mechanism.

  17. Theoretical assessment of graphene-metal contacts.

    Science.gov (United States)

    Janthon, Patanachai; Viñes, Francesc; Kozlov, Sergey M; Limtrakul, Jumras; Illas, Francesc

    2013-06-28

    Graphene-metal contacts have emerged as systems of paramount importance in the synthesis of high-quality and large-size patches of graphene and as vital components of nanotechnological devices. Herein, we study the accuracy of several density functional theory methods using van der Waals functionals or dispersive forces corrections when describing the attachment of graphene on Ni(111). Two different experimentally observed chemisorption states, top-fcc and bridge-top, were put under examination, together with the hcp-fcc physisorption state. Calculated geometric, energetic, and electronic properties were compared to experimental data. From the calculations, one finds that (i) predictions made by different methodologies differ significantly and (ii) optB86b-vdW functional and Grimme dispersion correction seem to provide the best balanced description of stability of physisorption and chemisorption states, the attachment strength of the latter on Ni(111) surface, the graphene-Ni(111) separation, and the bandstructure of chemisorbed graphene. The collation suggests that accurate and affordable theoretical studies on technologies based on graphene-metal contacts are already at hand.

  18. Studies of biosorption of Pb2+, Cd2+ and Cu2+ from aqueous solutions using Adansonia digitata root powders.

    Science.gov (United States)

    Ekere, N R; Agwogie, A B; Ihedioha, J N

    2016-01-01

    The potentials of Adansonia digitata root powders (ADRP) for adsorption of Pb(2+), Cd(2+) and Cu(2+) from aqueous solutions was investigated. Physico-chemical analysis of the adsorbent (ADRP) shows that hydroxyl, carbonyl and amino groups were predominant on the surface of the adsorbent. Scanning Electron Microscope (SEM) image revealed its high porosity and irregular pores in the adsorbent while the Energy Dispersive X-ray Spectrum showed the major element with 53.0% Nitrogen, 23.8% carbon, 9.1% calcium, 7.5% potassium and 6.6% magnesium present. The found optimal conditions were: initial concentration of the metal ions = 0.5 mg/L, pH = 5, contact time = 90 min, adsorbent dose = 0.4 g and particle size = 32 µm. Freundlich isotherm showed good fit for the adsorption of Pb(2+), Cd(2+) and Cu(2+). Dubinin-Radushkevich isotherm revealed that the adsorption processes were physisorption Cd(II) and Cu(II) but chemisorption with respect to Pb(II) ions. The kinetics and thermodynamic studies showed that Pseudo-second order and chemisorptions provided the best fit to the experimental data of Pb (II) ions only. Batch desorption result show that desorption in the acidic media for the metal ions were more rapid and over 90% of the metal ions were recovered from the biomass.

  19. Catalytic activity vs. size correlation in platinum catalysts of PEM fuel cells prepared on carbon black by different methods

    Energy Technology Data Exchange (ETDEWEB)

    Nores-Pondal, F.J.; Granada, M.; Corti, H.R. [Departamento de Fisica de la Materia Condensada, Centro Atomico Constituyentes, Comision Nacional de Energia Atomica (CNEA), General Paz 1499, 1650 San Martin, Buenos Aires (Argentina); Vilella, I.M.J.; de Miguel, S.R.; Scelza, O.A. [Instituto de Investigaciones en Catalisis y Petroquimica (INCAPE), Facultad de Ingenieria Quimica (Universidad Nacional del Litoral) - CONICET, Santiago del Estero 2654, 3000 Santa Fe (Argentina); Troiani, H. [Departamento de Fisica, Centro Atomico Bariloche, Comision Nacional de Energia Atomica (CNEA), Av. Bustillo 9500, 8400 San Carlos de Bariloche (Argentina)

    2009-10-15

    In this work nanoparticulated platinum catalysts have been prepared on carbon Vulcan XC-72 using three methods starting with chloroplatinic acid as a precursor: (i) formic acid as a reductor agent; (ii) impregnation method followed by reduction in hydrogen atmosphere at moderated temperature; and (iii) microwave-assisted reduction in ethylene glycol. The catalytic and size studies were also performed on a commercial Pt catalyst (E-Tek, De Nora). The characterization of the particle size and distribution was performed by means of transmission electron microscopy (TEM) and X-ray diffraction (XRD). The characterizations of the catalytic and electrocatalytic properties of the catalysts were determined by studying the cyclohexane dehydrogenation reaction (CHD) and the behavior under cyclic voltammetry (CV) in sulfuric acid solutions. The measured electrochemical activity, along with the hydrogen chemisorption of the catalysts allows the estimation of effective particle sizes, which are much larger than those measured by TEM and XRD. The catalysts prepared by reduction with formic acid and ethylene glycol (microwave-assisted) show electrochemical activities very close to those of the commercial catalyst, and are almost insensitive to the Pt dispersion or Pt particle size. The chemical activity in CHD correlates well with the metallic dispersion determined by hydrogen chemisorption, indicating similar accesibility of H{sub 2} and cyclohexane to the catalyst surface. (author)

  20. Quantum state-resolved gas/surface reaction dynamics probed by reflection absorption infrared spectroscopy.

    Science.gov (United States)

    Chen, Li; Ueta, Hirokazu; Bisson, Régis; Beck, Rainer D

    2013-05-01

    We report the design and characterization of a new molecular-beam/surface-science apparatus for quantum state-resolved studies of gas/surface reaction dynamics combining optical state-specific reactant preparation in a molecular beam by rapid adiabatic passage with detection of surface-bound reaction products by reflection absorption infrared spectroscopy (RAIRS). RAIRS is a non-invasive infrared spectroscopic detection technique that enables online monitoring of the buildup of reaction products on the target surface during reactant deposition by a molecular beam. The product uptake rate obtained by calibrated RAIRS detection yields the coverage dependent state-resolved reaction probability S(θ). Furthermore, the infrared absorption spectra of the adsorbed products obtained by the RAIRS technique provide structural information, which help to identify nascent reaction products, investigate reaction pathways, and determine branching ratios for different pathways of a chemisorption reaction. Measurements of the dissociative chemisorption of methane on Pt(111) with this new apparatus are presented to illustrate the utility of RAIRS detection for highly detailed studies of chemical reactions at the gas/surface interface.

  1. Investigation of Tribological Behavior of Lanthanum-Based Thin Films Deposited on Sulfonated Self-Assembled Monolayer

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    3-mercaptopropyl trimethoxysilane (MPTS) was prepared on glass substrate so as to form a two-dimensional self-assembled monolayer (SAM), and the terminal -SH group in the film was in situ oxidized to -SO3H group to confer good chemisorption ability to the film. Thus, lanthanum-based thin films were deposited on oxidized MPTS-SAM, making use of the chemisorption ability of -SO3H group. Atomic force microscopy (AFM) and X-ray photoelectron spectrometry (XPS) and contact angle measurements were used to characterize the thin films. The tribological properties of the as-prepared thin films sliding against a steel ball were evaluated on a friction and wear tester. Tribological experiment shows that the friction coefficient of glass substrate decreases from 0.8 to 0.08 after the rare earth (RE) self-assembled films (SAMs) are formed on its surface. And the RE self-assembled films have longer wear life (500 sliding passes). It is demonstrated that RE self-assembled film exhibits good wear-resistant property. The marked decrease in friction and the longer wear life of RE films are attributed to the excellent adhesion of the film to the substrate and to the special characteristics of the RE elements. The frictional behaviors of RE thin-films-coated silicon surface were sensitive to the applied load and the sliding velocity of the steel ball.

  2. Tungstophosphoric acid supported onto hydrous zirconia: Physicochemical characterization and esterification of 1° and 2° alcohol

    Indian Academy of Sciences (India)

    Pankaj Sharma; Anjali Patel

    2006-10-01

    The Keggin type heteropolyacid, 12-tungstophosphoric acid (PW), was supported onto hydrous zirconia (Z) by impregnation method and designated as ZH3. The ZH3 was calcinated at 300°C and 500°C and designated as ZH33 and ZH35, respectively. The resulting materials were characterized by FTIR, diffuse reflectance spectroscopy (DRS), XRD, surface area measurement (BET method) and particle size distribution. The surface morphology was studied by scanning electron microscopy. The acidity of all materials was evaluated by carrying out chemisorption of ammonia and esterification of 1° alcohol (-butanol) with different acids like formic acid, acetic acid and propionic acid and 2° alcohol (cyclohexanol, iso-butanol) with acetic acid. Above studies show the high dispersion of HPA in a non-crystalline form on the support as well as uniform distribution of particles of ZH3 which contains 30% 12-tungstophosphoric acid. It also shows that when ZH3 was calcinated at 500°C, it possesses highest acidity for both chemisorption of NH3 as well as esterification reactions.

  3. Microcalorimetry of oxygen adsorption on fcc Co{110}.

    Science.gov (United States)

    Liao, Kristine; Fiorin, Vittorio; Jenkins, Stephen J; King, David A

    2012-05-28

    The coverage dependent heats of adsorption and sticking probabilities for oxygen on fcc Co{110} have been measured at 300 K using single crystal adsorption calorimetry (SCAC). Initial adsorption is consistent with dissociative chemisorption at low coverage followed by oxide formation above 0.6 ML coverage. The initial heat of adsorption of 633 kJ mol(-1) is similar to heat values calorimetrically measured on other ferromagnetic metal surfaces, such as nickel and iron. As the coverage increases, the heat of adsorption and sticking probability drop very rapidly up to the onset of oxidation. As already observed for other oxygen-metal surface systems, strong lateral adatom repulsions are responsible for the transition from the chemisorption regime to oxide film formation at higher coverage. The heat of oxide formation at the onset is 475 kJ mol(-1), which is consistent with the formation of CoO crystallites. The oxide film formation is discussed in terms of nucleation and island growth, and the Mott-Cabrera mechanisms, the latter being evidenced by the relatively constant heat of adsorption and sticking probability in contrast to the nickel and iron oxidation cases.

  4. Kinetic modeling of liquid-phase adsorption of phosphate on dolomite.

    Science.gov (United States)

    Karaca, S; Gürses, A; Ejder, M; Açikyildiz, M

    2004-09-15

    The adsorption of phosphate from aqueous solution on dolomite was investigated at 20 and 40 degrees C in terms of pseudo-second-order mechanism for chemical adsorption as well as an intraparticle diffusion mechanism process. Adsorption was changed with increased contact time, initial phosphate concentration, temperature, solution pH. A pseudo-second-order model and intraparticle diffusion model have been developed to predict the rate constants of adsorption and equilibrium capacities. The activation energy of adsorption can be evaluated using the pseudo-second-order rate constants. The adsorption of phosphate onto dolomite are an exothermically activated process. A relatively low activation energy and a model highly fitting to intraparticle diffusion suggest that the adsorption of phosphate by dolomite may involve not only physical but also chemisorption. This was likely due to its combined control of chemisorption and intraparticle diffusion. However, for phosphate/dolomite system chemical reaction is important and significant in the rate-controlling step, and for the adsorption of phosphate onto dolomite the pseudo-second-order chemical reaction kinetics provides the best correlation of the experimental data.

  5. Reduction of NO by CO using Pd-CeTb and Pd-CeZr catalysts supported on SiO2 and La2O3-Al2O3

    Institute of Scientific and Technical Information of China (English)

    Victor Ferrer; Dora Finol; Roger Solano; Alexander Moronta; Miguel Ramos

    2015-01-01

    The catalytic activity of Pd catalysts supported on Ce0.73Tb0.27Ox/SiO2,Ce0.6Zr0.4Ox/SiO2,Ce0.73Tb0.27Ox/La2O3-Al2O3 and Ce0.6Zr0.4Ox/La2O3-Al2O3 was studied using the reduction of NO by CO.The catalysts were characterized by X-ray fluorescence,surface area,X-ray diffraction,temperature-programmed reduction,CO chemisorption and oxygen storage capacity.Temperature-programmed reduction results indicated that Tb or Zr incorporation improves the reducibility and oxygen storage capacity.CO chemisorption data suggested the presence of large PdO particles due to the low CO/Pd ratio.No significant differences were obtained in light offtemperatures (TLight off) for all Pd catalysts and the most active was 1.5%Pd/Ce0.6Zr0.4Ox/SiO2.

  6. Ethanol steam reforming over Rh/Ce{sub x}Zr{sub 1-x}O{sub 2} catalysts. Impact of the CO-CO{sub 2}-CH{sub 4} interconversion reactions on the H{sub 2} production

    Energy Technology Data Exchange (ETDEWEB)

    Birot, Anne; Epron, Florence; Duprez, Daniel [Laboratoire de Catalyse en Chimie Organique (LACCO), UMR 6503 CNRS and University of Poitiers, 40 Avenue du Recteur Pineau, 86022 Poitiers Cedex (France); Descorme, Claude [IRCELYON, UMR 5256 CNRS/Universite Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France)

    2008-02-21

    Ce{sub x}Zr{sub 1-x}O{sub 2} mixed oxide-supported 1 wt.% Rh catalysts were prepared by wet impregnation using Rh nitrate as a precursor and calcined at 900 C. They were characterized by BET surface area, XRD, CO{sub 2} chemisorption and H{sub 2} chemisorption at -85 C and tested in the ethanol steam reforming at 600 C under atmospheric pressure, with water to ethanol molar ratio equal to 4, without carrier gas. The best performances, i.e. the highest hydrogen yield and the lowest coke deposition, were obtained over Rh/Ce{sub 0.5}Zr{sub 0.5}O{sub 2}, i.e. 3.63 mol H{sub 2}/mol{sub ethanol}. This catalyst was subsequently evaluated under various reaction conditions. Whatever the temperature and the water to ethanol ratio, the ethanol steam reforming yielded a large amount of methane, which tends to reduce the H{sub 2} production. To elucidate the origin of the methane production, CO/CO{sub 2}/CH{sub 4} interconversion reactions were studied. It was shown that such catalyst favours the formation of methane via CO hydrogenation. The direct hydrogenation of CO{sub 2} was not observed. In parallel, the catalyst was active in the reverse water gas shift (RWGS) reaction between CO{sub 2} and H{sub 2}, leading CO and H{sub 2}O. (author)

  7. Lifetime of combustion-generated environmentally persistent free radicals on Zn(II)O and other transition metal oxides.

    Science.gov (United States)

    Vejerano, Eric; Lomnicki, Slawo; Dellinger, Barry

    2012-10-26

    Previous studies indicated that Environmentally Persistent Free Radicals (EPFRs) are formed in the post-flame, cool zone of combustion. They result from the chemisorption of gas-phase products of incomplete combustion (particularly hydroxyl- and chlorine-substituted aromatics) on Cu(II)O, Fe(III)(2)O(3), and Ni(II)O domains of particulate matter (fly ash or soot particles). This study reports our detailed laboratory investigation on the lifetime of EPFRs on Zn(II)O/silica surface. Similarly, as in the case of other transition metals, chemisorption of the adsorbate on the Zn(II)O surface and subsequent transfer of electron from the adsorbate to the metal forms a surface-bound EPFR and a reduced metal ion center. The EPFRs are stabilized by their interaction with the metal oxide domain surface. The half-lives of EPFRs formed on Zn(II)O domains were the longest observed among the transition metal oxides studied and ranged from 3 to 73 days. These half-lives were an order of magnitude longer than those formed on nickel and iron oxides, and were 2 orders of magnitude longer compared to the EPFRs on copper oxide which have half-lives only on the order of hours. The longest-lived radicals on Zn(II)O correspond to the persistency in ambient air particles of almost a year. The half-life of EPFRs was found to correlate with the standard reduction potential of the associated metal.

  8. Water vapor interactions with polycrystalline titanium surfaces

    Science.gov (United States)

    Azoulay, A.; Shamir, N.; Volterra, V.; Mintz, M. H.

    1999-02-01

    The initial interactions of water vapor with polycrystalline titanium surfaces were studied at room temperature. Measurements of water vapor surface accumulation were performed in a combined surface analysis system incorporating direct recoils spectrometry (DRS), Auger electron spectroscopy and X-ray photoelectron spectroscopy. The kinetics of accommodation of the water dissociation fragments (H, O and OH) displayed a complex behavior depending not only on the exposure dose but also on the exposure pressure. For a given exposure dose the efficiency of chemisorption increased with increasing exposure pressure. DRS measurements indicated the occurrence of clustered hydroxyl moieties with tilted O-H bonds formed even at very low surface coverage. A model which assumes two parallel routes of chemisorption, by direct collisions (Langmuir type) and by a precursor state is proposed to account for the observed behavior. The oxidation efficiency of water seemed to be much lower than that of oxygen. No Ti 4+ states were detected even at high water exposure values. It is likely that hydroxyl species play an important role in the reduced oxidation efficiency of water.

  9. Cr(VI) sorption behavior from aqueous solutions onto polymeric microcapsules containing a long-chain quaternary ammonium salt: Kinetics and thermodynamics analysis

    Energy Technology Data Exchange (ETDEWEB)

    Barassi, Giancarlo; Valdes, Andrea; Araneda, Claudio; Basualto, Carlos; Sapag, Jaime; Tapia, Cristian [Laboratorio de Operaciones Unitarias, Facultad de Ciencias Quimicas y Farmaceuticas, Universidad de Chile, Av. Vicuna Mackenna 20, Santiago (Chile); Valenzuela, Fernando, E-mail: fvalenzu@uchile.cl [Laboratorio de Operaciones Unitarias, Facultad de Ciencias Quimicas y Farmaceuticas, Universidad de Chile, Av. Vicuna Mackenna 20, Santiago (Chile)

    2009-12-15

    This work studies the adsorption of Cr(VI) ions from an aqueous acid solution on hydrophobic polymeric microcapsules containing a long-chain quaternary ammonium salt-type extractant immobilized in their pore structure. The microcapsules were synthesized by adding the extractant Aliquat 336 during the in situ radical copolymerization of the monomers styrene (ST) and ethylene glycol dimethacrylate (EGDMA). The microcapsules, which had a spherical shape with a rough surface, behaved as efficient adsorbents for Cr(VI) at the tested temperatures. The results of kinetics experiments carried out at different temperatures showed that the adsorption process fits well to a pseudo-second-order with an activation energy of 82.7 kJ mol{sup -1}, confirming that the sorption process is controlled by a chemisorption mechanism. Langmuir's isotherms were found to represent well the experimentally observed sorption data. Thermodynamics parameters, namely, changes in standard free energy ({Delta}G{sup 0}), enthalpy ({Delta}H{sup 0}), and entropy ({Delta}S{sup 0}), are also calculated. The results indicate that the chemisorption process is spontaneous and exothermic. The entropy change value measured in this study shows that metal adsorbed on microcapsules leads to a less chaotic system than a liquid-liquid extraction system.

  10. Molecular hydrogen formation on grain surfaces

    CERN Document Server

    Cazaux, S; Tielens, A G G M; Le Bourlot, J; Walmsley, M C

    2005-01-01

    We reconsider H2 formation on grain surfaces. We develop a rate equation model which takes into account the presence of both physisorbed and chemisorbed sites on the surface, including quantum mechanical tunnelling and thermal diffusion. In this study, we took into consideration the uncertainties on the characteristics of graphitic surfaces. We calculate the H2 formation efficiency with the Langmuir Hinshelwood and Eley Rideal mechanisms, and discuss the importance of these mechanisms for a wide range of grain and gas temperatures. We also develop a Monte Carlo simulation to calculate the H2 formation efficiency and compare the results to our rate equation models. Our results are the following: (1) Depending on the barrier against chemisorption, we predict the efficiency of H2 formation for a wide range of grain and gas temperatures. (2) The Eley-Rideal mechanism has an impact on the H2 formation efficiency at high grain and gas temperatures. (3) The fact that we consider chemisorption in our model makes the ...

  11. Two-photon photoemission investigation of electronic and dynamical properties of alkali atoms adsorbed on noble metal surfaces

    Science.gov (United States)

    Sametoglu, Vahit

    We present a systematic time-resolved two-photon photoemission study of the electronic and dynamical properties of Li through Cs adsorbed on Cu(111) and Ag(111) surfaces. A fundamental problem in surface science is how to describe the electronic structure of a chemisorption interface based on the intrinsic properties of the interacting materials. Because of their simple s-electron structure, elements of the alkali atom group comprise paradigmatic adsorbates in many theories of chemisorption, whereas the complementary experimental studies are sparse and incomplete. Through a combination of spectroscopic and femtosecond time-resolved surface measurements, we are able to probe systematically the binding energies, symmetries, and electron and nuclear relaxation dynamics of the initially unoccupied alkali atom resonances. As a prelude, we study the two-photon photoemission process occurring at the bare Ag(111) surface. We develop a quantitative model for two-photon photoemission process, where the nonresonant and k-dependent two-photon absorption between the lower and upper sp-bands is modeled by the optical Bloch equations, and the angle-dependent intensities are described by the Fresnel equations. Our two-photon photoemission spectra of Li through Cs chemisorbed Cu(111) and Ag(111) surfaces reveal two resonances with the m = 0 and m = +/-1 symmetry ('m' is the projection of the orbital angular momentum 'l' onto the surface plane). For the m = 0 resonance, which is derived from the hybridization of the ns and npz orbitals of alkali atoms, we find a binding energy of 1.84--1.99 eV below the vacuum level, which is independent of the alkali atom period, and tunes with coverage in a universal manner. At 0.3--0.7 eV higher energy, we discover and identify the m = +/-1 resonance by its characteristic angular intensity distribution, which derives from the antisymmetry of the npx and npy orbitals. We implement a quantitative model for the alkali atom chemisorption based on the

  12. Gas adsorption and desorption effects on cylinders and their importance for long-term gas records

    Directory of Open Access Journals (Sweden)

    M. C. Leuenberger

    2015-08-01

    Full Text Available It is well known that gases adsorb on many surfaces, in particular metal surfaces. There are two main forms responsible for these effects (i physisorption and (ii chemisorption. Physisorption is associated with lower binding energies in the order of 1–10 kJ mol−1 compared to chemisorption ranging from 100 to 1000 kJ mol−1. Furthermore, chemisorption forms only monolayers, contrasting physisorption that can form multilayer adsorption. The reverse process is called desorption and follows similar mathematical laws, however, it can be influenced by hysteresis effects. In the present experiment we investigated the adsorption/desorption phenomena on three steel and three aluminium cylinders containing compressed air in our laboratory and under controlled conditions in a climate chamber, respectively. We proved the pressure effect on physisorption for CO2, CH4 and H2O by decanting one steel and two aluminium cylinders completely. The CO2 results for both cylinders are in excellent agreement with the pressure dependence of a monolayer adsorption model. However, adsorption on aluminium (2 and H2O was about 10 times less than on steel (2 amounts adsorbed (5.8 × 1019 CO2 molecules corresponds to about the five-fold monolayer adsorption indicating that the effective surface exposed for adsorption is significantly larger than the geometric surface area. Adsorption/desorption effects were minimal for CH4 and for CO. However, the latter dependence requires further attention since it was only studied on one aluminium cylinder with a very low mole fraction. In the climate chamber the cylinders were exposed to temperatures between −10 and +50 °C to determine the corresponding temperature coefficients of adsorption. Again, we found distinctly different values for CO2 ranging from 0.0014 to 0.0184 ppm °C−1 for steel cylinders and −0.0002 to −0.0003 ppm °C−1 for aluminium cylinders. The reversed temperature dependence for aluminium cylinders

  13. The structure, energetics, and nature of the chemical bonding of phenylthiol adsorbed on the Au(111) surface: implications for density-functional calculations of molecular-electronic conduction.

    Science.gov (United States)

    Bilić, Ante; Reimers, Jeffrey R; Hush, Noel S

    2005-03-01

    The adsorption of phenylthiol on the Au(111) surface is modeled using Perdew and Wang density-functional calculations. Both direct molecular physisorption and dissociative chemisorption via S-H bond cleavage are considered as well as dimerization to form disulfides. For the major observed product, the chemisorbed thiol, an extensive potential-energy surface is produced as a function of both the azimuthal orientation of the adsorbate and the linear translation of the adsorbate through the key fcc, hcp, bridge, and top binding sites. Key structures are characterized, the lowest-energy one being a broad minimum of tilted orientation ranging from the bridge structure halfway towards the fcc one. The vertically oriented threefold binding sites, often assumed to dominate molecular electronics measurements, are identified as transition states at low coverage but become favored in dense monolayers. A similar surface is also produced for chemisorption of phenylthiol on Ag(111); this displays significant qualitative differences, consistent with the qualitatively different observed structures for thiol chemisorption on Ag and Au. Full contours of the minimum potential energy as a function of sulfur translation over the crystal face are described, from which the barrier to diffusion is deduced to be 5.8 kcal mol(-1), indicating that the potential-energy surface has low corrugation. The calculated bond lengths, adsorbate charge and spin density, and the density of electronic states all indicate that, at all sulfur locations, the adsorbate can be regarded as a thiyl species that forms a net single covalent bond to the surface of strength 31 kcal mol(-1). No detectable thiolate character is predicted, however, contrary to experimental results for alkyl thiols that indicate up to 20%-30% thiolate involvement. This effect is attributed to the asymptotic-potential error of all modern density functionals that becomes manifest through a 3-4 eV error in the lineup of the adsorbate and

  14. Studies on Mercury Adsorption on Bromine Modified Activated Carbon%溴素改性活性炭汞吸附特性研究

    Institute of Scientific and Technical Information of China (English)

    周强; 冒咏秋; 段钰锋; 朱纯; 佘敏; 洪亚光

    2014-01-01

    在固定床实验台上进行了1% NH4Br改性活性炭汞吸附实验.利用吸附动力学模型从动力学角度探讨了汞吸附速率控制步,汞吸附活化能与初始汞吸附速率.结果表明:150℃时,1% NH4Br改性活性炭脱汞能力显著增强,其原因是改性后活性炭表面活性位点(Br)明显增加,强化了化学吸附作用.但低温时,化学吸附增强作用不明显.汞在改性活性炭表面的吸附活化能为29.69 kJ/mol,说明吸附以物理吸附为主,化学吸附为辅.改性活性炭的初始汞吸附速率随温度增加而增加.活性位吸附是汞吸附速率控制步,外部传质控制也影响整个汞吸附过程,吸附遵循Langmuir吸附等温方程.%An experimental study on mercury adsorption of 1% NH4Br modified activated carbon was carried out in a fixed-bed reactor.Adsorption kinetic models were used to investigate mercury adsorption rate controlling step,adsorption activation energy and initial mercury adsorption rate from the kinetic point of view.The results show that mercury adsorption capacity of modified activated carbon increases significantly at 150℃ due to addition of active site (Br) on activated carbon surface,which improves chemisorption.However,performance of chemisorption at low flue gas temperature is not dominant.The activation energy of mercury adsorption on modified activated carbon surface is 29.69 kJ/mol,which illustrates that mercury adsorption is mainly physisorption but enhanced by chemisorption.The initial mercury adsorption rate of modified activated carbon increases with temperature elevation.Mercury adsorption on active sites is the adsorption rate controlling step and external mass transfer also plays an important role.Mercury adsorption on modified activated carbon follows the Langmuir isotherm equation.

  15. Catalisadores Ni/Al2O3 promovidos com molibdênio para a reação de reforma a vapor de metano Mo-Ni/AL2O3 catalysts for the methane steam reforming reaction

    Directory of Open Access Journals (Sweden)

    Silvia Sálua Maluf

    2003-03-01

    Full Text Available Mo-promoted Ni/Al2O3 catalysts for the methane steam reforming reaction were studied in this work. The Ni/Al2O3 catalysts were prepared by precipitation and molibdenum was added by impregnation up to 2%wt. The solids were tested using a micro-reactor under two H2Ov/C conditions and were characterized by ICP-OES, XRD, N2 adsoption, H2 chemisorption and TPR. NiO and NiAl2O4 phases were observed and the metallic area decreased with the increase of the Mo content. From the catalytic tests high stability was verified for H2Ov/C=4.0. On the other hand, only the catalyst containing 0,05% Mo stayed stable during 30 hours of the test at H2Ov/C=2.0.

  16. Design Principles of Inert Substrates for Exploiting Gold Clusters’ Intrinsic Catalytic Reactivity

    Science.gov (United States)

    Gao, Wang; Ting Cui, Ting; Fu Zhu, Yong; Wen, Zi; Zhao, Ming; Chen Li, Jian; Jiang, Qing

    2015-10-01

    Ultralow stability of gold clusters prohibits the understanding of their intrinsic reactivity (that is vital for revealing the origin of gold’s catalytic properties). Using density functional theory including many-body dispersion method, we aim to ascertain effective ways in exploiting gold clusters’ intrinsic reactivity on carbon nanotubes (CNTs). We find that the many body van der Waals interactions are essential for gold clusters’ reactivity on CNTs and even for O2 activation on these supported clusters. Furthermore, curvature and dopant of CNTs are found to qualitatively change the balance between physisorption and chemisorption for gold clusters on CNTs, determining the clusters’ morphology, charge states, stability, and reactivity, which rationalize the experimental findings. Remarkably, N doped small curvature CNTs, which effectively stabilize gold clusters and retain their inherent geometric/electronic structures, can be promising candidates for exploiting gold clusters’ intrinsic reactivity.

  17. van der Waals forces and confinement in carbon nanopores: Interaction between CH4, COOH, NH3, OH, SH and single-walled carbon nanotubes

    Science.gov (United States)

    Weck, Philippe F.; Kim, Eunja; Wang, Yifeng

    2016-05-01

    Interactions between CH4, COOH, NH3, OH, SH and armchair (n, n) (n = 4, 7, 14) and zigzag (n, 0) (n = 7, 12, 25) single-walled carbon nanotubes (SWCNTs) have been systematically investigated within the framework of dispersion-corrected density functional theory (DFT-D2). Endohedral and exohedral molecular adsorption on SWCNT walls is energetically unfavorable or weak, despite the use of C6 /r6 pairwise London-dispersion corrections. The effects of pore size and chirality on the molecule/SWCNTs interaction were also assessed. Chemisorption of COOH, NH3, OH and SH at SWCNT edge sites was examined using a H-capped (7, 0) SWCNT fragment and its impact on electrophilic, nucleophilic and radical attacks was predicted by means of Fukui functions.

  18. Investigating the adsorption of H2O on ZnO nanoclusters by first principle calculations

    KAUST Repository

    Al-Sunaidi, Abdullah A.

    2011-04-01

    The interaction of a single H2O molecule on selected ZnO nanoclusters is investigated by carrying out calculations based on the density-functional theory at the hybrid-GGA (B97-2) level. These clusters have ring, drum, tube and bubble shapes and their physical properties like the binding energy and the band gap energy depend strongly on the shape and size of the cluster. Depending on the stability of the cluster, H2O show both chemisorption and dissociation on the surfaces of the clusters. We analyzed the effect of H2O adsorption on the properties of clusters of size n = 12 via the density of state, HOMO-LUMO orbitals and the changes in the IR frequencies. © 2011 Elsevier B.V. All rights reserved.

  19. Gas sorption in solid surfaces: a computational study using rigid and Einstein-solid models.

    Science.gov (United States)

    Lara-Peña, Mayra; Domínguez, Hector

    2015-11-01

    The reactive Monte Carlo (RxMC) method was proposed to describe the sorption of gases in solid materials due to the chemical reaction A + B ⇌ C. Two models were used to simulate the solid; the first model considered simulations with rigid particles in the solid whereas in the second model the particles were allowed to vibrate inside the solid with a given spring constant, i.e. an Einstein solid was used to simulate the substrate. In both models not only physisorption but also chemisorption of the fluid was observed. Sorption curves, at different spring constants, were simulated and it was noted that sorption was always enhanced with the Einstein solid model. Moreover, an inverse dependent function of the spring constant with the temperature was found. Finally, the second model might be used to explain the unusual sorption behavior observed in actual experimental reactions such as CO2 + Li2O ⇌ Li2CO3.

  20. Molecular beam study of dissociative sticking of methane on Ni(100)

    DEFF Research Database (Denmark)

    Holmblad, Peter Mikal; Wambach, Jørg; Chorkendorff, Ib

    1995-01-01

    This paper reports a detailed molecular beam study of the dissociative sticking of methane incident on clean Ni(100). It is demonstrated that the sticking coefficient depends strongly on the translational energy of the molecule. It is also observed that an increase in the vibrational energy...... of the methane leads to a dramatic enhancement of the sticking, emphasizing that the initial vibrational state is of crucial importance. These results are consistent with a mechanism of direct activated dissociative chemisorption where the dynamics is dominated by a barrier in the potential energy surface mainly......(Ei), considering only the vibrational C–H stretch modes of methane as relevant for the sticking, gives a good description of the data. These sticking curves enables a calculation of the thermal sticking coefficient which is found to be in excellent agreement with bulb experiments directly probing this. ©1995...

  1. Adsorption of dissolved Reactive red dye from aqueous phase onto activated carbon prepared from agricultural waste.

    Science.gov (United States)

    Senthilkumaar, S; Kalaamani, P; Porkodi, K; Varadarajan, P R; Subburaam, C V

    2006-09-01

    The adsorption of Reactive red dye (RR) onto Coconut tree flower carbon (CFC) and Jute fibre carbon (JFC) from aqueous solution was investigated. Adsorption studies were carried out at different initial dye concentrations, initial solution pH and adsorbent doses. The kinetic studies were also conducted; the adsorption of Reactive red onto CFC and JFC followed pseudosecond-order rate equation. The effective diffusion coefficient was evaluated to establish the film diffusion mechanism. Quantitative removal of Reactive red dye was achieved at strongly acidic conditions for both the carbons studied. The adsorption isotherm data were fitted well to Langmuir isotherm and the adsorption capacity were found to be 181.9 and 200 mg/g for CFC and JFC, respectively. The overall rate of dye adsorption appeared to be controlled by chemisorption, in this case in accordance with poor desorption studies.

  2. Phosphonic acid functionalized asymmetric phthalocyanines: synthesis, modification of indium tin oxide, and charge transfer.

    Science.gov (United States)

    Polaske, Nathan W; Lin, Hsiao-Chu; Tang, Anna; Mayukh, Mayunk; Oquendo, Luis E; Green, John T; Ratcliff, Erin L; Armstrong, Neal R; Saavedra, S Scott; McGrath, Dominic V

    2011-12-20

    Metalated and free-base A(3)B-type asymmetric phthalocyanines (Pcs) bearing, in the asymmetric quadrant, a flexible alkyl linker of varying chain lengths terminating in a phosphonic acid (PA) group have been synthesized. Two parallel series of asymmetric Pc derivatives bearing aryloxy and arylthio substituents are reported, and their synthesis and characterization through NMR, combustion analysis, and MALDI-MS are described. We also demonstrate the modification of indium tin oxide (ITO) substrates using the PA functionalized asymmetric Pc derivatives and monitoring their electrochemistry. The PA functionalized asymmetric Pcs were anchored to the ITO surface through chemisorption and their electrochemical properties characterized using cyclic voltammetry to investigate the effects of PA structure on the thermodynamics and kinetics of charge transfer. Ionization energies of the modified ITO surfaces were measured using ultraviolet photoemission spectroscopy.

  3. Toward an Enhancement of the Photoactivity of Multiphotochromic Dimers Using Plasmon Resonance: A Theoretical Study.

    Science.gov (United States)

    Fihey, Arnaud; Le Guennic, Boris; Jacquemin, Denis

    2015-08-06

    Building dimers of organic photochromic compounds paves the way to multifunctional switches, but such architectures often undergo partial photoreactivity only. Combining photochromism of molecules and plasmon resonance of gold nanoparticles (NPs) is known to affect the photochromism of monomers, yet the impact on multimers remains unknown. Here we propose a theoretical study of dimers of dithienylethenes by the mean of a hybrid calculation scheme (discrete-interaction model/quantum mechanics). We aim to assess how the optical properties of multiphotochromes are tuned by the influence of the plasmon resonances. We show that, for a typical chemisorption orientation on the NP, the absorption bands responsible for the photochromism are significantly enhanced for both the doubly open and mixed closed-open isomers of the dyad, hinting that plasmon resonance could be used to boost the generally poor photoactivity of dithienylethene dyads.

  4. Influence of alkali promoters in the selective hydrogenation of 3-methyl-2-butenal over Ru/SiO{sub 2} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Waghray, A.; Wang, Jian; Oukaci, R.; Blackmond, D.G. [Univ. of Pittsburgh, PA (United States)

    1992-07-09

    The addition of potassium as a promoter to a Ru/SiO{sub 2} catalyst resulted in a striking shift in product selectivity in the hydrogenation of 3-methyl-2-butenal. The rate of hydrogenation of the C=O bond to produce the unsaturated alcohol increased concomitant with a decrease in the rate of C=C hydrogenation. IR spectroscopy showed a strong perturbation of the C=O bond for the alkali-promoted catalyst, and volumetric chemisorption and TPD results suggested that the alkali species blocked adsorption at low-coordination Ru sites. These adsorption and reaction studies suggest that polarization of the adsorbed substrate at the C=O bond is responsible for the significant shift in product selectivity upon alkali promotion. This work combines spectroscopic tools with the use of the catalytic reaction itself as a probe of catalyst surface chemistry. 40 refs., 6 figs., 3 tabs.

  5. Density functional theory study of ATA, BTAH, and BTAOH as copper corrosion inhibitors: adsorption onto Cu(111) from gas phase.

    Science.gov (United States)

    Kokalj, Anton; Peljhan, Sebastijan

    2010-09-21

    A low-coverage gas-phase adsorption of three corrosion inhibitors-3-amino-1,2,4-triazole (ATA), benzotriazole (BTAH), and 1-hydroxybenzotriazole (BTAOH)-on perfect Cu(111) surface has been studied and characterized using density functional theory calculations. We find that the molecules in neutral form chemisorb weakly to the perfect surface in an upright geometry. The strength of the chemisorption increases in the order BTAH BTA· with the adsorption energies of -1.65, -2.22, and -2.78 eV, respectively. This order is compatible with the trend of experimentally observed corrosion inhibition effectiveness on copper in near-neutral chloride solutions. Although the calculations are performed at the metal/vacuum interface, they provide enough insight to rationalize why in some experiments the BTAH was observed to be adsorbed with an upright geometry and in the others with parallel geometry.

  6. Removal of Cd (II) from water using the waste of jatropha fruit (Jatropha curcas L.)

    Science.gov (United States)

    Nacke, Herbert; Gonçalves, Affonso Celso; Coelho, Gustavo Ferreira; Schwantes, Daniel; Campagnolo, Marcelo Angelo; Leismann, Eduardo Ariel Völz; Junior, Élio Conradi; Miola, Alisson Junior

    2016-09-01

    The aim of this work was to evaluate the removal of Cd (II) from water using three biosorbents originated from the biomass of jatropha (bark, endosperm, and endosperm + tegument). For that, batch tests were performed to verify the effect of solution pH, adsorbent mass, contact time, initial concentration of Cd (II), and the temperature of the process. The adsorption process was evaluated by the studies of kinetics, isotherms, and thermodynamics. The ideal conditions of solution pH were 5.5 and 8 g L-1 of adsorbent mass of biosorbents by solution volume, with an equilibrium time of 60 min. According to the Langmuir model, the maximum adsorption capacity for bark, endosperm, and bark + endosperm of jatropha was, respectively, 29.665, 19.562, and 34.674 mg g-1, predominating chemisorption in monolayers. The biosorbents presented potential for the remediation of waters contaminated with Cd (II).

  7. Berberine as an Environmental-Friendly Inhibitor for Hot-Dip Coated Steels in Diluted Hydrochloric Acid

    Institute of Scientific and Technical Information of China (English)

    Hong Ju; Yulin Ju; Yan Li

    2012-01-01

    The inhibition effect of an excellent environmental-friendly corrosion inhibitor--berberine on hot-dip coated steels in the diluted HCI has been investigated by using quantum chemistry analysis, mass-loss tests, elec- trochemical measurements and scanning electron microscopy (SEM) observation. Calculation results show that berberine has a nearly planar structure with a number of active centers. The value of Mulliken charge, and the distribution of the highest occupied molecular orbital (HOMO) and the lower unoccupied molecular orbital (LUMO) imply that berberine has a good ability of electron exchange with metal surface. The test results indicate that inhibition efficiency (IE%) increases with the inhibitor concentration and the highest IE can reach 99%. Adsorption of berberine on the coating surface follows Langmuir adsorption isotherm with a single molecular layer by chemisorption.

  8. Corrosion Inhibition Performance of Triazole Derivatives on Copper-Nickel Alloy in 3.5 wt.% NaCl Solution

    Science.gov (United States)

    Jiang, B.; Jiang, S. L.; Liu, X.; Ma, A. L.; Zheng, Y. G.

    2015-12-01

    This study investigates the performance of three triazole derivatives with different molecular structures as corrosion inhibitors for the copper-nickel alloy CuNi 90/10 in 3.5 wt.% NaCl solution. Inhibition behavior was systematically determined through electrochemical measurements, scanning electron microscopy, energy-dispersive spectroscopy, and Fourier transform infrared spectroscopy. In addition, adsorption behavior and the inhibition mechanism were investigated via quantum chemical calculation and molecular dynamic simulation. Experimental results indicate that the three inhibitors with triazole rings and heteroatoms exhibited excellent corrosion inhibition capabilities on the copper-nickel alloy surface through physisorption and chemisorption. In particular, 3-amino-5-mercapto-1,2,4-triazole showed the best inhibition capability according to the concentration ranges considered in the experiments. The results of quantum chemical calculation agreed with the experimental findings.

  9. Photocatalytic degradation of carbofuran in TiO2 aqueous solution: kinetics using design of experiments and mechanism by HPLC/MS/MS.

    Science.gov (United States)

    Yang, Hai; Zhou, Shuolin; Liu, Huajie; Yan, Weiwei; Yang, Liping; Yij, Bing

    2013-08-01

    The photocatalytic degradation kinetics of carbofuran was optimized by central composite design based on response surface methodology for the first time. Three variables, TiO2 concentration, initial pH value and the concentration of carbofuran, were selected to determine the dependence of degradation efficiencies on independent variables. Response surface methodology modeling results indicated that the degradation efficiency of carbofuran was highly affected by the initial pH value and the concentration of carbofuran. Then nine degradation intermediates were detected by HPLC/MS/MS. The Frontier Electron Densities of carbofuran were calculated to predict the active sites on carbofuran attacked by hydroxyl radicals and photoholes. Point charges were used to elucidate the chemisorption pattern on TiO2 catalysts during the photocatalytic process. By combining the experimental results and calculation data, the photocatalytic degradation pathways of carbofuran were proposed, including the addition of hydroxyl radicals and the cleavage of the carbamate side chain.

  10. Synthesis and adsorption performance of dithiocarbamate-modified glycidyl methacrylate starch.

    Science.gov (United States)

    Cheng, Xiumei; Cheng, Rumei; Ou, Shengju; Li, Yijiu

    2013-07-01

    The design of chelating polymers with fast complexation of the metal ions is particularly interest. In this work, the dithiocarbamate-modified glycidyl methacrylate starch was synthesized and characterized by FT-IR, (13)C NMR and XRD spectra. Its sorption performance for heavy metals fixation was studied. It was found that the removal process of metal ions involved a fast increase stage followed by a slower stage. There was a higher match between the pseudo-second-order equation and the experimental data. The sorption rate constants were related to the substitution rates of hydrated metal ions in aqueous solutions, showing typical chemisorption. The Langmuir isotherm gave satisfying fits to equilibrium data of metals adsorption. And the capacities followed the sequence Cu(2+)>Cd(2+)>Co(2+)>Zn(2+)>Ni(2+)>Mn(2+), which could be well demonstrated with chelating interaction caused by sulfur atoms. Such understanding provides new insights as how to synthesize and use the dithiocarbamate-based polysaccharides.

  11. The Effect of Nb Loading on Catalytic Properties of Ni/Ce0.75Zr0.25O2 Catalyst for Methane Partial Oxidation

    Institute of Scientific and Technical Information of China (English)

    Sitthiphong Pengpanich; Vissanu Meeyoo; Thirasak Rirksomboon; Johannes Schwank

    2007-01-01

    In this study,the effect of Nb loading on the catalytic activity of Ce0.75Zr0.25O2-supported Ni catalysts was studied for methane partial oxidation.The catalysts were characterized by BET,H2 chemisorption,XRD,TPR,TEM and tested for methane partial oxidation to syngas in the temperature range of 400-800 ℃ at atmospheric pressure.The results showed that the activity of methane partial oxidation on the catalysts was apparently dependent on Nb loading.It seemed that the addition of Nb lowered the catalytic activity for methane partial oxidation and increased the extent of carbon deposition.This might be due to the strong interaction between NiO and Nb-modified support and reduction of surfaceoxygen reducibility.

  12. Electronic transport properties of BN sheet on adsorption of ammonia (NH3) gas.

    Science.gov (United States)

    Srivastava, Anurag; Bhat, Chetan; Jain, Sumit Kumar; Mishra, Pankaj Kumar; Brajpuriya, Ranjeet

    2015-03-01

    We report the detection of ammonia gas through electronic and transport properties analysis of boron nitride sheet. The density functional theory (DFT) based ab initio approach has been used to calculate the electronic and transport properties of BN sheet in presence of ammonia gas. Analysis confirms that the band gap of the sheet increases due to presence of ammonia. Out of different positions, the bridge site is the most favorable position for adsorption of ammonia and the mechanism of interaction falls between weak electrostatic interaction and chemisorption. On relaxation, change in the bond angles of the ammonia molecule in various configurations has been reported with the distance between NH3 and the sheet. An increase in the transmission of electrons has been observed on increasing the bias voltage and I-V relationship. This confirms that, the current increases on applying the bias when ammonia is introduced while a very small current flows for pure BN sheet.

  13. Two-photon photoemission study of the coverage-dependent electronic structure of chemisorbed alkali atoms on a Ag(111) surface.

    Science.gov (United States)

    Wang, Lei-Ming; Sametoglu, Vahit; Winkelmann, Aimo; Zhao, Jin; Petek, Hrvoje

    2011-09-01

    We report a systematic investigation of the electronic structure of chemisorbed alkali atoms (Li-Cs) on a Ag(111) surface by two-photon photoemission spectroscopy. Angle-resolved two-photon photoemission spectra are obtained for 0-0.1 monolayer coverage of alkali atoms. The interfacial electronic structure as a function of periodic properties and the coverage of alkali atoms is observed and interpreted assuming ionic adsorbate/substrate interaction. The energy of the alkali atom σ-resonance at the limit of zero coverage is primarily determined by the image charge interaction, whereas at finite alkali atom coverages, it follows the formation of a dipolar surface field. The coverage- and angle-dependent two-photon photoemission spectra provide information on the photoinduced charge-transfer excitation of adsorbates on metal surfaces. This work complements the previous work on alkali/Cu(111) chemisorption [Phys. Rev. B 2008, 78, 085419].

  14. Phosphonic Acid Functionalized Asymmetric Phthalocyanines: Synthesis, Modification of Indium Tin Oxide (ITO), and Charge Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Polaske, Nathan W.; Lin, Hsiao-Chu; Tang, Anna; Mayukh, Mayank; Oquendo, Luis E.; Green, John; Ratcliff, Erin L.; Armstrong, Neal R.; Saavedra, S. Scott; McGrath, Dominic V.

    2011-12-20

    Metalated and free-base A₃B-type asymmetric phthalocyanines (Pcs) bearing, in the asymmetric quadrant, a flexible alkyl linker of varying chain lengths terminating in a phosphonic acid (PA) group have been synthesized. Two parallel series of asymmetric Pc derivatives bearing aryloxy and arylthio substituents are reported, and their synthesis and characterization through NMR, combustion analysis, and MALDI-MS are described. We also demonstrate the modification of indium tin oxide (ITO) substrates using the PA functionalized asymmetric Pc derivatives and monitoring their electrochemistry. The PA functionalized asymmetric Pcs were anchored to the ITO surface through chemisorption and their electrochemical properties characterized using cyclic voltammetry to investigate the effects of PA structure on the thermodynamics and kinetics of charge transfer. Ionization energies of the modified ITO surfaces were measured using ultraviolet photoemission spectroscopy.

  15. Dissociation of acetaldehyde on beta-Mo2C to yield ethylidene and oxo surface groups: a possible pathway for active site formation in heterogeneous olefin metathesis.

    Science.gov (United States)

    Siaj, Mohamed; Reed, Corey; Oyama, S Ted; Scott, Susannah L; McBreen, Peter H

    2004-08-11

    The dissociative adsorption of acetaldehyde on beta-Mo2C was studied using reflection absorption infrared spectroscopy. In contrast to what is observed for all metals previously studied, acetaldehyde undergoes selective carbonyl bond scission on the carbide surface. By comparison to calculated spectra, the surface product is identified as an oxo-ethylidene species. The study thus provides the first extended-range infrared spectrum of a propene metathesis initiator or propagator alkylidene. Aldehydes may be formed in the presence of olefins during the induction period of supported metal oxide olefin metathesis catalysts. Hence, the observed dissociative chemisorption of acetaldehyde suggests a possible answer to the question of how initiator sites are formed in heterogeneous olefin metathesis. This question has never been satisfactorily answered. In the proposed mechanism, aldehydes formed during the induction period subsequently react with the catalyst surface to generate alkylidene sites.

  16. Molybdenum carbide catalysed hydrogen production from formic acid - A density functional theory study

    Science.gov (United States)

    Luo, Qiquan; Wang, Tao; Walther, Guido; Beller, Matthias; Jiao, Haijun

    2014-01-01

    Density functional theory computations have been employed to investigate the decomposition of formic acid (HCO2H) into CO2 and hydrogen on the β-Mo2C(101) surface. The adsorption configurations and energies of the surface intermediates (HCO2H, CO2, CO, H2O, HCO2, CO2H, CHO, OH, O and H) have been systematically characterized. Among the different dissociation steps considered, our results showed the formate route (HCO2H → H + HCO2; HCO2 → H + CO2) is the minimum energy path for hydrogen formation and CO2 has very strong chemisorption. The adsorption and dissociation of formic acid on the Mo2C(101) surface have been compared with those of Pt group metals.

  17. Effect of gamma irradiation on the texture, acidity and catalytic activity of silica-aluminium and silica-magnesia catalysts

    Science.gov (United States)

    Youssef, A. M.; Samra, S. E.; Ahmed, Awad I.

    The textural properties of non-irradiated and γ-irradiated silica-aluminium and silica-magnesia catalysts were determined from nitrogen adsorption. The acidities of these catalysts were measured by the chemisorption of pyridine. Cracking of cumene and dehydration of isopropanol were investigated on non-irradiated and γ-irradiated catalysts. Irradiation with γ-rays enhanced sintering, i.e. decreased the surface area and increased pore size. For silica-magnesia, γ-irradiation enhanced crystallization of Forsterite and Enstatite. The surface acidity decreased upon γ-irradiation and consequently the activity of the catalysts towards cracking of cumene and dehydration of isopropanol was reduced. The former reaction is structure-sensitive, while the latter is structure-insensitive.

  18. An attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopic study of gas adsorption on colloidal stearate-capped ZnO catalyst substrate.

    Science.gov (United States)

    Silverwood, Ian P; Keyworth, Colin W; Brown, Neil J; Shaffer, Milo S P; Williams, Charlotte K; Hellgardt, Klaus; Kelsall, Geoff H; Kazarian, Sergei G

    2014-01-01

    Attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopy has been applied in situ to study gas adsorption on a colloidal stearate-capped zinc oxide (ZnO) surface. Infrared spectra of a colloidal stearate-capped ZnO catalyst substrate were assigned at room temperature using zinc stearate as a reference compound. Heating was shown to create a monodentate species that allowed conformational change to occur, leading to altered binding geometry of the stearate ligands upon cooling. CO2 and H2 adsorption measurements demonstrated that the ligand shell was permeable and did not cover the entire surface, allowing adsorption and reaction with at least some portion of the ZnO surface. It has been demonstrated that stearate ligands did not prevent the usual chemisorption processes involved in catalytic reactions on a model ZnO catalyst system, yet the ligand-support system is dynamic under representative reaction conditions.

  19. Enzymatic saccharification of acid pretreated corn stover: Empirical and fractal kinetic modelling.

    Science.gov (United States)

    Wojtusik, Mateusz; Zurita, Mauricio; Villar, Juan C; Ladero, Miguel; Garcia-Ochoa, Felix

    2016-11-01

    Enzymatic hydrolysis of corn stover was studied at agitation speeds from 50 to 500rpm in a stirred tank bioreactor, at high solid concentrations (20% w/w dry solid/suspension), 50°C and 15.5mgprotein·gglucane(-1). Two empirical kinetic models have been fitted to empirical data, namely: a potential model and a fractal one. For the former case, the global order dramatically decreases from 13 to 2 as agitation speed increases, suggesting an increment in the access of enzymes to cellulose in terms of chemisorption followed by hydrolysis. For its part, the fractal kinetic model fits better to data, showing its kinetic constant a constant augmentation with increasing agitation speed up to a constant value at 250rpm and above, when mass transfer limitations are overcome. In contrast, the fractal exponent decreases with rising agitation speed till circa 0.19, suggesting higher accessibility of enzymes to the substrate.

  20. Sorption and desorption of remazol yellow by a Fe-zeolitic tuff

    Energy Technology Data Exchange (ETDEWEB)

    Solache R, M. J. [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Villalva C, R.; Diaz N, M. C., E-mail: marcos.solache@inin.gob.m [Instituto Tecnologico de Toluca, Division de Estudios del Posgrado, Av. Tecnologico s/n, Ex-Rancho La Virgen, 52140 Metepec, Estado de Mexico (Mexico)

    2010-07-01

    The adsorption of remazol yellow from aqueous solution was evaluated using a Fe-zeolitic tuff. The adsorbent was characterized by scanning electron microscopy, IR spectroscopy and X-ray diffraction. Sorption kinetic and isotherms were determined and the adsorption behavior was analyzed. Kinetic pseudo-second order and Langmuir-Freundlich models were successfully applied to the experimental results, indicating chemisorption on a heterogeneous material. The regeneration of the material was best accomplished by using a H{sub 2}O{sub 2} solution. The sorption capacity of the Fe-zeolitic tuff increased when the saturated samples were treated with a H{sub 2O2} or FeCl{sub 3} solution. (Author)

  1. Gas sensing at the nanoscale: engineering SWCNT-ITO nano-heterojunctions for the selective detection of NH3 and NO2 target molecules

    Science.gov (United States)

    Rigoni, F.; Drera, G.; Pagliara, S.; Perghem, E.; Pintossi, C.; Goldoni, A.; Sangaletti, L.

    2017-01-01

    The gas response of single-wall carbon nanotubes (SWCNT) functionalized with indium tin oxide (ITO) nanoparticles (NP) has been studied at room temperature and an enhanced sensitivity to ammonia and nitrogen dioxide is demonstrated. The higher sensitivity in the functionalized sample is related to the creation of nano-heterojunctions at the interface between SWCNT bundles and ITO NP. Furthermore, the different response of the two devices upon NO2 exposure provides a way to enhance also the selectivity. This behavior is rationalized by considering a gas sensing mechanism based on the build-up of space-charge layers at the junctions. Finally, full recovery of the signal after exposure to NO2 is achieved by UV irradiation for the functionalized sample, where the ITO NP can play a role to hinder the poisoning effects on SWCNT due to NO2 chemisorption.

  2. New insight in the microscopic mechanism of the catalytic synthesis of ammonia

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Henriksen, Niels Engholm; Billing, Gert D.

    1995-01-01

    Theoretical quantum calculations and molecular beam experiments of the dissociative chemisorption of N-2 molecules on catalytic active metal surfaces have given new insight in the fundamental process of the ammonia synthesis. This new approach to the study of catalytic process supplements...... to dissociation. Our analysis of the dissociation process suggests that it is not possible to define, in some well specified way, a precursor state at typical temperatures in the technical ammonia synthesis. The kinetic scheme for the complete ammonia synthesis without the precursor state can still account...... for the observed conversion to ammonia. We have constructed an empirical potential energy surface for N-2/Fe(111) which has barriers to dissociation even larger than for the previously studied N-2/Re system. It is shown that the presence of barriers is consistent with the observation that the activation energy...

  3. Characterization and performance of Cu/ZnO/Al2O3 catalysts prepared via decomposition of M(Cu,Zn)-ammonia complexes under sub-atmospheric pressure for methanol synthesis from H2 and CO2

    Institute of Scientific and Technical Information of China (English)

    Danjun Wang; Jun Zhao; Huanling Song; Lingjun Chou

    2011-01-01

    Methanol synthesis from hydrogenation of CO2 is investigated over Cu/ZnO/Al2O3 catalysts prepared by decomposition of M(Cu,Zn)-ammonia complexes (DMAC) at various temperatures.The catalysts were characterized in detail,including X-ray diffraction,N2 adsorption-desorption,N2O chemisorption,temperature-programmed reduction and evolved gas analyses.The influences of DMAC temperature,reaction temperature and specific Cu surface area on catalytic performance are investigated.It is considered that the aurichalcite phase in the precursor plays a key role in improving the physiochemical properties and activities of the final catalysts.The catalyst from rich-aurichalcite precursor exhibits large specific Cu surface area and high space time yield of methanol (212 g/(Lcat·h); T =513 K,p =3 MPa,S V =12000 h-1).

  4. Synthesis of nanosized platinum based catalyst using sol-gel process

    Science.gov (United States)

    Ingale, S. V.; Wagh, P. B.; Bandyopadhyay, D.; Singh, I. K.; Tewari, R.; Gupta, S. C.

    2015-02-01

    The nano-sized platinum based catalysts using high surface area silica support have been prepared by sol-gel method. Tetramethoxysilane (TMOS) diluted in methanol was hydrolyzed to form a porous silica gel. Platinum (2%) was loaded at sol state using platinum chloride solution. After gelation, the solvent from the gel pores was extracted at ambient temperature which resulted in porous silica matrix incorporated with nanosized platinum. X-ray diffraction studies indicated the presence of elemental platinum in the silica-platinum composites. Transmission electron microscopy of the platinum -silica composites revealed that nanosized platinum particles of about 5-10 nm are homogeneously dispersed in silica matrix. Chemisorptions studies showed high dispersion (more than 50%) of platinum on silica support with specific surface area of 400 m2/g which puts them as promising candidates as catalyst in heterogeneous reactions.

  5. Corrosion inhibition of carbon steel pipelines by some novel Schiff base compounds during acidizing treatment of oil wells studied by electrochemical and quantum chemical methods

    Science.gov (United States)

    Abd El-Lateef, Hany M.; Abu-Dief, Ahmed M.; Mohamed, Mounir A. A.

    2017-02-01

    Three novel Schiff bases compounds were prepared and their structures were characterized by X-ray, 13C-NMR, 1H-NMR, mass, UV-Vis, FT-IR, spectral data and elemental analyses. The corrosion inhibition of the investigated inhibitors towards carbon steel in 15% HCl was investigated by using electrochemical measurements (EIS, LPR corrosion rate and Tafel plots), SEM, EDX and quantum chemical methods. The results showed that, the inhibitors are efficient mixed type corrosion inhibitors, and their inhibition performance increased with the rise of inhibitor concentration and temperature. The adsorption of the inhibitors on steel surface was found to obey Langmuir's adsorption isotherm and chemisorption. Quantum chemical calculations provide good support to empirical results.

  6. Measurement, by adsorption, of the dispersion of platinum on supported catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Castells, R.C.

    1979-12-01

    A gas chromatographic pulsed adsorption technique similar to that of Freel was used in hydrogen and oxygen chemisorption measurements, and in ''titrating'' adsorbed hydrogen with oxygen pulses (H-O) and adsorbed oxygen with hydrogen pulses (O-H) on the surfaces of a Houdry 3H (0.30-0.70% platinum/alumina) catalyst and of 3.7 and 2.3% Pt/silica catalysts. In successive H-O and O-H titration cycles, hydrogen and oxygen consumption increased, leveling off after 8-10 cycles for Pt/alumina and after 3-4 cycles for the Pt/silica catalyst. The adsorption of hydrogen increased, whereas that of oxygen decreased with increasing number of cycles. The H-O titration sequence was a more accurate method of measuring metal dispersion than hydrogen adsorption or the O-H sequence.

  7. Equilibrium Isotherm Modeling, Kinetics and Thermodynamics Study for Removal of Lead from Waste Water

    Directory of Open Access Journals (Sweden)

    Z. Chowdhury

    2011-01-01

    Full Text Available The low cost adsorbent palm oil fuel ash (POFA derived from an agricultural waste material was investigated as a replacement of current expensive methods for treating wastewater contaminated by Pb(II cation. Adsorption studies were carried out to delineate the effect of contact time, temperature, pH and initial metal ion concentration. The experimental data followed pseudo second order kinetics which confirms chemisorptions. The values of Langmuir dimensionless constant, RL and Freundlich constant, 1/n were less than 1 representing favorable process for adsorption. Thermodynamic parameters such as ΔG°, ΔH° and ΔS°, related to Gibbs free energy, enthalpy and entropy were evaluated. It was concluded that, chemically treated palm oil fuel ash (POFA can be used successfully for adsorption of Pb(II from aqueous solution.

  8. Enhancing the in vivo transdermal delivery of gold nanoparticles using poly(ethylene glycol) and its oleylamine conjugate.

    Science.gov (United States)

    Hsiao, Pa Fan; Peng, Sydney; Tang, Ting-Cheng; Lin, Shuian-Yin; Tsai, Hsieh-Chih

    2016-01-01

    In this study, we investigated the effect of (ethylene glycol) (PEG) and PEG-oleylamine (OAm) functionalization on the skin permeation property of gold nanoparticles (GNS) in vivo. Chemisorption of polymers onto GNS was verified by a red shift in the ultraviolet-visible spectrum as well as by a change in the nanoparticle surface charge. The physicochemical properties of pristine and functionalized nanoparticles were analyzed by ultraviolet-visible spectroscopy, zeta potential analyzer, and transmission electron microscopy. Transmission electron microscopy revealed that the interparticle distance between nanoparticles increased after GNS functionalization. Comparing the skin permeation profile of pristine and functionalized GNS, the follicular deposition of GNS increased twofold after PEG-OAm functionalization. Moreover, PEG- and PEG-OAm-functionalized nanoparticles were able to overcome the skin barrier and deposit in the deeper subcutaneous adipose tissue. These findings demonstrate the potential of PEG- and PEG-OAm-functionalized GNS in serving a multitude of applications in transdermal pharmaceuticals.

  9. In Situ 3D Imaging of Catalysis Induced Strain in Gold Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Ulvestad, Andrew; Sasikumar, Kiran; Kim, Jong Woo; Harder, Ross; Maxey, Evan; Clark, Jesse N.; Narayanan, Badri; Deshmukh, Sanket A.; Ferrier, Nicola; Mulvaney, Paul; Sankaranarayanan, Subramanian K. R. S.; Shpyrko, Oleg G.

    2016-08-04

    Multielectron transfer processes are crucially important in energy and biological science but require favorable catalysts to achieve fast kinetics. Nanostructuring catalysts can dramatically improve their properties, which can be difficult to understand due to strain- and size-dependent thermodynamics, the influence of defects, and substrate-dependent activities. Here, we report three-dimensional (3D) imaging of single gold nanoparticles during catalysis of ascorbic acid decomposition using Bragg coherent diffractive imaging (BCDI). Local strains were measured in single nanoparticles and modeled using reactive molecular dynamics (RMD) simulations and finite element analysis (FEA) simulations. RMD reveals the pathway for local strain generation in the gold lattice: chemisorption of hydroxyl ions. FEA reveals that the RMD results are transferable to the nanocrystal sizes studied in the experiment. Our study probes the strain-activity connection and opens a powerful avenue for theoretical and experimental studies of nanocrystal catalysis.

  10. Photostability enhancement of azoic dyes adsorbed and intercalated into Mg-Al-layered double hydroxide

    Science.gov (United States)

    Liu, Pengfei; Liu, Pei; Zhao, Kongcao; Li, Lei

    2015-11-01

    Two azoic dyes 4-aminoazobenzene-4-sulfonic (AS) and ethyl orange (EO) were adsorbed on or intercalated into Mg-Al-CO3 layered double hydroxide (LDH) for photostability enhancement. Fluorescence analysis results showed that the photostability of two dyes could be greatly improved after being adsorbed on the surface of Mg-Al-CO3-LDH matrix. Furthermore, photostability of adsorbed dyes was superior to that of intercalated dyes. It was suggested that AS or EO was adsorbed on LDHs surface through a strong chemisorption interaction, resulting in the enhancement of photostability. After the UV irradiation under N2 atmosphere, the absorbed dyes not only show great increase of fluorescence intensity but also exhibited high stability against UV irradiation. This work provides a feasible approach to enhance the photostability of azoic dye confined in an inorganic two-dimensional (2D) matrix via changing the microenvironment, which may be considered to be a promising method of improving photostability of solid fluorescent materials.

  11. Radioactive Iodine (I-129) Gas Adsorption by Using Bismuth-Embedded SBA-15

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Jae Hwan; Cho, Yong-Jun; Park, Jang Jin; Ahn, Do-Hee [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Yim, Man-Sung [Korea Advanced Institute of Science and Technology, Daejeon (Korea, Republic of)

    2015-05-15

    The efficient capture of the long-lived I-129, released as off-gas from nuclear fuel reprocessing, have been of significant concern in the waste management field. In this study, bismuth-embedded SBA-15 mesoporous silica was firstly applied for iodine capture and storage. SBA-15 was functionalized with thiol (-SH) groups, followed by bismuth adsorption with Bi-S bonding, which was thermally treated to form Bi{sub 2}S{sub 3} within SBA-15. The bismuth-embedded SBA-15s demonstrated high iodine loading capacities with 540 mg-I/g-sorbent maximally, which benefitted from the high surface area and porosity of SBA-15 as well as the formation of thermodynamically stable BiI{sub 3} compound. Iodine physisorption could effectively be suppressed due to the large pores present in SBA-15, resulting in chemisorption as a main mechanism for iodine confinement.

  12. Influence of the aluminium impregnation [ Al(NO33] in the beta zeolite over its acidity

    Directory of Open Access Journals (Sweden)

    Francisco José Sánchez Castellanos

    2010-04-01

    Full Text Available Beta zeolite was impregnated with [ Al(NO33], increasing the aluminium content in increments of 0.05% from 0.00% to 0.25%. A parallel treatment with 0.05% sulphuric acid was also performed; in both cases, methanol was used as solvent (disperse phase. Cation exchange capacity (CEC, ammonia chemisorption, infrared spectroscopy (FIT-IR, scanning electronic microscopy (SEM, X-Ray powder diffraction (XRD, atomic absorption spectroscopy (AAS, titration with sodium hydroxide and nitrogen physisorption at 77K were used to carry out the physical and chemical characterization of the catalysts. Futhermore, the catalysts were employed in the esterification of ethanol with acetic acid, to quantify the effect of aluminium impregnation over the beta zeolite.

  13. Investigation of Hydrogen Adsorption on Single Wall Carbon Nanotubes

    Science.gov (United States)

    Nam, Sang-Hun; Jeong, Seong Hun; Lee, Soon-Bo; Boo, Jin-Hyo

    We have investigated adsorption and desorption condition of atomic hydrogen on single-walled nanotubes (SWCNTs) using ultraviolet photoelectron spectroscopy (UPS) and thermal desorption spectroscopy (TDS). The SWCNTs were made by the high pressure carbon monoxide (HiPCO) method. In our results, we observe from UPS data absorptive states reduce with increasing hydrogen doses and a new peak is developed near 8.6 eV and other points. But this peak is gradually diminished with pumping time. The TDS data show two characteristic peaks at 640 and 790K. By comparing with density functional calculations, we propose these peaks to be related to the presence of atomic hydrogen. Therefore, we can know that there are two adsorption sites on SWCNTs. Also we observed physisorption and chemisorption site by pumping time. We note that the UPS data are fully recoverable after hydrogen desorption at 1200K.

  14. Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals

    DEFF Research Database (Denmark)

    Hammer, Bjørk; Hansen, Lars Bruno; Nørskov, Jens Kehlet

    1999-01-01

    A simple formulation of a generalized gradient approximation for the exchange and correlation energy of electrons has been proposed by Perdew, Burke, and Ernzerhof (PBE) [Phys. Rev. Lett. 77, 3865 (1996)]. Subsequently Zhang and Yang [Phys. Rev. Lett. 80, 890 (1998)] have shown that a slight...... revision of the PBE functional systematically improves the atomization energies for a large database of small molecules. In the present work, we show that the Zhang and Yang functional (revPBE) also improves the chemisorption energetics of atoms and molecules on transition-metal surfaces. Our test systems...... comprise atomic and molecular adsorption of oxygen, CO, and NO on Ni(100), Ni(111), Rh(100), Pd(100), and Pd(111) surfaces. As the revPBE functional may locally violate the Lieb-Oxford criterion, we further develop an alternative revision of the PBE functional, RPBE, which gives the same improvement...

  15. Bonding configurations for nickelocene on Ag(100) and steric effects in thermal desorption

    Energy Technology Data Exchange (ETDEWEB)

    Borca, C.N.; Welipitiya, D.; Dowben, P.A.; Boag, N.M.

    2000-02-10

    The molecular adsorption and desorption of nickelocene, Ni(C{sub 5}H{sub 5}){sub 2}, on Ag(100) has been studied by coverage dependent angle-resolved thermal desorption. The angle-resolved thermal desorption of nickelocene is unusual in that the molecular orientation is seen to affect the angular dependence of molecular desorption. The coexistence of two chemisorption phases for molecular nickelocene adsorption on Ag(100) near the desorption temperature of approximately 230 K is identified. One phase, with the bonding configuration of the nickelocene molecular axis along the surface normal, appears to dominate at higher coverages. The results are discussed in the context of rehybridization and recent angle-resolved photoemission and high-resolution electron energy loss measurements.

  16. The adsorption of nickelocene Part 1: molecular bonding on Ag(100)

    Science.gov (United States)

    Welipitiya, D.; Borca, C. N.; Waldfried, C.; Hutchings, C.; Sage, L.; Woodbridge, C. M.; Dowben, P. A.

    1997-12-01

    The molecular adsorption and desorption of nickelocene, Ni(C 5H 5) 2, on Ag(100) have been studied by both angle-resolved photoemission and thermal desorption. Photoemission results indicate that the initially adsorbed surface species closely resemble that of molecular nickelocene. The molecular axis is not along the surface normal, as determined by angle-resolved photoemission and angle-resolved thermal desorption spectroscopy. This is a different bonding orientation than that adopted by molecular ferrocene on Ag(100). The molecular nickelocene desorption energies resemble those observed for ferrocene on Ag(100) but are complicated by multiple chemisorption states and steric effects in the desorption process. Nickelocene is unusual in that the molecular orientation is seen to affect the angular dependence of molecular desoprtion.

  17. Molecular Dynamics Investigation of the Products of Alkoxysilane Condensation: Bulk Gels and Surface Coatings

    Science.gov (United States)

    Faller, Roland; Deetz, Joshua

    We characterize silica gels and organo-silicon surface coatings using reactive molecular dynamics simulations. To model the chemical reactions, we use a reactive force field (ReaxFF) which we have optimized in a novel parallelized semi-automatic way to model hydrolysis and condensation reactions. The morphologies of silica gels obtained from tetra- and tri-alkoxysilanes are determined by allowing the system to condense while simultaneously removing water and replacing it with precursor solution. It is found that the gels obtained from trialkoxysilanes are more loosely bonded, and that the chemistry of the headgroup is important to the gel morphology. We furthermore simulated the chemisorption of alkoxysilanes with organic headgroups to hydroxylated silica surfaces. We observe a competition between alkoxysilanes condensing with themselves or with the silica surface.

  18. Investigation of the oxidation of NO over platinum catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Despres, J.; Koebel, M.; Elsener, M.; Wokaun, A.

    2002-03-01

    The oxidation of NO to NO{sub 2} over Pt/SiO{sub 2} was investigated in the temperature range 150-450{sup o}C. Powdered catalysts were prepared by incipient wetness impregnation, followed by calcination and reduction. The feed gas typically contained oxygen, nitrogen monoxide, water and nitrogen. The concentration of NO in the feed was varied at constant concentration of O{sub 2} in order to study its influence on the reaction. A decrease of the conversion with increasing concentration of NO was observed. A similar study was performed with various oxygen concentrations at constant concentration of NO. Oxygen involved in the surface reaction originates from the dissociative chemisorption of O{sub 2} on the platinum surface. (author)

  19. Engineering Nanomaterial Surfaces for Biomedical Applications

    Science.gov (United States)

    Wang, Xin; Liu, Li-Hong; Ramström, Olof; Yan, Mingdi

    2014-01-01

    Nanomaterials, possessing unique physical and chemical properties, have attracted much interest and generated wide varieties of applications. Recent investigations of functionalized nanomaterials have expanded into the biological area, providing a versatile platform in biomedical applications such as biomolecular sensing, biological imaging, drug delivery and disease therapy. Bio-functions and bio-compatibility of nanomaterials are realized by introducing synthetic ligands or natural biomolecules onto nanomaterials, and combining ligand-receptor biological interactions with intrinsic nanomaterial properties. Common strategies of engineering nanomaterial surfaces involve physisorption or chemisorption of desired ligands. We developed a photochemically initiated surface coupling chemistry, bringing versatility and simplicity to nanomaterial functionalization. The method was applied to attach underivatized carbohydrates efficiently on gold and iron oxide nanoparticles, and the resulting glyconanoparticles were successfully used as a sensitive biosensing system probing specific interactions between carbohydrates and proteins as well as bacteria. PMID:19596820

  20. Electrochemical promotion of NO reduction by hydrogen on a platinum/polybenzimidazole catalyst

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bandur, Viktor; Cappeln, Frederik Vilhelm;

    2003-01-01

    The electrochemical promotion of catalytic NO reduction by hydrogen was studied using a (NO, H-2, Ar), Pt polybenzimidazole (PBI)-H3PO4\\Pt, (H-2, Ar) fuel cell at 135degreesC. A mixture of NO/H-2/Ar was used as the working mixture at one electrode and a mixture of H-2/Ar was used as reference...... and 140 mL/min, respectively), NO reduction increased 20 times even without polarization compared to the high gas flow rate. The electrochemical promotion effect occurs at positive polarization with a maximum increase at approximately 0.08 V and with 1.5 times the zero polarization value. The promotion...... at the negative polarization can be attributed to the electrochemical production of the promoters. At low gas flow rates, a charge-induced change of the strength of chemisorptive bonds can take place....

  1. Simulation of Initial Stages of the Methanol to Gasoline Process in Acidic Zeolites

    Science.gov (United States)

    Stich, I.; Hytha, M.; Gale, J. D.; Terakura, K.; Payne, M. C.

    2000-03-01

    Methanol to gasoline process is one of the most studied applications of zeolites in current commercial production. This complex process involves: (1) initial adsorption of methanol in the zeolite, (2) activation of the adsorbed methanol molecules, (3) formation of the first intermediates (dimethyl ether (DME)), (4) formation of the first -C-C- bonds. Extensive studies of the stages (1)-(3) have been performed using the method of ab initio molecular dynamics (within DFT in the GGA approximation) and the method of thermodynamic integration to compute the free energy profile for formation of the first intermediate. We find that the initial adsorption (physisorption vs. chemisorption) depends on the adsorption conditions such as zeolite framework and methanol loading. Under certain combination of these conditions the chemisorbed species undergo activation. The activated species are very susceptible to nucleophilic attack to form DME. The computed free energy profile shows that this reaction is entropically controlled with significant differences between the total and free energy profiles.

  2. Sorbitol hydrogenolysis to glycols by supported ruthenium catalysts

    Institute of Scientific and Technical Information of China (English)

    Inmaculada Murillo Leo; Manuel Lopez Granados; Jose Luis Garcia Fierro; Rafael Mariscal

    2014-01-01

    Supported Ru catalysts were prepared by wet impregnation to evaluate the role of different oxide supports (Al2O3, SiO2, TiO2, ZrO2) in sorbitol hydrogenolysis to glycols. X-ray diffraction, transmis-sion electron microscopy, hydrogen chemisorption, X-ray photoelectron spectroscopy, and NH3 temperature-programmed desorption were used to characterize the catalysts, which were active in the hydrogenolysis of sorbitol. The support affected both the physicochemical properties and cata-lytic behavior of the supported Ru particles. The characterization results revealed that the Ru/Al2O3 catalyst has a high surface acidity, partially oxidized Ru species on the surface, and a higher surface Ru/Al atomic ratio, which gave it the highest selectivity and yield to glycols.

  3. Tribology in Gaseous Hydrogen

    Science.gov (United States)

    Sawae, Yoshinori; Sugimura, Joich

    Hydrogen is expected as a clean and renewable energy carrier for future environment-friendly society. Many machine elements in hydrogen energy systems should be operating within hydrogen gas and tribological behavior, such as friction and wear, of bearings and seals are affected by the hydrogen environment through some interactions between material surfaces and gaseous hydrogen, i.e., physisorption of hydrogen molecules and following chemisorptions of dissociated atoms on metal surfaces, formation of metal hydride and reduction of metal oxide layer by hydrogen atoms diffused into bulk. Therefore, friction and wear characteristics of tribomaterials in the hydrogen environment should be appropriately understood to establish a design guideline for reliable hydrogen utilizing systems. This paper reviews the current knowledge about the effect of hydrogen on friction and wear of materials, and then describes our recent progress of hydrogen research in the tribology field.

  4. A novel co-precipitation method for preparation of Mn--Ce/TiO2 composites for NOx reduction with NH3 at low temperature.

    Science.gov (United States)

    Sheng, Zhongyi; Hu, Yufeng; Xue, Jianming; Wang, Xiaoming; Liao, Weiping

    2012-01-01

    Mn--Ce/TiO2 catalyst prepared by a novel co-precipitation method was used in this study for low-temperature selective catalytic reduction (SCR) of NOx with ammonia. The catalyst showed high activity and good SO2 resistance. The NO conversion on the catalyst increased to 100% when 700 ppm of SO2 flowed in, and reached 60.8% in 2.5 h. The characterized results indicated that the catalyst prepared by the new method had good dispersion of the active phase, uniform micro-size particles and large Brunauer-Emmett-Teller surface. The temperature programmed reduction and temperature programmed desorption experiments showed that the improvement in SCR activity on the Mn--Ce/TiO2 catalyst might be due to the increase of active oxygen species and the enhancement of NH3 chemisorption, both of which were conducive to NH3 activation.

  5. Accelerating the development of transparent graphene electrodes through basic science driven chemical functionalization.

    Energy Technology Data Exchange (ETDEWEB)

    Chan, Calvin [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Beechem, III, Thomas Edwin [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Ohta, Taisuke [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Brumbach, Michael T. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Wheeler, David Roger [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Veneman, Alexander [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Gearba, I. Raluca [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Stevenson, Keith J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2013-09-01

    Chemical functionalization is required to adapt graphenes properties to many applications. However, most covalent functionalization schemes are spontaneous or defect driven and are not suitable for applications requiring directed assembly of molecules on graphene substrates. In this work, we demonstrated electrochemically driven covalent bonding of phenyl iodoniums onto epitaxial graphene. The amount of chemisorption was demonstrated by varying the duration of the electrochemical driving potential. Chemical, electronic, and defect states of phenyl-modified graphene were studied by photoemission spectroscopy, spatially resolved Raman spectroscopy, and water contact angle measurement. Covalent attachment rehybridized some of the delocalized graphene sp2 orbitals to localized sp3 states. Control over the relative spontaneity (reaction rate) of covalent graphene functionalization is an important first step to the practical realization of directed molecular assembly on graphene. More than 10 publications, conference presentations, and program highlights were produced (some invited), and follow-on funding was obtained to continue this work.

  6. Kinetic Approach for the Adsorption of Organophosphorous Pesticides from Aqueous Solution Using “Waste” Jute Fiber Carbon

    Directory of Open Access Journals (Sweden)

    S. Senthilkumaar

    2010-01-01

    Full Text Available Chemically activated “Waste” Jute Fiber carbon has been effectively used for the removal of five organophosphorous pesticides (malathion, monocrotophos, methylparathion, phosphamidon and dimethoate from aqueous solutions. The prepared activated jute fiber carbon was characterized by using Elemental analyzer and proximate analysis methods. The adsorption equilibrium was examined at 28 ºC. Three different kinetic models, the pseudo first order, pseudo second order and Elovich kinetic models were selected to analyses the adsorption process. To compare the fitness of pseudo first order and pseudo second order, sum of the squares of the errors and correlation coefficient, r2 values were calculated. The Elovich model was used to confirm the chemisorptions.

  7. Influence of superficial oxidation on the pyrophoric behaviour of uranium hydride and uranium powders in air

    Energy Technology Data Exchange (ETDEWEB)

    Ablitzer, C., E-mail: carine.ablitzer@cea.fr [CEA, DEN, DEC/SPUA/LCU, 13108 Saint-Paul lez Durance (France); Le Guyadec, F. [CEA, DEN, DTEC/SDTC, 30207 Bagnols sur Ceze (France); Raynal, J. [CEA, DEN, DEC/SPUA/LCU, 13108 Saint-Paul lez Durance (France); Genin, X. [CEA, DEN, DTEC/SDTC, 30207 Bagnols sur Ceze (France); Duhart-Barone, A. [CEA, DEN, DEC/SPUA/LCU, 13108 Saint-Paul lez Durance (France)

    2013-01-15

    Pyrophoric behaviours in air of uranium hydride and uranium powders have been studied on samples of small mass - several tens of milligrams - in a thermogravimetric device and on samples of several grams in an instrumented furnace. Results show that ignition can occur at room temperature for both materials but only in the second device and provided that powders are not superficially oxidized. Chemisorption of oxygen on particles is suspected to be responsible for ignition at room temperature. This phenomenon is not taken into account in classical theories of ignition. When ignition does not occur at room temperature, it occurs above at least 90 Degree-Sign C when heating at a rate of 5 Degree-Sign C min{sup -1}. Ignition seems then to result principally from the large increase of oxidation rates with temperature.

  8. Nitrogen substitution impacts organic-metal interface energetics

    Science.gov (United States)

    Yang, Ao; Franco-Cañellas, Antoni; Sato, Mikio; Wang, Bin; Wang, Rong-Bin; Koike, Harunobu; Salzmann, Ingo; Thakur, Pardeep Kumar; Lee, Tien-Lin; Liu, Lijia; Kera, Satoshi; Gerlach, Alexander; Kanai, Kaname; Fan, Jian; Schreiber, Frank; Duhm, Steffen

    2016-10-01

    We investigated the structural and electronic properties of vacuum sublimed 7,8,15,16-tetraazaterrylene (TAT) thin films on Au(111), Ag(111), and Cu(111) substrates using inverse photoemission spectroscopy, ultraviolet photoelectron spectroscopy (UPS), x-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED), and the x-ray standing wave (XSW) technique. The LEED reveals a flat adsorption geometry of the monolayer TAT on these three substrates, which is in accordance with the XSW results. The molecules are slightly distorted in monolayers on all three substrates with the nitrogen atoms having smaller averaged bonding distances than the carbon atoms. On Ag(111) and Cu(111), chemisorption with a net electron transfer from the substrate to the adsorbate takes place, as evidenced by UPS and XPS. Combining these results, we gain full insight into the correlation between electronic properties and interface geometry.

  9. n-Dodecane Hydroconversion over Nickel Supported on Different Mesoporous Aluminosilicates

    Institute of Scientific and Technical Information of China (English)

    FANG, Ke-Gong(房克功); REN, Jie(任杰); SUN, Yu-Han(孙予罕)

    2004-01-01

    Several 2.0 wt% nickel catalysts supported on nanometer bimodal mesoporous aluminosilicate (NBMAS),AlHMS and AlMCM-41 were prepared by means of the wetness impregnation method. The characterization techniques such as Py-FTIR and H2 chemisorption showed that the amount of Bronsted acid sites decreased in the order of Ni/AlHMS>Ni/AlMCM-41 >Ni/NBMAS, while the nickel dispersion differed a little. In the catalytic n-dodecane hydroconversion, the highest conversion was obtained over Ni/NBMAS, and the lowest isomerization selectivity occurred over Ni/AlHMS. For the cracked products, the symmetrical carbon number distribution centered at C6 was obtained on the Ni/AlMCM-41 catalyst due to the well balanced metal/acid functions, whereas the Ni/AlHMS and Ni/NBMAS catalysts led to more C3-C5 and C1 +C11 products, respectively.

  10. First-principles study of CO adsorption on ZnO surfaces

    CERN Document Server

    Meyer, B

    2003-01-01

    Using density-functional theory we have calculated the equilibrium geometries and binding energies of a CO monolayer adsorbed on the nonpolar (1010) and the polar (0001)-Zn and (0001)-O surfaces of ZnO. Different adsorption sites and CO orientations were considered, and for the polar surfaces the influence of a hydrogen coverage upon CO adsorption was studied. For the clean surfaces we find that CO exclusively binds to Zn ions with a binding energy of 0.24 and 0.37 eV for the nonpolar (1010) and the polar (0001)-Zn surface, respectively. A purely repulsive interaction of CO with surface oxygen ions is obtained. On the other hand, if the polar surfaces are hydrogen saturated, we predict a weak chemisorption of CO to the OH-terminated (0001) surface with a binding energy of 0.20 eV but no CO adsorption for the ZnH-terminated (0001) face. (letter to the editor)

  11. Activation and micropore structure of carbon-fiber composites

    Energy Technology Data Exchange (ETDEWEB)

    Jagtoyen, M.; Derbyshire, F.; Kimber, G. [Univ. of Kentucky, Lexington, KY (United States). Center for Applied Energy Research

    1997-12-01

    Rigid, high surface area activated carbon fiber composites have been produced with high permeabilities for environmental applications in gas and water purification. The project involves a collaboration between the Oak Ridge National Laboratory (ORNL) and the Center for Applied Energy Research (CAER), University of Kentucky. The main focus of recent work has been to find a satisfactory means to uniformly activate large samples of carbon fiber composites to produce controlled pore structures. Processes have been developed using activation in steam and CO{sub 2}, and a less conventional method involving oxygen chemisorption and subsequent heat treatment. Another objective has been to explore applications for the activated composites in environmental applications related to fossil energy production.

  12. Transformation of Heavy Metal Compounds during the Remediation of Contaminated Soils

    Directory of Open Access Journals (Sweden)

    Tatiana Minkina

    2011-03-01

    Full Text Available The effect of ameliorants, chalk, glauconite and semidecomposed cattle manure, on ordinary chernozem contaminated with Zn and Pb was studied in a long-term field experiment. The application of ameliorants significantly decreased the mobility of metals. Their effect depended on the ameliorant and was most significant at the simultaneous application of chalk and manure. This effect was presumably due to the strong binding of metals by carbonates through chemisorption and formation of lowsoluble Zn and Pb compounds and to the additional fixation in the form of complexes at the addition of organic material. The share of loosely bound metal compounds in the contaminated soils decreased to the level typical for the clean soils or even below. The general evolution of the transformation of metal compounds (from less to more firmly bound compounds accelerated by ameliorants remained for both metals.

  13. Effects of Ce on catalytic combustion of methane over Pd-Pt/Al2O3 catalyst

    Institute of Scientific and Technical Information of China (English)

    Xing Fan; Fan Wang; Tianle Zhu; Hong He

    2012-01-01

    Activity and stability of 1%Pd-0.2%Pt/Al2O3 and 1%Pd-0.2%Pt/0.6%Ce/Al2O3 catalysts prepared by impregnation method for catalytic combustion of methane in air were investigated.The catalysts before and after reaction were characterized by BET,CO chemisorption,XRD and XPS techniques.Results showed that the presence of Ce significantly increased the activity and thermal stability of the Pd-Pt/Al2O3 catalyst towards methane combustion,which could be attributed to more highly-dispersed active PdO particles over the Pd-Pt/Ce/Al2O3 catalyst surface as well as the retarded sintering of PdO and the maintained oxidized state of surface Pd during the combustion process in the presence of Ce.

  14. Effect of La2O3 on Methanation of CO and CO2 over Ni-Mo/γ-Al2O3 Catalyst

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    A series of Ni-Mo/γ-Al2O3 methanation catalysts containing La2O3 were prepared by impregnation. The activities of catalysts for CO and CO2 methanation were investigated. The surface properties of the catalysts were studied by TEM, XPS and chemisorption of CO. The experimental results show that the addition of La2O3 increases the activities for the methanation of CO and CO2, the dispersity of nickel on catalysts, the active nickel surface area and the concentration of nickel atoms on the surface of Ni-Mo/γ-Al2O3 catalysts. At the same time, it also decreases the binding energy of Ni2P3/2 in catalysts.

  15. Effect of modified humic acid binder on pelletisation of specularite concentrates

    Institute of Scientific and Technical Information of China (English)

    周友连; 张元波; 刘兵兵; 李光辉; 姜涛

    2015-01-01

    A modified humic acid (MHA) binder was tested as a substitute for bentonite to prepare qualified specularite pellets. The results show that there is stronger chemisorption between organic functional groups in MHA binder molecular and specularite particles, improving the green pellet strength. MHA binder has obvious effect on the strength and microstructure of preheated pellets due to the thermal decomposition of organic matters in MHA binder. Appropriately increasing preheating temperature or time can eliminate the adverse impact of organic matters on the preheated pellet strength. Compared with the bentonite pellets, the roasted pellets with MHA binder have a more compact microstructure, and the recrystallization of the Fe2O3 crystal grains is better. Consequently, under optimal conditions, 0.75%(mass fraction) MHA binder pellets have equal or better pellet strengths and contain 1.06%more total iron than 2%bentonite pellets. The testing results indicate that MHA binder is a promising and effective alternative to bentonite for the specularite pellets.

  16. Electronic Structure and Catalysis on Metal Surfaces

    Science.gov (United States)

    Greeley, Jeff; Norskov, Jens K.; Mavrikakis, Manos

    2002-10-01

    The powerful computational resources available to scientists today, together with recent improvements in electronic structure calculation algorithms, are providing important new tools for researchers in the fields of surface science and catalysis. In this review, we discuss first principles calculations that are now capable of providing qualitative and, in many cases, quantitative insights into surface chemistry. The calculations can aid in the establishment of chemisorption trends across the transition metals, in the characterization of reaction pathways on individual metals, and in the design of novel catalysts. First principles studies provide an excellent fundamental complement to experimental investigations of the above phenomena and can often allow the elucidation of important mechanistic details that would be difficult, if not impossible, to determine from experiments alone.

  17. Bioinspired nanodevice based on the folic acid/titanium dioxide system.

    Science.gov (United States)

    Gaweda, Sylwia; Stochel, Grazyna; Szaciłowski, Konrad

    2007-05-04

    A new bioinspired nanomaterial has been obtained by chemisorption of folic acid onto nanocrystalline titanium dioxide. The organic chromophore is linked with the semiconductor surface via the glutamate chain and anchored with the carboxylate group. The geometry and electronic structure of the chromophore was studied in detail with DFT. Photoelectrochemical studies revealed photosensitization of the new material towards visible light. The photoelectrodes composed of the folic acid/titanium dioxide hybrid material generated photocurrent over a 300-600-nm window. Moreover, the direction of the photocurrent could be changed from anodic to cathodic and vice versa by application of the appropriate photoelectrode potential. Photoelectrochemical and spectroscopic studies allowed the elucidation of the mechanism of photocurrent switching. Photoelectrodes composed of folate-modified titanium dioxide may serve as a simple model of optoelectronic switches and may constitute the basis for molecular photoelectronic devices.

  18. Redox-controlled photosensitization of nanocrystalline titanium dioxide.

    Science.gov (United States)

    Szaciłowski, Konrad; Macyk, Wojciech; Hebda, Maciej; Stochel, Grazyna

    2006-11-13

    Photosensitization of nanocrystalline titanium dioxide materials has been achieved by chemisorption of the pentacyanothiamineferrate(II) complex, which offers a relatively high redox potential that determines the photoelectrochemical properties of the photosensitized TiO(2). The adsorbed pentacyanoferrate complex binds to TiO(2) through the cyanide bridge and forms a new surface complex characterized by a metal-to-metal charge-transfer transition (MMCT) (Fe(II)-->Ti(IV)). The photosensitization can be observed only at low potentials at which Fe(II) moieties are present. Photocurrent switching between anodic and cathodic can be induced by varying either the photoelectrode potential or the wavelength of the incident light. Simple molecular modeling-together with spectroscopic and electrochemical measurements-allows the elucidation of the mechanism of the observed photoelectrochemical behavior.

  19. Estudo microestrutural do catalisador Ni/gama-Al2O3: efeito da adição de CeO2 na reforma do metano com dióxido de carbono Microstructural study of Ni/gamma-Al2O3 catalyst: addition effects of CeO2 on carbon dioxide reforming of methane

    Directory of Open Access Journals (Sweden)

    Antoninho Valentini

    2003-10-01

    Full Text Available The carbon dioxide reforming of methane was carried out over nickel catalysts supported on the gamma-Al2O3/CeO2 system prepared by wet impregnation. With the increase of the CeO2 weight in the catalyst, a higher stability was observed in the catalytic activity, together with an excellent resistance to carbon deposition and a better Ni dispersion. The catalysts were characterized by means of surface area measurements, TPR, H2 chemisorption, XRD, SEM, EDX, XPS and TEM. An interaction between Ni and CeO2 was observed to the Ni/CeO2 sample after activation in a H2 atmosphere above 300 ºC. Such behavior has a significantly influence on the catalytic activity.

  20. Perlite as a potential support for nickel catalyst in the process of sunflower oil hydrogenation

    Science.gov (United States)

    Radonjić, V.; Krstić, J.; Lončarević, D.; Jovanović, D.; Vukelić, N.; Stanković, M.; Nikolova, D.; Gabrovska, M.

    2015-12-01

    Investigation was conducted in order to elucidate the possibility of using perlite as support for preparation of nickel based precursor catalyst, potentially applicable in vegetable oil hydrogenation process. On three differently prepared expanded perlite, nickel catalyst precursors with identical Ni/SiO2 = 1.1 and Ni/Mg = 10/1 ratios were synthesized by precipitation-deposition method. Different techniques, SEM micrography, He-pycnometry, calcimetry, Hg-porosimetry, N2-physisorption, H2-chemisorption and temperature programmed reduction, were used for characterization of obtained samples. Determining the precursor texture, morphology and reducibility shows a successfully deposited nickel phase on perlite support with promising properties for vegetable oil hydrogenation. Chosen precursor was reduced and passivated in paraffin oil and the obtained catalyst showed significant catalytic activity in the test of sunflower oil hydrogenation.

  1. Adsorptive Thermodynamic Properties and Kinetics of trans-1,2- Cyclohexandiol onto AB-8 Resin

    Institute of Scientific and Technical Information of China (English)

    谢艳新; 侯丽丽; 杨倩; 蒋登高

    2012-01-01

    AB-8 resin was used as an adsorbent for the removal of trans-1,2-cyclohexandiol(CHD) from aqueous solutions.Batch experiments were carried out to investigate the effect of contact time and temperature on sorption efficiency.The adsorptive thermodynamic properties and kinetics of CHD from water onto AB-8 resin were studied.The Langmuir and Freundlich isotherm models were employed to discuss the adsorption behavior.Thermodynamic parameters such as G,H and S were calculated.The results indicate that the equilibrium data are perfectly represented by Langmuir isotherm model.Thermodynamic study reveals that it is an exothermic process in nature and mainly physical adsorption enhanced by chemisorption with a decrease of entropy process.The kinetics of CHD adsorption is well described by the pseudo second-order model.The adsorbed CHD can be eluted from AB-8 resin by 5% ethanol aqueous solution with 100% elution percentage.

  2. Efficient electronic structure methods applied to metal nanoparticles

    DEFF Research Database (Denmark)

    Larsen, Ask Hjorth

    Nano-scale structures are increasingly applied in the design of catalysts and electronic devices. A theoretical understanding of the basic properties of such systems is enabled through modern electronic structure methods such as density functional theory. This thesis describes the development...... more strongly than large ones. This can be understood mostly as a geometric eect. Convergence of chemisorption energies within 0.1 eV of bulk values happens at about 200 atoms for Pt and 600 atoms for Au. Particularly for O on Au, large variations due to electronic effects are seen for smaller clusters....... The basis set method is used to study the electronic effects for the contiguous range of clusters up to several hundred atoms. The s-electrons hybridize to form electronic shells consistent with the jellium model, leading to electronic magic numbers for clusters with full shells. Large electronic gaps...

  3. Structure and properties of ultrathin iron films on Ru(10 overline10) : The formation of metastable surface phases of γ-Fe

    Science.gov (United States)

    Harrison, Kevin; Prince, Robert H.; Lambert, Richard M.

    1988-07-01

    The chemisorption and desorption of Fe at the (10 overline10) surface of Ru has been investigated by LEED, Auger spectroscopy, Δφ and thermal desorption measurements over a substrate temperature range of 300-900 K. The growth mode of the iron deposit was found to be strongly dependent on the temperature. At 300 K up to seven iron monolayers could be grown, these adopting the configuration of the fcc (111) plane of bulk γ-iron. The layers were metastable and heating of such films or deposition at elevated temperatures resulted in nucleation and growth of crystallites. Only a single Fe desorption peak ( Ed≈ 250 kJ mol-1) was observed over the whole coverage regime; this is assigned to the evaporation of iron atoms in contact with the ruthenium substrate, either pre-existing in the first monolayer or supplied from the Fe crystallites.

  4. Adsorption of hydrogen atoms onto the exterior wall of carbon nanotubes and their thermodynamics properties

    Energy Technology Data Exchange (ETDEWEB)

    Ng, T.Y.; Ren, Y.X. [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Liew, K.M. [Department of Building and Construction, City University of Hong Kong, Tat Chee Avenue, Kowloon (China)

    2010-05-15

    In the present work, we present a systematic analysis of the chemisorption process pathway of hydrogen atoms onto the exterior wall of (5,5) carbon nanotubes using the ONIOM2 (B3LYP(6-31+G(d,p):UFF)) scheme, and we avoid the gross assumption of fixing any of the carbon atoms during the simulation. It is shown that the adsorption of hydrogen atoms onto the sidewall of CNTs are energetically favorable and the most stable state is to form two H-C {sigma}-bonds while the original {sigma}-bond between the carbon atoms is totally severed. In particular, we examined the molecular thermodynamics properties for the reaction at a range of temperatures from 77 K to 1000 K, and the results suggests that the reaction is possible at ambient temperature, but it is less favorable than that at lower temperatures. (author)

  5. Solid Sorbents for Removal of Carbon Dioxide from Gas Streams at Low Temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Sirwardane, Ranjani V.

    2005-06-21

    New low-cost CO2 sorbents are provided that can be used in large-scale gas-solid processes. A new method is provided for making these sorbents that involves treating substrates with an amine and/or an ether so that the amine and/or ether comprise at least 50 wt. percent of the sorbent. The sorbent acts by capturing compounds contained in gaseous fluids via chemisorption and/or physisorption between the unit layers of the substrate's lattice where the polar amine liquids and solids and/or polar ether liquids and solids are located. The method eliminates the need for high surface area supports and polymeric materials for the preparation of CO2 capture systems, and provides sorbents with absorption capabilities that are independent of the sorbents' surface areas. The sorbents can be regenerated by heating at temperatures in excess of 35 degrees C.

  6. Ti-Si composite oxide-supported cobalt catalysts for CO2 hydrogenation

    Institute of Scientific and Technical Information of China (English)

    Jakrapan Janlamool; Piyasan Praserthdam; Bunjerd Jongsomjit

    2011-01-01

    In the present work,different silica-based supported cobalt (Co) catalysts were synthesized and used for CO2 hydrogenation for methanation.Different supports,such as SSP,MCM-41,TiSSP and TiMCM were used to prepare Co catalysts with 20 wt% Co loading.The supports and catalysts were characterized by means of N2 physisorption,XRD,SEM/EDX,XPS,TPR and CO chemisorption.It is found that after calcination of catalysts,Ti is present in the form of anatase.The introduction of Ti plays important roles in the properties of Co catalysts by.(i) facilitating the reduction of Co oxides species which are strongly interacted with support,(ii) preventing the formation of silicate compounds,and (iii) inhibiting the RWGS reaction.Based on CO2 hydrogenation,the CoTiMCM catalyst exhibites the highest activity and stability.

  7. A theoretical study of H{sub 2}S adsorption on graphene doped with B, Al and Ga

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Sheetal; Verma, A.S., E-mail: ajay_phy@rediffmail.com

    2013-10-15

    An effort has been made to exploit the adsorption potential of pure and doped graphene for H{sub 2}S molecule using density functional theory (DFT) modelling. Boron, aluminium and gallium atoms (IIIB) are used as dopant. For each pure and doped graphene system optimum position of adsorbed H{sub 2}S molecule is determined and adsorption energies are calculated. Further electronic properties are investigated by the analysis of Mulliken's charges and energy band-structures. The results indicate that H{sub 2}S molecule weakly binds to the pure graphene and boron doped graphene with small adsorption values; on the other hand aluminium doped graphene and gallium doped graphene have large adsorption energies values and binding distances typical for the chemisorptions. Local curvature in aluminium and gallium doped graphene is mainly responsible for the increased reactivity.

  8. Surface-Controlled Metal Oxide Resistive Memory

    KAUST Repository

    Ke, Jr-Jian

    2015-10-28

    To explore the surface effect on resistive random-access memory (ReRAM), the impact of surface roughness on the characteristics of ZnO ReRAM were studied. The thickness-independent resistance and the higher switching probability of ZnO ReRAM with rough surfaces indicate the importance of surface oxygen chemisorption on the switching process. Furthermore, the improvements in switching probability, switching voltage and resistance distribution observed for ReRAM with rough surfaces can be attributed to the stable oxygen adatoms under various ambience conditions. The findings validate the surface-controlled stability and uniformity of ReRAM and can serve as the guideline for developing practical device applications.

  9. Multiple Coordination of CO on Molybdenum Nanoparticles: Evidence for Intermediate Mox(CO)y Species by XPS and UPS.

    Science.gov (United States)

    Jiang, Zhiquan; Huang, Weixin; Zhang, Zhen; Zhao, Hong; Tan, Dali; Bao, Xinhe

    2006-12-28

    CO chemisorption on the metallic molybdenum nanoparticles supported on the thin alumina film was investigated by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). A binary compound of molybdenum and CO is found to be formed on the surface upon CO dose, accompanied with a positive binding energy shift of the Mo 3d doublet and a localized Mo 4d valence band. A loose packing of the metallic molybdenum favors the formation of this intermediate Mox(CO)y species. The formation of the Mox(CO)y species implies that the property of the metallic molybdenum nanoparticles on the thin alumina film is much different from that of the bulk molybdenum, indicating a significant nanometer size effect.

  10. Tribochemical peculiarities of lubricant composition with surface-modified metal powder

    Science.gov (United States)

    Syrkov, A. G.; Silivanov, M. O.; Kushchenko, A. N.

    2016-07-01

    The influence of different factors (adhesion, surface hydrophobicity, etc.) on antifrictional properties of lubricant with modified metal additives was discussed. The measurings of friction coefficient (f) and friction force (F fr) were carried out for the heterogeneous systems as oil I-20 with Al-additives modified by triamon (T), alkamon (A) and ethylhydridesiloxane according to various programs. It was established that as a number of T-underlayers, included in Al-additives with chemisorpted external layer of ethylhydridsiloxane reduces from 3 to 1 the force of friction and coefficient of friction reduce. It was discovered that the value of summand which stands for the amount of intermolecular forces in the boundary friction equation can be regulated in Al-additives by using low-molecular T-underlayer.

  11. Adsorption and dissociation of O2 on Ni-doped (5, 5) SWCNT: A DFT study

    Science.gov (United States)

    Li, Xiaodong; Liu, Liangliang; Wang, Mingguang; Wang, Zhu

    2016-05-01

    The effect of nickel doping on the adsorption and dissociation of the O2 molecule on a (5, 5) single-walled carbon nanotube (SWCNT) is investigated using first-principles density functional theory calculations in company with the nudged elastic band (NEB). Our calculated results show that nickel doping can make it much easier for oxygen adsorbed on the SWCNT, and the chemisorption energy is high enough to alter the O-O bond. What's more, the activation barrier for oxygen dissociation is lowered to 0.399 eV through nickel doping, which is much lower than Pt doped CNT. Our work have done here would be of help to develop platinum-free oxygen reduction reaction catalysts based on SWCNTs.

  12. Surface effects in metal oxide-based nanodevices

    KAUST Repository

    Lien, Der Hsien

    2015-10-29

    As devices shrink to the nanoscale, surface-to-volume ratio increases and the surface-environment interaction becomes a major factor for affecting device performance. The variation of electronic properties, including the surface band bending, gas chemisorption or photodesorption, native surface defects, and surface roughness, is called "surface effects". Such effects are ambiguous because they can be either negative or beneficial effects, depending on the environmental conditions and device application. This review provides an introduction to the surface effects on different types of nanodevices, offering the solutions to respond to their benefits and negative effects and provides an outlook on further applications regarding the surface effect. This review is beneficial for designing nano-enabled photodetectors, harsh electronics, memories, sensors and transistors via surface engineering.

  13. Formation, phase composition, texture and catalytic properties of Co-MgO-alumino-calcium catalysts in synthesis of hydrocarbons from CO and H/sub 2/

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Bruk, I.A.; Mal' tsev, V.V.; Iem, K.C.; Yakerson, V.I.; Golosman, Y.Z.; Mamayeva, I.A.; Kalacheva, N.B.; Danyushevskii, V.Y.; Nissenbaum, V.D.

    1981-01-01

    A study was made of the mechanism of formation of catalysts; a special feature of this mechanism is the interaction of components (calcium aluminates and basic carbonates of cobalt and magnesium); the carrier with a developed surface and the active component distributed on this surface are formed during this process. Catalysts show maximum selectivity in synthesis of liquid hydrocarbons from CO and H/sub 2/ with a degree of reduction of the metal of 65-84% and a dispersion (according to chemisorption of CO) of 6 x 10/sup -3/ - 10 x 10/sup -3/. Maximum yield of liquid hydrocarbons (114.1 g/nm/sup 3/) was obtained in the pressure of a system of 33Co-3MgO-64 talum treated with hydrogen at 550/sup 0/C.

  14. Gas dynamics, optics and chemistry of an aircraft condensable wake

    Energy Technology Data Exchange (ETDEWEB)

    Grinats, E.S.; Kashevarov, A.V.; Stasenko, A.L. [Central Aerohydrodynamic Inst., Zhukovsky (Russian Federation)

    1997-12-31

    Prediction of the properties of a jet-and-vortex wake from an individual airplane is of great interest as the first step to assessment of the possible global changes in the atmosphere due to the world civil aviation. Several mathematical models of the different regions of an aircraft wake and corresponding numerical results are presented. The axisymmetric exhaust jet was simulated on the base of the well-known k-{epsilon} model of turbulence. Jet chemistry was investigated on the base of kinetic scheme of the gas phase reactions of enriched by including chemisorption by water droplets of several species and by taking into account of the photochemical processes. In the 3D far wake model, the numerical results for distribution of species exhausted by the engines and entrapped by the velocity field of two parallel vortices are shown. (R.P.) 7 refs.

  15. Reversible CO2 Capture by Conjugated Ionic Liquids through Dynamic Covalent Carbon-Oxygen Bonds.

    Science.gov (United States)

    Pan, Mingguang; Cao, Ningning; Lin, Wenjun; Luo, Xiaoyan; Chen, Kaihong; Che, Siying; Li, Haoran; Wang, Congmin

    2016-09-08

    The strong chemisorption of CO2 is always accompanied by a high absorption enthalpy, and traditional methods to reduce the absorption enthalpy lead to decreased CO2 capacities. Through the introduction of a large π-conjugated structure into the anion, a dual-tuning approach for the improvement of CO2 capture by anion-functionalized ionic liquids (ILs) resulted in a high capacity of up to 0.96 molCO2  mol-1IL and excellent reversibility. The increased capacity and improved desorption were supported by quantum chemical calculations, spectroscopic investigations, and thermogravimetric analysis. The increased capacity may be a result of the strengthened dynamic covalent bonds in these π-electron-conjugated structures through anion aggregation upon the uptake of CO2 , and the improved desorption originates from the charge dispersion of interaction sites through the large π-electron delocalization. These results provide important insights into effective strategies for CO2 capture.

  16. Transport Properties of Amine/Carbon Dioxide Reactive Mixtures and Implications to Carbon Capture Technologies.

    Science.gov (United States)

    Turgman-Cohen, Salomon; Giannelis, Emmanuel P; Escobedo, Fernando A

    2015-08-19

    The structure and transport properties of physisorbed and chemisorbed CO2 in model polyamine liquids (hexamethylenediamine and diethylenetriamine) are studied via molecular dynamics simulations. Such systems are relevant to CO2 absorption processes where nonaqueous amines are used as absorbents (e.g., when impregnated or grafted onto mesoporous media or misted in the gas phase). It is shown that accounting for the ionic speciation resulting from CO2 chemisorption enabled us to capture the qualitative changes in extent of absorption and fluidity with time that are observed in thermogravimetric experiments. Simulations reveal that high enough concentration of reacted CO2 leads to strong intermolecular ionic interactions and the arrest of molecular translations. The transport properties obtained from the simulations of the ionic speciated mixtures are also used to construct an approximate continuum-level model for the CO2 absorption process that mimics thermogravimetric experiments.

  17. Sorption of indigo carmine by a Fe-zeolitic tuff and carbonaceous material from pyrolyzed sewage sludge

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez-Segura, E. [Facultad de Quimica, Universidad Autonoma del Estado de Mexico, Paseo Colon y Tollocan s/n., C.P. 50000 Toluca (Mexico); Departamento de Quimica, Instituto Nacional de Investigaciones Nucleares, A.P. 18-1027, Col. Escandon, Delegacion Miguel Hidalgo, C.P. 11801 Mexico, D.F. (Mexico); Solache-Rios, M., E-mail: marcos.solache@inin.gob.mx [Departamento de Quimica, Instituto Nacional de Investigaciones Nucleares, A.P. 18-1027, Col. Escandon, Delegacion Miguel Hidalgo, C.P. 11801 Mexico, D.F. (Mexico); Colin-Cruz, A. [Facultad de Quimica, Universidad Autonoma del Estado de Mexico, Paseo Colon y Tollocan s/n., C.P. 50000 Toluca (Mexico)

    2009-10-30

    Indigo carmine removal from aqueous solution has been evaluated using Fe-zeolitic tuff and carbonaceous material from pyrolyzed sewage sludge treated with HCl (CM). The adsorbents were characterized by scanning electron microscopy, BET surface area and X-ray diffraction. Sorption kinetics and isotherms were determined and the adsorption behaviors analyzed. Kinetic pseudo-second order and Langmuir-Freundlich models were successfully applied to the experimental results obtained with the Fe-zeolitic material, while kinetic first order and Langmuir-Freundlich models were applied to the results from the carbonaceous materials. This indicates mechanisms of chemisorption and physic sorption, respectively, on the heterogeneous materials. The results indicate that the carbonaceous material from the pyrolysis of sewage sludge (sorption capacity 92.83 mg/g) is a better adsorbent of indigo carmine than the zeolitic material (sorption capacity 32.83 mg/g).

  18. Spatial, Hysteretic, and Adaptive Host-Guest Chemistry in a Metal-Organic Framework with Open Watson-Crick Sites.

    Science.gov (United States)

    Cai, Hong; Li, Mian; Lin, Xiao-Rong; Chen, Wei; Chen, Guang-Hui; Huang, Xiao-Chun; Li, Dan

    2015-09-01

    Biological and artificial molecules and assemblies capable of supramolecular recognition, especially those with nucleobase pairing, usually rely on autonomous or collective binding to function. Advanced site-specific recognition takes advantage of cooperative spatial effects, as in local folding in protein-DNA binding. Herein, we report a new nucleobase-tagged metal-organic framework (MOF), namely ZnBTCA (BTC=benzene-1,3,5-tricarboxyl, A=adenine), in which the exposed Watson-Crick faces of adenine residues are immobilized periodically on the interior crystalline surface. Systematic control experiments demonstrated the cooperation of the open Watson-Crick sites and spatial effects within the nanopores, and thermodynamic and kinetic studies revealed a hysteretic host-guest interaction attributed to mild chemisorption. We further exploited this behavior for adenine-thymine binding within the constrained pores, and a globally adaptive response of the MOF host was observed.

  19. Ambient carbon dioxide capture by different dimensional AlN nanostructures: A comparative DFT study

    Science.gov (United States)

    Esrafili, Mehdi D.; Nurazar, Roghaye; Nematollahi, Parisa

    2016-08-01

    Strong binding of an isolated carbon dioxide molecule over three different aluminium nitride (AlN) nanostructures (nanocage, nanotube and nanosheet) is verified using density functional calculations. Equilibrium geometries, electronic properties, adsorption energies and thermodynamic stability of each adsorbed configuration are also identified. Optimized configurations are shown at least one corresponding physisorption and chemisorption of CO2 molecule over different AlN nanostructures. Also, the effect of chirality on the adsorption of CO2 molecule is studied over two different finite-sized zigzag (6,0) and armchair (4,4) AlN nanotubes. It is found that the electronic properties of the Al12N12 nanocage are more sensitive to the CO2 molecule than other AlN nanostructures. This indicates the significant potential of Al12N12 nanocage toward the CO2 adsorption, fixation and catalytic applications in contrast to other AlN nanostructures.

  20. Quantum chemical modeling of adsorption of ureides, that used as inhibitor of microbiological corrosion, on the iron of st3s grade of steel

    Directory of Open Access Journals (Sweden)

    Andrei Sikachina

    2016-07-01

    Full Text Available In published work presents modeled using quantum chemical package HyperChem version 8.0.7 using the semiempirical method ZINDO/1, the process of adsorption of organic compounds of ureidе ranging from simple to more complex, a cluster of iron (present in the steel in amounts of 97%. This approach, as will be shown, with high accuracy reflects the process of corrosion protection with bacterial content by chemisorption of organic compounds on the metal surface with the formation of complex compounds. In the research process were obtained and analyzed global and local electrophilicity heteroatoms, reflects the composition of the complexes, lit a graph showing the dependence of the local electrophilicity from protective anti-corrosion effect.

  1. Low metal loading catalysts used for the selective hydrogenation of styrene

    Energy Technology Data Exchange (ETDEWEB)

    Badano, Juan; Lederhos, Cecilia; Quiroga, Monica; L' Argentiere, Pablo [Consejo Nacional de Investigaciones Cientificas y Tecnicas, Santa Fe (Argentina). Universidad Nacional del Litoral. Inst. de Investigaciones en Catalisis y Petroquimica; Coloma-Pascual, Fernando [Universidad de Alicante (Spain). Facultad de Ciencias. Servicios Tecnicos de Investigacion

    2010-07-01

    A series of Group VIII metal catalysts was obtained for the semi-hydrogenation of styrene. Catalysts were characterized by Hydrogen Chemisorption, TPR and XPS. Palladium, rhodium and platinum low metal loading prepared catalysts presented high activity and selectivity (ca. 98%) during the semi-hydrogenation of styrene, being palladium the most active catalyst. The ruthenium catalyst also presented high selectivity (ca. 98%), but the lowest activity. For the palladium catalyst, the influence of the precursor salt and of the reduction temperature on the activity and selectivity were studied. The following activity series was obtained: PdN-423 > PdCl-673 > PdCl-373> PtCl-673 > RhCl-673 >> RuCl-673. As determined by XPS, differences in activity could be attributed, at least in part, to electronic effects (author)

  2. Structures and vibrational frequencies of CO adlayers on Rh(111) surface

    Institute of Scientific and Technical Information of China (English)

    XIAO; Haiyan(肖海燕); LAI; Wenzhen(赖文珍); XIE; Daiqian(谢代前); YAN; Guosen(鄢国森)

    2003-01-01

    Density functional theory calculations within the generalized gradient approximation (GGA) have been carried out to study the structural and vibrational properties of carbon monoxide adsorption on Rh(111) surface. The optimized geometries, adsorption energies and vibrational frequencies have been obtained and the preferred binding sites have been determined. The results show that at low coverage CO prefers to adsorb at top site and at high coverage one molecule occupies top site while the two other molecules occupy hcp and fcc hollow sites respectively. The investigation of the vibrational properties of CO chemisorption on Rh(111) shows that the top C-O stretching frequency increases along with the increase of the coverage. The site assignments, optimized geometries and calculated vibrational frequencies are found to be in good agreement with the experimental results.

  3. Synthesis and Understanding of Novel Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Stair, Peter C. [Northwestern University

    2013-07-09

    The research took advantage of our capabilities to perform in-situ and operando Raman spectroscopy on complex systems along with our developing expertise in the synthesis of uniform, supported metal oxide materials to investigate relationships between the catalytically active oxide composition, atomic structure, and support and the corresponding chemical and catalytic properties. The project was organized into two efforts: 1) Synthesis of novel catalyst materials by atomic layer deposition (ALD). 2) Spectroscopic and chemical investigations of coke formation and catalyst deactivation. ALD synthesis was combined with conventional physical characterization, Raman spectroscopy, and probe molecule chemisorption to study the effect of supported metal oxide composition and atomic structure on acid-base and catalytic properties. Operando Raman spectroscopy studies of olefin polymerization leading to coke formation and catalyst deactivation clarified the mechanism of coke formation by acid catalysts.

  4. Two stage sorption type cryogenic refrigerator including heat regeneration system

    Science.gov (United States)

    Jones, Jack A.; Wen, Liang-Chi; Bard, Steven

    1989-01-01

    A lower stage chemisorption refrigeration system physically and functionally coupled to an upper stage physical adsorption refrigeration system is disclosed. Waste heat generated by the lower stage cycle is regenerated to fuel the upper stage cycle thereby greatly improving the energy efficiency of a two-stage sorption refrigerator. The two stages are joined by disposing a first pressurization chamber providing a high pressure flow of a first refrigerant for the lower stage refrigeration cycle within a second pressurization chamber providing a high pressure flow of a second refrigerant for the upper stage refrigeration cycle. The first pressurization chamber is separated from the second pressurization chamber by a gas-gap thermal switch which at times is filled with a thermoconductive fluid to allow conduction of heat from the first pressurization chamber to the second pressurization chamber.

  5. Two-statge sorption type cryogenic refrigerator including heat regeneration system

    Science.gov (United States)

    Jones, Jack A. (Inventor); Wen, Liang-Chi (Inventor); Bard, Steven (Inventor)

    1989-01-01

    A lower stage chemisorption refrigeration system physically and functionally coupled to an upper stage physical adsorption refrigeration system. Waste heat generated by the lower stage cycle is regenerated to fuel the upper stage cycle thereby greatly improving the energy efficiency of a two-stage sorption refrigerator. The two stages are joined by disposing a first pressurization chamber providing a high pressure flow of a first refrigerant for the lower stage refrigeration cycle within a second pressurization chamber providing a high pressure flow of a second refrigerant for the upper stage refrigeration cycle. The first pressurization chamber is separated from the second pressurization chamber by a gas-gap thermal switch which at times is filled with a thermoconductive fluid to allow conduction of heat from the first pressurization chamber to the second pressurization chamber.

  6. Properties and efficiency of a Pt/Al2O3 catalyst applied in a solid fuel thermo-accumulating furnace

    Directory of Open Access Journals (Sweden)

    SRDJAN BELOSEVIC

    2007-08-01

    Full Text Available A prototype of a solid fuel thermo-accumulating furnace has been developed. In order to achieve a higher combustion efficiency, a Pt/Al2O3 catalyst in the form of 3 ± 0.3 mm spheres was applied, which enabled further combustion of flue gases within the furnace. Experimental investigation of the influence of the catalyst on the conversion of CO has been done for different operation regimes and positions of the catalyst. Paper presents selected results regarding CO emission during wood and coal combustion. Investigations suggest a considerable effect of the catalyst and a strong influence of the catalyst position to CO emission reduction. The microstructure of the catalyst beads, characterized by selective chemisorption of CO, has shown the decrease of the number of Pt sites as a consequence of blockage by coke deposits formed during the combustion of solid fuel.

  7. Synthesis of tripodal catecholates and their immobilization on zinc oxide nanoparticles

    Directory of Open Access Journals (Sweden)

    Franziska Klitsche

    2015-05-01

    Full Text Available A common approach to generate tailored materials and nanoparticles (NPs is the formation of molecular monolayers by chemisorption of bifunctional anchor molecules. This approach depends critically on the choice of a suitable anchor group. Recently, bifunctional catecholates, inspired by mussel-adhesive proteins (MAPs and bacterial siderophores, have received considerable interest as anchor groups for biomedically relevant metal surfaces and nanoparticles. We report here the synthesis of new tripodal catecholates as multivalent anchor molecules for immobilization on metal surfaces and nanoparticles. The tripodal catecholates have been conjugated to various effector molecules such as PEG, a sulfobetaine and an adamantyl group. The potential of these conjugates has been demonstrated with the immobilization of tripodal catecholates on ZnO NPs. The results confirmed a high loading of tripodal PEG-catecholates on the particles and the formation of stable PEG layers in aqueous solution.

  8. Insight into biosorption equilibrium, kinetics and thermodynamics of crystal violet onto Ananas comosus (pineapple) leaf powder

    Science.gov (United States)

    Chakraborty, Sagnik; Chowdhury, Shamik; Saha, Papita Das

    2012-06-01

    Biosorption performance of pineapple leaf powder (PLP) for removal of crystal violet (CV) from its aqueous solutions was investigated. To this end, the influence of operational parameters such as pH, biosorbent dose, initial dye concentration and temperature were studied employing a batch experimental setup. The biosorption process followed the Langmuir isotherm model with high correlation coefficients ( R 2 > 0.99) at different temperatures. The maximum monolayer biosorption capacity was found to be 78.22 mg g-1 at 293 K. The kinetic data conformed to the pseudo-second-order kinetic model. The activation energy of the system was calculated as 58.96 kJ mol- 1 , indicating chemisorption nature of the ongoing biosorption process. A thermodynamic study showed spontaneous and exothermic nature of the biosorption process. Owing to its low cost and high dye uptake capacity, PLP has potential for application as biosorbent for removal of CV from aqueous solutions.

  9. Photoemission electron microscopy of arrays of submicron nickel rods in a silicon dioxide matrix

    Science.gov (United States)

    Turishchev, S. Yu.; Parinova, E. V.; Kronast, F.; Ovsyannikov, R.; Malashchenok, N. V.; Streltsov, E. A.; Ivanov, D. K.; Fedotov, A. K.

    2014-09-01

    Arrays of Ni rods (˜500 nm diameter) formed by the ion-track technology in combination with electrochemical deposition into a SiO2 matrix on the surface of single-crystal silicon plates have been investigated using photoemission electron microscopy with high-intensity synchrotron (undulator) radiation. An analysis of the Ni L 2,3 X-ray absorption near-edge structure (XANES) spectra has demonstrated that rod-like structures in pores and connecting bridges between the rods are formed by a metallic nickel phase, which is stable to oxidation by atmospheric oxygen. No formation of intermediate compound phases (nickel silicides and oxides) is observed at the Ni/SiO2 heterojunction, whereas oxidized nickel(II) species are identified on the surface of the SiO2 matrix, which presumably can be attributed to nickel silicate and hydroxide compounds formed upon nickel(II) chemisorption in electrochemical deposition electrolytes.

  10. Morphology and adsorption of chromium ion on uranium 1,2,4,5-benzenetetracarboxylic acid metal organic framework (MOF

    Directory of Open Access Journals (Sweden)

    Vala Remy M.K.

    2016-01-01

    Full Text Available In this paper, we report the synthesis of metal organic framework of uranium 1,2,4,5-benzene tetracarboxylic acid (U-H4btec MOF by solvothermal method. The obtained MOF was characterized by Fourier transform infrared spectroscopy (FTIR, Scanning electron microscopy (SEM, Transmission electron microscopy (TEM, X-ray diffraction spectroscopy (XRD, Energy dispersive spectroscopy (EDS, thermogravimetric and differential thermogravimetric analysis (TGA/DTA. The morphology of the uranium 1,2,4,5-benzene tetracarboxylic acid MOF observed by SEM, revealed the presence of flaky porous structure. Adsorption of Cr3+ from aqueous solution onto the uranium 1,2,4,5-benzene tetracarboxylic acid MOF was systematically studied. Langmuir and Freundlich adsorption isotherms were applied to determine the adsorption capacity of the MOF to form a monolayer. Kinetic determination of the adsorption of Cr3+ suggested both chemisorption and physisorption probably due to the presence of carbonyl groups within the MOF and its porous structure.

  11. Tailoring the surface properties and carrier dynamics in SnO2 nanowires.

    Science.gov (United States)

    Kar, Ayan; Stroscio, Michael A; Meyyappan, M; Gosztola, David J; Wiederrecht, Gary P; Dutta, Mitra

    2011-07-15

    We report a study of the role of mid-gap defect levels due to surface states in SnO(2) nanowires on carrier trapping. Ultrafast pump-probe spectroscopy provides carrier relaxation time constants that reveal the nature and positions of various defect levels due to the surface states which in turn provide details on how the carriers relax after their injection. The effect of oxygen annealing on carrier concentration is also studied through XPS valence band photoemission spectroscopy, a sensitive non-contact surface characterization technique. These measurements show that charge transfer associated with chemisorption of oxygen in different forms produces an upward band bending and leads to an increase in the depletion layer width by approximately 70 nm, thereby decreasing surface conductivity and forming the basis for the molecular sensing capability of the nanowires.

  12. Tailoring the surface properties and carrier dynamics in SnO{sub 2} nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Kar, Ayan; Stroscio, Michael A; Dutta, Mitra [Electrical and Computer Engineering Department, University of Illinois, Chicago, IL 60607 (United States); Meyyappan, M [Center for Nanotechnology, NASA Ames Research Center, Moffett Field, CA 94035 (United States); Gosztola, David J; Wiederrecht, Gary P, E-mail: dutta@ece.uic.edu [Center for Nanoscale Materials, Argonne National Laboratory, Argonne, IL 60439 (United States)

    2011-07-15

    We report a study of the role of mid-gap defect levels due to surface states in SnO{sub 2} nanowires on carrier trapping. Ultrafast pump-probe spectroscopy provides carrier relaxation time constants that reveal the nature and positions of various defect levels due to the surface states which in turn provide details on how the carriers relax after their injection. The effect of oxygen annealing on carrier concentration is also studied through XPS valence band photoemission spectroscopy, a sensitive non-contact surface characterization technique. These measurements show that charge transfer associated with chemisorption of oxygen in different forms produces an upward band bending and leads to an increase in the depletion layer width by approximately 70 nm, thereby decreasing surface conductivity and forming the basis for the molecular sensing capability of the nanowires.

  13. Adsorption of hexavalent chromium by graphite–chitosan binary composite

    Indian Academy of Sciences (India)

    RAJENDRA S DONGRE

    2016-06-01

    Graphite chitosan binary (GCB) composite was prepared for hexavalent chromium adsorption from studied water. GCB was characterized by TGA, FTIR, SEM and X-ray diffraction techniques.Wide porous sorptive surface of 3.89 m$^2$ g$^{−1}$ and absorptive functionalities of GCB was due to 20% (w/w) graphite support on chitosan evidenced from FTIR and SEM that impart maximum adsorption at pH 4, agitation with 200 rpm for 180 min. Adsorption studies revealed intraparticle diffusion models and best-fitted kinetics was pseudo 2nd order one. A wellfitted Langmuir isotherm model suggested monolayer adsorption with an adsorption capacity ($q_m$) of 105.6 mg g$^{−1}$ and $R^2 = 0.945$. Sorption mechanisms based on metal ionic interactions, intrusion/diffusion and chemisorptions onto composite. This graphite chitosan binary composite improve sorbent capacity for Cr(VI).

  14. Transition metal contacts to graphene

    Energy Technology Data Exchange (ETDEWEB)

    Politou, Maria, E-mail: Maria.Politou@imec.be; De Gendt, Stefan; Heyns, Marc [KU Leuven, 3001 Leuven (Belgium); imec, Kapeldreef 75, 3001 Leuven (Belgium); Asselberghs, Inge; Radu, Iuliana; Conard, Thierry; Richard, Olivier; Martens, Koen; Huyghebaert, Cedric; Tokei, Zsolt [imec, Kapeldreef 75, 3001 Leuven (Belgium); Lee, Chang Seung [SAIT, Samsung Electronics Co., Suwon 443-803 (Korea, Republic of); Sayan, Safak [imec, Kapeldreef 75, 3001 Leuven (Belgium); Intel Corporation, 2200 Mission College Blvd, Santa Clara, California 95054 (United States)

    2015-10-12

    Achieving low resistance contacts to graphene is a common concern for graphene device performance and hybrid graphene/metal interconnects. In this work, we have used the circular Transfer Length Method (cTLM) to electrically characterize Ag, Au, Ni, Ti, and Pd as contact metals to graphene. The consistency of the obtained results was verified with the characterization of up to 72 cTLM structures per metal. Within our study, the noble metals Au, Ag and Pd, which form a weaker bond with graphene, are shown to result in lower contact resistance (Rc) values compared to the more reactive Ni and Ti. X-ray Photo Electron Spectroscopy and Transmission Electron Microscopy characterization for the latter have shown the formation of Ti and Ni carbides. Graphene/Pd contacts show a distinct intermediate behavior. The weak carbide formation signature and the low Rc values measured agree with theoretical predictions of an intermediate state of weak chemisorption of Pd on graphene.

  15. Engineering nanomaterial surfaces for biomedical applications.

    Science.gov (United States)

    Wang, Xin; Liu, Li-Hong; Ramström, Olof; Yan, Mingdi

    2009-10-01

    Nanomaterials, possessing unique physical and chemical properties, have attracted much interest and generated wide varieties of applications. Recent investigations of functionalized nanomaterials have expanded into the biological area, providing a versatile platform in biomedical applications such as biomolecular sensing, biological imaging, drug delivery and disease therapy. Bio-functions and bio-compatibility of nanomaterials are realized by introducing synthetic ligands or natural biomolecules onto nanomaterials, and combining ligand-receptor biological interactions with intrinsic nanomaterial properties. Common strategies of engineering nanomaterial surfaces involve physisorption or chemisorption of desired ligands. We developed a photochemically initiated surface coupling chemistry, bringing versatility and simplicity to nanomaterial functionalization. The method was applied to attach underivatized carbohydrates efficiently on gold and iron oxide nanoparticles, and the resulting glyconanoparticles were successfully used as a sensitive biosensing system probing specific interactions between carbohydrates and proteins as well as bacteria.

  16. THE ADSORPTION BEHAVIORS OF 2,6-DICHLOROPHENOL ONTO HYPERCROSSLINKED RESINS

    Institute of Scientific and Technical Information of China (English)

    WANG Jingping; LI Zhixia; ZHANG Gencheng; FEI Zhenghao; TANG Shuhe

    2006-01-01

    Experimental investigations were conducted on the adsorption characteristics of 2,6-dichlorophenol by two hypercrosslinked resin, ZH-01 and XAD-4. The static adsorption was studied. Within temperature range of 288K~313K, the equilibrium adsorption date was fitted to freundlich adsorption isotherm models to evaluate the model parameters. The enthalpies, free energy,entropy were indicative of an exothermic, a spontaneous and disorder decreasing process. The magnitudes for 2,6-dichlorophenol on ZH-01 showed a chemisorption's transitions while on XAD-4shows a physical adsorption process. The results showed that the ZH-01 adsorbents were better than the Amberlite XAD-4 for removing the 2,6-dichlorophenol in aqueous solutions.

  17. Sorption Kinetics for the Removal of Cadmium and Zinc onto Palm Kernel Shell Based Activated Carbon

    Directory of Open Access Journals (Sweden)

    Muhammad Muhammad

    2010-12-01

    Full Text Available The kinetics and mechanism of cadmium and zinc adsorption on palm kernel shell based activated carbons (PKSAC have been studied. A series of batch laboratory studies were conducted in order to investigate the suitability of palm kernel shell based activated carbon (PKSAC for the removal of cadmium (cadmium ions and zinc (zinc ions from their aqueous solutions. All batch experiments were carried out at pH 7.0 and a constant temperature of 30+-1°C using an incubator shaker that operated at 150 rpm. The kinetics investigated includes the pseudo first order, the pseudo-second order and the intraparticle diffusion models. The pseudo-second order model correlate excellently the experimental data, suggesting that chemisorption processes could be the rate-limiting step. Keywords: adsorption, cadmium, kinetics, palm kernel shell, zinc

  18. Electronic structure of disordered alloys, surfaces and interfaces

    CERN Document Server

    Turek, Ilja; Kudrnovský, Josef; Šob, Mojmír; Weinberger, Peter

    1997-01-01

    At present, there is an increasing interest in the prediction of properties of classical and new materials such as substitutional alloys, their surfaces, and metallic or semiconductor multilayers. A detailed understanding based on a thus of the utmost importance for fu­ microscopic, parameter-free approach is ture developments in solid state physics and materials science. The interrela­ tion between electronic and structural properties at surfaces plays a key role for a microscopic understanding of phenomena as diverse as catalysis, corrosion, chemisorption and crystal growth. Remarkable progress has been made in the past 10-15 years in the understand­ ing of behavior of ideal crystals and their surfaces by relating their properties to the underlying electronic structure as determined from the first principles. Similar studies of complex systems like imperfect surfaces, interfaces, and mul­ tilayered structures seem to be accessible by now. Conventional band-structure methods, however, are of limited use ...

  19. Lattice-strain control of the activity in dealloyed core-shell fuel cell catalysts.

    Science.gov (United States)

    Strasser, Peter; Koh, Shirlaine; Anniyev, Toyli; Greeley, Jeff; More, Karren; Yu, Chengfei; Liu, Zengcai; Kaya, Sarp; Nordlund, Dennis; Ogasawara, Hirohito; Toney, Michael F; Nilsson, Anders

    2010-06-01

    Electrocatalysis will play a key role in future energy conversion and storage technologies, such as water electrolysers, fuel cells and metal-air batteries. Molecular interactions between chemical reactants and the catalytic surface control the activity and efficiency, and hence need to be optimized; however, generalized experimental strategies to do so are scarce. Here we show how lattice strain can be used experimentally to tune the catalytic activity of dealloyed bimetallic nanoparticles for the oxygen-reduction reaction, a key barrier to the application of fuel cells and metal-air batteries. We demonstrate the core-shell structure of the catalyst and clarify the mechanistic origin of its activity. The platinum-rich shell exhibits compressive strain, which results in a shift of the electronic band structure of platinum and weakening chemisorption of oxygenated species. We combine synthesis, measurements and an understanding of strain from theory to generate a reactivity-strain relationship that provides guidelines for tuning electrocatalytic activity.

  20. Catalytic synthesis of 2-methylpyrazine over Cr-promoted copper based catalyst via a cyclo-dehydrogenation reaction route

    Indian Academy of Sciences (India)

    Fangli Jing; Yuanyuan Zhang; Shizhong Luo; Wei Chu; Hui Zhang; Xinyu Shi

    2010-07-01

    The cyclo-dehydrogenation of ethylene diamine and propylene glycol to 2-methylpyrazine was performed under the atmospheric conditions at 380°C. The Cr-promoted Cu-Zn/Al2O3 catalysts were prepared by impregnation method and characterized by ICP-AES, N2 adsorption/desorption, XRD, XPS, N2O chemisorption, TPR and NH3-TPD techniques. The amorphous chromium species existing in Cu-Zn-Cr/Al2O3 catalyst enhanced the dispersion of active component Cu, promoted the reduction of catalyst. Furthermore, the catalytic performance was significantly improved. The acidity of the catalyst played an important role in increasing the 2-MP selectivity. To optimize the reaction parameters, influences of different chromium content, reaction temperature, liquid hourly space velocity (LHSV), reactants molar ratio and time on stream on the product pattern were studied. The results demonstrated that addition of chromium promoter revealed satisfying catalytic activity, stability and selectivity of 2-methylpyrazine.

  1. Study on Deactivation by Sulfur and Regeneration of Pd/C Catalyst in Hydrogenation of N-(3-nitro-4-methoxyphenyl) Acetamide

    Institute of Scientific and Technical Information of China (English)

    ZHANG Qunfeng; L(U) Jinghui; MA Lei; LU Chunshan; LIU Wei; LI Xiaonian

    2013-01-01

    Deactivation of Pd/C catalyst often occurs in liquid hydrogenation using industrial materials.For instance,the Pd/C catalyst is deactivated severely in the hydrogenation of N-(3-nitro-4-methoxyphenyl) acetamide.In this study,the chemisorption of sulfur on the surface of deactivated Pd/C was detected by energy dispersive spectrometer and X-ray photoelectron spectroscopy.Sulfur compounds poison the Pd/C catalyst and increase the formation of azo deposit,reducing the activity of catalyst.We report a mild method to regenerate the Pd/C catalyst:wash the deposit by N,N-dimethylformamide and oxidize the chemisorbed sulfur by hot air.The regenerated Pd/C catalyst can be reused at least ten runs with stable activity.

  2. Single-step synthesis of magnetic chitosan composites and application for chromate (Cr(VI)) removal

    Institute of Scientific and Technical Information of China (English)

    杨卫春; 唐琼芝; 董舒宇; 柴立元; 王海鹰

    2016-01-01

    Magnetic chitosan composites (Fe3O4@chitosan) were synthesized in one single-step, characterized and applied in Cr(VI) removal from water. With the increase of loading proportion of chitosan, Cr(VI) adsorption capacity of Fe3O4@chitosan composites increased from 10.771 to 21.040 mg/g. The optimum adsorption capacities of Cr(VI) on Fe3O4@chitosan-3 were found in a pH range of 3.0−5.0. Kinetic study results show that the adsorption process follows pseudo-second-order model, indicating that the rate-limiting step in the adsorption of Cr(VI) involves chemisorptions. Moreover, FT-IR spectra analysis confirms that the amine and hydroxyl groups of chitosan are predominantly responsible for binding. Results from this work demonstrate that the prepared Fe3O4@chitosan composites possess great potential in Cr(VI) removal from contaminated water.

  3. A Novel Schiff Base of 3-acetyl-4-hydroxy-6-methyl-(2Hpyran-2-one and 2,2'-(ethylenedioxydiethylamine as Potential Corrosion Inhibitor for Mild Steel in Acidic Medium

    Directory of Open Access Journals (Sweden)

    Jonnie N. Asegbeloyin

    2015-05-01

    Full Text Available The corrosion inhibition activity of a newly synthesized Schiff base (SB from 3-acetyl-4-hydroxy-6-methyl-(2H-pyran-2-one and 2,2'-(ethylenedioxydiethylamine was investigated on the corrosion of mild steel in 1 M HCl solution using potentiodynamic polarization and electrochemical impedance spectroscopic techniques. Ultraviolet-visible (UV-vis and Raman spectroscopic techniques were used to study the chemical interactions between SB and mild steel surface. SB was found to be a relatively good inhibitor of mild steel corrosion in 1 M HCl. The inhibition efficiency increases with increase in concentration of SB. The inhibition activity of SB was ascribed to its adsorption onto mild steel surface, through physisorption and chemisorption, and described by the Langmuir adsorption model. Quantum chemical calculations indicated the presence of atomic sites with potential nucleophilic and electrophilic characteristics with which SB can establish electronic interactions with the charged mild steel surface.

  4. Solid sorbents for removal of carbon dioxide from gas streams at low temperatures

    Science.gov (United States)

    Sirwardane, Ranjani V.

    2005-06-21

    New low-cost CO.sub.2 sorbents are provided that can be used in large-scale gas-solid processes. A new method is provided for making these sorbents that involves treating substrates with an amine and/or an ether so that the amine and/or ether comprise at least 50 wt. percent of the sorbent. The sorbent acts by capturing compounds contained in gaseous fluids via chemisorption and/or physisorption between the unit layers of the substrate's lattice where the polar amine liquids and solids and/or polar ether liquids and solids are located. The method eliminates the need for high surface area supports and polymeric materials for the preparation of CO.sub.2 capture systems, and provides sorbents with absorption capabilities that are independent of the sorbents' surface areas. The sorbents can be regenerated by heating at temperatures in excess of 35.degree. C.

  5. Optimization and adsorption kinetic studies of aqueous manganese ion removal using chitin extracted from shells of edible Philippine crabs

    Science.gov (United States)

    Quimque, Mark Tristan J.; Jimenez, Marvin C.; Acas, Meg Ina S.; Indoc, Danrelle Keth L.; Gomez, Enjelyn C.; Tabuñag, Jenny Syl D.

    2017-01-01

    Manganese is a common contaminant in drinking water along with other metal pollutants. This paper investigates the use of chitin, extracted from crab shells obtained as restaurant throwaway, as an adsorbent in removing manganese ions from aqueous medium. In particular, this aims to optimize the adsorption parameters and look into the kinetics of the process. The adsorption experiments done in this study employed the batch equilibration method. In the optimization, the following parameters were considered: pH and concentration of Mn (II) sorbate solution, particle size and dosage of adsorbent chitin, and adsorbent-adsorbate contact time. At the optimal condition, the order of the adsorption reaction was estimated using kinetic models which describes the process best. It was found out that the adsorption of aqueous Mn (II) ions onto chitin obeys the pseudo-second order model. This model assumes that the adsorption occurred via chemisorption

  6. Inhibition effect of 2-amino-5-ethyl-1, 3, 4-thiadiazole on corrosion behaviour of austenitic stainless steel type 304 in dilute HCl solution

    Institute of Scientific and Technical Information of China (English)

    Roland T Loto; Cleophas A Loto; Abimbola P Popoola; Tatiana Fedotova

    2016-01-01

    The corrosion inhibition of type 304 austenitic stainless steel by 2-amino-5-ethyl-1, 3, 4-thiadiazole (TTD) compound and the electrochemical behaviour in dilute HCl solution were investigated through potentiodynamic polarization test, mass loss techniques and potential measurements. The results show that the organic derivative is highly effective with a maximum inhibition efficiency of 70.22% from mass loss analysis, while 74.2% is obtained from polarization tests. Observation of the scanning electron micrographs shows the absence of corrosion products due to electrochemical influence of TTD on the surface morphology of the steel. X-ray diffractometry reveals the absence of phase compounds and complexes on the steel samples after exposure. TTD adsorption on the steel surface obeys the Langmuir, Frumkin and Freundlich adsorption isotherms. Corrosion thermodynamic calculations reveal the inhibition mechanism occurs through chemisorption process and results from statistical analysis depict the strong influence of inhibitor concentration on the electrochemical performance of the TTD.

  7. Guidelines for choosing molecular "alligator clip" binding motifs in electron transport devices

    Science.gov (United States)

    Reuter, Matthew G.; Seideman, Tamar; Ratner, Mark A.

    2011-04-01

    We employ a one-electron, tight-binding model of an electrode-molecule-electrode junction to explore the fundamental relationship between adsorption geometry and electron transport, producing exact results (within this model). By varying the chemisorption location (e.g., atop a surface atom or in a hollow site between surface atoms) and the molecule-electrode coupling, we find that the largest currents are realized when the molecule (i) is highly coordinated by the surface and (ii) has favorable overlap with electrode states near the Fermi level. We also show the importance of electrode-induced molecular level shifting for certain adsorption geometries, which can cause molecular levels far from the Fermi level to conduct better than those near the Fermi level. Since all of these factors are greatly influenced by the chemical moiety used to link the molecule to an electrode, these results present a set of guidelines to help choose "alligator clips" for molecular electronic devices.

  8. Synthesis of nickel nanoparticles supported on metal oxides using electroless plating: controlling the dispersion and size of nickel nanoparticles.

    Science.gov (United States)

    Wu, Zhijie; Ge, Shaohui; Zhang, Minghui; Li, Wei; Tao, Keyi

    2009-02-15

    Nickel nanoparticles supported on metal oxides were prepared by a modified electroless nickel-plating method. The process and mechanism of electroless plating were studied by changing the active metal (Ag) loading, acidity, and surface area of metal oxides and were characterized by UV-vis spectroscopy, transmission electron microscopy, scanning electron microscopy, and H(2) chemisorption. The results showed that the dispersion of nickel nanoparticles was dependent on the interface reaction between the metal oxide and the plating solution or the active metal and the plating solution. The Ag loading and acidity of the metal oxide mainly affected the interface reaction to change the dispersion of nickel nanoparticles. The use of ultrasonic waves and microwaves and the change of solvents from water to ethylene glycol in the electroless plating could affect the dispersion and size of nickel nanoparticles.

  9. Synthesis of supported bimetallic nanoparticles with controlled size and composition distributions for active site elucidation

    Energy Technology Data Exchange (ETDEWEB)

    Hakim, Sikander H.; Sener, Canan; Alba Rubio, Ana C.; Gostanian, Thomas M.; O' neill, Brandon J; Ribeiro, Fabio H.; Miller, Jeffrey T.; Dumesic, James A

    2015-08-01

    Elucidation of active sites in supported bimetallic catalysts is complicated by the high level of dispersity in the nanoparticle size and composition that is inherent in conventional methods of catalyst preparation. We present a synthesis strategy that leads to highly dispersed, bimetallic nanoparticles with uniform particle size and composition by means of controlled surface reactions. We demonstrate the synthesis of three systems, RhMo, PtMo, and RhRe, consisting of a highly reducible metal with an oxophilic promoter. These catalysts are characterized by FTIR, CO chemisorption, STEM/EDS, TPR, and XAS analysis. The catalytic properties of these bimetallic nanoparticles were probed for the selective CO hydrogenolysis of (hydroxymethyl)tetrahydropyran to produce 1,6 hexanediol. Based on the characterization results and reactivity trends, the active sites in the hydrogenolysis reaction are identified to be small ensembles of the more noble metal (Rh, Pt) adjacent to highly reduced moieties of the more oxophilic metal (Mo, Re).

  10. Ni catalysts supported on nanocrystalline magnesium oxide for syngas production by CO2 reforming of CH4

    Institute of Scientific and Technical Information of China (English)

    Fereshteh Meshkani; Mehran Rezaei

    2011-01-01

    CO2 reforming of methane(CDRM)was carried out over MgO supported Ni catalysts with various Ni loadings.The preparation of MgO supported Ni catalysts via surfactant-assisted precipitation method led to the formation of a nanocrystalline carrier for nickel catalysts.The synthesized samples were characterized by XRD,N2 adsorption-desorption,H2 chemisorption,TPR,TPO and SEM techniques.It was found that the high catalytic activity and stability of the prepared catalysts could be attributable to high dispersion of reduced Ni species and basicity of support surface.In addition,the effect of feed ratio,nickel loading and GHSV on the catalytic performance of CDRM over the catalysts were investigated.

  11. Effect of Y{sub 2}O{sub 3} addition to Rh/Al{sub 2}O{sub 3} catalysts on the autothermal reforming of methane; Efeito da adicao de Y{sub 2}O{sub 3} a catalisadores de Rh/Al{sub 2}O{sub 3} na reforma autotermica do metano

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro, Vanessa Monteiro; Cardoso, Gabriel Alexandre Lima; Coutinho, Ana Carla da S. Lomba S.; Passos, Fabio Barboza [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Dept. de Engenharia Quimica e de Petroleo. Lab. de Reatores, Cinetica e Catalise (RECAT)]. E-mail: vanessafisqui@yahoo.com.br

    2008-07-01

    In this work, the effect of the addition of Y{sub 2}O{sub 3} (with 2%, 5% and 10% weight content) on Rh/{alpha}-Al{sub 2}O{sub 3} catalysts in the autothermal reforming reaction of methane to the production of hydrogen for fuel cells was investigated. The catalysts were characterized by the following techniques: N{sub 2} adsorption, H{sub 2} chemisorption, X-ray diffraction (XRD) and cyclohexane dehydrogenation reaction. The catalysts were also evaluated in the reaction of autothermal reforming. The catalyst with higher Y{sub 2}O{sub 3} content showed the best results both in the cyclohexane dehydrogenation rate and in the conversion of methane. (author)

  12. Field-Assisted and Thermionic Contributions to Conductance in SnO Thick-Films

    Directory of Open Access Journals (Sweden)

    C. Malagù

    2009-01-01

    Full Text Available A deep analysis of conductance in nanostructured SnO2 thick films has been performed. A model for field-assisted thermionic barrier crossing is being proposed to explain the film conductivity. The model has been applied to explain the behavior of resistance in vacuum of two sets of nanostructured thick-films with grains having two well-distinct characteristic radii (=25 nm and =125 nm. In the first case the grain radius is shorter than the depletion region width, a limit at which overlapping of barriers takes place, and in the second case it is longer. The behavior of resistance in the presence of dry air has been explained through the mechanism of barrier modulation through gas chemisorption.

  13. Formaldehyde molecule adsorbed on doped graphene: A first-principles study

    Science.gov (United States)

    Liu, Xu-Ying; Zhang, Jian-Min

    2014-02-01

    Adsorption of formaldehyde (H2CO) on B-, N-, Si-, Al-, Cr-, Mn-, and Au-doped graphene was theoretically studied using first-principles approach based on density functional theory in order to exploit their potential applications as H2CO gas sensors. The electronic and magnetic properties of the graphene-molecule adsorption adducts are strongly dependent on the dopants. H2CO molecule is adsorbed weakly on B- and N-doped graphene; in general, strong chemisorption is observed on Si-, Al-, Cr-, Mn-, and Au-doped graphene. The most stable adsorption geometries, adsorption energies, magnetic moments, charge transfers, and density of states of these systems are thoroughly discussed. This work reveals that the sensitivity of graphene-based chemical gas sensors for H2CO can be drastically improved by introducing appropriate dopant. Al and Mn are found to be the best choices among all the dopants.

  14. Formaldehyde molecule adsorbed on doped graphene: A first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xu-Ying; Zhang, Jian-Min, E-mail: jianm_zhang@yahoo.com

    2014-02-28

    Adsorption of formaldehyde (H{sub 2}CO) on B-, N-, Si-, Al-, Cr-, Mn-, and Au-doped graphene was theoretically studied using first-principles approach based on density functional theory in order to exploit their potential applications as H{sub 2}CO gas sensors. The electronic and magnetic properties of the graphene-molecule adsorption adducts are strongly dependent on the dopants. H{sub 2}CO molecule is adsorbed weakly on B- and N-doped graphene; in general, strong chemisorption is observed on Si-, Al-, Cr-, Mn-, and Au-doped graphene. The most stable adsorption geometries, adsorption energies, magnetic moments, charge transfers, and density of states of these systems are thoroughly discussed. This work reveals that the sensitivity of graphene-based chemical gas sensors for H{sub 2}CO can be drastically improved by introducing appropriate dopant. Al and Mn are found to be the best choices among all the dopants.

  15. Density functional theory study on the full ALD process of silicon nitride thin film deposition via BDEAS or BTBAS and NH3.

    Science.gov (United States)

    Huang, Liang; Han, Bo; Han, Bing; Derecskei-Kovacs, Agnes; Xiao, Manchao; Lei, Xinjian; O'Neill, Mark L; Pearlstein, Ronald M; Chandra, Haripin; Cheng, Hansong

    2014-09-14

    A detailed reaction mechanism has been proposed for the full ALD cycle of Si3N4 deposition on the β-Si3N4(0001) surface using bis(diethylamino)silane (BDEAS) or bis(tertiarybutylamino)silane (BTBAS) as a Si precursor with NH3 acting as the nitrogen source. Potential energy landscapes were derived for all elementary steps in the proposed reaction network using a periodic slab surface model in the density functional approximation. Although the dissociative reactivity of BTBAS was slightly better than that of BDEAS, the thermal deposition process was still found to be an inherently high temperature process due to the high activation energies during the dissociative chemisorption of both precursors and the surface re-amination steps. These results underline the need to develop new precursors and alternative nitrogen sources when low temperature thermal silicon nitride films are targeted.

  16. Electron emission degradation of nano-structured sp2-bonded amorphous carbon films

    Institute of Scientific and Technical Information of China (English)

    Lu Zhan-Ling; Wang Chang-Qing; Jia Yu; Zhang Bing-Lin; Yao Ning

    2007-01-01

    The initial field electron emission degradation behaviour of original nano-structured sp2-bonded amorphous carbon films has been observed.which can be attributed to the increase of the work function of the film in the field emission process analysed using a Fowler-Nordheim plot.The possible re.on for the change of work function is suggested to be the desorption of hydrogen from the original hydrogen termination film surface due to field emission current-induced local heating.For the explanation of the emission degradation behaviour of the nano-structured sp2-bonded amorphous carbon film,a cluster model with a series of graphite(0001) basal surfaces has been presented,and the theoretical calculations have been performed to investigate work functions of graphite(0001) surfaces with different hydrogen atom and ion chemisorption sites by using first principles method based on density functional theory-local density approximation.

  17. Eletrodos quimicamente modificados aplicados à eletroanálise: uma breve abordagem Chemically modified electrodes applyes to electroanalysis: a brief presentation

    Directory of Open Access Journals (Sweden)

    Maria de Fátima Brito Souza

    1997-04-01

    Full Text Available Chemically modified electrodes (CMEs have been subject of considerable attention since its inception about 23 years ago. CMEs result of a deliberate immobilization of a modifier agent onto the electrode surface obtained through chemical reactions, chemisorption, composite formation or polymer coating. This immobilization seeks transfer the physicochemical properties of the modifier to the electrode surface and thus to dictate and control the behavior of the electrode/solution interface. In recent years the interest in CMEs has increased particularly to enhance the sensitivity and/or the selectivity of electroanalytical techniques. In general higher sensitivity and/or selectivity may be achieved by exploiting one or more of the following phenomena: electrocatalysis, preconcentration and interferents exclusion. This paper deals with the application of CMEs in electroanalysis, including a brief presentation of the more general procedures that have been employed for the modification of electrode surfaces.

  18. Effect of Cobalt Particle Size on Acetone Steam Reforming

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Junming; Zhang, He; Yu, Ning; Davidson, Stephen; Wang, Yong

    2015-06-11

    Carbon-supported cobalt nanoparticles with different particle sizes were synthesized and characterized by complementary characterization techniques such as X-ray diffraction, N-2 sorption, acetone temperature-programmed desorption, transmission electron microscopy, and CO chemisorption. Using acetone steam reforming reaction as a probe reaction, we revealed a volcano-shape curve of the intrinsic activity (turnover frequency of acetone) and the CO2 selectivity as a function of the cobalt particle size with the highest activity and selectivity observed at a particle size of approximately 12.8nm. Our results indicate that the overall performance of acetone steam reforming is related to a combination of particle-size-dependent acetone decomposition, water dissociation, and the oxidation state of the cobalt nanoparticles.

  19. Surface features and catalytic performance of platinum/alumina catalysts in slurry-phase hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez-Ortiz, M.A.; Gonzalez-Marcos, M.P.; Arnaiz-Aguilar, S.; Gonzalez-Marcos, J.A.; Gonzalez-Velasco, J.R. (Univ. del Pais Vasco/Euskal Hirrika Unibertsitatea, Bilbao (Spain). Dept. de Ingenierlla Quimica)

    1993-11-01

    Several platinum catalysts supported on three commercial [gamma]-aluminas were prepared by impregnation and anionic exchange using aqueous solutions of H[sub 2]PtCl[sub 6]. A number of methods were used to characterize the precursors as well as the final catalysts, including TGA, TPR, and hydrogen chemisorption at 298 K. TPR measurements showed two reduction peaks for the catalysts: the first one corresponding to reduction of the metal precursor to platinum and the second one associated to formation of a surface complex, Pt-Al[sub 2]O[sub 3[minus]x], With partial reduction of the support. The activity of the different catalysts was tested in the slurry-phase hydrogenation of benzene. The results obtained in the activity measurements have been correlated to the characteristics of the catalysts.

  20. Biosorption of Azo dyes by spent Rhizopus arrhizus biomass

    Science.gov (United States)

    Salvi, Neeta A.; Chattopadhyay, S.

    2016-05-01

    In the present study, spent Rhizopus arrhizus biomass was used for the removal of six azo dyes from aqueous solutions. The dye removal capacity of the biomass was evaluated by conducting batch tests as a function of contact time, biomass dosage, pH and initial dye concentrations. The pseudo-second-order kinetic model fitted well with the experimental data with correlation coefficients greater than 0.999, suggesting that chemisorptions might be the rate limiting step. The equilibrium sorption data showed good fit to the Langmuir isotherm model. Among the six dyes tested, the maximum monolayer adsorption capacity for fast red A and metanil yellow was found to be 108.8 and 128.5 mg/g, respectively. These encouraging results suggest that dead Rhizopus arrhizus biomass could be a potential biomaterial for the removal of azo dyes from aqueous dye solution.

  1. An investigation of environmental effects on fatigue crack growth in Q1N (HY80) steel

    Science.gov (United States)

    Soboyejo, W. O.; Knott, J. F.

    1990-11-01

    Fatigue threshold tests have been conducted on through-thickness and semielliptic cracks in laboratory air, vacuum, and salt water at stress ratios (R = Kmin/Kmax @#@) of 0.2 and 0.7. The effects of stress ratio are rationalized by crack closure concepts. Environmental effects are explained by considerations of the irreversibility of slip at the crack tip and the role of debris on the fracture surfaces. Differences in the fatigue crack growth rates in the three environments are attributed largely to the extent of the irreversibility of slip due to the chemisorption of water/ water vapor at the crack tip. Debris in saltwater solutions is also shown to significantly affect the near-threshold growth through its influence on crack closure and the transportation of environment to the crack tip.

  2. Nitrogen-Doped Carbon Nanotube/Graphite Felts as Advanced Electrode Materials for Vanadium Redox Flow Batteries.

    Science.gov (United States)

    Wang, Shuangyin; Zhao, Xinsheng; Cochell, Thomas; Manthiram, Arumugam

    2012-08-16

    Nitrogen-doped carbon nanotubes have been grown, for the first time, on graphite felt (N-CNT/GF) by a chemical vapor deposition approach and examined as an advanced electrode for vanadium redox flow batteries (VRFBs). The unique porous structure and nitrogen doping of N-CNT/GF with increased surface area enhances the battery performance significantly. The enriched porous structure of N-CNTs on graphite felt could potentially facilitate the diffusion of electrolyte, while the N-doping could significantly contribute to the enhanced electrode performance. Specifically, the N-doping (i) modifies the electronic properties of CNT and thereby alters the chemisorption characteristics of the vanadium ions, (ii) generates defect sites that are electrochemically more active, (iii) increases the oxygen species on CNT surface, which is a key factor influencing the VRFB performance, and (iv) makes the N-CNT electrochemically more accessible than the CNT.

  3. Photocatalytic Synthesis of Hydrocarbon Oxygenates from C2H6 and CO2 over Pd-MoO3/SiO2 Catalyst

    Institute of Scientific and Technical Information of China (English)

    Xitao Wang; Zhong He; Shunhe Zhong; Xiufen Xiao

    2007-01-01

    Pd-MoO3/SiO2 catalyst has been prepared using the method of incipient wetness impregnation. The photo absorbing behaviors and chemisorbing properties of the catalyst have been characterized by UV-vis spectra and TPD-MS experiments. The results indicated that metal Pd loaded on MoO3/SiO2 has a significant effect on the photo absorbing performance of MoO3/SiO2, and an obvious blue shift of the absorption edge is produced. Under UV irradiation, the chemisorption state of CO2 undergoes decomposing process to form CO at 481 K, and a two-site adsorption state of ethane can be formed at around 496 K. Photo-oxidation of ethane using carbon dioxide can mainly produce propanal, ethanol and acetaldehyde in the temperature range of 353-423 K. The presence of metal Pd improves the catalytic activity remarkably.

  4. Required catalytic properties for alkane production from carboxylic acids: Hydrodeoxygenation of acetic acid

    Institute of Scientific and Technical Information of China (English)

    Zhong; He; Xianqin; Wang

    2013-01-01

    The supported Pt catalysts(1 wt%)were prepared by the incipient impregnation method and analyzed using synchrotron-based X-ray diffraction,BET surface area,oxygen adsorption,CO pulse chemisorption,temperature-programmed desorption(TPD)of acetic acid,H2-TPD,NH3-TPD,O2-TPD,and H2-TPR.The reactivity of Pt-based catalysts was studied using a fixed bed reactor at 300 C and 4 MPa for hydrodeoxygenation of acetic acid,where Pt/TiO2 was very selective for ethane production.TPD experiments revealed that several conditions must be satisfied to achieve this high selectivity to ethane from acetic acid,such as Pt sites,moderate acidity,and medium metal-oxygen bond strength in the oxide support.This work provides insights in developing novel catalytic materials for hydrocarbon productions from various organics including bio-fuels.

  5. Alloy Thin-films and Surfaces for New Materials. Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Sprunger, P.T.

    2003-08-10

    Within the framework of a DOE National Laboratory/EPSCoR state partnership, investigations by researchers at Louisiana State University and Oak Ridge National Laboratory were focused on revealing the unique nanophase properties of alloy thin-films and bimetallic surfaces. Employing a number of experimental preparation techniques and characterization probes (synchrotron-based angle-resolved and valence/core-level PES and variable-temperature STM/STS), the goal of this program was to elucidate of the interconnecting physical and chemical properties of a variety of alloy surfaces and thin-films, specifically, determining the correlation between atomic structure/composition, electronic structure, and catalytic/chemisorption properties of these nanoscale.

  6. Equilibrium and kinetic studies of adsorption of phosphate onto ZnCl2 activated coir pith carbon.

    Science.gov (United States)

    Namasivayam, C; Sangeetha, D

    2004-12-15

    Phosphate removal from aqueous solution was investigated using ZnCl(2)-activated carbon developed from coir pith, an agricultural solid waste. Studies were conducted to delineate the effect of contact time, adsorbent dose, phosphate concentration, pH, and temperature. The adsorption equilibrium data followed both Langmuir and Freundlich isotherms. Langmuir adsorption capacity was found to be 5.1 mg/g. Adsorption followed second-order kinetics. The removal was maximum in the pH range 3-10. pH effect and desorption studies showed that adsorption occurred by both ion exchange and chemisorption mechanisms. Adsorption was found to be spontaneous and endothermic. Effect of foreign ions on adsorption shows that perchlorate, sulfate, and selenite decreased the percent removal of phosphate.

  7. Interactions of amino acids with adatoms(Ti, C, O) decorated graphene via effect of charging

    Science.gov (United States)

    Salmankurt, Bahadır; Gürel, Hikmet Hakan

    2017-02-01

    As amino acids take an important role in biology, it is envisaged that understanding of their interactions with nanomate-rials can resolve critical problems in the field of biomedicine. Graphene, single atom thick hexagonal lattice of sp2-bonded carbon, can be used for this purpose. The remarkable properties of graphene sheets could facilitate their application in areas like hydrogen technology, electronics, and sensing. In this work, we report density functional theory calculations of the adsorption of Histidine and Leucine molecules on pristine and decorated (Ti,C and O) graphene. The obtained binding energies of molecules on graphene surface are in good agreement previous studies. The chemisorption is achieved when Graphene is decorated with Ti and C. It is also shown that how modify structural properties of the molecules on pristine Graphene by applied charging for the first time.

  8. Ultrasonic Extraction and TLC Determination of Glyphosate in the Spiked Red Soils

    Directory of Open Access Journals (Sweden)

    Sandra Babić

    2005-09-01

    Full Text Available Pesticides that get into soil bind mostly to its solid phase by physical or chemical processes. In the valley of the Neretva River the use of herbicides, especially of glyphosate is widespread and sometimes uncontrolled. In this work ultrasonic solvent extraction (USE followed by thin-layer chromatography (TLC was applied for determining glyphosate presence in soil. The experiments were conducted with two characterised soil types. The impact of soil composition on extraction efficiency is discussed. Chemical analysis showed that soil 1 contained much more iron and aluminium oxides than soil 2, which was richer in humic substances. Low glyphosate efficiency (ca 44 % in both soils could be attributed either to its binding to iron and aluminium oxides (soil 1, or to chemisorption on humic macromolecules (soil 2.

  9. Collisions between carbonaceous grains in the interstellar medium

    CERN Document Server

    Papoular, R J

    2004-01-01

    Semi-empirical molecular dynamics is used to simulate hydrocarbon grain sputtering and collisions which are extremely difficult to study experimentally. This microscopic and dynamic approach is particularly suited to high velocity impacts, where target destruction occurs far from equilibrium. A wide variety of processes are encountered, depending on grain size and velocity: vaporization, fragmentation, atomic implantation, sticking, elastic recoil, atomic chemisorption, H abstraction and H2 formation, etc. The impact-velocity threshold is about 10 km/s but complete grain destruction requires much higher velocities and nearly equal grain sizes. The main outcome of strong collisions is vaporization, i.e. formation of small molecules rather than solid fragments; most of the impact energy is carried away by these molecules in the form of kinetic energy. As a consequence, the energy left in the bulk is insufficient for shattering or even thermal processing. Grain size distribution is hardly affected by such collis...

  10. Hydroxyethyl cellulose as efficient organic inhibitor of zinc-carbon battery corrosion in ammonium chloride solution: Electrochemical and surface morphology studies

    Science.gov (United States)

    Deyab, M. A.

    2015-04-01

    Hydroxyethyl cellulose (HEC) has been investigated as corrosion inhibitor for zinc-carbon battery by polarization and electrochemical impedance spectroscopy (EIS) measurements. The obtained results show that the maximum inhibition efficiency by HEC in 26% NH4Cl solution at 300 ppm and 298 K is 92.07%. Tafel polarization studies reveal that HEC acts as an efficient mixed inhibitor. The corrosion rate is suppressed by the adsorption of HEC on the zinc surface. HEC adsorption obeys the Langmuir isotherm and the thermodynamic parameters Kads and Δ Gadso have been also calculated and discussed. Both physisorption and chemisorption may occur on the zinc surface. Surface characterization investigation using Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) is used to ascertain the nature of the protective film.

  11. Correlation between Fischer-Tropsch catalytic activity and composition of catalysts

    Directory of Open Access Journals (Sweden)

    Subbarao Duvvuri

    2011-11-01

    Full Text Available Abstract This paper presents the synthesis and characterization of monometallic and bimetallic cobalt and iron nanoparticles supported on alumina. The catalysts were prepared by a wet impregnation method. Samples were characterized using temperature-programmed reduction (TPR, temperature-programmed oxidation (TPO, CO-chemisorption, transmission electron microscopy (TEM, field emission scanning electron microscopy (FESEM-EDX and N2-adsorption analysis. Fischer-Tropsch synthesis (FTS was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/CO = 2 v/v and space velocity, SV = 12L/g.h. The physicochemical properties and the FTS activity of the bimetallic catalysts were analyzed and compared with those of monometallic cobalt and iron catalysts at similar operating conditions. H2-TPR analysis of cobalt catalyst indicated three temperature regions at 506°C (low, 650°C (medium and 731°C (high. The incorporation of iron up to 30% into cobalt catalysts increased the reduction, CO chemisorption and number of cobalt active sites of the catalyst while an opposite trend was observed for the iron-riched bimetallic catalysts. The CO conversion was 6.3% and 4.6%, over the monometallic cobalt and iron catalysts, respectively. Bimetallic catalysts enhanced the CO conversion. Amongst the catalysts studied, bimetallic catalyst with the composition of 70Co30Fe showed the highest CO conversion (8.1% while exhibiting the same product selectivity as that of monometallic Co catalyst. Monometallic iron catalyst showed the lowest selectivity for C5+ hydrocarbons (1.6%.

  12. Changes in the Vibrational Spectra of Zeolites Due to Sorption of Heavy Metal Cations

    Science.gov (United States)

    Król, M.; Mozgawa, W.; Barczyk, K.; Bajda, T.; Kozanecki, M.

    2013-11-01

    This work presents the results of spectroscopic (MIR and Raman) studies of zeolite structures after immobilization of heavy metal cations from aqueous solutions. The sorption of Ag+, Cu2+, Cd2+, Pb2+, Zn2+, and Cr3+ ions has been conducted on zeolites belonging to different structural groups, i.e., sodium forms of natural chabazite, mordenite, ferrierite, and clinoptilolite, as well as on synthetic zeolite Y. Systematic changes in intensities and positions of the bands corresponding to the characteristic ring vibrations have been observed in the measured spectra. The most visible changes are observed in the FT-IR spectra of the samples in the range of 850-450 cm-1, and in the Raman spectra in the range of 600-250 cm-1. Depending on the zeolite structure, the bands, which can be regarded as a kind of indicator of ion exchange, were indentifi ed. For example, in the case of IR spectra, these bands are at 766, 703, 648, 578, and 506 cm-1 for zeolite Y, at 733 and 560 cm-1 for mordenite, at 675 cm-1 for clinoptilolite, etc. The degree of changes depends on both the type of cation and its concentration in the initial solution. This is connected with the way of binding of metal ions to the zeolite aluminosilicate framework, i.e., a proportion of the ion exchange and chemisorption in the process. Cations mainly undergoing ion exchange, such as Cd2+ or Pb2+, have the greatest impact on the character of the spectra. On the other hand, Cr3+ ions practically do not modify the spectra of zeolites. Results of IR and Raman spectroscopic studies have been compared with those obtained by atomic absorption spectroscopy (AAS), from which the proportion of ion exchange to chemisorption in the process and the effective cation exchange capacity of the individual samples have been estimated.

  13. Decoration of gold nanoparticles with cysteine in solution: reactive molecular dynamics simulations

    Science.gov (United States)

    Monti, Susanna; Carravetta, Vincenzo; Ågren, Hans

    2016-06-01

    The dynamics of gold nanoparticle functionalization by means of adsorption of cysteine molecules in water solution is simulated through classical reactive molecular dynamics simulations based on an accurately parametrized force field. The adsorption modes of the molecules are characterized in detail disclosing the nature of the cysteine-gold interactions and the stability of the final material. The simulation results agree satisfactorily with recent experimental and theoretical data and confirm previous findings for a similar system. The covalent attachments of the molecules to the gold support are all slow physisorptions followed by fast chemisorptions. However, a great variety of binding arrangements can be observed. Interactions with the adsorbate caused surface modulations in terms of adatoms and dislocations which contributed to strengthen the cysteine adsorption.The dynamics of gold nanoparticle functionalization by means of adsorption of cysteine molecules in water solution is simulated through classical reactive molecular dynamics simulations based on an accurately parametrized force field. The adsorption modes of the molecules are characterized in detail disclosing the nature of the cysteine-gold interactions and the stability of the final material. The simulation results agree satisfactorily with recent experimental and theoretical data and confirm previous findings for a similar system. The covalent attachments of the molecules to the gold support are all slow physisorptions followed by fast chemisorptions. However, a great variety of binding arrangements can be observed. Interactions with the adsorbate caused surface modulations in terms of adatoms and dislocations which contributed to strengthen the cysteine adsorption. Electronic supplementary information (ESI) available: Different views of the AuNP surface coverage. Distance map describing the position of each molecule in relation to the others on the AuNP (alpha carbon distances). See DOI: 10.1039/C

  14. The selective hydrogenation of crotonaldehyde over bimetallic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Schoeb, Ann M. [Iowa State Univ., Ames, IA (United States)

    1997-10-17

    The selective hydrogenation of crotonaldehyde has been investigated over a monometallic Pt/SiO2 catalyst and platinum bimetallic catalysts where the second metal was either silver, copper, or tin. The effects of addition of a second metal to the Pt/SiO2 system on the selectivity to crotyl alcohol were investigated. The Pt-Sn bimetallic catalysts were characterized by hydrogen chemisorption, 1H NMR and microcalorimetry. The Pt-Ag/SiO2 and Pt-Cu/SiO2 catalysts were characterized by hydrogen chemisorption. Pt-Sn/SiO2 catalysts selectively hydrogenated crotonaldehyde to crotyl alcohol and the method of preparation of these catalysts affected the selectivity. The most selective Pt-Sn/SiO2 catalysts for the hydrogenation of crotonaldehyde to crotyl alcohol were those in which the Sn precursor was dissolved in a HCl solution. Sn increased both the rate of formation of butyraldehyde and the rate of formation of crotyl alcohol. The Pt/SiO2, Pt-Ag/SiO2 and Pt-Cu/SiO2 catalysts produced only butyraldehyde. Initial heats of adsorption (~90 kJ/mol) measured using microcalorimetry were not affected by the presence of Sn on Pt. We can conclude that there is no through metal electronic interaction between Pt and Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn had similar initial heats of adsorption coupled with the invariance of the 1H NMR Knight shift.

  15. a Photoemission Study of the Adsorption of Benzotriazole on Copper.

    Science.gov (United States)

    Fang, Bo-Shung

    1985-12-01

    A photoemission study was performed on the chemisorption of benzotriazole (BTA) on polycrystalline copper (clean and oxidized) surfaces to understand the corrosion inhibition mechanism. The energy distribution curves indicate benzotriazole bonding to copper through nitrogen lone pair orbitals. They also disagree with the models which suggest that the benzotriazole molecular plane is oriented parallel to the copper surface by showing a lack of (pi)-d interaction. The observed chemisorption of benzotriazole on atomi- cally clean copper surfaces at room temperature suggests that an oxide layer is not necessary for the adsorption of benzotriazole. No structural difference was observed in the photoemission studies on BTA-clean copper and BTA-cuprous oxide surface film. This results demonstrates the major role of the copper atom upon benzotriazole adsorption. A new model of the CuBTA chemisorbed structure is presented. The Cu-BTA polymer is formed by strong charge -transfer interac- tions between benzotriazole molecules instead of by BTA-Cu-BTA connections. It successfully interprets the experimental results from solubility and tarnish resistance tests on adsorbed films on copper surfaces. It also gives a reasonable explanation for the different inhibition coefficients among BTA-treated copper single crystal surfaces. This study leads to an understanding of the benzotriazole inhi- bition mechanism: (1) All the copper atoms can be bound to BTA nitrogen atoms and the absence of active surface sites prevents attack by corrosive ions. (2) The BTA molecule stands vertically, or nearly so, to the copper surface, but still allows the formation of a compact protective surface film. (3) The strong infinite polymer. chains stabilize the protective film and strengthen its inhibition capability. ('1)DOE Report IS-T-1196. This work was performed under contract No. W-7405-Eng-82 with the U.S. Department of Energy.

  16. Nanoscale Metal Oxide Semiconductors for Gas Sensing

    Science.gov (United States)

    Hunter, Gary W.; Evans, Laura; Xu, Jennifer C.; VanderWal, Randy L.; Berger, Gordon M.; Kulis, Michael J.

    2011-01-01

    A report describes the fabrication and testing of nanoscale metal oxide semiconductors (MOSs) for gas and chemical sensing. This document examines the relationship between processing approaches and resulting sensor behavior. This is a core question related to a range of applications of nanotechnology and a number of different synthesis methods are discussed: thermal evaporation- condensation (TEC), controlled oxidation, and electrospinning. Advantages and limitations of each technique are listed, providing a processing overview to developers of nanotechnology- based systems. The results of a significant amount of testing and comparison are also described. A comparison is made between SnO2, ZnO, and TiO2 single-crystal nanowires and SnO2 polycrystalline nanofibers for gas sensing. The TECsynthesized single-crystal nanowires offer uniform crystal surfaces, resistance to sintering, and their synthesis may be done apart from the substrate. The TECproduced nanowire response is very low, even at the operating temperature of 200 C. In contrast, the electrospun polycrystalline nanofiber response is high, suggesting that junction potentials are superior to a continuous surface depletion layer as a transduction mechanism for chemisorption. Using a catalyst deposited upon the surface in the form of nanoparticles yields dramatic gains in sensitivity for both nanostructured, one-dimensional forms. For the nanowire materials, the response magnitude and response rate uniformly increase with increasing operating temperature. Such changes are interpreted in terms of accelerated surface diffusional processes, yielding greater access to chemisorbed oxygen species and faster dissociative chemisorption, respectively. Regardless of operating temperature, sensitivity of the nanofibers is a factor of 10 to 100 greater than that of nanowires with the same catalyst for the same test condition. In summary, nanostructure appears critical to governing the reactivity, as measured by electrical

  17. A step towards molecular electronics. The ferrocene molecule on a metal-semiconductor system

    Energy Technology Data Exchange (ETDEWEB)

    Schmeidel, Jedrzej Piotr

    2012-05-14

    In the first part, the domain walls on Ag {radical}(3) x {radical}(3) are investigated and structural and electronic model are introduced and discussed. Furthermore, the temperature dependence is investigated, showing the Peierls-type transition along the domain wall chain. In the second part, the high resolution STM data of the local adsorption geometry of FDT on Ag {radical}(3)< x {radical}(3) are presented. The comparison of theoretical results obtained for the molecule, on Ag(lll) and Ag {radical}(3) x {radical}(3) surfaces, with STM measurement at RT, support the chemisorption with thiolate bonds to the Ag trimers on the HCT surface. The molecule is aligned with the Cp-Fe-Cp axis parallel to the surface, while the rotational freedom of the molecule is limited due to chemisorption. The presented adsorption model is supported by experiment and simulation. In the third part, the perfect Ag {radical}(3) x {radical}(3) is prepared and investigated by means of STM, focusing on structural and electronic characteristics. The different reconstructions and amounts of Ag on Si are investigated; the submonolayer amounts, Ag {radical}(3) x {radical}(3) wetting layers, perfect epitaxial layers and multilayer systems. The influence of wetting layer on electronic character of deposited Ag nanostructures is studied. The occurrence of effective single and double barriers in tunnelling microscopy and spectroscopy for the Ag {radical}(3) x <{radical}(3) system is investigated in the monolayer regime by varying the measurement and preparation conditions. The Coulomb Blockade oscillations are found for granular multilayer Ag films, whereas similar structures with existence of Ag {radical}(3) x {radical}(3) show only a single barrier characteristic. The vertical transport properties in this metal/ semiconductor system depend on the structure and bonding on the atomic scale and on the lateral two-dimensional properties of the interface.

  18. Synthesis and characterization of Co–Fe nanoparticles supported on mesoporous silicas

    Energy Technology Data Exchange (ETDEWEB)

    Bragança, L.F.F.P.G., E-mail: proffatimabra@gmail.com [Departamento de Engenharia Química e Petróleo, Universidade Federal Fluminense, Niterói, Rio de Janeiro (Brazil); Departamento de Química, Pontifícia Universidade Católica do Rio de Janeiro, Rua Marquês de São Vicente 225, 22453-900 Rio de Janeiro (Brazil); Avillez, R.R. [Departamento de Engenharia de Materiais, Pontifícia Universidade Católica do Rio de Janeiro, Rua Marquês de São Vicente 225, 22453-900 Rio de Janeiro (Brazil); Moreira, C.R. [Departamento de Química, Pontifícia Universidade Católica do Rio de Janeiro, Rua Marquês de São Vicente 225, 22453-900 Rio de Janeiro (Brazil); Pais da Silva, M.I., E-mail: isapais@puc-rio.br [Departamento de Química, Pontifícia Universidade Católica do Rio de Janeiro, Rua Marquês de São Vicente 225, 22453-900 Rio de Janeiro (Brazil)

    2013-02-15

    Co–Fe bimetallic samples containing 25 wt% total of metal content were prepared by incipient wetness impregnation of cobalt nitrate and iron nitrate salts over hexagonal mesoporous silica (HMS) and SBA-15 supports. Changes in the textural properties and reduction behavior were compared with monometallic cobalt/iron-based samples. The samples were characterized by N{sub 2} physisorption, X-ray diffraction (XRD), H{sub 2}-temperature programmed reduction (TPR), transmission electron microscopy (TEM) and H{sub 2} chemisorption. The amount of incorporated metal was estimated by atomic absorption spectroscopy (AAS). Morphological properties revealed that after introduction of the metal to the SBA-15 support, the specific area, pore volume and pore diameter decreased to a lesser extent for bimetallic samples. XRD measurements detected the formation of Co{sub 3}O{sub 4} and CoFe{sub 2}O{sub 4} phases for both bimetallic samples. TPR profiles indicated similar behavior for both the bimetallic and monometallic samples. Higher temperatures were observed for the reducibility of Co–Fe/HMS as compared to Co–Fe/SBA-15. Dispersion values of the bimetallic samples were higher than Fe monometallic samples and lower than Co monometallic samples according to hydrogen chemisorption. The particle size distribution of the bimetallic samples estimated by TEM microphotographs showed a smaller fraction of larger size particles for Co–Fe/SBA-15. - Highlights: ► Co–Fe samples supported on both SBA-15 and HMS mesoporous silicas were obtained. ► Co–Fe/HMS and Co–Fe/SBA-15 samples presented Co{sub 3}O{sub 4} (cubic) and CoFe{sub 2}O{sub 4} (cubic) phases. ► Co is lesser reduced than Fe in bimetallic samples. ► Co–Fe/HMS and Co–Fe/SBA-15 presented great mechanical stability. ► Bimetallic samples revealed smaller particles than the monometallic ones.

  19. Adsorption removal of Congo red from aqueous solution by polyhedral Cu{sub 2}O nanoparticles: Kinetics, isotherms, thermodynamics and mechanism analysis

    Energy Technology Data Exchange (ETDEWEB)

    Shu, Jinxia [Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002 (China); Wang, Zhonghua, E-mail: zhwangs@163.com [Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002 (China); Huang, Yijiang; Huang, Ni [Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002 (China); Ren, Chunguang [Graduate School of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, Nara 630-0192 (Japan); Zhang, Wei [College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China)

    2015-06-05

    Highlights: • Polyhedral Cu{sub 2}O NPs with rough surfaces were prepared by a one-pot sonochemical precipitation method. • The Cu{sub 2}O NPs show unprecedented adsorption capability toward Congo red. • CR adsorption onto Cu{sub 2}O is a spontaneous, endothermic and chemisorption process. • The Cu{sub 2}O adsorbent can be photocatalytically regenerated by visible light irradiation. - Abstract: Polyhedral cuprous oxide nanoparticles (Cu{sub 2}O NPs) with rough surfaces were prepared by a one-pot sonochemical precipitation method. The products were characterized by SEM, XRD, EDS, XPS, and UV–Vis DRS, respectively. The adsorption behavior of Congo red (CR) from aqueous solution onto the as-prepared Cu{sub 2}O NPs was systematically investigated. The equilibrium and kinetic studies suggested that the adsorption process followed Freundlich isotherm and pseudo-second order model, respectively. The as-prepared Cu{sub 2}O NPs exhibited remarkable adsorption properties toward CR. The maximum adsorption capacity at 20 °C was 3904 mg g{sup −1}, which was the highest reported value so far in adsorption removal of CR. Together with the evaluation of the thermodynamic parameters such as Gibbs free energy, enthalpy and entropy change, our results show that the adsorption of CR onto Cu{sub 2}O is a spontaneous, endothermic and chemisorption process. A putative interaction model between CR and Cu{sub 2}O NPs was proposed. Moreover, the Cu{sub 2}O adsorbent could be photocatalytically regenerated and reused without significant loss of its adsorption capability.

  20. Chemistry of the interaction between azole type corrosion inhibitor molecules and metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Kovacevic, Natasa [Department of Physical and Organic Chemistry, Jozef Stefan Institute, Jamova 39, SI-1000 Ljubljana (Slovenia); Kokalj, Anton, E-mail: tone.kokalj@ijs.si [Department of Physical and Organic Chemistry, Jozef Stefan Institute, Jamova 39, SI-1000 Ljubljana (Slovenia)

    2012-11-15

    By means of density functional theory calculations, it has been shown how typical organic corrosion inhibitors-molecules that have the ability to remarkably slow down the corrosion of metals and alloys-interact with bare surfaces of various types of metals. As representative model systems, benzimidazole and benzotriazole inhibitors on iron, copper, and aluminum surfaces are considered. It is found that bonding depends sensitively on the type of metal. On transition metals with open d-band the inhibitor molecules can chemisorb strongly either parallel to the surface with a pronounced {pi}-d hybridization or perpendicularly with unsaturated N atom(s) through {sigma}-molecular orbitals, whereas on transition metals with fully occupied d-band and on sp-metals the molecules weakly chemisorb only with the latter mode. In addition to neutral inhibitor molecules also inhibitors in deprotonated (anionic) and protonated (cationic) forms are considered, because many corrosion inhibitors possess acidic hydrogens as well as basic heteroatoms. It is shown that the chemisorptive bonding is far the strongest for deprotonated inhibitors and, moreover, that even protonated inhibitors may chemisorb, although such bonding is characteristic of more reactive metals. However adsorbed protonated inhibitors are likely to deprotonate on all considered metals, whereas further deprotonation from neutral to deprotonated form is more likely on more reactive metals. Highlights: Black-Right-Pointing-Pointer Bonding of azole corrosion inhibitors onto metal surfaces characterized by DFT calculations. Black-Right-Pointing-Pointer Adsorption bonding depends sensitively on the type of metal. Black-Right-Pointing-Pointer Azoles bond with either {pi}-system or {sigma}-orbitals to transition metals with open d-band. Black-Right-Pointing-Pointer Azoles bond with {sigma}-orbitals to transition metals with fully occupied d-band and to sp-metals. Black-Right-Pointing-Pointer Among various molecular forms

  1. Surface chemistry of group 11 atomic layer deposition precursors on silica using solid-state nuclear magnetic resonance spectroscopy

    Science.gov (United States)

    Pallister, Peter J.; Barry, Seán T.

    2017-02-01

    The use of chemical vapour deposition (CVD) and atomic layer deposition (ALD) as thin film deposition techniques has had a major impact on a number of fields. The deposition of pure, uniform, conformal thin films requires very specific vapour-solid reactivity that is largely unknown for the majority of ALD and CVD precursors. This work examines the initial chemisorption of several thin film vapour deposition precursors on high surface area silica (HSAS) using 13C, 31P, and quantitative 29Si nuclear magnetic resonance spectroscopy (NMR). Two copper metal precursors, 1,3-diisopropyl-imidazolin-2-ylidene copper (I) hexamethyldisilazide (1) and 1,3-diethyl-imidazolin-2-ylidene copper(I) hexamethyldisilazide (2), and one gold metal precursor, trimethylphosphine gold(III) trimethyl (3), are examined. Compounds 1 and 2 were found to chemisorb at the hydroxyl surface-reactive sites to form a ||-O-Cu-NHC surface species and fully methylated silicon (||-SiMe3, due to reactivity of the hexamethyldisilazane (HMDS) ligand on the precursor) at 150 °C and 250 °C. From quantitative 29Si solid-state NMR (SS-NMR) spectroscopy measurements, it was found that HMDS preferentially reacts at geminal disilanol surface sites while the copper surface species preferentially chemisorbed to lone silanol surface species. Additionally, the overall coverage was strongly dependent on temperature, with higher overall coverage of 1 at higher temperature but lower overall coverage of 2 at higher temperature. The chemisorption of 3 was found to produce a number of interesting surface species on HSAS. Gold(III) trimethylphosphine, reduced gold phosphine, methylated phosphoxides, and graphitic carbon were all observed as surface species. The overall coverage of 3 on HSAS was only about 10% at 100 °C and, like the copper compounds, had a preference for lone silanol surface reactive sites. The overall coverage and chemisorbed surface species have implications to the overall growth rate and purity of

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-09-09

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

  3. Probing hydrodesulfurization over bimetallic phosphides using monodisperse Ni2-xMxP nanoparticles encapsulated in mesoporous silica

    Science.gov (United States)

    Danforth, Samuel J.; Liyanage, D. Ruchira; Hitihami-Mudiyanselage, Asha; Ilic, Boris; Brock, Stephanie L.; Bussell, Mark E.

    2016-06-01

    Metal phosphide nanoparticles encapsulated in mesoporous silica provide a well-defined system for probing the fundamental chemistry of the hydrodesulfurization (HDS) reaction over this new class of hydrotreating catalysts. To investigate composition effects in bimetallic phosphides, the HDS of dibenzothiophene (DBT) was carried out over a series of Ni-rich Ni2-xMxP@mSiO2 (M = Co, Fe) nanocatalysts (x ≤ 0.50). The Ni2-xMxP nanoparticles (average diameters: 11-13 nm) were prepared by solution-phase arrested precipitation and encapsulated in mesoporous silica, characterized by a range of techniques (XRD, TEM, IR spectroscopy, BET surface area, CO chemisorption) and tested for DBT HDS activity and selectivity. The highest activity was observed for a Ni1.92Co0.08P@mSiO2 nanocatalyst, but the overall trend was a decrease in HDS activity with increasing Co or Fe content. In contrast, the highest turnover frequency (TOF) was observed for the most Co- and Fe-rich compositions based on sites titrated by CO chemisorption. IR spectral studies of adsorbed CO on the Ni2-xMxP@mSiO2 catalysts indicate that an increase in electron density occurs on Ni sites as the Co or Fe content is increased, which may be responsible for the increased TOFs of the catalytic sites. The Ni2-xMxP@mSiO2 nanocatalysts exhibit a strong preference for the direct desulfurization pathway (DDS) for DBT HDS that changes only slightly with increasing Co or Fe content.

  4. Adsorption of Cd(II) and Pb(II) by in situ oxidized Fe3O4 membrane grafted on 316L porous stainless steel filter tube and its potential application for drinking water treatment.

    Science.gov (United States)

    Zhu, Mengfei; Zhu, Li; Wang, Jianlong; Yue, Tianli; Li, Ronghua; Li, Zhonghong

    2017-03-08

    Removing heavy metal ions from aqueous solutions is one of the most challenging separations. In situ oxidized Fe3O4 membranes using 316L porous stainless steel filter tube have shown great potential for removing anion Cr(VI). Here we report the performances of the in situ oxidized Fe3O4 membranes for removing two toxic cations Cd(II) and Pb(II) commonly existing in water and their potential applications for drinking water purification. The membranes exhibited high removal efficiency: 97% at pH 9.0 for Cd(II) of 1.0 mg/L initial concentration and 100% at pH 5.0-6.0 for Pb(II) of 5.0 mg/L initial concentration. The maximum adsorption capabilities were estimated at 0.800 mg/g and 2.251 mg/g respectively for Cd(II) and Pb(II) at 318 K by the Langmuir model. Results of batch tests revealed the existence of electrostatic attraction and chemisorption. XRD and FT-IR analyses indicated that the chemisorption might be the insertion of Cd(II) and Pb(II) into the Fe3O4 crystal faces of 311 and 511 to form mononuclear or binuclear coordination with O atoms of Fe-O6 groups. Competitive adsorption of Cd(II) and Pb(II) in binary solutions revealed a preferential adsorption for Pb(II). Na2EDTA solution was used to regenerate the membranes, and the maximum desorption ratio was 90.29% and 99.75% respectively for Cd(II) and Pb(II). The membranes were able to efficiently lower Cd(II) and Pb(II) concentrations to meet the drinking water standards recommended by the World Health Organization and are promising for engineering applications aimed at drinking water purification.

  5. Mesoporous TiO2 Nanocrystals/Graphene as an Efficient Sulfur Host Material for High-Performance Lithium-Sulfur Batteries.

    Science.gov (United States)

    Li, Yuanyuan; Cai, Qifa; Wang, Lei; Li, Qingwei; Peng, Xiang; Gao, Biao; Huo, Kaifu; Chu, Paul K

    2016-09-14

    Rechargeable lithium-sulfur (Li-S) batteries are promising in high-energy storage due to the large specific energy density of about 2600 W h kg(-1). However, the low conductivity of sulfur and discharge products as well as polysulfide-shuttle effect between the cathode and anode hamper applications of Li-S batteries. Herein, we describe a novel and efficient S host material consisting of mesoporous TiO2 nanocrystals (NCs) fabricated in situ on reduced graphene oxide (rGO) for Li-S batteries. The TiO2@rGO hybrid can be loaded with 72 wt % sulfur. The strong chemisorption ability of the TiO2 NCs toward polysulfide combined with high electrical conductivity of rGO effectively localize the soluble polysulfide species within the cathode and facilitate electron and Li ions transport to/from the cathode materials. The sulfur-incorporated TiO2@rGO hybrid (S/TiO2@rGO) shows large capacities of 1116 and 917 mA h g(-1) at the current densities of 0.2 and 1 C (1 C = 1675 mA g(-1)) after 100 cycles, respectively. When the current density is increased 20 times from 0.2 to 4 C, 60% capacity is retained, thereby demonstrating good cycling stability and rate capability. The synergistic effects of TiO2 NCs toward effective chemisorption of polysulfides and conductive rGO with high electron mobility make a promising application of S/TiO2@rGO hybrid in high-performance Li-S batteries.

  6. New insights into the effects of alloying Pt with Ni on oxygen reduction reaction mechanisms in acid medium: a first-principles study.

    Science.gov (United States)

    Ou, Li-Hui

    2015-11-01

    The effects of alloying Pt with transition metal Ni on oxygen reduction reaction (ORR) mechanisms was investigated based on a systematic density functional theory (DFT) calculation explored in the present work. New insights into the ORR mechanisms were reported at the atomic level on Pt-segregated Pt3Ni(111). Only one molecular chemisorption state with the end-on OOH configuration was identified through geometry optimization and minimum energy path (MEP) analysis; top-bridge-top configuration as observed on pure Pt(111) was not identified on Pt-segregated Pt3Ni(111), indicating that alloying Pt with Ni influences the intermediates of ORR, and leads to only the dissociation mechanism of chemisorption state OOH species being involved in acid medium on Pt-segregated Pt3Ni(111). By contrast, the dissociation mechanisms of chemisorbed O2 molecule with top-bridge-top configuration and OOH species both were involved on pure Pt(111). The rds of the entire four-electron ORR was changed after Pt alloying with Ni. The rds of the entire ORR is the proton and electron transfer to O2 to form OOH on Pt-segregated Pt3Ni(111), whereas it is the reaction of O atom protonation to form OH species on pure Pt(111), indicating that sublayer Ni strongly influences the rds of ORR. The comparison of the ORR mechanisms explained that Pt3Ni alloy enhanced the ORR electrocatalytic activity more than pure Pt. The effect of electrode potential on ORR pathway on the pure Pt and Pt3Ni alloy was considered to obtain further insights into the electrochemical reduction of O2. Results showed that the proton and electron transfer becomes difficult at high potential. The ORR can easily proceed when the electrode potential lowers. For pure Pt- and Pt-based alloys, this phenomenon may imply the origin of the overpotential.

  7. Removal of Ni{sup 2+} and Cu{sup 2+} ions from aqueous solution on to lignite-based carbons

    Energy Technology Data Exchange (ETDEWEB)

    Samra, S.E. [University of Mansoura, Mansoura (Egypt). Faculty of Science, Dept. of Chemistry

    2000-07-01

    Non-activated lignites were prepared by the carbonization of Egyptian lignite in a limited quantity of air at 500{degree}C, 700 {degree}C and 900 {degree}C, respectively. Zinc chloride-activated carbons were also prepared by the carbonization of lignite with 20 wt%, 40 wt% and 60 wt% zinc chloride in a limited quantity of air at 600 {degree}C. The surface areas of the resulting samples were determined from nitrogen adsorption studies at 77 K and from carbon dioxide adsorption studies at 298 K. The functional acidic groups on the surface were determined by neutralization with aqueous solutions of NaHCO{sub 3}, Na{sub 2}CO{sub 3} and NaOH, respectively. The sorption of Ni{sup 2+} and Cu{sup 2+} ions on the prepared carbons as well as on the as-received lignite were investigated. The influence of the time of contact, the initial ion concentration and the temperature was studied and the kinetics of the process were investigated. Equilibrium sorption isotherms were determined and the results interpreted by applying the Freundlich and Langmuir equations. The surface area was found to generally increase with increasing carbonization temperature. For activated carbons, the surface area increased with an increase in the amount of zinc chloride used in the activation process. The chemisorption of Ni{sup 2+} and Cu{sup 2+} ions on lignite-based carbon was found to be a pseudo-second order process. The acid sites on the surface provide active sites for the chemisorption of Ni{sup 2+} and Cu{sup 2+} ions and a qualitative relationship was found to exist between the maximum sorption capacity of these metal ions and the total surface acidity.

  8. The Modification of Diphenyl Sulfide to Pd/C Catalyst and Its Application in Selective Hydrogenation of p-Chloronitrobenzene☆

    Institute of Scientific and Technical Information of China (English)

    Qunfeng Zhang; Chang Su; Jie Cen; Feng Feng; Lei Ma; Chunshan Lu; Xiaonian Li⁎

    2014-01-01

    In this study, diphenyl sulfide (Ph2S) was employed to prepare a series of Ph2S-modified Pd/C catalysts (Pd–Ph2S/C). Catalyst characterization carried out by Brunner–Emmet–Teller (BET), energy dispersive spectrom-eter (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and CO chemisorption uptake mea-surements suggested a chemical interaction between Ph2S and Pd. The ligand was preferably absorbed on the active site of Pd metal but after increasing the amount of Ph2S, the adsorption of Ph2S on Pd metal tended to be saturated and the excess of Ph2S partially adsorbed on the activated carbon. A part of Pd atoms without adsorbing any Ph2S stil existed, even for the saturated Pd–Ph2S/C catalyst. The Pd–Ph2S/C catalysts exhibited a good selectivity of p-chloroaniline (p-CAN) in the hydrogenation of p-chloronitrobenzene (p-CNB). However, the chemisorption between Ph2S and Pd was not so strong that part of Ph2S was leached from Pd–Ph2S/C catalyst during the hydrogenation, which caused the decline of the selectivity of p-CAN over the used Pd–Ph2S/C catalyst. Resulfidation of the used Pd–Ph2S/C catalyst was effective to resume its stability, and the regenerated Pd–Ph2S/C catalyst could be reused for at least ten runs with a stable catalytic performance.

  9. Quinoxaline derivatives as corrosion inhibitors for mild steel in hydrochloric acid medium: Electrochemical and quantum chemical studies

    Science.gov (United States)

    Olasunkanmi, Lukman O.; Kabanda, Mwadham M.; Ebenso, Eno E.

    2016-02-01

    The corrosion inhibition potential of four quinoxaline derivatives namely, 1-[3-(4-methylphenyl)-5-(quinoxalin-6-yl)-4,5-dihydropyrazol-1-yl]butan-1-one (Me-4-PQPB), 1-(3-(4-methoxyphenyl)-5-(quinoxalin-6-yl)-4,5-dihydropyrazol-1-yl)butan-1-one (Mt-4-PQPB), 1-[3-(3-methoxyphenyl)-5-(quinoxalin-6-yl)-4,5-dihydropyrazol-1-yl]butan-1-one (Mt-3-PQPB) and 1-[3-(2H-1,3-benzodioxol-5-yl)-5-(quinoxalin-6-yl)-4,5-dihydropyrazol-1-yl]butan-1-one (Oxo-1,3-PQPB) was studied for mild steel corrosion in 1 M HCl solution using electrochemical, spectroscopic techniques and quantum chemical calculations. The results of both potentiodynamic polarization and electrochemical impedance spectroscopic studies revealed that the compounds are mixed-type inhibitors and the order of corrosion inhibition efficiency at 100 ppm is Me-4-PQPB>Mt-3-PQPB>Oxo-1,3-PQPB>Mt-4-PQPB. Fourier transform infrared (FTIR) and ultraviolet-visible (UV-vis) spectroscopic analyses confirmed the presence of chemical interactions between the inhibitors and mild steel surface. The adsorption of the inhibitor molecules on mild steel surface was found to be both physisorption and chemisorption but predominantly chemisorption. The experimental data obey Langmuir adsorption isotherm. Scanning electron microscopy studies revealed the formation of protective films of the inhibitors on mild steel surface. Quantum chemical parameters obtained from density functional theory (DFT) calculations support experimental results.

  10. Effects of an iron-silicon material, a synthetic zeolite and an alkaline clay on vegetable uptake of As and Cd from a polluted agricultural soil and proposed remediation mechanisms.

    Science.gov (United States)

    Yao, Aijun; Wang, Yani; Ling, Xiaodan; Chen, Zhe; Tang, Yetao; Qiu, Hao; Ying, Rongrong; Qiu, Rongliang

    2017-04-01

    Economic and highly effective methods of in situ remediation of Cd and As polluted farmland in mining areas are urgently needed. Pot experiments with Brassica chinensis L. were carried out to determine the effects of three soil amendments [a novel iron-silicon material (ISM), a synthetic zeolite (SZ) and an alkaline clay (AC)] on vegetable uptake of As and Cd. SEM-EDS and XRD analyses were used to investigate the remediation mechanisms involved. Amendment with ISM significantly reduced the concentrations of As and Cd in edible parts of B. chinensis (by 84-94 % and 38-87 %, respectively), to levels that met food safety regulations and was much lower than those achieved by SZ and AC. ISM also significantly increased fresh biomass by 169-1412 % and 436-731 % in two consecutive growing seasons, while SZ and AC did not significantly affect vegetable growth. Correlation analysis suggested that it was the mitigating effects of ISM on soil acidity and on As and Cd toxicity, rather than nutrient amelioration, that contributed to the improvement in plant growth. SEM-EDS analysis showed that ISM contained far more Ca, Fe and Mn than did SZ or AC, and XRD analysis showed that in the ISM these elements were primarily in the form of silicates, oxides and phosphates that had high capacities for chemisorption of metal(loid)s. After incubation with solutions containing 800 mg L(-1) AsO4(2-) or Cd(2+), ISM bound distinctly higher levels of As (6.18 % in relative mass percent by EDS analysis) and Cd (7.21 % in relative mass percent by EDS analysis) compared to SZ and AC. XRD analysis also showed that ISM facilitated the precipitation of Cd(2+) as silicates, phosphates and hydroxides, and that arsenate combined with Fe, Al, Ca and Mg to form insoluble arsenate compounds. These precipitation mechanisms were much more active in ISM than in SZ or AC. Due to the greater pH elevation caused by the abundant calcium silicate, chemisorption and precipitation mechanisms in ISM

  11. A computational study on water adsorption on Cu{sub 2}O(1 1 1) surfaces: The effects of coverage and oxygen defect

    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); Feng, Gang, E-mail: fengg.sshy@sinopec.com [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001 (China); Shanghai Research Institute of Petrochemical Technology SINOPEC, Shanghai 201208 (China)

    2015-07-15

    Graphical abstract: Water adsorption on the clean and defective Cu{sub 2}O(1 1 1) surfaces with different coverages was investigated using spin-polarized density functional theory. - Highlights: • Only molecular H{sub 2}O chemisorption is preferred on clean Cu{sub 2}O(1 1 1) surface. • Ordered surface layer structures are observed at 1–2 ML H{sub 2}O adsorption. • The defect surface with oxygen vacancy favors dissociative H{sub 2}O adsorption. • The adsorption mechanism was analyzed on the basis of the density of states. - Abstract: The interaction of water with solid surfaces plays an important role in many chemical reactions. The present work investigates water adsorption on the clean and defective Cu{sub 2}O(1 1 1) surfaces using spin-polarized density functional theory. The results show that at low water coverage, only molecular H{sub 2}O chemisorption is preferred on clean Cu{sub 2}O(1 1 1) surface, and the water adsorption results in surface reconstruction. Up to 1 monolayer (ML), the adsorbed H{sub 2}O molecules interact with the coordinatively unsaturated Cu atoms as well as the coordinatively unsaturated surface oxygen atoms via H-bonding. Up to 2 ML, the adsorbed H{sub 2}O molecules interact with the coordinatively unsaturated surface oxygen atoms and the first layer adsorbed H{sub 2}O molecules via H-bonding. Ordered surface layer structures are observed at 1 and 2 ML H{sub 2}O adsorption. In contrast to the clean surface, the defect surface with oxygen vacancy favors dissociative H{sub 2}O adsorption with the dissociated OH group bridging the surface Cu atoms and the H atom on the coordinatively saturated third layer O atom. The adsorption mechanisms are analyzed on the basis of the total density of states. It is found that wet electron states on the clean and H{sub 2}O adsorbed Cu{sub 2}O(1 1 1) surfaces might be important for their photocatalytic properties. Water adsorption on Cu{sub 2}O surface is stronger than on MgO, Fe{sub 3}O{sub 4

  12. Surface modification of solid state gas sensors

    Science.gov (United States)

    Morris, Ljuibov

    The phenomenon of electrical conductivity being controlled by the chemical state of a surface grafted reactive centre, resulting in a room temperature gas response, is demonstrated. The reactive centres can be chosen to be specific to a particular gas, providing a route to new types of gas detectors tailored for a particular application. Generalization of the phenomenon was verified. Surface grafting of Ti, Ru and Pt centres onto SnO2; Ti and Pt centres onto Ti02 ; and Pt centres onto BaSn0.97Sb0.03O3 resulted in a room temperature gas sensitivity specific to each system. Surface grafting of Ru centres onto SnO2 resulted in additional electronic states in the SnO2 band gap associated with surface Ru species, revealed by XPS and correlated with resistance increase of the material. An electronic interaction between grafted Ru centres and the SnO2 support was manifested in conductivity being controlled by the surface state of the Ru. Variations in the chemical state of the surface grafted Ru caused by gas chemisorption were revealed by XPS and this was correlated with conductivity change measured as gas response of the device at room temperature. The samples were characterized by EXAFS to confirm the structure of the surface Ru species, TPD, UV- visible spectroscopy, XPS and electrical measurements. DFT molecular cluster calculations were also performed to ascertain the origin of the gas response. The mechanism of the room temperature CO response of SnO2 decorated with small Pt particles was refined. In this case Pt was applied by common impregnation techniques. The conductivity was shown to be controlled by the surface state of the Pt. The CO response at room temperature was found to be specific to the presence of Pt(II) species. The mechanism was assigned to CO chemisorption onto Pt(II), resulting in charge transfer, measured as conductivity increase. The samples were characterized by XPS, TPD, SEM, mass spectrometry and electrical measurements. Comparison of the

  13. Catalytic coal liquefaction. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Weller, S W

    1981-01-01

    Monolith catalysts of MoO/sub 3/-CoO-Al/sub 2/O/sub 3/ were prepared and tested for coal liquefaction in a stirred autoclave. In general, the monolith catalysts were not as good as particulate catalysts prepared on Corning alumina supports. Measurement of O/sub 2/ chemisorption and BET surface area has been made on a series of Co/Mo/Al/sub 2/O/sub 3/ catalysts obtained from PETC. The catalysts were derived from Cyanamid 1442A and had been tested for coal liquefaction in batch autoclaves and continuous flow units. MoO/sub 3/-Al/sub 2/O/sub 3/ catalysts over the loading range 3.9 to 14.9 wt % MoO/sub 3/ have been studied with respect to BET surface (before and after reduction), O/sub 2/ chemisorption at -78/sup 0/C, redox behavior at 500/sup 0/C, and activity for cyclohexane dehydrogenation at 500/sup 0/C. In connection with the fate of tin catalysts during coal liquefaction, calculations have been made of the relative thermodynamic stability of SnCl/sub 2/, Sn, SnO/sub 2/, and SnS in the presence of H/sub 2/, HCl, H/sub 2/S and H/sub 2/O. Ferrous sulfate dispersed in methylnaphthalene has been shown to be reduced to ferrous sulfide under typical coal hydroliquefaction conditions (1 hour, 450/sup 0/C, 1000 psi initial p/sub H/sub 2//). This suggests that ferrous sulfide may be the common catalytic ingredient when either (a) ferrous sulfate impregnated on powdered coal, or (b) finely divided iron pyrite is used as the catalyst. Old research on impregnated ferrous sulfate, impregnated ferrous halides, and pyrite is consistent with this assumption. Eight Co/Mo/Al/sub 2/O/sub 3/ catalysts from commercial suppliers, along with SnCl/sub 2/, have been studied for the hydrotreating of 1-methylnaphthalene (1-MN) in a stirred autoclave at 450 and 500/sup 0/C.

  14. Insight into chemoselectivity of nitroarene hydrogenation: A DFT-D3 study of nitroarene adsorption on metal surfaces under the realistic reaction conditions

    Science.gov (United States)

    Zhang, Lidong; Cao, Xiao-Ming; Hu, P.

    2017-01-01

    The adsorption of nitrobenzene and 4-nitrostyrene on the Pt(111) and the Au(111) surfaces under the general reaction condition of nitroarene catalytic hydrogenation is investigated utilizing periodic density functional theory calculations with the Grimme's empirical three-body dispersion correction to understand the influence of adsorption configurations on chemoselectivity of nitroarene compound hydrogenation. It is found that at the low coverage both nitrobenzene and 4-nitrostyrene tend to adsorb paralleling to the Pt(111) and the Au(111) surfaces. Based on the crystal orbital Hamilton population analysis, it is found that the chemical bonding between nitro group and Pt(111) surface is weak. The adsorption configurations of nitrobenzene and 4-nitrostyrene are determined by the chemisorption strength of phenyl group and vinyl group. Under the reaction condition, the 1/9 ML nitrobenzene and 4/9 ML hydrogen atom can be coadsorbed while the 1/6 ML 4-nitrostyrene and 1/3 ML hydrogen atom can be coadsorbed on Pt(111). With the increase of the coverage, nitrobenzene still remains its paralleled adsorption configuration while the adsorption configuration of 4-nitrostyrene is switched to the tilted adsorption configuration through vinyl group without the chemisorption of phenyl and nitro group on Pt(111). In addition, the competitive adsorption with hydrogen will not change the adsorption configuration of nitrobenzene and 4-nitrostyrene under the reaction condition. On Au(111), the physical adsorption strength determines the adsorption configuration. The paralleled adsorption with the shortest average distance between the adsorbate and Au(111) surface is preferred. At the paralleled adsorption configuration, the chemoselectivities of the hydrogenation on these functional groups are similar if only in terms of geometric configuration. However, the hydrogenation on nitro group encounters the problem of steric hindrance at the tilted adsorption configuration through vinyl

  15. Plasma immersion ion implantation: A viable candidate for low cost purification of mc-Si by nanocavities?

    Energy Technology Data Exchange (ETDEWEB)

    Kouadri-boudjelthia, E.-A., E-mail: e.kouadri@cder.dz [Centre de Développement des Energies Renouvelables, CDER, 16340 Algiers (Algeria); Ntsoenzok, E. [Conditions Extrêmes et Matériaux: Haute Température et Irradiation (CEMHTI), CNRS UPR 3079, 3A Rue de la Férollerie, 45071 Orléans Cedex 2 (France); Benoit, R. [Centre de Recherche sur la Matière Divisée (CRMD), 1B rue de la Férollerie, 45071 Orléans Cedex 2 (France); Regula, G. [Aix-Marseille Université, CNRS, IM2NP, UMR 7334, 13397 Marseille (France); Etienne, H.; Michel, T. [Ion Beam Services (IBS), Rue G. Imbert Prolongée, F-13790 Peynier (France); Ashok, S. [Pennsylvania State University, 212 Earth and Engineering Science Building, University Park, PA 16802 (United States)

    2016-01-01

    Highlights: • The ability of the H implantation by PIII, to form cavities in mc-Si. • The difference between PIII and Classical implantation (multi and mono-energy). • The good trapping ability in real conditions (low impurities concentration). - Abstract: A low-cost purification technique was evaluated on multicrystalline silicon (mc-Si). It consists of an efficient impurity trapping process involving nanocavities created by plasma immersion ion implantation (PIII). The study consisted of assessing (i) the creation of nanocavities by PIII and (ii) their ability to trap impurities in real conditions (without intentional contamination). Square pieces of p-type mc-Si samples, having a surface of 4 cm{sup 2} were used. They were implanted with hydrogen by PIII at 20 kV with a fluence of 5 × 10{sup 16} cm{sup −2} and then annealed for 30 min, in the temperature range 673–1273 K. The evolution of shape, size and spatial distribution of nanocavities was studied by transmission electron microscopy and time of flight secondary ion mass spectrometry in order to check both the formation of cavities and to test their ability to getter impurities by either precipitation or chemisorption. Results reveal surprisingly that, despite the triangular as-implanted H profile, nanocavities can be created by H-PIII, evidently because of the multi-energetic and high flux implantation (about 8 × 10{sup 13} cm{sup −2} s{sup −1}, 40–80 times greater than in conventional implantation) and that they are able to trap various impurities, initially present in mc-Si, such as Fe, Cu and Ni (according to their Gibbs energy), competing with the many existing gettering sites available in mc-Si, such as Si-related precipitates (oxygen, carbon, nitrogen or metal silicides), dislocations and grain boundaries. The area containing the biggest cavities have the highest density of gettering sites, especially for Cu, which can be trapped either by chemisorption (since it has higher binding

  16. COMBINED THEORETICAL AND EXPERIMENTAL INVESTIGATION OF MECHANISMS AND KINETICS OF VAPOR-PHASE MERCURY UPTAKE BY CARBONACOUES SURFACES

    Energy Technology Data Exchange (ETDEWEB)

    Radisav D. Vidic

    2002-05-01

    The first part of this study evaluated the application of a versatile optical technique to study the adsorption and desorption of model adsorbates representative of volatile polar (acetone) and non-polar (propane) organic compounds on a model carbonaceous surface under ultra high vacuum (UHV) conditions. The results showed the strong correlation between optical differential reflectance (ODR) and adsorbate coverage determined by temperature programmed desorption (TPD). ODR technique was proved to be a powerful tool to investigate surface adsorption and desorption from UHV to high pressure conditions. The effects of chemical functionality and surface morphology on the adsorption/desorption behavior of acetone, propane and mercury were investigated for two model carbonaceous surfaces, namely air-cleaved highly oriented pyrolytic graphite (HOPG) and plasma-oxidized HOPG. They can be removed by thermal treatment (> 500 K). The presence of these groups almost completely suppresses propane adsorption at 90K and removal of these groups leads to dramatic increase in adsorption capacity. The amount of acetone adsorbed is independent of surface heat treatment and depends only on total exposure. The effects of morphological heterogeneity is evident for plasma-oxidized HOPG as this substrate provides greater surface area, as well as higher energy binding sites. Mercury adsorption at 100 K on HOPG surfaces with and without chemical functionalities and topological heterogeneity created by plasma oxidation occurs through physisorption. The removal of chemical functionalities from HOPG surface enhances mercury physisorption. Plasma oxidation of HOPG provides additional surface area for mercury adsorption. Mercury adsorption by activated carbon at atmospheric pressure occurs through two distinct mechanisms, physisorption below 348 K and chemisorption above 348 K. No significant impact of oxygen functionalities was observed in the chemisorption region. The key findings of this study

  17. CO2 capture properties of lithium silicates with different ratios of Li2O/SiO2: an ab initio thermodynamic and experimental approach.

    Science.gov (United States)

    Duan, Yuhua; Pfeiffer, Heriberto; Li, Bingyun; Romero-Ibarra, Issis C; Sorescu, Dan C; Luebke, David R; Halley, J Woods

    2013-08-28

    The lithium silicates have attracted scientific interest due to their potential use as high-temperature sorbents for CO2 capture. The electronic properties and thermodynamic stabilities of lithium silicates with different Li2O/SiO2 ratios (Li2O, Li8SiO6, Li4SiO4, Li6Si2O7, Li2SiO3, Li2Si2O5, Li2Si3O7, and α-SiO2) have been investigated by combining first-principles density functional theory with lattice phonon dynamics. All these lithium silicates examined are insulators with band-gaps larger than 4.5 eV. By decreasing the Li2O/SiO2 ratio, the first valence bandwidth of the corresponding lithium silicate increases. Additionally, by decreasing the Li2O/SiO2 ratio, the vibrational frequencies of the corresponding lithium silicates shift to higher frequencies. Based on the calculated energetic information, their CO2 absorption capabilities were extensively analyzed through thermodynamic investigations on these absorption reactions. We found that by increasing the Li2O/SiO2 ratio when going from Li2Si3O7 to Li8SiO6, the corresponding lithium silicates have higher CO2 capture capacity, higher turnover temperatures and heats of reaction, and require higher energy inputs for regeneration. Based on our experimentally measured isotherms of the CO2 chemisorption by lithium silicates, we found that the CO2 capture reactions are two-stage processes: (1) a superficial reaction to form the external shell composed of Li2CO3 and a metal oxide or lithium silicate secondary phase and (2) lithium diffusion from bulk to the surface with a simultaneous diffusion of CO2 into the shell to continue the CO2 chemisorption process. The second stage is the rate determining step for the capture process. By changing the mixing ratio of Li2O and SiO2, we can obtain different lithium silicate solids which exhibit different thermodynamic behaviors. Based on our results, three mixing scenarios are discussed to provide general guidelines for designing new CO2 sorbents to fit practical needs.

  18. Measuring binding kinetics of aromatic thiolated molecules with nanoparticles via surface-enhanced Raman spectroscopy

    Science.gov (United States)

    Devetter, Brent M.; Mukherjee, Prabuddha; Murphy, Catherine J.; Bhargava, Rohit

    2015-05-01

    Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min-1. This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes.Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this

  19. Selectivity in the carbon-oxygen reaction

    Science.gov (United States)

    Skokova, Kristina A.

    The dependence of the carbon-oxygen reaction rate and the CO/COsb2 ratio on temperature, oxygen pressure, carbon crystallite size, concentration of surface C(O) complexes, and content of heteroatoms was studied. It was shown that the temperature dependence of the CO/COsb2 ratio obeys an Arrhenius-type relationship, but the pre-exponential factor and the activation energy depend on oxygen pressure and carbon nature. The Arrhenius parameters were found to be directly proportional to each other. This confirmed the importance of the compensation effect in carbon oxidation. It was explained by active site heterogeneity in carbon materials. For all experimental conditions, the CO/COsb2 ratio was lower for carbons with more ordered graphitic structure. It was shown that the CO/COsb2 ratio is inversely proportional to the surface coverage with reactive C(O) complexes. More ordered carbons were revealed to possess lower concentrations of stable complexes, higher surface coverages with reactive complexes and thus lower CO/COsb2 ratios. The influence of B and N heteroatoms on carbon reactivity and the CO/COsb2 ratio was studied. It was confirmed that B acts as an inhibitor of carbon oxidation due to the formation of a protective Bsb2Osb3 coating. The N presence in the carbon structure increases its rate of oxidation, maybe due to decreasing carbon crystallite dimensions. The CO/COsb2 ratio did not correlate with the N content in the carbon, but depended on the concentration of surface carbon-oxygen complexes. A new reaction mechanism is proposed. A key feature of the mechanism is that it takes into account the presence and mobility of oxygen atoms on the basal plane. It was shown with the aid of theoretical molecular orbital calculations that chemisorption on a pair of adjacent edge and basal sites is thermodynamically favorable as a parallel process to the generally accepted path of chemisorption on two edge carbon atoms. The former process can lead to the formation of a

  20. Photoelectrochemical properties of mesoporous NiO x deposited on technical FTO via nanopowder sintering in conventional and plasma atmospheres.

    Science.gov (United States)

    Awais, Muhammad; Dowling, Denis D; Decker, Franco; Dini, Danilo

    2015-01-01

    Nanoporous nickel oxide (NiO x ) has been deposited with two different procedures of sintering (CS and RDS). Both samples display solid state oxidation at about 3.1 V vs Li+/Li. Upon sensitization of CS/RDS NiO x with erythrosine b (ERY), nickel oxide oxidation occurs at the same potential. Impedance spectroscopy revealed a higher charge transfer resistance for ERY-sensitized RDS NiO x with respect to sensitized CS NiO x . This was due to the chemisorption of a larger amount of ERY on RDS with respect to CS NiO x . Upon illumination the photoinduced charge transfer between ERY layer and NiO x could be observed only with oxidized CS. Photoelectrochemical effects of sensitized RDS NiO x were evidenced upon oxide reduction. With the addition of iodine RDS NiOx electrodes could give the reduction iodine → iodide in addition to the reduction of RDS NiO x . p-type dye sensitized solar cells were assembled with RDS NiO x photocathodes sensitized either by ERY or Fast Green. Resulting overall efficiencies ranged between 0.02 and 0.04 % upon irradiation with solar spectrum simulator (I in: 0.1 W cm(-2)).

  1. Interaction between alkyl radicals and single wall carbon nanotubes.

    Science.gov (United States)

    Denis, Pablo A

    2012-06-30

    The addition of primary, secondary, and tertiary alkyl radicals to single wall carbon nanotubes (SWCNTs) was studied by means of dispersion corrected density functional theory. The PBE, B97-D, M06-L, and M06-2X functionals were used. Consideration of Van der Waals interactions is essential to obtain accurate addition energies. In effect, the enthalpy changes at 298 K, for the addition of methyl, ethyl, isopropyl, and tert-butyl radicals onto a (5,5) SWCNT are: -25.7, -25.1, -22.4, and -16.6 kcal/mol, at the M06-2X level, respectively, whereas at PBE/6-31G* level they are significantly lower: -25.0, -19.0, -16.7, and -5.0 kcal/mol respectively. Although the binding energies are small, the attached alkyl radicals are expected to be stable because of the large desorption barriers. The importance of nonbonded interactions was more noticeable as we moved from primary to tertiary alkyl radicals. Indeed, for the tert-butyl radical, physisorption onto the (11,0) SWCNT is preferred rather than chemisorption. The bond dissociation energies determined for alkyl radicals and SWCNT follow the trend suggested by the consideration of radical stabilization energies. However, they are in disagreement with some degrees of functionalization observed in recent experiments. This discrepancy would stem from the fact that for some HiPco nanotubes, nonbonded interactions with alkyl radicals are stronger than covalent bonds.

  2. The role of metal-support interaction for CO-free hydrogen from low temperature ethanol steam reforming on Rh-Fe catalysts.

    Science.gov (United States)

    Choong, Catherine K S; Chen, Luwei; Du, Yonghua; Schreyer, Martin; Daniel Ong, S W; Poh, Chee Kok; Hong, Liang; Borgna, Armando

    2017-02-08

    Rh-Fe catalysts supported on Ca-Al2O3, MgO and ZrO2 were evaluated in ethanol steam reforming at 623 K and compared to Rh catalysts on the same supports without iron promotion. The metal-support interaction among the three entities, i.e. Rh ↔ Fe2O3 ← support (ZrO2, MgO and Ca-Al2O3) was investigated using H2-chemisorption, TEM, XPS and in situ techniques such as DRIFTS, temperature-resolved XRD and XAS. As compared to the unpromoted Rh catalysts on the same supports, the CO selectivity is depressed in the presence of iron on Rh/MgO and Rh/Ca-Al2O3, the latter being significantly superior. The role of metal-support interaction for CO-free hydrogen generation was unravelled using a combination of techniques. It was found that the reducibility of iron oxide determines the extent of the strong metal support interaction between Rh and Fe2O3 and the reducibility of iron oxide was affected by the support. On Rh-Fe/Ca-Al2O3, a good balance of the interaction between Rh, Fe2O3 and Ca-Al2O3 prevents strong metal support interaction between Rh and Fe2O3 and thus promotes CO elimination via water-gas-shift reaction on Rh-FexOy sites.

  3. Synthesis of Ethanol from Syngas over Rh/MCM-41 Catalyst: Effect of Water on Product Selectivity

    Directory of Open Access Journals (Sweden)

    Luis Lopez

    2015-10-01

    Full Text Available The thermochemical processing of biomass is an alternative route for the manufacture of fuel-grade ethanol, in which the catalytic conversion of syngas to ethanol is a key step. The search for novel catalyst formulations, active sites and types of support is of current interest. In this work, the catalytic performance of an Rh/MCM-41 catalyst has been evaluated and compared with a typical Rh/SiO2 catalyst. They have been compared at identical reaction conditions (280 °C and 20 bar, at low syngas conversion (2.8% and at same metal dispersion (H/Rh = 22%. Under these conditions, the catalysts showed different product selectivities. The differences have been attributed to the concentration of water vapor in the pores of Rh/MCM-41. The concentration of water vapor could promote the water-gas-shift-reaction generating some extra carbon dioxide and hydrogen, which in turn can induce side reactions and change the product selectivity. The extra hydrogen generated could facilitate the hydrogenation of a C2-oxygenated intermediate to ethanol, thus resulting in a higher ethanol selectivity over the Rh/MCM-41 catalyst as compared to the typical Rh/SiO2 catalyst; 24% and 8%, respectively. The catalysts have been characterized, before and after reaction, by N2-physisorption, X-ray photoelectron spectroscopy, X-ray diffraction, H2-chemisorption, transmission electron microscopy and temperature programmed reduction.

  4. Insight into the effects of different ageing protocols on Rh/Al{sub 2}O{sub 3} catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Baohuai [Key Laboratory of Advanced Materials (MOE), School of Materials Science and Engineering, Tsinghua University, 100084 Beijing (China); Ran, Rui, E-mail: ranr@tsinghua.edu.cn [Key Laboratory of Advanced Materials (MOE), School of Materials Science and Engineering, Tsinghua University, 100084 Beijing (China); Cao, Yidan; Wu, Xiaodong; Weng, Duan [Key Laboratory of Advanced Materials (MOE), School of Materials Science and Engineering, Tsinghua University, 100084 Beijing (China); Fan, Jun [The Administrative Center for China' s Agenda 21, 100038 Beijing (China); Wu, Xueyuan [Key Laboratory of Advanced Materials (MOE), School of Materials Science and Engineering, Tsinghua University, 100084 Beijing (China)

    2014-07-01

    In this work, a catalyst of Rh loaded on Al{sub 2}O{sub 3} was prepared by impregnating method with rhodium nitrate aqueous solution as the Rh precursor. The catalyst was aged under different protocols (lean, rich, inert and cyclic) to obtain several aged samples. All the Rh/Al{sub 2}O{sub 3} samples were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, CO-chemisorption, H{sub 2}-temperature programmed reduction (H{sub 2}-TPR), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS). It was found that a specific ageing treatment could strongly affect the catalytic activity. The N{sub 2} aged and the H{sub 2} aged samples had a better catalytic activity for CO + NO reaction than the fresh sample while the air aged and the cyclic aged samples exhibited much worse activity. More surface Rh content and better reducibility were obtained in the N{sub 2} and the H{sub 2} aged samples and the Rh particles existed with an appropriate size, which were all favorable to the catalytic reaction. However, the air and the cyclic ageing protocols induced a strong interaction between Rh species and the Al{sub 2}O{sub 3} support, which resulted in a severe sintering of particles of Rh species and the loss of active sites. The structure evolution scheme of the catalysts aged in different protocols was also established in this paper.

  5. Removal of arsenic from water using manganese (III) oxide: Adsorption of As(III) and As(V).

    Science.gov (United States)

    Babaeivelni, Kamel; Khodadoust, Amid P

    2016-01-01

    Removal of arsenic from water was evaluated with manganese (III) oxide (Mn2O3) as adsorbent. Adsorption of As(III) and As(V) onto Mn2O3 was favorable according to the Langmuir and Freundlich adsorption equilibrium equations, while chemisorption of arsenic occurred according to the Dubinin-Radushkevich equation. Adsorption parameters from the Langmuir, Freundlich, and Temkin equations showed a greater adsorption and removal of As(III) than As(V) by Mn2O3. Maximum removal of As(III) and As(V) occurred at pH 3-9 and at pH 2, respectively, while removal of As(V) in the pH range of 6-9 was 93% (pH 6) to 61% (pH 9) of the maximum removal. Zeta potential measurements for Mn2O3 in As(III) was likely converted to As(V) solutions indicated that As(III) was likely converted to As(V) on the Mn2O3 surface at pH 3-9. Overall, the effective Mn2O3 sorbent rapidly removed As(III) and As(V) from water in the pH range of 6-9 for natural waters.

  6. Removal of yellow 5 by a zeolitic material conditioned with iron; Remocion de amarillo 5 por un material zeolitico acondicionado con hierro

    Energy Technology Data Exchange (ETDEWEB)

    Alcantara C, A.

    2010-07-01

    The waste waters are at the present time a serious problem because are contaminated by diverse industrial wastes among which are azo dyes used to dye a lot of products, and although there are various methods for the removal of these colorants do not are effective sufficiently, so that diverse techniques more sophisticated have been proposed, such as the elimination by sorption processes. Zeolites are materials found in various regions of Mexico and due to have a good sorption capacity are used to remove metals. In this paper a zeolitic material of the Chihuahua State was conditioned with FeCl{sub 3} and used for remove yellow 5 (tartrazine) in aqueous solutions, also the sorption capacity of modified zeolite with FeCl{sub 3} was examined for the azo dy yellow 5 in aqueous solutions. The sorption kinetics results was adapted to the pseudo second order model, indicating that the process is chemisorption, the sorption isotherms at different temperatures were adjusted to the Langmuir-Freundlich model, which usually it is adapt to systems with heterogeneous adsorbents. On the other hand, the ph value of the aqueous solutions does not affect on the sorption of this dye by the zeolitic material. (Author)

  7. Promotion Effects of Nickel Catalysts of Dry Reforming with Methane

    Institute of Scientific and Technical Information of China (English)

    YAN,Zi-Feng(阎子峰); DING,Rong-Gang(丁荣刚); LIU,Xin-Mei(刘欣梅); SONG,Lin-Hua(宋林花)

    2001-01-01

    The promotion effects of nickel catalyst of dry reforming with methane were extensively investigated by means of XRD,SEM, EDX, N2-adsorption and H2-adsorption. XRD characterization indicated that good dispersion of nickel oxide and MgO promoter is achieved over γ-Al2O3 support. Addition of MgO promoter effectively retards the formation of NiS12O4 phase. SEM and EDX analysis exhibited that the addition ofrare-earth metal oxide CeO2 effectively promotes the Ni metal dispersion on the surface of the catalysts despite of undesirable self-dispersion of CeO2 promoter. Furthermore, the nickel component is gradually dispersed on the surface of the support following the exposure to reaction gas mixture for a period of time. The addition of MgO inhibited the self-dispersion and promotion effect of CeO2 on Ni dispersion on the catalysts. H2 chemisorption revealed that the addition of the alkaline oxide MgO promoter significantly prohibits the metal dispersion on the catalyst. Inappropriate promoter addition can result in sharp decrease of the metal dispersion. N2-adsorption indicated that oxide promoter was mostly concentrated on the outer layer of the alumina support while the nickel metal was generally dispersed in the support pores. Addition of promoters contributed to more reduction in mesopore volume.

  8. Al-doped graphene as a new nanostructure adsorbent for some halomethane compounds: DFT calculations

    Science.gov (United States)

    Rad, Ali Shokuhi

    2016-03-01

    We have studied the electronic structure and property of pristine as well as Al-doped graphene sheets towards adsorption of some halomethane compounds (trichloromethane, dichloromethane, and difluoromethane) using density functional theory (DFhsT) calculations. The adsorption energies have been calculated for each adsorbed-adsorbent system. Based on our results, compared to pristine graphene, the Al-doped graphene causes significant adsorption energy, higher charge transferring, and smaller bond distances to halomethane compounds. Our calculated adsorption energies of trichloromethane, dichloromethane, and difluoromethane on Al-doped graphene were - 54.1, - 68.3, and - 123.2 kJ mol- 1, respectively, which are categorized in the chemisorption region while the adsorption of these molecules on pristine graphene release insignificant energies which correspond to very weak adsorption on it. Furthermore, we used charge transfer analysis to search the amount of electron allocation. Orbital analysis including the density of states (DOS) was done to find the possible orbital hybridization between adsorbates and two graphene sheets. These results imply the suitability of Al-doped graphene as a good adsorbent/sensor for halomethane compounds.

  9. Enhanced capture of elemental mercury by bamboo-based sorbents

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Zengqiang [State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan, Hubei 430074 (China); Xiang, Jun, E-mail: xiangjun@mail.hust.edu.cn [State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan, Hubei 430074 (China); Su, Sheng, E-mail: susheng_sklcc@hotmail.com [State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan, Hubei 430074 (China); Zeng, Hancai; Zhou, Changsong; Sun, Lushi; Hu, Song; Qiu, Jianrong [State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan, Hubei 430074 (China)

    2012-11-15

    Highlights: Black-Right-Pointing-Pointer The KI-modified BC has excellent capacity for elemental mercury removal. Black-Right-Pointing-Pointer The chemisorption plays a dominant role for the modified BC materials. Black-Right-Pointing-Pointer The BC-I has strong anti-poisoning ability with the presence of NO or SO{sub 2}. - Abstract: To develop cost-effective sorbent for gas-phase elemental mercury removal, the bamboo charcoal (BC) produced from renewable bamboo and KI modified BC (BC-I) were used for elemental mercury removal. The effect of NO, SO{sub 2} on gas-phase Hg{sup 0} adsorption by KI modified BC was evaluated on a fixed bed reactor using an online mercury analyzer. BET surface area analysis, temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) were used to determine the pore structure and surface chemistry of the sorbents. The results show that KI impregnation reduced the sorbents' BET surface area and total pore volume compared with that of the original BC. But the BC-I has excellent adsorption capacity for elemental mercury at a relatively higher temperature of 140 Degree-Sign C and 180 Degree-Sign C. The presence of NO or SO{sub 2} could inhibit Hg{sup 0} capture, but BC-I has strong anti-poisoning ability. The specific reaction mechanism has been further analyzed.

  10. Catalytic oxidation of volatile organic compounds (n-hexane, benzene, toluene, o-xylene promoted by cobalt catalysts supported on γ-Al2O3-CeO2

    Directory of Open Access Journals (Sweden)

    R. Balzer

    2014-09-01

    Full Text Available Cobalt catalysts supported on γ-alumina, ceria and γ-alumina-ceria, with 10 or 20%wt of cobalt load, prepared by the wet impregnation method and characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, field emission transmission electron microscopy (FETEM, N2 adsorption-desorption isotherms (BET/BJH methods, energy-dispersive X-ray spectroscopy (EDX, X-ray photoemission spectroscopy (XPS, O2-chemisorption and temperature programmed reduction (TPR were used to promote the oxidation of volatile organic compounds (n-hexane, benzene, toluene and o-xylene. For a range of low temperatures (50-350 °C, the activity of the catalysts with a higher cobalt load (20% wt was greater than that of the catalysts with a lower cobalt load (10% wt. The Co/γ-Al2O3-CeO2 catalytic systems presented the best performances. The results obtained in the characterization suggest that the higher catalytic activity of the Co20/γ-Al2O3-CeO2 catalyst may be attributed to the higher metal content and amount of oxygen vacancies, as well as the effects of the interaction between the cobalt and the alumina and cerium oxides.

  11. Active carbon-ceramic sphere as support of ruthenium catalysts for catalytic wet air oxidation (CWAO) of resin effluent.

    Science.gov (United States)

    Liu, Wei-Min; Hu, Yi-Qiang; Tu, Shan-Tung

    2010-07-15

    Active carbon-ceramic sphere as support of ruthenium catalysts were evaluated through the catalytic wet air oxidation (CWAO) of resin effluent in a packed-bed reactor. Active carbon-ceramic sphere and ruthenium catalysts were characterized by N(2) adsorption and chemisorption measurements. BET surface area and total pore volume of active carbon (AC) in the active carbon-ceramic sphere increase with increasing KOH-to-carbon ratio, and AC in the sample KC-120 possesses values as high as 1100 m(2) g(-1) and 0.69 cm(3) g(-1) (carbon percentage: 4.73 wt.%), especially. Active carbon-ceramic sphere supported ruthenium catalysts were prepared using the RuCl(3) solution impregnation onto these supports, the ruthenium loading was fixed at 1-5 wt.% of AC in the support. The catalytic activity varies according to the following order: Ru/KC-120>Ru/KC-80>Ru/KC-60>KC-120>without catalysts. It is found that the 3 wt.% Ru/KC-120 catalyst displays highest stability in the CWAO of resin effluent during 30 days. Chemical oxygen demand (COD) and phenol removal were about 92% and 96%, respectively at the reaction temperature of 200 degrees C, oxygen pressure of 1.5 MPa, the water flow rate of 0.75 L h(-1) and the oxygen flow rate of 13.5 L h(-1).

  12. Catalytic performance of V2O5-MoO3/γ-Al2O3 catalysts for partial oxidation of n-hexane1

    Science.gov (United States)

    Mahmoudian, R.; Khodadadi, Z.; Mahdavi, Vahid; Salehi, Mohammed

    2016-01-01

    In the current study, a series of V2O5-MoO3 catalyst supported on γ-Al2O3 with various V2O5 and MoO3 loadings was prepared by wet impregnation technique. The characterization of prepared catalysts includes BET surface area, powder X-ray diffraction (XRD), and oxygen chemisorptions. The partial oxidation of n-hexane by air over V2O5-MoO3/γ-Al2O3 catalysts was carried out under flow condition in a fixed bed glass reactor. The effect of V2O5 loading, temperature, MoO3 loading, and n-hexane LHSV on the n-hexane conversion and the product selectivity were investigated. The partial oxygenated products of n-hexane oxidation were ethanol, acetic anhydride, acetic acid, and acetaldehyde. The 10% V2O5-1%MoO3/γ-Al2O3 was found in most active and selective catalyst during partial oxidation of n-hexane. The results indicated that by increasing the temperature, the n-hexane conversion increases as well, although the selectivity of the products passes through a maximum by increasing the temperature.

  13. Liquid phase adsorption of Crystal violet onto activated carbons derived from male flowers of coconut tree.

    Science.gov (United States)

    Senthilkumaar, S; Kalaamani, P; Subburaam, C V

    2006-08-25

    Adsorption of Crystal violet, a basic dye onto phosphoric and sulphuric acid activated carbons (PAAC and SAAC), prepared from male flowers coconut tree has been investigated. Equilibrium data were successfully applied to study the kinetics and mechanism of adsorption of dye onto both the carbons. The kinetics of adsorption was found to be pseudo second order with regard to intraparticle diffusion. The pseudo second order is further supported by the Elovich model, which in turn intensifies the fact of chemisorption of dye onto both the carbons. Quantitative removal of dye at higher initial pH of dye solution reveals the basic nature of the Crystal violet and acidic nature of the activated carbons. Influence of temperature on the removal of dye from aqueous solution shows the feasibility of adsorption and its endothermic nature. Mass transfer studies were also carried out. The adsorption capacities of both the carbons were found to be 60.42 and 85.84 mg/g for PAAC and SAAC, respectively. Langmuir's isotherm data were used to design single-stage batch adsorption model.

  14. Site-specific dissociation dynamics of H{sub 2}/D{sub 2} on Ag(111) and Co(0001) and the validity of the site-averaging model

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Xixi [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States); Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China); Jiang, Bin [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States); Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (China); Xie, Daiqian, E-mail: dqxie@nju.edu.cn, E-mail: hguo@unm.edu [Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Guo, Hua, E-mail: dqxie@nju.edu.cn, E-mail: hguo@unm.edu [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)

    2015-09-21

    Dissociative chemisorption of polyatomic molecules on metal surfaces involves high-dimensional dynamics, of which quantum mechanical treatments are computationally challenging. A promising reduced-dimensional approach approximates the full-dimensional dynamics by a weighted average of fixed-site results. To examine the performance of this site-averaging model, we investigate two distinct reactions, namely, hydrogen dissociation on Co(0001) and Ag(111), using accurate first principles potential energy surfaces (PESs). The former has a very low barrier of ∼0.05 eV while the latter is highly activated with a barrier of ∼1.15 eV. These two systems allow the investigation of not only site-specific dynamical behaviors but also the validity of the site-averaging model. It is found that the reactivity is not only controlled by the barrier height but also by the topography of the PES. Moreover, the agreement between the site-averaged and full-dimensional results is much better on Ag(111), though quantitative in neither system. Further quasi-classical trajectory calculations showed that the deviations can be attributed to dynamical steering effects, which are present in both reactions at all energies.

  15. A new surface catalytic model for silica-based thermal protection material for hypersonic vehicles

    Directory of Open Access Journals (Sweden)

    Li Kai

    2015-10-01

    Full Text Available Silica-based materials are widely employed in the thermal protection system for hypersonic vehicles, and the investigation of their catalytic characteristics is crucially important for accurate aerothermal heating prediction. By analyzing the disadvantages of Norman’s high and low temperature models, this paper combines the two models and proposes an eight-reaction combined surface catalytic model to describe the catalysis between oxygen and silica surface. Given proper evaluation of the parameters according to many references, the recombination coefficient obtained shows good agreement with experimental data. The catalytic mechanisms between oxygen and silica surface are then analyzed. Results show that with the increase of the wall temperature, the dominant reaction contributing to catalytic coefficient varies from Langmuir–Hinshelwood (LH recombination (TW  1350 K. The surface coverage of chemisorption areas varies evidently with the dominant reactions in the high temperature (HT range, while the surface coverage of physisorption areas varies within quite low temperature (LT range (TW < 250 K. Recommended evaluation of partial parameters is also given.

  16. Structural and Electronic Properties of Folic Acid Adsorption on the Carbon Nanotubes: A Density Functional Theory Study

    Directory of Open Access Journals (Sweden)

    Shahla Hamedani

    2015-03-01

    Full Text Available In this study, we studied the adsorption behavior of folic acid on the (5,0 zigzag and (5,5 armchair single-walled carbon nanotube (SWCNT by Density Functional Theory (DFT. Geometry optimizations were carried out at the B3LYP/6-31 G* level of theory using the Gaussian 09 suite of programs. The adsorption energies, the quantum molecular descriptors analysis and the structural changes at the adsorption site are indicative of chemisorption (adsorption energy -31.673 kcal/mol on the zigzag SWCNT surface, while the adsorption is physical (adsorption energy -9.70 kcal/mol in nature on the armchair SWCNT surface. The density of the states (DOS Plots, Natural bond orbital (NBO analysis, and HOMO and LUMO are witness to the substantial changes in the electronic properties of the SWCNT systems after the attachment adsorbed species with the tube surface. These results are extremely relevant in order to diagnosis the potential applications of carbon nanotubes as drug delivery systems.

  17. Adsorptive Removal of Reactive Black 5 from Wastewater Using Bentonite Clay: Isotherms, Kinetics and Thermodynamics

    Directory of Open Access Journals (Sweden)

    Muhammad Tahir Amin

    2015-11-01

    Full Text Available The studies of the kinetics and isotherms adsorption of the Reactive Black 5 (RB5 onto bentonite clay were explored in a batch study in a laboratory. The maximum RB5 adsorption conditions of bentonite clay were optimized such as shaking speed (100 rpm, temperature (323 K, pH (10, contact time (40 min, initial dye concentration (170 mg·L−1, and particle size (177 µm. The adsorbent surface was characterized using Fourier Transform Infrared Spectroscopy spectroscopy. The mechanisms and characteristic parameters of the adsorption process were analyzed using two parameter isotherm models which revealed the following order (based on the coefficient of determination: Harkin-Jura (0.9989 > Freundlich (0.9986 and Halsey (0.9986 > Langmuir (0.9915 > Temkin (0.9818 > Dubinin–Radushkevich (0.9678. This result suggests the heterogeneous nature of bentonite clay. Moreover, the adsorption process was chemisorption in nature because it follows the pseudo-second order reaction model with R2 value of 0.9998, 0.9933 and 0.9891 at 25, 75 and 100 mg·L−1 RB5 dye in the solution, respectively. Moreover, based on the values of standard enthalpy, Gibbs free energy change, and entropy, bentonite clay showed dual nature of exothermic and endothermic, spontaneous and non-spontaneous as well as increased and decreased randomness at solid–liquid interface at 303–313 K and 313–323 K temperature, respectively.

  18. A surface-chemistry study of barium ferrite nanoplates with DBSa-modified surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Lisjak, Darja, E-mail: darja.lisjak@ijs.si [Jožef Stefan Institute, Ljubljana (Slovenia); Ovtar, Simona; Kovač, Janez [Jožef Stefan Institute, Ljubljana (Slovenia); Gregoratti, Luca; Aleman, Belen; Amati, Matteo [Elettra – Sincrotrone Trieste S.C.p.A. di interesse nazionale, Trieste (Italy); Fanetti, Mattia [University of Nova Gorica, Nova Gorica (Slovenia); Istituto Officina dei Materiali CNR, Area Science Park, Trieste (Italy); Makovec, Darko [Jožef Stefan Institute, Ljubljana (Slovenia)

    2014-06-01

    Barium ferrite (BaFe{sub 12}O{sub 19}) is a ferrimagnetic oxide with a high magnetocrystalline anisotropy that can be exploited in magnetically aligned ceramics or films for self-biased magnetic applications. Magnetic alignment of the films can be achieved by the directed assembly of barium ferrite nanoplates. In this investigation the nanoplates were synthesized hydrothermally and suspended in 1-butanol using dodecylbenzene sulphonic acid (DBSa) as a surfactant. They were then deposited in an electric or magnetic field on flat substrates and exhibited a significant preferential alignment in the plane of the substrate, allowing a differentiation between the analysis of their basal and side planes using scanning photoelectron microscopy with a lateral resolution down to 100 nm. The surface chemistry of the nanoplates was additionally studied with X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry. For a comparison, bare barium ferrite nanoplates were also analyzed after decomposing the DBSa at 460 °C. The deviation of the surface chemistry from the stoichiometric composition was observed and the adsorption of the DBSa molecules on the nanoplates was confirmed with all three methods. Different types of bonding (physi- or chemisorption) were possible and considered with respect to the assembly of the barium ferrite nanoplates into anisotropic magnetic films.

  19. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design

    Science.gov (United States)

    Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

    2016-04-01

    Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

  20. ANTIMICROBIAL TEXTILE PREPARED BY SILVER DEPOSITION ON DIELECTRIC BARRIER DISCHARGE TREATED COTTON/POLYESTER FABRIC

    Directory of Open Access Journals (Sweden)

    Mirjana Kostić

    2008-11-01

    Full Text Available The objective of this research was to impart the additional value on cotton//polyester (Co/PES fabrics (i.e. antimicrobial properties to improve the quality of life and thus to tap new markets with the product. In this paper, silver ions were incorporated in Co/PES fabrics by chemisorptions into the fabric previously treated in a dielectric barrier discharge (DBD. A series of the DBD fabric treatments were done in order to determine the most suitable experimental conditions for the DBD activation of the fabric surface, while the optimal conditions for silver ions sorption by Co/PES fabrics were determined by changing sorption conditions. The antimicrobial Co/PES fabrics prepared by dielectric barrier discharge mediated silver deposition show an antimicrobial activity against tested pathogens: S. aureus, E. coli, and C. albicans under in vitro conditions. The obtained results confirm the practicability of the plasma modification process and furthermore show that with some delays in the next step, i.e. silver ion sorption, we can get the increase in the amount of the sorbed silver ions; the maximum sorption capacity of modified Co/PES fabrics was 0.135 mmol of Ag+ ions per gram of a fabric.

  1. Adsorption of atomic oxygen, electron structure and elastic moduli of TiC(0 0 1) surface during its laser reconstruction: Ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Ilyasov, V.V., E-mail: viily@mail.ru; Pham, Khang D., E-mail: dinhkhang307@gmail.com; Holodova, O.M.; Ershov, I.V., E-mail: thijd@mail.ru

    2015-10-01

    We have performed ab initio simulation of oxygen atom adsorption on TiC(0 0 1) laser-reconstructed surface. Relaxed atomic structures of the O/Ti{sub x}C{sub y}(0 0 1) surface observed upon thermal impact have been studied. DFT calculations of their thermodynamic, electronic, and elastic properties have been carried out. For the first time we have established the bond length and adsorption energy for various reconstructions of the O/Ti{sub x}C{sub y}(0 0 1) surface atomic structure. We have examined the effects of the oxygen adatom upon the band and electron spectra of the O/TiC(0 0 1) surface in its various reconstructions. For the first time we have established a correlation between the energy level of flat bands (−5.4 eV and −5.8 eV) responsible for the doublet of singular peaks of partial densities of oxygen 2p electrons, and the adsorption energy of oxygen atom in non-stoichiometric O/TiC{sub y}(0 0 1) systems. Effective charges of titanium and carbon atoms surrounding the oxygen adatom in various reconstructions have been identified. We have established charge transfer from titanium atom to oxygen and carbon atoms determined by the reconstruction of local atomic and electron structures which correlate with atomic electronegativity values and chemisorption processes. Potential mechanisms for laser nanostructuring of titanium carbide surface have been suggested.

  2. Evaluation of the inhibitive effect of benzotriazole on archeological bronze in acidic medium

    Science.gov (United States)

    Hassairi, Hèla; Bousselmi, Latifa; Khosrof, Slim; Triki, Ezzeddine

    2013-12-01

    An archaeological bronze artefact was a Punic coin excavated from the north east of Tunisia in 2001. The composition of the copper alloy revealed a content of 3.5 % of tin and 1.4 % of lead with the presence of some sulphur heterogeneity. The surface presents some roughnesses and cracks and is covered by a corrosion layer of 20-40 μm thickness. The use of benzotriazole (BTA) as an inhibitor has become a standard element for the preservation of cuprous-based metals. In order to investigate the behaviour of BTA in an acidic medium, an Electrochemical Impedance Spectroscopy (EIS) investigation was performed to characterize the electrochemical behaviour of the interface of the archaeological bronze sample/acidic medium without and with BTA addition. Impedance diagrams obtained at different immersion times show that the presence of the inhibitor prevents the diffusional process observed in the absence of BTA. The inhibition of the pre-polarized bronze surface revealed that the mechanism of action of the benzotriazole molecule in an acidic medium is governed by the chemisorption process.

  3. Understanding corrosion inhibition with van der Waals DFT methods: the case of benzotriazole.

    Science.gov (United States)

    Gattinoni, Chiara; Michaelides, Angelos

    2015-01-01

    The corrosion of materials is an undesirable and costly process affecting many areas of technology and everyday life. As such, considerable effort has gone into understanding and preventing it. Organic molecule based coatings can in certain circumstances act as effective corrosion inhibitors. Although they have been used to great effect for more than sixty years, how they function at the atomic-level is still a matter of debate. In this work, computer simulation approaches based on density functional theory are used to investigate benzotriazole (BTAH), one of the most widely used and studied corrosion inhibitors for copper. In particular, the structures formed by protonated and deprotonated BTAH molecules on Cu(111) have been determined and linked to their inhibiting properties. It is found that hydrogen bonding, van der Waals interactions and steric repulsions all contribute in shaping how BTAH molecules adsorb, with flat-lying structures preferred at low coverage and upright configurations preferred at high coverage. The interaction of the dehydrogenated benzotriazole molecule (BTA) with the copper surface is instead dominated by strong chemisorption via the azole moiety with the aid of copper adatoms. Structures of dimers or chains are found to be the most stable structures at all coverages, in good agreement with scanning tunnelling microscopy results. Benzotriazole thus shows a complex phase behaviour in which van der Waals forces play an important role and which depends on coverage and on its protonation state and all of these factors feasibly contribute to its effectiveness as a corrosion inhibitor.

  4. Negative effect of dissolved organic compounds on settling behavior of synthetic monominerals in red mud

    Institute of Scientific and Technical Information of China (English)

    王梦; 胡慧萍; 刘锦伟; 陈启元

    2016-01-01

    Hydration grossular and hematite monominerals were synthesized. The effects of dissolved organic compounds (including sodium formate, sodium acetate, sodium oxalate, sodium salicylate or disodium phthalate) on the settling performance of hydration grossular or hematite slurries were studied. The settling of the slurries was also investigated with the addition of sodium polyacrylate (PAAS) or hydroxamated polyacrylamide flocculant (HCPAM). The adsorption mechanism of organic compounds on monominerals surfaces was studied by FT-IR and XPS, respectively. A deterioration in settling is observed in order of disodium phthalate>sodium salicylate>sodium oxalate>sodium formate (or sodium acetate). Moreover, PAAS can efficiently eliminate the negative effects of organic compounds on the settling performance of the hydration grossular slurry. HCPAM can efficiently eliminate the negative effects of sodium formate, sodium acetate and sodium oxalate on the settling performance of the hematite slurry, but it only partially improves the settling performance of hematite slurry containing sodium salicylate or disodium phthalate. FT-IR and XPS results show that organic compounds are physically adsorbed on hydration grossular surface, and chemisorptions of organic compounds occur on hematite surface with a bidentate chelating complex.

  5. Continuous production of nanostructured particles using spatial atomic layer deposition

    Energy Technology Data Exchange (ETDEWEB)

    Ommen, J. Ruud van, E-mail: j.r.vanommen@tudelft.nl; Kooijman, Dirkjan; Niet, Mark de; Talebi, Mojgan; Goulas, Aristeidis [Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL Delft (Netherlands)

    2015-03-15

    In this paper, the authors demonstrate a novel spatial atomic layer deposition (ALD) process based on pneumatic transport of nanoparticle agglomerates. Nanoclusters of platinum (Pt) of ∼1 nm diameter are deposited onto titania (TiO{sub 2}) P25 nanoparticles resulting to a continuous production of an active photocatalyst (0.12–0.31 wt. % of Pt) at a rate of about 1 g min{sup −1}. Tuning the precursor injection velocity (10–40 m s{sup −1}) enhances the contact between the precursor and the pneumatically transported support flows. Decreasing the chemisorption temperature (from 250 to 100 °C) results in more uniform distribution of the Pt nanoclusters as it decreases the reaction rate as compared to the rate of diffusion into the nanoparticle agglomerates. Utilizing this photocatalyst in the oxidation reaction of Acid Blue 9 showed a factor of five increase of the photocatalytic activity compared to the native P25 nanoparticles. The use of spatial particle ALD can be further expanded to deposition of nanoclusters on porous, micron-sized particles and to the production of core–shell nanoparticles enabling the robust and scalable manufacturing of nanostructured powders for catalysis and other applications.

  6. Atomic layer deposition of diisopropylaminosilane on WO3(001) and W(110): a density functional theory study.

    Science.gov (United States)

    Lee, Kyungtae; Lee, Woojin; Lee, Hyo Sug; Shin, Jaikwang; Park, Jieun; Lee, Seongsuk; Choi, Samjong; Kim, Sueryeon; Kim, Jinseong; Shim, Youngseon

    2016-10-26

    The decomposition reactions of the Si precursor, diisopropylaminosilane (DIPAS), on W(110) and hydroxylated WO3(001) surfaces are investigated to elucidate the initial reaction mechanism of the atomic layer deposition (ALD) process using density functional theory (DFT) calculations combined with ab initio molecular dynamics (AIMD) simulations. The decomposition reaction of DIPAS on WO3(001) consists of two steps: Si-N dissociative chemisorption and decomposition of SiH3*. It is found that the Si-N bond cleavage of DIPAS is facile on WO3(001) due to hydrogen bonding between the surface OH group and the N atom of DIPAS. The rate-determining step of DIPAS decomposition on WO3(001) is found to be the Si-H dissociation reaction of the SiH3* reaction intermediate which has an activation barrier of 1.19 eV. On the contrary, sequential Si-H dissociation reactions first occur on W(110) and then the Si-N dissociation reaction of the C5H7NSi* reaction intermediate is found to be the rate-determining step, which has an activation barrier of 1.06 eV. As a result, the final products in the DIPAS decomposition reaction on WO3(001) are Si* and SiH*, whereas Si* atoms remain with carbon impurities on W(110), which imply that the hydroxylated WO3 surface is more efficient for the ALD process.

  7. Adsorption of atomic nitrogen and oxygen on [Formula: see text] surface: a density functional theory study.

    Science.gov (United States)

    Breedon, M; Spencer, M J S; Yarovsky, I

    2009-04-08

    The adsorption of atomic nitrogen and oxygen on the ([Formula: see text]) crystal face of zinc oxide (ZnO) was studied. Binding energies, workfunction changes, vibrational frequencies, charge density differences and electron localization functions were calculated. It was elucidated that atomic oxygen binds more strongly than nitrogen, with the most stable [Formula: see text] structure exhibiting a binding energy of -2.47 eV, indicating chemisorption onto the surface. Surface reconstructions were observed for the most stable minima of both atomic species. Positive workfunction changes were calculated for both adsorbed oxygen and nitrogen if the adsorbate interacted with zinc atoms. Negative workfunction changes were calculated when the adsorbate interacted with both surface oxygen and zinc atoms. Interactions between the adsorbate and the surface zinc atoms resulted in ionic-type bonding, whereas interactions with oxygen atoms were more likely to result in the formation of covalent-type bonding. The positive workfunction changes correlate with an experimentally observed increase in resistance of ZnO conductometric sensor devices.

  8. DFT study on the adsorption of diethyl, ethyl methyl, and dimethyl ethers on the surface of gallium doped graphene

    Science.gov (United States)

    Shokuhi Rad, Ali; Sani, Emad; Binaeian, Ehsan; Peyravi, Majid; Jahanshahi, Mohsen

    2017-04-01

    In this study, we used density functional theory (DFT) to search on the adsorption properties of three important compounds of ether family; diethyl ether (DEE), ethyl methyl ether (EME), and dimethyl ether (DME) on the surface of Gallium doped graphene (GaG). We used three functionals (B3LYP, wb97xd, and MPW1PW91) for optimization and calculation of adsorption energy. After fully optimization, we scrutinized on the charge allocations on the adsorbed ethers as well as GaG (at the area of interaction) based on natural bond orbitals (NBO). Besides, we have calculated the amount of charge transfer upon adsorption of each analyte. We revel that GaG is an ideal adsorbent for chemisorption of all above-mentioned ethers. There is a little difference between the values of adsorption; -123.5, -120, and -118.3 kJ/mol (based on wb97xd) for DEE, EME, and DME, respectively. We found significant changes in the electronic structure of both adsorbent and adsorbate upon adsorption. Moreover, results of charge analyses confirm GaG is a p-type semiconductor.

  9. Investigation of adsorption of the dyestuff astrazon red violet 3rn (basic violet 16 on montmorillonite clay

    Directory of Open Access Journals (Sweden)

    B. A. Fil

    2014-03-01

    Full Text Available In this study, color removal by absorption from synthetically prepared wastewater was investigated using montmorillonite clay by adsorption. As dyestuff Astrazon Red Violet 3RN (Basic Violet 16 was used. Experimental parameters selected were pH, temperature, agitation speed, initial dyestuff concentration, adsorbent dosage and ionic strength. It was established that adsorption rate increased with increasing pH, temperature, dye concentration and agitation speed, but decreased with increased ionic strength and adsorbent dosage. Adsorption equilibrium data obtained by a series of experiments carried out in a water bath were employed with common isotherm equations such as Langmuir, Freundlich, Temkin, Elovich and Dubinin-Radushkevich. It was found that the Langmuir equation appears to fit the equilibrium data better than the other models. Furthermore, the fit of the kinetic data to common kinetic models such as the pseudo-first-order, second-order, Elovich and intraparticle diffusion models was tested to elucidate the adsorption mechanism. Kinetic data conformed to the pseudo-second-order model, indicating chemisorptions. In addition, the thermodynamic parameters activation energy, Ea, enthalpy ΔH*, entropy, ΔS*, and free energy change, ΔG*, were calculated. The values of the calculated parameters indicated that physical adsorption of ARV on the clay was dominant and that the adsorption process was endothermic.

  10. Stimulatory effect and adsorption behavior of rhamnolipids on lignocelluloses degradation system.

    Science.gov (United States)

    Hou, Jinju; Zhang, Shudong; Qiu, Zhen; Han, Hui; Zhang, Qiuzhuo

    2017-01-01

    Di-rhamnolipid and mixed rhamnolipid were added to rice straw degrading system to investigate their mechanism of stimulatory effect. By batch adsorption experiments, it was shown that the equilibrium adsorption time of rhamnolipids on rice straw single system was the shortest (50min). The adsorption capacity of Trichoderma reesei single system was the strongest, whose Qe,exp for di-rhamnolipid and mixed rhamnolipid was 10.57×10(-2)mg·g(-1) and 8.13×10(-2)mg·g(-1), respectively. The adsorption of rhamnolipids on consortia system was not the simple adduct of the two single systems. The adsorption of rhamnolipids on the three different systems might belong to chemisorptions. SEM and FTIR analyses were used to observe the morphology and to analyze the chemical functions in lignocellulosic biomass degradation with rhamnolipid. It was shown that after addition of rhamnolipids, the basic tissue in rice straw was severely destroyed and hydrogen bond was formed between biosurfactant and bacteria in lignocellulose degrading system.

  11. Efficient adsorption of both methyl orange and chromium from their aqueous mixtures using a quaternary ammonium salt modified chitosan magnetic composite adsorbent.

    Science.gov (United States)

    Li, Kun; Li, Pei; Cai, Jun; Xiao, Shoujun; Yang, Hu; Li, Aimin

    2016-07-01

    A quaternary ammonium salt modified chitosan magnetic composite adsorbent (CS-CTA-MCM) was prepared by combination of Fe3O4 nanoparticles. Various techniques were used to characterize the molecular structure, surface morphology, and magnetic feature of this composite adsorbent. CS-CTA-MCM was employed for the removal of Cr(VI) and methyl orange (MO), an anionic dye, from water in respective single and binary systems. Compared with chitosan magnetic adsorbent (CS-MCM) without modification, CS-CTA-MCM shows evidently improved adsorption capacities for both pollutants ascribed to the additional quaternary ammonium salt groups. Based on the adsorption equilibrium study, MO bears more affinity to CS-CTA-MCM than Cr(VI) causing a considerable extent of preferential adsorption of dye over metal ions in their aqueous mixture. However, at weak acidic solutions, Cr(VI) adsorption is evidently improved due to more efficient Cr(VI) forms, i.e. dichromate and monovalent chromate, binding to this chitosan-based adsorbent. Thus chromium could be efficient removal together with MO at suitable pH conditions. The adsorption isotherms and kinetics indicate that adsorptions of Cr(VI) and MO by CS-CTA-MCM both follow a homogeneous monolayer chemisorption process. This magnetic adsorbent after saturated adsorption could be rapidly separated from water and easily regenerated using dilute NaOH aqueous solutions then virtually reused with little adsorption capacity loss.

  12. Adsorption behavior of tetracycline by extracellular polymeric substrates extracted from Klebsiella sp. J1.

    Science.gov (United States)

    Li, Ang; Pi, Shanshan; Wei, Wei; Chen, Ting; Yang, Jixian; Ma, Fang

    2016-12-01

    The extracellular polymeric substrate (EPS) extracted from Klebsiella sp. J1 was used to adsorb low concentrations of tetracycline, and the efficiency and mechanism of tetracycline adsorption by EPS from strain J1 were studied. Adsorption efficiency was evaluated at different conditions. Results showed that optimal adsorption efficiency was 71.68 % with 60 mg L(-1) of EPS from strain J1 and 90 μL of 10 % (w/v) CaCl2 in 100 mL of tetracycline solution (80 μg L(-1)) with pH of 8.0. Experimental data was fitted well with Langmuir, Freundlich isotherm, and pseudo-second-order models. Analyses of E value, Ea value, thermodynamics, zeta potential variation, and Fourier transform infrared spectroscopy (FTIR) spectra proved that chemisorption was the main adsorption type and bridging was the main adsorption mechanism. Thermodynamic analysis indicated that adsorptive reaction was exothermic from 20 to 40 °C. In addition, humic acid (HA) showed little effect on the tetracycline adsorption by MFX.

  13. Evaluation of carbon-based nanosorbents synthesised by ethylene decomposition on stainless steel substrates as potential sequestrating materials for nickel ions in aqueous solution

    Institute of Scientific and Technical Information of China (English)

    X.J.Lee; L.Y.Lee; L.P.Y.Foo; K.W.Tan; D.G.Hassell

    2012-01-01

    The present work covers the preparation of carbon-based nanosorbents by ethylene decomposition on stainless steel mesh without the use of external catalyst for the treatment of water containing nickel ions (Ni2+).The reaction temperature was varied from 650 to 850℃,while reaction time and ethylene to nitrogen flow ratio were maintained at 30 min and 1:1 cm3/min,respectively.Results show that nanosorbents synthesised at a reaction temperature of 650℃ had the smallest average diameter (75 nm),largest BET surface area (68.95m2/g) and least amount of impurity (0.98 wt.% Fe).A series of batch sorption tests were performed to evaluate the effects of initial pH,initial metal concentration and contact time on Ni2+ removal by the nanosorbents.The equilibrium data fitted well to Freundlich isotherm.The kinetic data were best correlated to a pseudo second-order model indicating that the process was of chemisorption type.Further analysis by the Boyd kinetic model revealed that boundary layer diffusion was the controlling step.This primary study suggests that the prepared material with Freundlich constants compared well with those in the literature,is a promising sorbent for the sequestration of Ni2+ in aqueous solutions.

  14. Quantum dynamics of hydrogen atoms on graphene. II. Sticking

    Energy Technology Data Exchange (ETDEWEB)

    Bonfanti, Matteo, E-mail: matteo.bonfanti@unimi.it [Dipartimento di Chimica, Università degli Studi di Milano, v. Golgi 19, 20133 Milano (Italy); Jackson, Bret [Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003 (United States); Hughes, Keith H. [School of Chemistry, Bangor University, Bangor, Gwynedd LL57 2UW (United Kingdom); Burghardt, Irene [Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue-Str. 7, 60438 Frankfurt/Main (Germany); Martinazzo, Rocco, E-mail: rocco.martinazzo@unimi.it [Dipartimento di Chimica, Università degli Studi di Milano, v. Golgi 19, 20133 Milano (Italy); Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Richerche, v. Golgi 19, 20133 Milano (Italy)

    2015-09-28

    Following our recent system-bath modeling of the interaction between a hydrogen atom and a graphene surface [Bonfanti et al., J. Chem. Phys. 143, 124703 (2015)], we present the results of converged quantum scattering calculations on the activated sticking dynamics. The focus of this study is the collinear scattering on a surface at zero temperature, which is treated with high-dimensional wavepacket propagations with the multi-configuration time-dependent Hartree method. At low collision energies, barrier-crossing dominates the sticking and any projectile that overcomes the barrier gets trapped in the chemisorption well. However, at high collision energies, energy transfer to the surface is a limiting factor, and fast H atoms hardly dissipate their excess energy and stick on the surface. As a consequence, the sticking coefficient is maximum (∼0.65) at an energy which is about one and half larger than the barrier height. Comparison of the results with classical and quasi-classical calculations shows that quantum fluctuations of the lattice play a primary role in the dynamics. A simple impulsive model describing the collision of a classical projectile with a quantum surface is developed which reproduces the quantum results remarkably well for all but the lowest energies, thereby capturing the essential physics of the activated sticking dynamics investigated.

  15. Fuel Cell Research at the University of Delaware

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jingguang G; Advani, Suresh G

    2006-01-27

    The grant initiated nine basic and applied research projects to improve fundamental understanding and performance of the proton exchange membrane (PEM) fuel cells, to explore innovative methods for hydrogen production and storage, and to address the critical issues and barriers to commercialization. The focus was on catalysis, hydrogen production and storage, membrane durability and flow modeling and characterization of Gas Diffusion Media. Three different types of equipment were purchase with this grant to provide testing and characterization infrastructure for fuel cell research and to provide undergraduate and graduate students with the opportunity to study fuel cell membrane design and operation. They are (i) Arbin Hydrogen cell testing station, (ii) MTS Alliance RT/5 material testing system with an ESPEC custom-designed environmental chamber for membrane Durability Testing and (iii) Chemisorption for surface area measurements of electrocatalysts. The research team included ten faculty members who addressed various issues that pertain to Fuel Cells, Hydrogen Production and Storage, Fuel Cell transport mechanisms. Nine research tasks were conducted to address the critical issues and various barriers to commercialization of Fuel Cells. These research tasks are subdivided in the general areas of (i) Alternative electrocatalysis (ii) Fuel Processing and Hydrogen Storage and (iii) Modeling and Characterization of Membranes as applied to Fuel Cells research.. The summary of accomplishments and approaches for each of the tasks is presented below

  16. Self-assembled nanofilm of 1,2-dihydro-3-(octadecylthio)benzotriazine on copper for corrosion protection

    Indian Academy of Sciences (India)

    B V Appa Rao; M D Yakub Iqbal; M Narsihma Reddy; K Chaitanya Kumar

    2014-04-01

    The self-assembled nanofilm of 1,2-dihydro-3-(octadecylthio)benzotriazine (DOTBT) was formed on fresh copper surface obtained by etching with 7 N nitric acid at a room temperature of 30°C. The conditions for formation of the DOTBT nanofilm have been optimized by electrochemical impedance and electrochemical quartz crystal nanobalance (EQCN) studies. The DOTBT nanofilm on copper surface was characterized by contact-angle measurement, X-ray photoelectron spectra (XPS), reflection absorption FTIR spectra and atomic force micrographs (AFM). It is inferred that formation of DOTBT film is due to chemisorption of DOTBT on copper surface through nitrogen and subsequent complex formation between DOTBT and Cu+ ions. Corrosion protection ability of DOTBT nanofilm was evaluated in dilute aqueous NaCl solution using electrochemical impedance, potentiodynamic polarization, weight-loss and XPS studies. These studies inferred that the DOTBT film protects effectively copper from corrosion. Potentiodynamic polarization studies revealed that the DOTBT film inhibits corrosion by controlling the cathodic reaction. The mechanism of corrosion protection of copper by DOTBT nanofilm is discussed in this paper.

  17. Estudo da adsorção de hidrogênio e sulfeto na superfície de paládio: aspectos experimentais (eletroquímica e teóricos (ab initio e Teoria do Funcional da Densidade

    Directory of Open Access Journals (Sweden)

    Ângelo Antônio Carlos D.

    2001-01-01

    Full Text Available The adsorption of H and S2- species on Pd (100 has been studied with ab initio, density-functional calculations and electrochemical methods. A cluster of five Pd atoms with a frozen geometry described the surface. The computational calculations were performed through the GAUSSIAN94 program, and the basis functions adapted to a pseudo-potential obtained by using the Generator Coordinate Method adapted to the this program. Using the cyclic voltammetry technique through a Model 283 Potentiostat/Galvanostat E.G.&G-PAR obtained the electrochemical results. The calculated chemisorption geometry has a Pd-H distance of 1.55Å, and the potential energy surface was calculated using the Becke3P86//(GCM/DFT/SBK methodology. The adsorption of S2- ions on Pd surface obtained both through comparison between the experimental and theoretical results, at MP2 level, suggest a S2- absorption into the metallic cluster. The produced Pd-(S2- system was show to be very stable under the employed experimental conditions. The paper has shows the powerful aid of computational methods to interpret adsorption experimental data.

  18. Aromatic molecules on low-index coinage metal surfaces: Many-body dispersion effects

    Science.gov (United States)

    Jiang, Yingda; Yang, Sha; Li, Shuang; Liu, Wei

    2016-12-01

    Understanding the binding mechanism for aromatic molecules on transition-metal surfaces in atomic scale is a major challenge in designing functional interfaces for to (opto)electronic devices. Here, we employ the state-of-the-art many-body dispersion (MBD) approach, coupled with density functional theory methods, to study the interactions of benzene with low-index coinage metal surfaces. The many-body effects contribute mostly to the (111) surface, and leastly to the (110) surface. This corresponds to the same sequence of planar atomic density of face-centered-cubic lattices, i.e., (111) > (100) > (110). The binding energy for benzene/Au(110) is even stronger than that for benzene/Ag(110), due to a larger broadening of molecular orbitals in the former case. On the other hand, our calculations show almost identical binding energies for benzene on Ag(111) and Au(111), which contradicts the classic d-band center theory that could well predict the trend in chemisorption energies for various small molecules on a number of metal surfaces. Our results provide important insight into the benchmark adsorption systems with opener surfaces, which could help in designing more complex functional interfaces.

  19. Mathematical modelling and optimization of synthetic textile dye removal using soil composites as highly competent liner material.

    Science.gov (United States)

    Das, Papita; Banerjee, Priya; Mondal, Sandip

    2015-01-01

    Soil is widely used as adsorbent for removing toxic pollutants from their aqueous solutions due to its wide availability and cost efficiency. This study investigates the potential of soil and soil composites for removal of crystal violet (CV) dye from solution on a comparative scale. Optimisation of different process parameters was carried out using a novel approach of response surface methodology (RSM) and a central composite design (CCD) was used for determining the optimum experimental conditions, as well as the result of their interactions. Around 99.85 % removal of CV was obtained at initial pH 6.4, which further increased to 99.98 % on using soil and cement composite proving it to be the best admixture of those selected. The phenomenon was found to be represented best by the Langmuir isotherm at different temperatures. The process followed the pseudo-second-order kinetic model and was determined to be spontaneous chemisorption in nature. This adsorbent can hence be suggested as an appropriate liner material for the removal of CV dye.

  20. Manganese Oxide-Surface Modified Titanium(IV Dioxide as Environmental Catalyst

    Directory of Open Access Journals (Sweden)

    Hiroaki Tada

    2013-04-01

    Full Text Available The purpose of this study is to present an “environmental catalyst” possessing both thermocatalytic activity and visible-light activity for the decomposition of organic pollutants. Molecule-sized MnOx clusters are highly dispersed on the surface of TiO2 (anatase/rutile = 4/1 w/w, P-25, Degussa by the chemisorption-calcination cycle technique using Mn(acac3 complex as a precursor (MnOx/TiO2. The thermo- and photo-catalytic activities of MnOx/TiO2 were studied for the degradation of 2-naphthol used as a model water pollutant. In contrast to the FeOx/TiO2 system, MnOx/TiO2 exhibits high thermocatalytic activity exceeding those of bulk β-β-MnO2 and Mn2O3. Also, visible-light activity is induced by the surface modification of TiO2 with MnOx clusters, whereas its UV-light activity decreases.

  1. N-benzoyl-n-phenylhydroxylamine impregnated Amberlite XAD-4 beads for selective removal of thorium.

    Science.gov (United States)

    Chandramouleeswaran, S; Ramkumar, Jayshree

    2014-09-15

    n-Benzoyl-n-phenylhydroxylamine impregnated Amberlite XAD-4 beads were used for the removal of Th(IV) from a mixture of ions. The impregnated XAD was characterized using different techniques like weight and colour change, IR spectra, surface area and pore size measurements to confirm the presence of n-BPHA within the macroreticular resin structure. The experimental conditions were optimized to make the separation fast and selective. It was seen that the maximum sorption was achieved in the pH range of 3-7.5 and uptake was nearly complete within half an hour. The results obtained in the present study were subjected to extensive modelling in order to get a complete understanding of the sorption process. It is seen that the maximum uptake was calculated to be 500 mg/g and has very fast kinetics it was seen that the process is chemisorption. It was further deduced from the modelling that the overall sorption process was controlled dominantly by external mass transfer. Considering the simplicity this procedure, the present study has a possible application for the removal of thorium from different mixtures.

  2. Electroless plating of PVC plastic through new surface modification method applying a semi-IPN hydrogel film

    Science.gov (United States)

    Wang, Ming-Qiu; Yan, Jun; Du, Shi-Guo; Li, Hong-Guang

    2013-07-01

    A novel palladium-free surface activation process for electroless nickel plating was developed. This method applied a semi-Interpenetrating Polymer Network (semi-IPN) hydrogel film to modify the poly(vinyl chloride) (PVC) surface by chemical bonds. The activation process involved the formation of semi-IPN hydrogel film on the PVC surface and the immobilization of catalyst for electroless plating linking to the pretreated substrate via Nsbnd Ni chemical bond. The hydrogel layer was used as the chemisorption sites for nickel ions, and the catalyst could initiate the subsequent electroless nickel plating onto the PVC surface. Finally, a Ni-P layer was deposited on the nickel-activated PVC substrate by electroless plating technique. The composition and morphology of nickel-plated PVC foils were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). The results of SEM and XRD show that a compact and continuous Ni-P layer with amorphous nickel phase is formed on the PVC surface. EDS shows that the content of the nickel and the phosphorus in the deposits is 89.4 wt.% and 10.6 wt.%, respectively.

  3. Effect of different mixing ways in palladium/ceria-zirconia/alumina preparation on partial oxidation of methane

    Institute of Scientific and Technical Information of China (English)

    ZHANG Qingwei; WEN Jing; SHEN Meiqing; WANG Jun

    2008-01-01

    The effect of the mixing ways of Ce0.7Zr0.3O2-Al2O3 mixed oxides on the partial oxidations of methane (POM) was investigated over Pd/Ce0.7Zr0.3O2-Al2O3 catalysts, the mixing ways including salt precursor mixing (ATOM), precipitator mixing (MOL), and powder mechanically mixing (MECH), respectively. The test results indicated that among the three samples, Pd/ATOM had the best catalytic activity,while Pd/MOL had the best stability in the stability test. Both the activity sequences of the fresh and used samples were consistent with the order of Pd dispersion. According to the X-ray diffraction (XRD) and BET characterization, the interaction of Ce4+, Zr4+, and Al3+ in the ATOM mixed oxide was in favor of performing higher catalytic activity and thermal stability. The stability test indicated that Pd/MOL had the highest Pd dispersion and least coke formation on the active sites calculated by the H2-chemisorption and TG results, which was consid-ered to relate to its superior activity of POM to other catalysts.

  4. Silica-titania composite aerogel photocatalysts by chemical liquid deposition of titania onto nanoporous silica scaffolds.

    Science.gov (United States)

    Zu, Guoqing; Shen, Jun; Wang, Wenqin; Zou, Liping; Lian, Ya; Zhang, Zhihua

    2015-03-11

    Silica-titania composite aerogels were synthesized by chemical liquid deposition of titania onto nanoporous silica scaffolds. This novel deposition process was based on chemisorption of partially hydrolyzed titanium alkoxides from solution onto silica nanoparticle surfaces and subsequent hydrolysis and condensation to afford titania nanoparticles on the silica surface. The titania is homogeneously distributed in the silica-titania composite aerogels, and the titania content can be effectively controlled by regulating the deposition cycles. The resultant composite aerogel with 15 deposition cycles possessed a high specific surface area (SSA) of 425 m(2)/g, a small particle size of 5-14 nm, and a large pore volume and pore size of 2.41 cm(3)/g and 18.1 nm, respectively, after heat treatment at 600 °C and showed high photocatalytic activity in the photodegradation of methylene blue under UV-light irradiation. Its photocatalytic activity highly depends on the deposition cycles and heat treatment. The combination of small particle size, high SSA, and enhanced crystallinity after heat treatment at 600 °C contributes to the excellent photocatalytic property of the silica-titania composite aerogel. The higher SSAs compared to those of the reported titania aerogels (aerogels promising candidates as photocatalysts.

  5. Temperature Dependence of Sensors Based on Silver-Decorated Nitrogen-Doped Multiwalled Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Eduardo Gracia-Espino

    2016-01-01

    Full Text Available Vapor sensors are easily fabricated onto alumina substrates using foils of silver-decorated nitrogen-doped multiwalled carbon nanotubes (CNX-MWNTs-Ag as active sensing material. The vapor sensors are tested using carbon disulfide, acetone, ethanol, and chloroform vapors. The CNX-MWNTs are produced by chemical vapor deposition process and then decorated with 14 nm Ag nanoparticles (Ag-NPs. The samples are characterized using scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. Our results demonstrate that Ag-decorated CNX-MWNTs exhibit a better response and sensitivity when compared with pristine CNX-MWNTs based sensors, making them promising candidates for air-pollutants environmental monitoring. The temperature effect on the sensor performance is also studied; we found that the detection mechanism could be tuned from physisorption, at room temperature, to chemisorption at higher working temperature. Finally, first-principles density functional calculations are carried out to understand the interactions between the systems involved in the sensors, finding good agreement between experimental results and the theoretical approach.

  6. Kinetics of nickel bioaccumulation and its relevance to selected cellular processes in leaves of Elodea canadensis during short-term exposure.

    Science.gov (United States)

    Maleva, Maria G; Malec, Przemysław; Prasad, Majeti Narasimha Vara; Strzałka, Kazimierz

    2016-03-01

    Elodea canadensis is an aquatic macrophyte used widely as a bioindicator for the monitoring of water quality and in the phytoremediation of metal-contaminated waters. This study considers the kinetics of nickel bioaccumulation and changes in accompanying metabolic and stress-related physiological parameters. These include photosynthetic activity, pigment content, the accumulation of thiol-containing compounds, thiobarbituric acid-reactive substance (TBARS) products, and the activity of selected antioxidant enzymes (catalase, glutathione reductase, superoxide dismutase). Elodea leaves accumulated nickel according to pseudo-second-order kinetics, and the protective responses followed a time sequence which was related to the apparent rates of nickel accumulation. The applicability of second-order kinetics to the Ni uptake by Elodea leaves during the first 8 h of exposure to the metal suggested that the passive binding of metal ions (chemisorption) was a rate-limiting step at the initial phase of Ni accumulation. This phase was accompanied by an increase in photosynthetic activity together with elevated photosynthetic pigments and protein synthesis, the enhanced activity of antioxidant enzymes, and increased thiol concentration. In contrast, there was a decrease in metabolic activity upon the accumulation of TBARS, and the decline in enzyme activity was observed in the saturation phase of Ni accumulation (8-24 h). These results show that a correlation exists between the protective response and the apparent kinetic rate of Ni uptake. Thus, the time of exposure to the toxicant is a crucial factor in the activation of specific mechanisms of Ni detoxification and stress alleviation.

  7. Part I: A Comparative Thermal Aging Study on the Regenerability of Rh/Al2O3 and Rh/CexOy-ZrO2 as Model Catalysts for Automotive Three Way Catalysts

    Directory of Open Access Journals (Sweden)

    Qinghe Zheng

    2015-10-01

    Full Text Available The rhodium (Rh component in automotive three way catalysts (TWC experiences severe thermal deactivation during fuel shutoff, an engine mode (e.g., at downhill coasting used for enhancing fuel economy. In a subsequent switch to a slightly fuel rich condition, in situ catalyst regeneration is accomplished by reduction with H2 generated through steam reforming catalyzed by Rh0 sites. The present work reports the effects of the two processes on the activity and properties of 0.5% Rh/Al2O3 and 0.5% Rh/CexOy-ZrO2 (CZO as model catalysts for Rh-TWC. A very brief introduction of three way catalysts and system considerations is also given. During simulated fuel shutoff, catalyst deactivation is accelerated with increasing aging temperature from 800 °C to 1050 °C. Rh on a CZO support experiences less deactivation and faster regeneration than Rh on Al2O3. Catalyst characterization techniques including BET surface area, CO chemisorption, TPR, and XPS measurements were applied to examine the roles of metal-support interactions in each catalyst system. For Rh/Al2O3, strong metal-support interactions with the formation of stable rhodium aluminate (Rh(AlO2y complex dominates in fuel shutoff, leading to more difficult catalyst regeneration. For Rh/CZO, Rh sites were partially oxidized to Rh2O3 and were relatively easy to be reduced to active Rh0 during regeneration.

  8. Surface Response of Brominated Carbon Media on Laser and Thermal Excitation: Optical and Thermal Analysis Study

    Science.gov (United States)

    Multian, Volodymyr V.; Kinzerskyi, Fillip E.; Vakaliuk, Anna V.; Grishchenko, Liudmyla M.; Diyuk, Vitaliy E.; Boldyrieva, Olga Yu.; Kozhanov, Vadim O.; Mischanchuk, Oleksandr V.; Lisnyak, Vladyslav V.; Gayvoronsky, Volodymyr Ya.

    2017-02-01

    The present study is objected to develop an analytical remote optical diagnostics of the functionalized carbons surface. Carbon composites with up to 1 mmol g-1 of irreversibly adsorbed bromine were produced by the room temperature plasma treatment of an activated carbon fabric (ACF) derived from polyacrylonitrile textile. The brominated ACF (BrACF) was studied by elastic optical scattering indicatrix analysis at wavelength 532 nm. The obtained data were interpreted within results of the thermogravimetric analysis, X-ray photoelectron spectroscopy and temperature programmed desorption mass spectrometry. The bromination dramatically reduces the microporosity producing practically non-porous material, while the incorporated into the micropores bromine induces the dielectric and structural impact on surface polarizability and conductivity due to the charging effect. We have found that the elastic optical scattering in proper solid angles in the forward and the backward hemispheres is sensitive to the kind of the bromine bonding, e.g., physical adsorption or chemisorption, and the bromination level, respectively, that can be utilized for the express remote fabrication control of the nanoscale carbons with given interfaces.

  9. Ab initio investigation of Al- and Ga-doped single-walled boron nitride nanotubes as ammonia sensor

    Energy Technology Data Exchange (ETDEWEB)

    Soltani, Alireza, E-mail: Alireza.soltani46@yahoo.com [Young Researchers Club, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of); Raz, Shima Ghafouri [Department of Chemistry, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of); Rezaei, Vahid Joveini [Young Researchers Club, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of); Dehno Khalaji, Aliakbar [Department of Chemistry, Faculty of Science, Golestan University, Gorgan (Iran, Islamic Republic of); Savar, Mohammad [Department of Chemistry, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of)

    2012-12-15

    Highlights: Black-Right-Pointing-Pointer The electronic properties of NH{sub 3} on Al- and Ga-doped (8, 0) and (5, 5) BNNT are studied. Black-Right-Pointing-Pointer The adsorption energy for NH{sub 3} on Al-doped (8, 0) BNNT is higher than that of Ga-doped (8, 0) BNNT. Black-Right-Pointing-Pointer The relation between adsorption energy and charge transfer was investigated. - Abstract: We performed first-principles calculations on the ammonia (NH{sub 3}) adsorption properties with zigzag and armchair single-walled BN nanotubes (SWBNNTs) using B3LYP/6-31G* basis set implemented in Gaussian 98 program. We considered the ammonia adsorption on structural and electronic properties of Al- and Ga-doped (8, 0), (5, 5) BNNTs. The adsorption energy for the most stable configuration of NH{sub 3} on Al-doped (8, 0) BNNT is about -0.182 eV, which is typical for the chemisorptions. We determined that both aluminum and gallium doping can significantly enhance the adsorption energy of NH{sub 3}/BNNTs complexes. Our electronic results reveal that there is a significant orbital hybridization between two species in adsorption process being an evidence of covalent interaction.

  10. Atomic force microscopy probing of receptor-nanoparticle interactions for riboflavin receptor targeted gold-dendrimer nanocomposites.

    Science.gov (United States)

    Witte, Amanda B; Leistra, Abigail N; Wong, Pamela T; Bharathi, Sophia; Refior, Kevin; Smith, Phillip; Kaso, Ola; Sinniah, Kumar; Choi, Seok Ki

    2014-03-20

    Riboflavin receptors are overexpressed in malignant cells from certain human breast and prostate cancers, and they constitute a group of potential surface markers important for cancer targeted delivery of therapeutic agents and imaging molecules. Here we report on the fabrication and atomic force microscopy (AFM) characterization of a core-shell nanocomposite consisting of a gold nanoparticle (AuNP) coated with riboflavin receptor-targeting poly(amido amine) dendrimer. We designed this nanocomposite for potential applications such as a cancer targeted imaging material based on its surface plasmon resonance properties conferred by AuNP. We employed AFM as a technique for probing the binding interaction between the nanocomposite and riboflavin binding protein (RfBP) in solution. AFM enabled precise measurement of the AuNP height distribution before (13.5 nm) and after chemisorption of riboflavin-conjugated dendrimer (AuNP-dendrimer; 20.5 nm). Binding of RfBP to the AuNP-dendrimer caused a height increase to 26.7 nm, which decreased to 22.8 nm when coincubated with riboflavin as a competitive ligand, supporting interaction of AuNP-dendrimer and its target protein. In summary, physical determination of size distribution by AFM imaging can serve as a quantitative approach to monitor and characterize the nanoscale interaction between a dendrimer-covered AuNP and target protein molecules in vitro.

  11. Functionalization of PDMS modified and plasma activated two-component polyurethane coatings by surface attachment of enzymes

    Science.gov (United States)

    Kreider, Alexej; Richter, Katharina; Sell, Stephan; Fenske, Mandus; Tornow, Christian; Stenzel, Volkmar; Grunwald, Ingo

    2013-05-01

    This article describes a new strategy for coupling the enzyme horseradish peroxidase to a two-component polyurethane (2C-PUR) coating. A stable polymer conjugate was achieved by combining the enzyme and the 2C-PUR coating which was modified with poly(dimethylsiloxane) (PDMS), located at the surface. An atmospheric pressure plasma jet system was used to convert alkyl groups from the PDMS into polar silanol functionalities. This conversion was proven by X-ray photoelectron spectroscopy and dynamic contact angle measurements. In addition, the stability of the activated 2C-PUR surface containing silanol groups was determined by measuring the contact angle as a function of time. Compared to the non-modified 2C-PUR systems the one with PDMS displayed a higher stability over a time period over 28 h. In a silanization process the coating was treated with (3-aminopropyl) trimethoxysilane and the enzyme was subsequently immobilized to the coating via the cross linker glutaraldehyde to receive new biomimetic catalytic/enzymatic functions. The chemical immobilization (chemisorption) of the enzyme to the surface showed statistically significant higher biological activity as compared to references samples without using a cross linker (physisorption). The presented technique offers the opportunity to design new and smart multifunctional surface coatings which employ biomimetic capabilities.

  12. Functionalization of PDMS modified and plasma activated two-component polyurethane coatings by surface attachment of enzymes

    Energy Technology Data Exchange (ETDEWEB)

    Kreider, Alexej; Richter, Katharina; Sell, Stephan; Fenske, Mandus; Tornow, Christian; Stenzel, Volkmar [Fraunhofer Institute for Manufacturing Technology and Advanced Materials - IFAM, Wiener Strasse 12, 28359 Bremen (Germany); Grunwald, Ingo, E-mail: ingo.grunwald@ifam.fraunhofer.de [Fraunhofer Institute for Manufacturing Technology and Advanced Materials - IFAM, Wiener Strasse 12, 28359 Bremen (Germany)

    2013-05-15

    This article describes a new strategy for coupling the enzyme horseradish peroxidase to a two-component polyurethane (2C-PUR) coating. A stable polymer conjugate was achieved by combining the enzyme and the 2C-PUR coating which was modified with poly(dimethylsiloxane) (PDMS), located at the surface. An atmospheric pressure plasma jet system was used to convert alkyl groups from the PDMS into polar silanol functionalities. This conversion was proven by X-ray photoelectron spectroscopy and dynamic contact angle measurements. In addition, the stability of the activated 2C-PUR surface containing silanol groups was determined by measuring the contact angle as a function of time. Compared to the non-modified 2C-PUR systems the one with PDMS displayed a higher stability over a time period over 28 h. In a silanization process the coating was treated with (3-aminopropyl) trimethoxysilane and the enzyme was subsequently immobilized to the coating via the cross linker glutaraldehyde to receive new biomimetic catalytic/enzymatic functions. The chemical immobilization (chemisorption) of the enzyme to the surface showed statistically significant higher biological activity as compared to references samples without using a cross linker (physisorption). The presented technique offers the opportunity to design new and smart multifunctional surface coatings which employ biomimetic capabilities.

  13. In situ attenuated total reflection FTIR investigations of thin water films in the silanization of ZnSe and Si

    Science.gov (United States)

    Imhof, Roman; Xie, Xianyue; Calzaferri, Gion

    1997-07-01

    In situ attenuated total reflection ATR-FTIR spectroscopy is used to investigate the reaction of trimethylchlorosilane (CH 3) 3SiCl in organic solvents at room temperature on ZnSe and on Si surfaces in the presence and absence of pyridine. In the absence of the base, siloxanes are formed, but they can be removed in situ with the reaction solvent along with the surplus of trimethylchlorosilane and no chemisorption is detected. Instead a thin water film is formed on the surface which shows a well resolved ATR-IR water spectrum with absorptions νas( O H) at 3477 cm -1, νs( O H) at 3421 cm -1, 2δ(HOH) at 3186 cm -1, δ(HOH) + νL at 2182 cm -1 where νL is a librational mode of water and δ(HOH) at 1601 cm -1. These thin water films are astonishingly stable and easy to handle, and their growth can be monitored. Addition of pyridine to the reaction solvent allows the detection of trimethylsilanol with an absorption band at 3706 cm -1. Concurrently pyridinium chloride is formed and partly precipitates on the substrate surface.

  14. Kinetic Modeling and Isotherm Studies for Copper(II Adsorption onto Palm Oil Boiler Mill Fly Ash (POFA as a Natural Low-Cost Adsorbent

    Directory of Open Access Journals (Sweden)

    Abdul Shukor Abdul Aziz

    2013-11-01

    Full Text Available Adsorption characteristics of palm oil boiler mill fly ash (POFA for the removal of Cu(II from aqueous solution were investigated using batch adsorption studies. The effects of relevant parameters such as contact time, solution pH, adsorbent dosage, and initial concentration of copper were examined. Fundamental batch investigations indicated that 90% of the Cu(II was removed in the first 30 min, achieving equilibration after only 270 min of agitation. The Cu(II uptake mechanism is particularly pH- and concentration-dependant, favoring a pH value of 6.0. A decrease in adsorption capacity (qe with an increase in Cu(II removal efficiency (RE % was obtained as the adsorbent dosage increased. The adsorption behavior of Cu(II fit well to the Langmuir isotherm, with a monolayer adsorption capacity of 17 mg/g. The applicability of the Langmuir isotherm suggested the formation of monolayer coverage of Cu(II ions onto equivalent sites of the adsorbent. Kinetics experimental data followed the trend of pseudo second-order kinetics, which is consistent with chemisorption with intraparticle diffusion as one of the rate-determining steps. Therefore, this study indicates that POFA could be used successfully as a natural low-cost adsorbent for Cu(II removal from aqueous solutions.

  15. A Mechanistic Study of CO2 Reduction at the Interface of a Gallium Phosphide (GaP) Surface using Core-level Spectroscopy - Oral Presentation

    Energy Technology Data Exchange (ETDEWEB)

    Flynn, Kristen [SLAC National Accelerator Lab., Menlo Park, CA (United States)

    2015-08-19

    Carbon dioxide (CO2) emission into the atmosphere has increased tremendously through burning of fossil fuels, forestry, etc.. The increased concentration has made CO2 reductions very attractive though the reaction is considered uphill. Utilizing the sun as a potential energy source, CO2 has the possibility to undergo six electron and four proton transfers to produce methanol, a useable resource. This reaction has been shown to occur selectively in an aqueous pyridinium solution with a gallium phosphide (GaP) electrode. Though this reaction has a high faradaic efficiency, it was unclear as to what role the GaP surface played during the reaction. In this work, we aim to address the fundamental role of GaP during the catalytic conversion, by investigating the interaction between a clean GaP surface with the reactants, products, and intermediates of this reaction using X-ray photoelectron spectroscopy. We have determined a procedure to prepare atomically clean GaP and our initial CO2 adsorption studies have shown that there is evidence of chemisorption and reaction to form carbonate on the clean surface at LN2 temperatures (80K), in contrast to previous theoretical calculations. These findings will enable future studies on CO2 catalysis.

  16. n-Benzoyl-n-phenylhydroxylamine impregnated Amberlite XAD-4 beads for selective removal of thorium

    Energy Technology Data Exchange (ETDEWEB)

    Chandramouleeswaran, S.; Ramkumar, Jayshree, E-mail: jrk@barc.gov.in

    2014-09-15

    Highlights: • XAD-4 was impregnated with a commonly used gravimetric agent n-benzoyl-n-phenylhydroxylamine. • Sorbent characterized by different techniques to understand the pore filling of XAD-4. • Sorption of Th was fast (30 min) and unaffected by initial solution pH. • Selectivity achieved by tuning the conditions of the mixture solution. - Abstract: n-Benzoyl-n-phenylhydroxylamine impregnated Amberlite XAD-4 beads were used for the removal of Th(IV) from a mixture of ions. The impregnated XAD was characterized using different techniques like weight and colour change, IR spectra, surface area and pore size measurements to confirm the presence of n-BPHA within the macroreticular resin structure. The experimental conditions were optimized to make the separation fast and selective. It was seen that the maximum sorption was achieved in the pH range of 3–7.5 and uptake was nearly complete within half an hour. The results obtained in the present study were subjected to extensive modelling in order to get a complete understanding of the sorption process. It is seen that the maximum uptake was calculated to be 500 mg/g and has very fast kinetics it was seen that the process is chemisorption. It was further deduced from the modelling that the overall sorption process was controlled dominantly by external mass transfer. Considering the simplicity this procedure, the present study has a possible application for the removal of thorium from different mixtures.

  17. Biosorption of cadmium and lead from aqueous solution by fresh water alga Anabaena sphaerica biomass

    Directory of Open Access Journals (Sweden)

    Azza M. Abdel -Aty

    2013-07-01

    Full Text Available The present work represents the biosorption of Cd(II and Pb(II from aqueous solution onto the biomass of the blue green alga Anabaena sphaerica as a function of pH, biosorbent dosage, contact time, and initial metal ion concentrations. Freundlich, Langmuir, and Dubinin–Radushkevich (D–R models were applied to describe the biosorption isotherm of both metals by A. sphaerica biomass. The biosorption isotherms studies indicated that the biosorption of Cd(II and Pb(II follows the Langmuir and Freundlish models. The maximum biosorption capacities (qmax were 111.1 and 121.95 mg/g, respectively, at the optimum conditions for each metal. From the D–R isotherm model, the mean free energy was calculated to be 11.7 and 14.3 kJ/mol indicating that the biosorption mechanism of Cd(II and Pb(II by A. sphaerica was chemisorption. The FTIR analysis for surface function group of algal biomass revealed the existence of amino, carboxyl, hydroxyl, and carbonyl groups, which are responsible for the biosorption of Cd(II and Pb(II. The results suggested that the biomass of A. sphaerica is an extremely efficient biosorbent for the removal of Cd(II and Pb(II from aqueous solutions.

  18. Biosorption behavior and mechanism of heavy metals by the fruiting body of jelly fungus (Auricularia polytricha) from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Haiwei; Wan, Yuxuan; Zhang, Renduo [Sun Yat-sen Univ., Guangzhou (China). School of Environmental Science and Engineering; Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology, Guangzhou (China); Cao, Lixiang; Wang, Wenfeng [Sun Yat-sen Univ., Guangzhou (China). School of Life Sciences

    2012-11-15

    The aim of this study was to investigate the biosorption characteristics of Cd{sup 2+}, Cu{sup 2+}, and Pb{sup 2+} by the fruiting body of jelly fungus Auricularia polytricha. Batch experiments were conducted to characterize the kinetics, equilibrium, and mechanisms of the biosorption process. Optimum values of pH 5, biomass dosage 4 g L{sup -1}, and contact time 60 min provided maximum biosorption capacities of A. polytricha for Cd{sup 2+}, Cu{sup 2+}, and Pb{sup 2+} of 63.3, 73.7, and 221 mg g{sup -1}, respectively. The maximum desorption was achieved using 0.05 mol L{sup -1} HNO{sub 3} as an elute. The fruiting body was reusable at least for six cycles of operations. The pseudo-second-order model was the best to describe the biosorption processes among the three kinetic models tested. Freundlich and Dubinin-Radushkevich models fitted the equilibrium data well, indicating a heterogeneous biosorbent surface and the favorable chemisorption nature of the biosorption process. A Fourier transform infrared spectroscopy analysis indicated that carboxyl, amine/hydroxyl, amino, phosphoryl, and C-N-C were the main functional groups to affect the biosorption process. Synergistic ion exchange and surface complexation were the dominant mechanisms in the biosorption process. The present work revealed the potential of jelly fungus (fruiting body of A. polytricha) to remove toxic heavy metals from contaminated water. (orig.)

  19. Removal of Cu (II and Zn (II from water with natural adsorbents from cassava agroindustry residues

    Directory of Open Access Journals (Sweden)

    Daniel Schwantes

    2015-07-01

    Full Text Available Current study employs solid residues from the processing industry of the cassava (Manihot esculenta Crantz (bark, bagasse and bark + bagasse as natural adsorbents for the removal of metal ions Cu(II and Zn(II from contaminated water. The first stage comprised surface morphological characterization (SEM, determination of functional groups (IR, point of zero charge and the composition of naturally existent minerals in the biomass. Further, tests were carried out to evaluate the sorption process by kinetic, equilibrium and thermodynamic studies. The adsorbents showed a surface with favorable adsorption characteristics, with adsorption sites possibly derived from lignin, cellulose and hemicellulose. The dynamic equilibrium time for adsorption was 60 min. Results followed pseudo-second-order, Langmuir and Dubinin-Radushkevich models, suggesting a chemisorption monolayer. The thermodynamic parameters suggested that the biosorption process of Cu and Zn was endothermic, spontaneous or independent according to conditions. Results showed that the studied materials were potential biosorbents in the decontamination of water contaminated by Cu(II and Zn(II. Thus, the above practice complements the final stages of the cassava production chain of cassava, with a new disposal of solid residues from the cassava agroindustry activity.

  20. Biosorption Potential of Bacillus salmalaya Strain 139SI for Removal of Cr(VI from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Arezoo Dadrasnia

    2015-12-01

    Full Text Available The present study investigated the biosorption capacity of live and dead cells of a novel Bacillus strain for chromium. The optimum biosorption condition was evaluated in various analytical parameters, including initial concentration of chromium, pH, and contact time. The Langmuir isotherm model showed an enhanced fit to the equilibrium data. Live and dead biomasses followed the monolayer biosorption of the active surface sites. The maximum biosorption capacity was 20.35 mg/g at 25 °C, with pH 3 and contact time of 50 min. Strain 139SI was an excellent host to the hexavalent chromium. The biosorption kinetics of chromium in the dead and live cells of Bacillus salmalaya (B. salmalaya 139SI followed the pseudo second-order mechanism. Scanning electron microscopy and fourier transform infrared indicated significant influence of the dead cells on the biosorption of chromium based on cell morphological changes. Approximately 92% and 70% desorption efficiencies were achieved using dead and live cells, respectively. These findings demonstrated the high sorption capacity of dead biomasses of B. salmalaya 139SI in the biosorption process. Thermodynamic evaluation (ΔG0, ΔH0, and ΔS0 indicated that the mechanism of Cr(VI adsorption is endothermic; that is, chemisorption. Results indicated that chromium accumulation occurred in the cell wall of B. salmalaya 139SI rather than intracellular accumulation.