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Sample records for metal halide catalyst

  1. Photofragmentation of metal halides

    Veen, N.J.A. van.

    1980-01-01

    The author deals with photodissociation of molecules of alkali halides. It is shown that the total absorption cross section consists of two contributions arising from transitions to excited states of total electronic angular momentum Ω=0 + and Ω=1. From the inversion of the absorption continua potential energy curves of the excited states can be constructed in the Franck-Condon region. It is found that for all alkali halides the 0 + state is higher in energy than the Ω=1 state. Extensive studies are reported on three thallium halides, TlI, TlBr and TlCl at various wavelengths covering the near ultraviolet region. (Auth.)

  2. Fullerenes doped with metal halides

    Martin, T.P.; Heinebrodt, M.; Naeher, U.; Goehlich, H.; Lange, T.; Schaber, H.

    1993-01-01

    The cage-like structure of fullerenes is a challenge to every experimental to put something inside - to dope the fullerenes. In fact, the research team that first identified C 60 as a football-like molecule quickly succeeded in trapping metal atoms inside and in shrinking the cage around this atom by photofragmentation. In this paper we report the results of ''shrink-wrapping'' the fullerenes around metal halide molecules. Of special interest is the critical size (the minimum number of carbon atoms) that can still enclose the dopant. A rough model for the space available inside a carbon cage gives good agreement with the measured shrinking limits. (author). 8 refs, 6 figs

  3. Structure of polyvalent metal halide melts

    Tosi, M.P.

    1990-12-01

    A short review is given of recent progress in determining and understanding the structure of molten halide salts involving polyvalent metal ions. It covers the following three main topics: (i) melting mechanisms and types of liquid structure for pure polyvalent-metal chlorides; (ii) geometry and stability of local coordination for polyvalent metal ions in molten mixtures of their halides with alkali halides; and (iii) structure breaking and electron localization on addition of metal to the melt. (author). 28 refs, 3 figs, 1 tab

  4. TRANSURANIC METAL HALIDES AND A PROCESS FOR THE PRODUCTION THEREOF

    Fried, S.

    1951-03-20

    Halides of transuranic elements are prepared by contacting with aluminum and a halogen, or with an aluminum halide, a transuranic metal oxide, oxyhalide, halide, or mixture thereof at an elevated temperature.

  5. Computational screening of mixed metal halide ammines

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich

    2013-01-01

    Metal halide ammines, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, can reversibly store ammonia, with high volumetric hydrogen storage capacities. The storage in the halide ammines is very safe, and the salts are therefore highly relevant as a carbon-free energy carrier in future transportation infrastructure...... selection. The GA is evolving from an initial (random) population and selecting those with highest fitness, a function based on e.g. stability, release temperature and storage capacity. The search space includes all alkaline, alkaline earth, 3d and 4d metals and the four lightest halides. In total...... the search spaces consists of millions combinations, which makes a GA ideal, to reduce the number of necessary calculations. We are screening for a one step release from either a hexa or octa ammine, and we have found promising candidates, which will be further investigated ? both computationally...

  6. Alkali metal and alkali earth metal gadolinium halide scintillators

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

    2016-08-02

    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  7. Complexes in polyvalent metal - Alkali halide melts

    Akdeniz, Z.; Tosi, M.P.

    1991-03-01

    Experimental evidence is available in the literature on the local coordination of divalent and trivalent metal ions by halogens in some 140 liquid mixtures of their halides with alkali halides. After brief reference to classification criteria for main types of local coordination, we focus on statistical mechanical models that we are developing for Al-alkali halide mixtures. Specifically, we discuss theoretically the equilibrium between (AlF 6 ) 3- and (AlF 4 ) - complexes in mixtures of AlF 3 and NaF as a function of composition in the NaF-rich region, the effect of the alkali counterion on this equilibrium, the possible role of (AlF 5 ) 2- as an intermediate species in molten cryolite, and the origin of the different complexing behaviours of Al-alkali fluorides and chlorides. We also present a theoretical scenario for processes of structure breaking and electron localization in molten cryolite under addition of sodium metal. (author). 26 refs, 2 tabs

  8. Metal induced gap states at alkali halide/metal interface

    Kiguchi, Manabu; Yoshikawa, Genki; Ikeda, Susumu; Saiki, Koichiro

    2004-01-01

    The electronic state of a KCl/Cu(0 0 1) interface was investigated using the Cl K-edge near-edge X-ray absorption fine structure (NEXAFS). A pre-peak observed on the bulk edge onset of thin KCl films has a similar feature to the peak at a LiCl/Cu(0 0 1) interface, which originates from the metal induced gap state (MIGS). The present result indicates that the MIGS is formed universally at alkali halide/metal interfaces. The decay length of MIGS to an insulator differs from each other, mainly due to the difference in the band gap energy of alkali halide

  9. Definition of a high intensity metal halide discharge reference lamp

    Stoffels, W.W.; Baede, A.H.F.M.; Mullen, van der J.J.A.M.; Haverlag, M.; Zissis, G.

    2006-01-01

    The design of a ref. metal halide discharge lamp is presented. This lamp is meant as a common study object for researchers working on metal halide discharge lamps, who by using the same design will be able to compare results between research groups, diagnostic techniques and numerical models. The

  10. High temperature reactions between molybdenum and metal halides

    Boeroeczki, A.; Dobos, G.; Josepovits, V.K.; Hars, Gy.

    2006-01-01

    Good colour rendering properties, high intensity and efficacy are of vital importance for high-end lighting applications. These requirements can be achieved by high intensity discharge lamps doped with different metal halide additives (metal halide lamps). To improve their reliability, it is very important to understand the different failure processes of the lamps. In this paper, the corrosion reactions between different metal halides and the molybdenum electrical feed-through electrode are discussed. The reactions were studied in the feed-through of real lamps and on model samples too. X-ray photoelectron spectroscopy (XPS) was used to establish the chemical states. In case of the model samples we have also used atomic absorption spectroscopy (AAS) to measure the reaction product amounts. Based on the measurement results we were able to determine the most corrosive metal halide components and to understand the mechanism of the reactions

  11. Structure and energetics of trivalent metal halides

    Hutchinson, F.

    1999-01-01

    Metal trihalide (MX 3 ) systems represent a stern challenge in terms of constructing transferable potential models. Starting from a previously published set of potentials, 'extended' ionic models are developed which, at the outset, include only anion polarization. Deficiencies in these models, particularly for smaller (highly polarizing) cations, axe shown to be significant. For example, crystal structures different to those observed experimentally axe adopted. The potentials axe improved upon by reference to ab initio information available for alkali halides with the 'constraint' that the parameters transfer systematically in a physically transparent manner, for example, in terms of ion radii. The possible influence of anion compression ('breathing') and the relative abundance of anion-anion interactions are considered. Simulation techniques axe developed to allow for the effective simulation of any system symmetry and for the study of transitions between different crystals (constant stress). The developed models are fully tested for a large range of metal trichloride (MCl 3 ) systems. Particular attention is paid to the comparison with recent neutron and X-ray diffraction data on the liquid state. Polarization effects axe shown to be vital in reproducing strong experimental features. The excellent agreement between simulation and experiment allows for differences in experimental procedures to be highlighted. The transferability is further tested by modelling mixtures of the lanthanides with alkali halides with potentials unchanged from the pure systems. The complex evolution of the melt structure is highlighted as the concentration of MCl 3 increases. The effectiveness of the models is tested by reference to dynamical properties. Particular attention is paid to the comparison with Raman scattering data available for a wide range of systems and mixture concentrations. The simulated spectra are generated both by a simple molecular picture of the underlying

  12. Highly dispersed metal catalyst

    Xiao, Xin; West, William L.; Rhodes, William D.

    2016-11-08

    A supported catalyst having an atomic level single atom structure is provided such that substantially all the catalyst is available for catalytic function. A process of forming a single atom catalyst unto a porous catalyst support is also provided.

  13. Treatment of alcaline metals halides for developing crystals

    Spurney, R.W.

    1974-01-01

    A process is described whereby crystals of an alkaline metal halide may be dried and placed in a crucible for development by the Bridgeman-Stockbarger method. Purified alkaline halides from a suspension are dried and formed into dense cakes of transverse section slightly smaller than that of the crucible, where they are packed, melted and grown into crystals according to the Bridgeman-Stockbarger technique. This method applies to the preparation of alkaline halide crystals, particularly sodium iodide for optical elements or scintillation counters [fr

  14. Energetics of the ruthenium-halide bond in olefin metathesis (pre)catalysts

    Falivene, Laura; Poater, Albert; Cazin, Catherine S J; Slugovc, Christian; Cavallo, Luigi

    2013-01-01

    A DFT analysis of the strength of the Ru-halide bond in a series of typical olefin metathesis (pre)catalysts is presented. The calculated Ru-halide bond energies span the rather broad window of 25-43 kcal mol-1. This indicates that in many systems dissociation of the Ru-halide bond is possible and is actually competitive with dissociation of the labile ligand generating the 14e active species. Consequently, formation of cationic Ru species in solution should be considered as a possible event. © 2013 The Royal Society of Chemistry.

  15. 78 FR 51463 - Energy Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures

    2013-08-20

    ... merging the metal halide lamp fixture and the high-intensity discharge (HID) lamp rulemakings. This NOPR... Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures; Proposed Rule #0;#0;Federal...: Energy Conservation Standards for Metal Halide Lamp Fixtures AGENCY: Office of Energy Efficiency and...

  16. Empirical formula for the parameters of metallic monovalent halides ...

    By collating the data on melting properties and transport coefficients obtained from various experiments and theories for certain halides of monovalent metals, allinclusive linear relationship has been fashioned out. This expression holds between the change in entropy and volume on melting; it is approximately obeyed by ...

  17. Demixing in a metal halide lamp, results from modelling

    Beks, M.L.; Hartgers, A.; Mullen, van der J.J.A.M.

    2006-01-01

    Convection and diffusion in the discharge region of a metal halide lamp is studied using a computer model built with the plasma modeling package Plasimo. A model lamp contg. mercury and sodium iodide is studied. The effects of the total lamp pressure on the degree of segregation of the light

  18. Demixing in a metal halide lamp, results from modeling

    Beks, M.L.; Hartgers, A.; Mullen, van der J.J.A.M.; Veldhuizen, van E.M.

    2005-01-01

    Metal Halide (MH) lamps are high pressure discharge devices, containing a complex chemical mixture, to emit light on a broad spectrum while maintaining good efficacies. Lamps of this type were first exhibited by General Electric at the 1964 World Fair in New York [1]. They typically consist of an

  19. Alternative route to metal halide free ionic liquids

    Takao, Koichiro; Ikeda, Yasuhisa

    2008-01-01

    An alternative synthetic route to metal halide free ionic liquids using trialkyloxonium salt is proposed. Utility of this synthetic route has been demonstrated by preparing 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid through the reaction between 1-methylimidazole and triethyloxonium tetra-fluoroborate in anhydrous ether. (author)

  20. Metal Halide Perovskite Polycrystalline Films Exhibiting Properties of Single Crystals

    Brenes, Roberto; Guo, D.; Osherov, Anna; Noel, Nakita K.; Eames, Christopher; Hutter, E.M.; Pathak, Sandeep K.; Niroui, Farnaz; Friend, Richard H.; Islam, M. Saiful; Snaith, Henry J.; Bulović, Vladimir; Savenije, T.J.; Stranks, Samuel D.

    2017-01-01

    Metal halide perovskites are generating enormous excitement for use in solar cells and light-emission applications, but devices still show substantial non-radiative losses. Here, we show that by combining light and atmospheric treatments, we can increase the internal luminescence quantum

  1. Spectroscopy on metal-halide lamps under varying gravity conditions

    Flikweert, A.J.

    2008-01-01

    Worldwide, 20% of all electricity is used for lighting. For this reason, efficient lamps are economically and ecologically important. High intensity discharge (HID) lamps are efficient lamps. The most common HID lamp these days is the metal-halide (MH) lamp. MH lamps have a good colour rendering

  2. Local coordination of polyvalent metal ions in molten halide mixtures

    Akdeniz, Z.; Tosi, M.P.

    1989-07-01

    Ample experimental evidence is available in the literature on the geometry and the stability of local coordination for polyvalent metal ions in molten mixtures of their halides with alkali halides. Recent schemes for classifying this evidence are discussed. Dissociation of tetrahedral halocomplexes in good ionic systems can be viewed as a classical Mott problem of bound-state stability in a conducting matrix. More generally, structural coordinates can be constructed from properties of the component elements, to separate out systems with long-lived fourfold or sixfold coordination and to distinguish between these. (author). 11 refs, 1 fig

  3. Metal catalysts fight back

    George Marsh

    1998-01-01

    In recent years organometallic catalysts, especially metallocenes, have been a major focus of attention in terms of polymerisation chemistry. But the news earlier this year of a family of iron-based catalysts able to rival the effectiveness of both conventional and metallocene catalysts in the polymerisation of ethylene has excited the plastics industry. Because of the impact of this discovery and its potential as a route to lower-priced commodity plastics in the future, it may be useful at t...

  4. Synthesis of halide- and solvent free metal borohydrides

    Grinderslev, Jakob; Møller, Kasper Trans; Richter, Bo

    have challenges due to their high desorption kinetics and limited reversibility at moderate conditions.[2],[3],[4] In this work, we present a new approach to synthesize halide- and solvent free metal borohydrides starting from the respective metal hydride. The synthetic strategy ensures that no metal...... to the metal. Hence, the powdered M(BH4)3∙DMS is heated to 140 °C for 4 hours to obtain pure M(BH4)3. The rare-earth metal borohydrides have been investigated by infrared spectroscopy and thermal analysis (TGA-DSC-MS). Furthermore, the structural trends are investigated by synchrotron radiation powder X...

  5. Chemoselective Radical Dehalogenation and C-C Bond Formation on Aryl Halide Substrates Using Organic Photoredox Catalysts.

    Poelma, Saemi O; Burnett, G Leslie; Discekici, Emre H; Mattson, Kaila M; Treat, Nicolas J; Luo, Yingdong; Hudson, Zachary M; Shankel, Shelby L; Clark, Paul G; Kramer, John W; Hawker, Craig J; Read de Alaniz, Javier

    2016-08-19

    Despite the number of methods available for dehalogenation and carbon-carbon bond formation using aryl halides, strategies that provide chemoselectivity for systems bearing multiple carbon-halogen bonds are still needed. Herein, we report the ability to tune the reduction potential of metal-free phenothiazine-based photoredox catalysts and demonstrate the application of these catalysts for chemoselective carbon-halogen bond activation to achieve C-C cross-coupling reactions as well as reductive dehalogenations. This procedure works both for conjugated polyhalides as well as unconjugated substrates. We further illustrate the usefulness of this protocol by intramolecular cyclization of a pyrrole substrate, an advanced building block for a family of natural products known to exhibit biological activity.

  6. Quantitative positron annihilation studies in citrates, halides and oxyhalides chemisorbed on γ-alumina catalyst

    Luo, X.H.; Jean, Y.C.; Cheng, K.L.

    1987-01-01

    A quantitative study of the γ-alumina catalyst chemisorbed by nitrates, halides, and oxyhalides has been conducted with the positron annihilation spectroscopy (PAS). Catalysts containing Fe, Co, or Ni have been extensively used in chemical industry and petroleum refining. The positron or Ps annihilation can provide a profile information about the bulk, near surface, and void. It is an in-situ surface technique. The PAS technique has shown its capability to determine the nitrate or chloride in γ-alumina as low as 0.02% in solids. It is interesting to note that the PAS may offer the oxidation state information in solids. This is not surprising because the positron annihilation is sensitive to the electron density variation in environments. Positron annihilation models for halides and oxyhalides are proposed

  7. Halides of BET-TTF: novel hydrated molecular metals

    Laukhina, E.; Ribera, E.; Vidal-Gancedo, J.; Canadell, E.; Veciana, J.; Rovira, C. [Universidad Autonoma de Barcelona, Bellaterra (Spain). Inst. de Ciencia de Materials; Khasanov, S.; Zorina, L.; Shibaeva, R. [Rossijskaya Akademiya Nauk, Chernogolovka (Russian Federation). Inst. Fiziki Tverdogo Tela; Laukhin, V. [Inst. of Problems of Chemical Physics, RAS, Chernogolovka (Russian Federation); Honold, M.; Nam, M.-S.; Singleton, J. [Clarendon Lab., Univ. of Oxford (United Kingdom)

    2000-01-07

    A hint of superconducting transition has been observed for the first time in a cation radical salt derived from bisethylenethio-tetrathiafulvalene (BET-TTF), the salt (BET-TTF){sub 2}Br.3H{sub 2}O. Here the synthesis, X-ray structure, and physical properties of two hydrated halides of BET-TTF that are isostructural and present stable metallic properties are described. (orig.)

  8. Metal-halide lamp design: atomic and molecular data needed

    Lapatovich, Walter P

    2009-01-01

    Metal-halide lamps are a subset of high intensity discharge (HID) lamps so named because of their high radiance. These lamps are low temperature (∼0.5 eV), weakly ionized plasmas sustained in refractory but light transmissive envelopes by the passage of electric current through atomic and molecular vapors. For commercial applications, the conversion of electric power to light must occur with good efficiency and with sufficient spectral content throughout the visible (380-780 nm) to permit the light so generated to render colors comparable to natural sunlight. This is achieved by adding multiple metals to a basic mercury discharge. Because the vapor pressure of most metals is very much lower than mercury itself, metal-halide salts of the desired metals, having higher vapor pressures, are used to introduce the material into the basic discharge. The metal compounds are usually polyatomic iodides, which vaporize and subsequently dissociate as they diffuse into the bulk plasma. Metals with multiple visible transitions are necessary to achieve high photometric efficiency (efficacy) and good color. Compounds of Sc, Dy, Ho, Tm, Ce, Pr, Yb and Nd are commonly used. The electrons, atoms and radicals are in local thermodynamic equilibrium (LTE), but not with the radiation field. Strong thermal (10 6 K m -1 ) and density gradients are sustained in the discharge. Atomic radiation produced in the high-temperature core transits through colder gas regions where it interacts with cold atoms and un-dissociated molecules before exiting the lamp. Power balance and spectral output of the lamp are directly affected by the strength of atomic transitions. Attempts to simulate the radiative output of functional metal-halide lamps have been successful only in very simple cases. More data (e.g. the atomic transition probabilities of Ce i) are necessary to improve lamp performance, to select appropriate radiators and in scaling the lamp geometry to various wattages for specific applications.

  9. Rare earth metals for automotive exhaust catalysts

    Shinjoh, Hirohumi

    2006-01-01

    The usage of rare earth metals for automotive exhaust catalysts is demonstrated in this paper. Rare earth metals have been widely used in automotive catalysts. In particular, three-way catalysts require the use of ceria compounds as oxygen storage materials, and lanthana as both a stabilizer of alumina and a promoter. The application for diesel catalysts is also illustrated. Effects of inclusion of rare earth metals in automotive catalysts are discussed

  10. Lamp-Ballast Compatibility Index for Efficient Ceramic Metal Halide Lamp Operation

    Sourish Chatterjee

    2013-01-01

    Development of energy efficient products and exploration of energy saving potential are major challenges for present day’s technology. Ceramic Metal Halide lamp is the latest improved version of metal halide lamp that finds its wide applications in indoor commercial lighting especially in retail shop lighting. This lamp shows better performance in terms of higher lumen per watt and colour constancy in comparison to conventional metal halide lamp. The inherent negative incremental impedance of...

  11. Novel non-platinum metal catalyst material

    2014-01-01

    The present invention relates to a novel non-platinum metal catalyst material for use in low temperature fuel cells and electrolysers and to fuel cells and electrolysers comprising the novel non-platinum metal catalyst material. The present invention also relates to a novel method for synthesizing...... the novel non-platinum metal catalyst material....

  12. Sodium-metal halide and sodium-air batteries.

    Ha, Seongmin; Kim, Jae-Kwang; Choi, Aram; Kim, Youngsik; Lee, Kyu Tae

    2014-07-21

    Impressive developments have been made in the past a few years toward the establishment of Na-ion batteries as next-generation energy-storage devices and replacements for Li-ion batteries. Na-based cells have attracted increasing attention owing to low production costs due to abundant sodium resources. However, applications of Na-ion batteries are limited to large-scale energy-storage systems because of their lower energy density compared to Li-ion batteries and their potential safety problems. Recently, Na-metal cells such as Na-metal halide and Na-air batteries have been considered to be promising for use in electric vehicles owing to good safety and high energy density, although less attention is focused on Na-metal cells than on Na-ion cells. This Minireview provides an overview of the fundamentals and recent progress in the fields of Na-metal halide and Na-air batteries, with the aim of providing a better understanding of new electrochemical systems. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Status quo of ceramic material for metal halide discharge lamps

    Kappen, Theo G M M

    2005-01-01

    Polycrystalline alumina is an excellent ceramic material for use as the envelope for metal halide discharge lamps. Although this material was introduced in the mid-1960s, and is thus already known for several decades, recent years have seen considerable effort aimed at further development of these ceramic envelope materials. Developments are not only in the field of ceramic shaping technologies, but are also concentrated on the material properties of the ceramic material itself. Optical, mechanical as well as the chemical properties of the ceramic envelope are strongly controlled by the shape as well as the microstructure of the ceramics used

  14. Halide based MBE of crystalline metals and oxides

    Greenlee, Jordan D.; Calley, W. Laws; Henderson, Walter; Doolittle, W. Alan [Georgia Institute of Technology, School of Electrical and Computer Engineering, Atlanta, Georgia (United States)

    2012-02-15

    A halide based growth chemistry has been demonstrated which can deliver a range of transition metals using low to moderate effusion cell temperatures (30-700 C) even for high melting point metals. Previously, growth with transition metal species required difficult to control electron beam or impurity inducing metal organic sources. Both crystalline oxide and metal films exhibiting excellent crystal quality are grown using this halide-based growth chemistry. Films are grown using a plasma assisted Molecular Beam Epitaxy (MBE) system with metal-chloride precursors. Crystalline niobium, cobalt, iron, and nickel were grown using this chemistry but the technology can be generalized to almost any metal for which a chloride precursor is available. Additionally, the oxides LiNbO{sub 3} and LiNbO{sub 2} were grown with films exhibiting X-ray diffraction (XRD) rocking curve full-widths at half maximum of 150 and 190 arcseconds respectively. LiNbO{sub 2} films demonstrate a memristive response due to the rapid movement of lithium in the layered crystal structure. The rapid movement of lithium ions in LiNbO{sub 2} memristors is characterized using impedance spectroscopy measurements. The impedance spectroscopy measurements suggest an ionic current of.1 mA for a small drive voltage of 5 mV AC or equivalently an ionic current density of {proportional_to}87 A/cm{sup 2}. This high ionic current density coupled with low charge transfer resistance of {proportional_to}16.5 {omega} and a high relaxation frequency (6.6 MHz) makes this single crystal material appealing for battery applications in addition to memristors. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  15. Melting and liquid structure of polyvalent metal halides

    Tosi, M.P.

    1992-08-01

    A short review is given of recent progress in determining and understanding liquid structure types and melting mechanisms for halides of polyvalent metals. The nature of the preferred local coordination for the polyvalent metal ion in the melt can usually be ascertained from data on liquid mixtures with halogen-donating alkali halides. The stability of these local coordination states and the connectivity that arises between them in the approach to the pure melt determines the character of its short-range and possible medium-range order. A broad classification of structural and melting behaviours can be given on the basis of measured melting parameters and transport coefficients for many compounds, in combination with the available diffraction data on the liquid structure of several compounds. Correlations have been shown to exist with a simple indicator of the nature of the chemical bond and also with appropriate parameters of ionic models, wherever the latter are usefully applicable for semiquantitative calculations of liquid structure. Consequences on the mechanisms for valence electron localization in solutions of metallic elements into strongly structured molten salts are also briefly discussed. (author). 46 refs, 4 figs, 2 tabs

  16. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    2010-01-01

    ... high intensity discharge fixture, the efficiency of a lamp and ballast combination, expressed as a... lamps. Metal halide lamp means a high intensity discharge lamp in which the major portion of the light... 10 Energy 3 2010-01-01 2010-01-01 false Definitions concerning metal halide lamp ballasts and...

  17. Broadly tunable metal halide perovskites for solid-state light-emission applications

    Adjokatse, Sampson; Fang, Hong-Hua; Loi, Maria Antonietta

    2017-01-01

    The past two years have witnessed heightened interest in metal-halide perovskites as promising optoelectronic materials for solid-state light emitting applications beyond photovoltaics. Metal-halide perovskites are low-cost solution-processable materials with excellent intrinsic properties such as

  18. Metal Halide Perovskite Single Crystals: From Growth Process to Application

    Shuigen Li

    2018-05-01

    Full Text Available As a strong competitor in the field of optoelectronic applications, organic-inorganic metal hybrid perovskites have been paid much attention because of their superior characteristics, which include broad absorption from visible to near-infrared region, tunable optical and electronic properties, high charge mobility, long exciton diffusion length and carrier recombination lifetime, etc. It is noted that perovskite single crystals show remarkably low trap-state densities and long carrier diffusion lengths, which are even comparable with the best photovoltaic-quality silicon, and thus are expected to provide better optoelectronic performance. This paper reviews the recent development of crystal growth in single-, mixed-organic-cation and fully inorganic halide perovskite single crystals, in particular the solution approach. Furthermore, the application of metal hybrid perovskite single crystals and future perspectives are also highlighted.

  19. Halide-Enhanced Catalytic Activity of Palladium Nanoparticles Comes at the Expense of Catalyst Recovery

    Azzedine Bouleghlimat

    2017-09-01

    Full Text Available In this communication, we present studies of the oxidative homocoupling of arylboronic acids catalyzed by immobilised palladium nanoparticles in aqueous solution. This reaction is of significant interest because it shares a key transmetallation step with the well-known Suzuki-Miyaura cross-coupling reaction. Additives can have significant effects on catalysis, both in terms of reaction mechanism and recovery of catalytic species, and our aim was to study the effect of added halides on catalytic efficiency and catalyst recovery. Using kinetic studies, we have shown that added halides (added as NaCl and NaBr can increase the catalytic activity of the palladium nanoparticles more than 10-fold, allowing reactions to be completed in less than half a day at 30 °C. However, this increased activity comes at the expense of catalyst recovery. The results are in agreement with a reaction mechanism in which, under conditions involving high concentrations of chloride or bromide, palladium leaching plays an important role. Considering the evidence for analogous reactions occurring on the surface of palladium nanoparticles under different reaction conditions, we conclude that additives can exert a significant effect on the mechanism of reactions catalyzed by nanoparticles, including switching from a surface reaction to a solution reaction. The possibility of this switch in mechanism may also be the cause for the disagreement on this topic in the literature.

  20. Nanoparticular metal oxide/anatase catalysts

    2010-01-01

    The present invention concerns a method of preparation of nanoparticular metal oxide catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular metal oxide catalyst precursors comprising combustible crystallization seeds upon which...... the catalyst metai oxide is co-precipitated with the carrier metal oxide, which crystallization seeds are removed by combustion in a final calcining step. The present invention also concerns processes wherein the nanoparticular metal oxide catalysts of the invention are used, such as SCR (deNOx) reactions...

  1. Thermal battery. [solid metal halide electrolytes with enhanced electrical conductance after a phase transition

    Carlsten, R.W.; Nissen, D.A.

    1973-03-06

    The patent describes an improved thermal battery whose novel design eliminates various disadvantages of previous such devices. Its major features include a halide cathode, a solid metal halide electrolyte which has a substantially greater electrical conductance after a phase transition at some temperature, and a means for heating its electrochemical cells to activation temperature.

  2. Metal halide arc discharge lamp having short arc length

    Muzeroll, Martin E. (Inventor)

    1994-01-01

    A metal halide arc discharge lamp includes a sealed light-transmissive outer jacket, a light-transmissive shroud located within the outer jacket and an arc tube assembly located within the shroud. The arc tube assembly includes an arc tube, electrodes mounted within the arc tube and a fill material for supporting an arc discharge. The electrodes have a spacing such that an electric field in a range of about 60 to 95 volts per centimeter is established between the electrodes. The diameter of the arc tube and the spacing of the electrodes are selected to provide an arc having an arc diameter to arc length ratio in a range of about 1.6 to 1.8. The fill material includes mercury, sodium iodide, scandium tri-iodide and a rare gas, and may include lithium iodide. The lamp exhibits a high color rendering index, high lumen output and high color temperature.

  3. Phase-resolved response of a metal-halide lamp

    Flikweert, A J; Beks, M L; Nimalasuriya, T; Kroesen, G M W; Van der Mullen, J J A M; Stoffels, W W

    2009-01-01

    The metal-halide (MH) lamp sometimes shows unwanted colour segregation, caused by a combination of convection and diffusion. In the past we investigated the lamp, running on a switched dc ballast of 120 Hz, using a dc approximation for the distribution of the radiating species. Here we present phase-resolved intensity measurements to verify this approximation. The MH lamp contains Hg as buffer gas and DyI 3 as salt additive; we measure the light emitted by Dy and by Hg atoms. An intensity fluctuation of ∼25% close to the electrodes is found only. The observed fluctuations are explained by the cataphoresis effect and temperature fluctuations; the time scales are in the same order. Furthermore, measurements at higher gravity in a centrifuge (up to 10g) show that the effect becomes smaller at increasing gravity levels. From these results it is concluded that a dc approximation, which is generally assumed by lamp developers, is allowed for this MH lamp.

  4. Water-Induced Dimensionality Reduction in Metal-Halide Perovskites

    Turedi, Bekir

    2018-03-30

    Metal-halide perovskite materials are highly attractive materials for optoelectronic applications. However, the instability of perovskite materials caused by moisture and heat-induced degradation impairs future prospects of using these materials. Here we employ water to directly transform films of the three-dimensional (3D) perovskite CsPbBr3 to stable two-dimensional (2D) perovskite-related CsPb2Br5. A sequential dissolution-recrystallization process governs this water induced transformation under PbBr2 rich condition. We find that these post-synthesized 2D perovskite-related material films exhibit excellent stability against humidity and high photoluminescence quantum yield. We believe that our results provide a new synthetic method to generate stable 2D perovskite-related materials that could be applicable for light emitting device applications.

  5. Non-hydrolytic metal oxide films for perovskite halide overcoating and stabilization

    Martinson, Alex B.; Kim, In Soo

    2017-09-26

    A method of protecting a perovskite halide film from moisture and temperature includes positioning the perovskite halide film in a chamber. The chamber is maintained at a temperature of less than 200 degrees Celsius. An organo-metal compound is inserted into the chamber. A non-hydrolytic oxygen source is subsequently inserted into the chamber. The inserting of the organo-metal compound and subsequent inserting of the non-hydrolytic oxygen source into the chamber is repeated for a predetermined number of cycles. The non-hydrolytic oxygen source and the organo-metal compound interact in the chamber to deposit a non-hydrolytic metal oxide film on perovskite halide film. The non-hydrolytic metal oxide film protects the perovskite halide film from relative humidity of greater than 35% and a temperature of greater than 150 degrees Celsius, respectively.

  6. Modelling current transfer to cathodes in metal halide plasmas

    Benilov, M S; Cunha, M D; Naidis, G V

    2005-01-01

    This work is concerned with investigation of the main features of current transfer to cathodes under conditions characteristic of metal halide (MH) lamps. It is found that the presence of MHs in the gas phase results in a small decrease of the cathode surface temperature and of the near-cathode voltage drop in the diffuse mode of current transfer; the range of stability of the diffuse mode expands. Effects caused by a variation of the work function of the cathode surface owing to formation of a monolayer of alkali metal atoms on the surface are studied for particular cases where the monolayer is composed of sodium or caesium. It is found that the formation of the sodium monolayer affects the diffuse mode of current transfer only moderately and in the same direction that the presence of metal atoms in the gas phase affects it. Formation of the caesium monolayer produces a dramatic effect: the cathode surface temperature decreases very strongly, the diffuse-mode current-voltage characteristic becomes N-S-shaped

  7. The Role of Surface Tension in the Crystallization of Metal Halide Perovskites

    Zhumekenov, Ayan A.; Burlakov, Victor M.; Saidaminov, Makhsud I.; Alofi, Abdulilah; Haque, Mohammed; Turedi, Bekir; Davaasuren, Bambar; Dursun, Ibrahim; Cho, Nam Chul; El-Zohry, Ahmed M.; de Bastiani, Michele; Giugni, Andrea; Torre, Bruno; Di Fabrizio, Enzo M.; Mohammed, Omar F.; Rothenberger, Alexander; Wu, Tao; Goriely, Alain; Bakr, Osman

    2017-01-01

    The exciting intrinsic properties discovered in single crystals of metal halide perovskites still await their translation into optoelectronic devices. The poor understanding and control of the crystallization process of these materials are current

  8. Solution enthalpies of alkali metal halides in water and heavy water mixtures with dimethyl sulfoxide

    Egorov, G.I.

    1994-01-01

    Solution enthalpies of CsF, LiCl, NaI, CsI and some other halides of alkali metals and tetrabutylammonium have been measured by the method of calorimetry. Standard solution enthalpies of all alkali metals (except rubidium) halides in water and heavy water mixtures with dimethylsulfoxide at 298.15 K have been calculated. Isotopic effects in solvation enthalpy of the electrolytes mentioned in aqueous solutions of dimethylsulfoxide have been discussed. 29 refs., 2 figs., 4 tabs

  9. Influence of electrode, buffer gas and control gear on metal halide lamp performance

    Lamouri, A; Naruka, A; Sulcs, J; Varanasi, C V; Brumleve, T R

    2005-01-01

    In this paper the influence of electrode composition, buffer gas fill pressure and control gear on the performance of metal halide lamps is investigated. It is shown that pure tungsten electrodes improve lumen maintenance and reduce voltage rise over lamp life. An optimum buffer gas fill pressure condition is discovered which allows for reduced electrode erosion during lamp starting as well as under normal operating conditions. Use of electronic control gear is shown to improve the performance of metal halide lamps

  10. Broadly tunable metal halide perovskites for solid-state light-emission applications

    Adjokatse, Sampson; Fang, Hong-Hua; Loi, Maria Antonietta

    2017-01-01

    The past two years have witnessed heightened interest in metal-halide perovskites as promising optoelectronic materials for solid-state light emitting applications beyond photovoltaics. Metal-halide perovskites are low-cost solution-processable materials with excellent intrinsic properties such as broad tunability of bandgap, defect tolerance, high photoluminescence quantum efficiency and high emission color purity (narrow full-width at half maximum). In this review, the photophysical propert...

  11. Observation of vapor pressure enhancement of rare-earth metal-halide salts in the temperature range relevant to metal-halide lamps

    Curry, J. J.; Henins, A.; Hardis, J. E. [National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); Estupinan, E. G. [Osram Sylvania Inc., Beverly, Massachusetts 01915 (United States); Lapatovich, W. P. [Independent Consultant, 51 Pye Brook Lane, Boxford, Massachusetts 01921 (United States); Shastri, S. D. [Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

    2012-02-20

    Total vapor-phase densities of Dy in equilibrium with a DyI{sub 3}/InI condensate and Tm in equilibrium with a TmI{sub 3}/TlI condensate have been measured for temperatures between 900 K and 1400 K. The measurements show strong enhancements in rare-earth vapor densities compared to vapors in equilibrium with the pure rare-earth metal-halides. The measurements were made with x-ray induced fluorescence on the sector 1-ID beam line at the Advanced Photon Source. The temperature range and salt mixtures are relevant to the operation of metal-halide high-intensity discharge lamps.

  12. Metal nanoparticles as a conductive catalyst

    Coker, Eric N [Albuquerque, NM

    2010-08-03

    A metal nanocluster composite material for use as a conductive catalyst. The metal nanocluster composite material has metal nanoclusters on a carbon substrate formed within a porous zeolitic material, forming stable metal nanoclusters with a size distribution between 0.6-10 nm and, more particularly, nanoclusters with a size distribution in a range as low as 0.6-0.9 nm.

  13. Metal halides vapor lasers with inner reactor and small active volume.

    Shiyanov, D. V.; Sukhanov, V. B.; Evtushenko, G. S.

    2018-04-01

    Investigation of the energy characteristics of copper, manganese, lead halide vapor lasers with inner reactor and small active volume 90 cm3 was made. The optimal operating pulse repetition rates, temperatures, and buffer gas pressure for gas discharge tubes with internal and external electrodes are determined. Under identical pump conditions, such systems are not inferior in their characteristics to standard metal halide vapor lasers. It is shown that the use of a zeolite halogen generator provides lifetime laser operation.

  14. Bi-metallic catalysts, methods of making, and uses thereof

    Basset, Jean-Marie

    2017-01-19

    Provided herein are bi-metallic catalysts, methods of making, and uses thereof. In some embodiments, the bi-metallic catalyst contains two different metal catalysts that can be used in hydrocarbon metathesis reactions, in some embodiments, the methods of making the bi-metallic catalysts can include two steps utilizing a surface organometallic chemistry approach in which the two different metal catalysts are sequentially grafted onto a support.

  15. Bi-metallic catalysts, methods of making, and uses thereof

    Basset, Jean-Marie; Samantaray, Manoja K.; Dey, Raju; Abou-Hamad, Edy; Kavitake, Santosh

    2017-01-01

    Provided herein are bi-metallic catalysts, methods of making, and uses thereof. In some embodiments, the bi-metallic catalyst contains two different metal catalysts that can be used in hydrocarbon metathesis reactions, in some embodiments, the methods of making the bi-metallic catalysts can include two steps utilizing a surface organometallic chemistry approach in which the two different metal catalysts are sequentially grafted onto a support.

  16. Reactivity of Aryl Halides for Reductive Dehalogenation in (Seawater Using Polymer-Supported Terpyridine Palladium Catalyst

    Toshimasa Suzuka

    2015-05-01

    Full Text Available A polymer-supported terpyridine palladium complex was prepared. The complex was found to promote hydrodechlorination of aryl chlorides with potassium formate in seawater. Generally, reductive cleavage of aryl chlorides using transition metal catalysts is more difficult than that of aryl bromides and iodides (reactivity: I > Br > Cl; however, the results obtained did not follow the general trend. Therefore, we investigated the reaction inhibition agents and found a method to remove these inhibitors. The polymeric catalysts showed high catalytic activity and high reusability for transfer reduction in seawater.

  17. Catalyst for hydrocarbon conversion

    Duhaut, P.; Miquel, J.

    1975-01-01

    A description is given for a catalyst and process for hydrocarbon conversions, e.g., reforming. The catalyst contains an alumina carrier, platinum, iridium, at least one metal selected from uranium, vanadium, and gallium, and optionally halogen in the form of metal halide of one of the aforesaid components. (U.S.)

  18. Designing mixed metal halide ammines for ammonia storage using density functional theory and genetic algorithms

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J.

    2014-01-01

    electrolyte membrane fuel cells (PEMFC). We use genetic algorithms (GAs) to search for materials containing up to three different metals (alkaline-earth, 3d and 4d) and two different halides (Cl, Br and I) – almost 27000 combinations, and have identified novel mixtures, with significantly improved storage......Metal halide ammines have great potential as a future, high-density energy carrier in vehicles. So far known materials, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, are not suitable for automotive, fuel cell applications, because the release of ammonia is a multi-step reaction, requiring too much heat...

  19. The impact of alkali metal halide electron donor complexes in the photocatalytic degradation of pentachlorophenol

    Khuzwayo, Z., E-mail: zack.khuzwayo@up.ac.za; Chirwa, E.M.N

    2017-01-05

    Highlights: • Facilitation of photocatalysis using simple metal-halides as VB hole scavengers. • Recombination prevention by coupled valence and conduction band approaches. • Determination of anions critical levels beyond which process retardation occurs. • Determination of the photocatalytic process rate of reaction kinetics. - Abstract: The performance of photocatalytic oxidation of chemical pollutants is subjected to the presence of anion complexes in natural waters. This study investigated the influence of alkali metal (Na{sup +} (sodium), K{sup +} (potassium)) halides (Cl{sup −} (chloride), Br{sup −} (bromide), F{sup −} (fluoride)) as inorganic ion sources in the photocatalytic degradation of pentachlorophenol (PCP) in batch systems. It was found that the exclusive presence of halides in the absence of an electron acceptor adequately facilitated the photocatalyst process below critical levels of anion populations, where beyond the critical point the process was significantly hindered. Below the determined critical point, the performance in some cases near matches that of the facilitation of the photocatalytic process by exclusive oxygen, acting as an electron scavenger. The coupling of halide ions and oxygenation presented significantly improved photo-oxidation of PCP, this was confirmed by the inclusion of formic acid as a comparative electron donor. The Langmuir-Hinshelwood kinetic expression was used to calculate the performance rate kinetics. The probable impact of the halide anions was discussed with regards to the process of electron hole pair recombination prevention.

  20. 2-D images of the metal-halide lamp obtained by experiment and model

    Flikweert, A.J.; Beks, M.L.; Nimalasuriya, T.; Kroesen, G.M.W.; Mullen, van der J.J.A.M.; Stoffels, W.W.

    2008-01-01

    The metal-halide lamp shows color segregation caused by diffusion and convection. Two-dimensional imaging of the arc discharge under varying gravity conditions aids in the understanding of the flow phenomena. In this paper, we show results obtained by experiments and by numerical simulations in

  1. A model for additive transport in metal halide lamps containing mercury and dysprosium tri-iodide

    Beks, M.L.; Haverlag, M.; Mullen, van der J.J.A.M.

    2008-01-01

    The distribution of additives in a metal halide lamp is examined through numerical modelling. A model for a lamp containing sodium iodide additives has been modified to study a discharge containing dysprosium tri-iodide salts. To study the complex chemistry the method of Gibbs minimization is used

  2. Transport phenomena in metal-halide lamps : a poly-diagnostic study

    Nimalasuriya, T.

    2007-01-01

    Worldwide about 20% of all electricity is used for lighting. It is therefore of great interest to develop a lamp that has high e±cacy, good colour rendering and long lifetime. The metal-halide lamp is a gas discharge lamp that meets all these demands. Unfortunately there are still issues with this

  3. Metal leaching from refinery waste hydroprocessing catalyst.

    Marafi, Meena; Rana, Mohan S

    2018-05-18

    The present study aims to develop an eco-friendly methodology for the recovery of nickel (Ni), molybdenum (Mo), and vanadium (V) from the refinery waste spent hydroprocessing catalyst. The proposed process has two stages: the first stage is to separate alumina, while the second stage involves the separation of metal compounds. The effectiveness of leaching agents, such as NH 4 OH, (NH 4 ) 2 CO 3 , and (NH 4 ) 2 S 2 O 8 , for the extraction of Mo, V, Ni, and Al from the refinery spent catalyst has been reported as a function of reagent concentration (0.5 to 2.0 molar), leaching time (1 to 6 h), and temperature (35 to 60°C). The optimal leaching conditions were achieved to obtain the maximum recovery of Mo, Ni, and V metals. The effect of the mixture of multi-ammonium salts on the metal extraction was also studied, which showed an adverse effect for Ni and V, while marginal improvement was observed for Mo leaching. The ammonium salts can form soluble metal complexes, in which stability or solubility depends on the nature of ammonium salt and the reaction conditions. The extracted metals and support can be reused to synthesize a fresh hydroprocessing catalyst. The process will reduce the refinery waste and recover the expensive metals. Therefore, the process is not only important from an environmental point of view but also vital from an economic perspective.

  4. Process for the regeneration of metallic catalysts

    Katzer, James R.; Windawi, Hassan

    1981-01-01

    A method for the regeneration of metallic hydrogenation catalysts from the class consisting of Ni, Rh, Pd, Ir, Pt and Ru poisoned with sulfur, with or without accompanying carbon deposition, comprising subjecting the catalyst to exposure to oxygen gas in a concentration of about 1-10 ppm. intermixed with an inert gas of the group consisting of He, A, Xe, Kr, N.sub.2 and air substantially free of oxygen to an extent such that the total oxygen molecule throughout is in the range of about 10 to 20 times that of the hydrogen sulfide molecular exposure producing the catalyst poisoning while maintaining the temperature in the range of about 300.degree. to 500.degree. C.

  5. Thorium valency in molten alkali halides in equilibrium with metallic thorium

    Smirnov, M.V.; Kudyakov, V.Ya.

    1983-01-01

    Metallic thorium is shown to corrode in molten alkali halides even in the absence of external oxidizing agents, alkali cations acting as oxidizing agents. Its corrosion rate grows in the series of alkali chlorides from LiCl to CsCl at constant temperature. Substituting halide anions for one another exerts a smaller influence, the rate rising slightly in going from chlorides to bromides and iodides, having the same alkali cations. Thorium valency is determined coulometrically, the metal being dissolved anodically in molten alkali halides and their mixtures. In fluoride melts it is equal to 4 but in chloride, bromide and iodide ones, as a rule, it has non-integral values between 4 and 2 which diminish as the temperature is raised, as the thorium concentration is lowered, as the radii of alkali cations decrease and those of halide anions increase. The emf of cells Th/N ThHlsub(n) + (1-N) MHl/MHl/C, Hlsub(2(g)) where Hl is Cl, Br or I, M is Li, Na, K, Cs or Na + K, and N < 0.05, is measured as a function of concentration at several temperatures. Expressions are obtained for its concentration dependence. The emf grows in the series of alkali chlorides from LiCl to CsCl, other conditions being equal. (author)

  6. Conversion of ion-exchange resins, catalysts and sludges to glass with optional noble metal recovery using the GMODS process

    Forsberg, C.W.; Beahm, E.C.

    1996-01-01

    Chemical processing and cleanup of waste streams (air and water) typically result in products, clean air, clean water, and concentrated hazardous residues (ion exchange resins, catalysts, sludges, etc.). Typically, these streams contain significant quantities of complex organics. For disposal, it is desirable to destroy the organics and immobilize any heavy metals or radioactive components into stable waste forms. If there are noble metals in the residues, it is desirable to recover these for reuse. The Glass Material Oxidation and Dissolution System (GMODS) is a new process that directly converts radioactive and hazardous chemical wastes to borosilicate glass. GMODS oxidizes organics with the residue converted to glass; converts metals, ceramics, and amorphous solids to glass; converts halides (eg chlorides) to borosilicate glass and a secondary sodium halide stream; and recovers noble metals. GMODS has been demonstrated on a small laboratory scale (hundreds of grams), and the equipment needed for larger masses has been identified

  7. Antipollution processing of a used refining catalyst and metal recovery

    Trinh Dinh Chan; Llido, E.

    1992-04-30

    The used catalyst, containing metals such as vanadium, nickel and iron, is unloaded from the plant and is first processed by stripping; it is then calcined in critical conditions, and the catalyst metals are leached with a sodium hydroxide or sodium carbonate aqueous solution. The antipollution process can be applied to oil fraction hydroconversion or hydroprocessing catalysts.

  8. Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides

    Magdesieva, Tatiana V.; Graczyk, Magdalena; Vallat, Alain; Nikitin, Oleg M.; Demyanov, Petr I.; Butin, Kim P.; Vorotyntsev, Mikhail A.

    2006-01-01

    We have studied a reaction between the reduced form of titanocene dichloride (Cp 2 TiCl 2 ) and a group of organic halides: benzyl derivatives (4-X-C 6 H 4 CH 2 Cl, X = H, NO 2 , CH 3 ; 4-X-C 6 H 4 CH 2 Br, X = H, NO 2 , PhC(O); 4-X-C 6 H 4 CH 2 SCN, X = H, NO 2 ) as well as three aryl halides (4-NO 2 C 6 H 4 Hal, Hal = Cl, Br; 4-CH 3 O-C 6 H 4 Cl). It has been shown that the electrochemical reduction of Cp 2 TiCl 2 in the presence of these benzyl halides leads to a catalytic cycle resulting in the reductive dehalogenation of these organic substrates to yield mostly corresponding toluene derivatives as the main product. No dehalogenation has been observed for aryl derivatives. Based on electrochemical data and digital simulation, possible schemes of the catalytic process have been outlined. For non-substituted benzyl halides halogen atom abstraction is a key step. For the reaction of nitrobenzyl halides the complexation of Ti(III) species with the nitro group takes place, with the electron transfer from Ti(III) to this group (owing to its highest coefficient in LUMO of the nitro benzyl halide) followed by an intramolecular dissociative electron redistribution in the course of the heterolytic C-Hal bond cleavage. The results for reduced titanocene dichloride centers immobilized inside a polymer film showed that the catalytic reductive dehalogenation of the p-nitrobenzyl chloride does occur but with a low efficiency because of the partial deactivation of the film due to the blocking of the electron charge transport between the electrode and catalytic centers

  9. Molecular metal-Oxo catalysts for generating hydrogen from water

    Long, Jeffrey R; Chang, Christopher J; Karunadasa, Hemamala I

    2015-02-24

    A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition having the general formula [(PY5W.sub.2)MO].sup.2+, wherein PY5W.sub.2 is (NC.sub.5XYZ)(NC.sub.5H.sub.4).sub.4C.sub.2W.sub.2, M is a transition metal, and W, X, Y, and Z can be H, R, a halide, CF.sub.3, or SiR.sub.3, where R can be an alkyl or aryl group. The two accompanying counter anions, in one embodiment, can be selected from the following Cl.sup.-, I.sup.-, PF.sub.6.sup.-, and CF.sub.3SO.sub.3.sup.-. In embodiments of the invention, water, such as tap water containing electrolyte or straight sea water can be subject to an electric potential of between 1.0 V and 1.4 V relative to the standard hydrogen electrode, which at pH 7 corresponds to an overpotential of 0.6 to 1.0 V, with the result being, among other things, the generation of hydrogen with an optimal turnover frequency of ca. 1.5 million mol H.sub.2/mol catalyst per h.

  10. Sodium-Metal-Halide Battery Energy Storage for DoD Installations

    2017-10-24

    electrical equipment for AC interface PDE Pacific Data Electric V&F Voltage and Frequency, power quality measurements VA Volt-Amp, units for apparent...Metal-Halide technology could operate at extreme ambient temperatures, but the early prototypes did struggle with managing sand ingress.  The...peak power Not tested 3. PV smoothing Measure improvement in power quality Power meter measurements Power quality improvements 15-min

  11. Development of processes for the production of solar grade silicon from halides and alkali metals

    Dickson, C. R.; Gould, R. K.

    1980-01-01

    High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon in volume at low cost were studied. Experiments were performed to evaluate product separation and collection processes, measure heat release parameters for scaling purposes, determine the effects of reactants and/or products on materials of reactor construction, and make preliminary engineering and economic analyses of a scaled-up process.

  12. Designing mixed metal halide ammines for ammonia storage using density functional theory and genetic algorithms.

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J; Vegge, Tejs

    2014-09-28

    Metal halide ammines have great potential as a future, high-density energy carrier in vehicles. So far known materials, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, are not suitable for automotive, fuel cell applications, because the release of ammonia is a multi-step reaction, requiring too much heat to be supplied, making the total efficiency lower. Here, we apply density functional theory (DFT) calculations to predict new mixed metal halide ammines with improved storage capacities and the ability to release the stored ammonia in one step, at temperatures suitable for system integration with polymer electrolyte membrane fuel cells (PEMFC). We use genetic algorithms (GAs) to search for materials containing up to three different metals (alkaline-earth, 3d and 4d) and two different halides (Cl, Br and I) - almost 27,000 combinations, and have identified novel mixtures, with significantly improved storage capacities. The size of the search space and the chosen fitness function make it possible to verify that the found candidates are the best possible candidates in the search space, proving that the GA implementation is ideal for this kind of computational materials design, requiring calculations on less than two percent of the candidates to identify the global optimum.

  13. Ionic behavior of organic-inorganic metal halide perovskite based metal-oxide-semiconductor capacitors.

    Wang, Yucheng; Zhang, Yuming; Pang, Tiqiang; Xu, Jie; Hu, Ziyang; Zhu, Yuejin; Tang, Xiaoyan; Luan, Suzhen; Jia, Renxu

    2017-05-24

    Organic-inorganic metal halide perovskites are promising semiconductors for optoelectronic applications. Despite the achievements in device performance, the electrical properties of perovskites have stagnated. Ion migration is speculated to be the main contributing factor for the many unusual electrical phenomena in perovskite-based devices. Here, to understand the intrinsic electrical behavior of perovskites, we constructed metal-oxide-semiconductor (MOS) capacitors based on perovskite films and performed capacitance-voltage (C-V) and current-voltage (I-V) measurements of the capacitors. The results provide direct evidence for the mixed ionic-electronic transport behavior within perovskite films. In the dark, there is electrical hysteresis in both the C-V and I-V curves because the mobile negative ions take part in charge transport despite frequency modulation. However, under illumination, the large amount of photoexcited free carriers screens the influence of the mobile ions with a low concentration, which is responsible for the normal C-V properties. Validation of ion migration for the gate-control ability of MOS capacitors is also helpful for the investigation of perovskite MOS transistors and other gate-control photovoltaic devices.

  14. Mesoporous metal catalysts formed by ultrasound

    Schaeferhans, Jana; Pazos Perez, Nicolas; Andreeva, Daria [Physikalische Chemie II, Universitaet Bayreuth (Germany)

    2010-07-01

    We study the ultrasound-driven formation of mesoporous metal sponges. The collapse of acoustic cavitations leads to very high temperatures and pressures on very short scales. Therefore, structures may be formed and quenched far from equilibrium. Mechanism of metal modification by ultrasound is complex and involves a variety of aspects. We propose that modification of metal particles and formation of mesoporous inner structures can be achieved due to thermal etching of metals by ultrasound stimulated high speed jets of liquid. Simultaneously, oxidation of metal surfaces by free radicals produced in water during cavitation stabilizes developed metal structures. Duration and intensity of the ultrasonication treatment is able to control the structure and morphology of metal sponges. We expect that this approach to the formation of nanoscale composite sponges is universal and opens perspective for a whole new class of catalytic materials that can be prepared in a one-step process. The developed method makes it possible to control the sponge morphology and can be used for formation of modern types of catalysts. For example, the sonication technique allows to combine the fabrication of mesoporous support and distribution of metal (Cu, Pd, Au, Pt etc.) nanoparticles in its pores into a single step.

  15. Metal Nanoparticle Catalysts for Carbon Nanotube Growth

    Pierce, Benjamin F.

    2003-01-01

    Work this summer involved and new and unique process for producing the metal nanoparticle catalysts needed for carbon nanotube (CNT) growth. There are many applications attributed to CNT's, and their properties have deemed them to be a hot spot in research today. Many groups have demonstrated the versatility in CNT's by exploring a wide spectrum of roles that these nanotubes are able to fill. A short list of such promising applications are: nanoscaled electronic circuitry, storage media, chemical sensors, microscope enhancement, and coating reinforcement. Different methods have been used to grow these CNT's. Some examples are laser ablation, flame synthesis, or furnace synthesis. Every single approach requires the presence of a metal catalyst (Fe, Co, and Ni are among the best) that is small enough to produce a CNT. Herein lies the uniqueness of this work. Microemulsions (containing inverse micelles) were used to generate these metal particles for subsequent CNT growth. The goal of this summer work was basically to accomplish as much preliminary work as possible. I strived to pinpoint which variable (experimental process, metal product, substrate, method of application, CVD conditions, etc.) was the determining factor in the results. The resulting SEM images were sufficient for the appropriate comparisons to be made. The future work of this project consists of the optimization of the more promising experimental procedures and further exploration onto what exactly dictated the results.

  16. Monitoring of heavy/toxic metals and halides in surface/ground water (abstract)

    Viqar-un-Nisa; Ahmed, R.; Husain, M.

    1999-01-01

    Water is essential for maintaining physical and social life. Human and animal consumption is perhaps the most evident essential use of water. Water quality and quantity have become critical issues, affecting all life. The importance of water in our lives, combined with the threats, make water resources use a global problem. Among the different pollutants toxic metals, metalloids and halides have special significance. Industrial effluents and municipal wastewater are normally drained into water streams, rivers and other reservoirs thus polluting these significantly. Quality of our water resources especially is an issue, which continues to arouse the attention of concerned scientists, legislators and the general public. Among various pollutant chemicals, the heavy metals and metalloids are present at trace levels in various compartments of the environment. Some metals become toxic even at trace levels because of the important features that distinguishes metals from other pollutants is that they are not biodegradable. The halides like Cl, Br, and I from different sources can enter easily into water systems and then they make their way directly into the human body. The intake of toxic as wells as essential elements through water and other food items like vegetables, milk wheat flour etc. is significant. The abundance or deficiency of these meals as well as halides results in abnormal metabolic functions. Due to excessive demand for trace analysis in water and other materials a variety of techniques and instrumentation has been developed. Determination of heavy metals ions is of the highest interest in environmental analysis. Among the food materials water is most important because of their large consumption by man. Also toxic metals in water may be in dissolved ionic form, which directly go into human metabolism and start their toxic action. Presence of even small amounts of toxic metals in drinking water can produce serious health hazards. (author)

  17. Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides

    Magdesieva, Tatiana V. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation)]. E-mail: tvm@org.chem.msu.ru; Graczyk, Magdalena [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France); Vallat, Alain [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France); Nikitin, Oleg M. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Demyanov, Petr I. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Butin, Kim P. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Vorotyntsev, Mikhail A. [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France)]. E-mail: MV@u-bourgogne.fr

    2006-11-12

    We have studied a reaction between the reduced form of titanocene dichloride (Cp{sub 2}TiCl{sub 2}) and a group of organic halides: benzyl derivatives (4-X-C{sub 6}H{sub 4}CH{sub 2}Cl, X = H, NO{sub 2}, CH{sub 3}; 4-X-C{sub 6}H{sub 4}CH{sub 2}Br, X = H, NO{sub 2}, PhC(O); 4-X-C{sub 6}H{sub 4}CH{sub 2}SCN, X = H, NO{sub 2}) as well as three aryl halides (4-NO{sub 2}C{sub 6}H{sub 4}Hal, Hal = Cl, Br; 4-CH{sub 3}O-C{sub 6}H{sub 4}Cl). It has been shown that the electrochemical reduction of Cp{sub 2}TiCl{sub 2} in the presence of these benzyl halides leads to a catalytic cycle resulting in the reductive dehalogenation of these organic substrates to yield mostly corresponding toluene derivatives as the main product. No dehalogenation has been observed for aryl derivatives. Based on electrochemical data and digital simulation, possible schemes of the catalytic process have been outlined. For non-substituted benzyl halides halogen atom abstraction is a key step. For the reaction of nitrobenzyl halides the complexation of Ti(III) species with the nitro group takes place, with the electron transfer from Ti(III) to this group (owing to its highest coefficient in LUMO of the nitro benzyl halide) followed by an intramolecular dissociative electron redistribution in the course of the heterolytic C-Hal bond cleavage. The results for reduced titanocene dichloride centers immobilized inside a polymer film showed that the catalytic reductive dehalogenation of the p-nitrobenzyl chloride does occur but with a low efficiency because of the partial deactivation of the film due to the blocking of the electron charge transport between the electrode and catalytic centers.

  18. NMR longitudinal relaxation enhancement in metal halides by heteronuclear polarization exchange during magic-angle spinning

    Shmyreva, Anna A. [Center for Magnetic Resonance, St. Petersburg State University, St. Petersburg 198504 (Russian Federation); Safdari, Majid; Furó, István [Department of Chemistry, KTH Royal Institute of Technology, SE-10044 Stockholm (Sweden); Dvinskikh, Sergey V., E-mail: sergeid@kth.se [Department of Chemistry, KTH Royal Institute of Technology, SE-10044 Stockholm (Sweden); Laboratory of Biomolecular NMR, St. Petersburg State University, St. Petersburg 199034 (Russian Federation)

    2016-06-14

    Orders of magnitude decrease of {sup 207}Pb and {sup 199}Hg NMR longitudinal relaxation times T{sub 1} upon magic-angle-spinning (MAS) are observed and systematically investigated in solid lead and mercury halides MeX{sub 2} (Me = Pb, Hg and X = Cl, Br, I). In lead(II) halides, the most dramatic decrease of T{sub 1} relative to that in a static sample is in PbI{sub 2}, while it is smaller but still significant in PbBr{sub 2}, and not detectable in PbCl{sub 2}. The effect is magnetic-field dependent but independent of the spinning speed in the range 200–15 000 Hz. The observed relaxation enhancement is explained by laboratory-frame heteronuclear polarization exchange due to crossing between energy levels of spin-1/2 metal nuclei and adjacent quadrupolar-spin halogen nuclei. The enhancement effect is also present in lead-containing organometal halide perovskites. Our results demonstrate that in affected samples, it is the relaxation data recorded under non-spinning conditions that characterize the local properties at the metal sites. A practical advantage of fast relaxation at slow MAS is that spectral shapes with orientational chemical shift anisotropy information well retained can be acquired within a shorter experimental time.

  19. Gasification of carbon deposits on catalysts and metal surfaces

    Figueiredo, J L

    1986-10-01

    'Coke' deposited on catalysts and reactor surfaces includes a variety of carbons of different structures and origins, their reactivities being conveniently assessed by Temperature Programmed Reaction (TPR). The gasification of carbon deposits obtained in the laboratory under well controlled conditions, and the regeneration of coked catalysts from petroleum refining processes are reviewed and discussed. Filamentary carbon deposits, containing dispersed metal particles, behave as supported metal catalysts during gasification, and show high reactivities. Pyrolytic and acid catalysis carbons are less reactive on their own, as the gasification is not catalysed; however, metal components of the catalyst or metal impurities deposited on the surface may enhance gasification. 26 refs., 8 figs., 2 tabs.

  20. Non-noble metal fuel cell catalysts

    Chen, Zhongwei; Zhang, Jiujun

    2014-01-01

    Written and edited by a group of top scientists and engineers in the field of fuel cell catalysts from both industry and academia, this book provides a complete overview of this hot topic. It covers the synthesis, characterization, activity validation and modeling of different non-noble metal and metalfree electrocatalysts for the reduction of oxygen, as well as their integration into acid or alkaline polymer exchange membrane (PEM) fuel cells and their performance validation, while also discussing those factors that will drive fuel cell commercialization. With its well-structured app

  1. Development of radioactive platinum group metal catalysts

    Chung, H.S.; Kim, Y.S.; Kim, Y.E.

    1999-03-01

    The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metals such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solutions was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400m 2 /g. The content of palladium impregnated on the support was 1 to 10 wt. %. Hydrogen isotope exchange efficiency of more than 93% to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its activity is unimportant as in nuclear industries. (author). 86 refs., 44 tabs., 88 figs

  2. Development of radioactive platinum group metal catalysts

    Chung, H.S.; Kim, Y.S.; Kim, Y.E. [and others

    1999-03-01

    The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metals such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solutions was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400m{sup 2}/g.The content of palladium impregnated on the support was 1 to 10 wt. %. Hydrogen isotope exchange efficiency of more than 93% to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its activity is unimportant as in nuclear industries. (author). 86 refs., 44 tabs., 88 figs.

  3. Interaction between Nafion ionomer and noble metal catalyst for PEMFCs

    Andersen, Shuang Ma

    The implement of polymer impregnation in electrode structure (catalyst layer) decreasing the noble metal catalyst loading by a factor of ten , , is one of the essential mile stones in the evolution of Proton Exchange Membrane Fuel Cells’ development among the application of catalyst support and e...

  4. Antimicrobial properties of metal and metal-halide nanoparticles and their potential applications

    Torrey, Jason Robert

    Heavy metals, including silver and copper, have been known to possess antimicrobial properties against bacterial, fungal, and viral pathogens. Metal nanoparticles (aggregations of metal atoms 1-200 nm in size) have recently become the subject of intensive study for their increased antimicrobial properties. In the current studies, metal and metal-halide nanoparticles were evaluated for their antibacterial efficacy. Silver (Ag), silver bromide (AgBr), silver iodide (AgI), and copper iodide (CuI) nanoparticles significantly reduced bacterial numbers of the Gram-negative Pseudomonas aeruginosa and the Gram-positive Staphylococcus aureus within 24 hours and were more effective against P. aeruginosa. CuI nanoparticles were found to be highly effective, reducing both organisms by >4.43 log 10 within 15 minutes at 60 ppm Cu. CuI nanoparticles formulated with different stabilizers (sodium dodecyl sulfate, SDS; polyvinyl pyrrolidone, PVP) were further tested against representative Gram-positive and Gram-negative bacteria, Mycobacteria, a fungus (Candida albicans ), and a non-enveloped virus (poliovirus). Both nanoparticles caused significant reductions in most of the Gram-negative bacteria within five minutes (>5.09-log10). The Gram-positive bacterial species and C. albicans were more sensitive to the CuI-SDS than the CuI-PVP nanoparticles. In contrast, the acid-fast Mycobacterium smegmatis was more resistant to CuI-SDS than CuI-PVP nanoparticles. Poliovirus was more resistant than the other organisms tested except for Mycobacterium fortuitum, which displayed the greatest resistance to CuI nanoparticles. As an example of a real world antimicrobial application, polymer coatings embedded with various concentrations of CuI nanoparticles were tested for antibacterial efficacy against P. aeruginosa and S. aureus. Polyester-epoxy powder coatings were found to display superior uniformity, stability and antimicrobial properties against both organisms (>4.92 log 10 after six hours at

  5. Synthesis of Halide- and Solvent free metal borohydrides

    Grinderslev, Jakob; Møller, Kasper Trans; Jensen, Torben René

    chloride or LiBH4 is present in the sample. The synthesis pathway has been shown to work for most of the already known metal borohydrides, M = Na, Ca, Sr, Ba, Y, La, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb, but also new borohydrides are formed, M = Pr, Nd and Lu. Besides new compounds, new polymorphs...

  6. Cluster harvesting by successive reduction of a metal halide with a nonconventional reduction agent: a benefit for the exploration of metal-rich halide systems.

    Ströbele, Markus; Mos, Agnieszka; Meyer, Hans-Jürgen

    2013-06-17

    The preparation of thermally labile compounds is a great temptation in chemistry which requires a careful selection of reaction media and reaction conditions. With a new scanning technique denoted here as Cluster Harvesting, a whole series of metal halide compounds is detected by differential thermal analysis (DTA) in fused silica tubes and structurally characterized by X-ray powder diffraction. Experiments of the reduction of tungsten hexahalides with elemental antimony and iron are presented. A cascade of six compounds is identified during the reduction with antimony, and five compounds or phases are monitored following the reduction with iron. The crystal structure of Fe2W2Cl10 is reported, and two other phases in the Fe-W-Cl system are discussed.

  7. Infrared Dielectric Screening Determines the Low Exciton Binding Energy of Metal-Halide Perovskites.

    Umari, Paolo; Mosconi, Edoardo; De Angelis, Filippo

    2018-02-01

    The performance of lead-halide perovskites in optoelectronic devices is due to a unique combination of factors, including highly efficient generation, transport, and collection of photogenerated charge carriers. The mechanism behind efficient charge generation in lead-halide perovskites is still largely unknown. Here, we investigate the factors that influence the exciton binding energy (E b ) in a series of metal-halide perovskites using accurate first-principles calculations based on solution of the Bethe-Salpeter equation, coupled to ab initio molecular dynamics simulations. We find that E b is strongly modulated by screening from low-energy phonons, which account for a factor ∼2 E b reduction, while dynamic disorder and rotational motion of the organic cations play a minor role. We calculate E b = 15 meV for MAPbI 3 , in excellent agreement with recent experimental estimates. We then explore how different material combinations (e.g., replacing Pb → Pb:Sn→ Sn; and MA → FA → Cs) may lead to different E b values and highlight the mechanisms underlying E b tuning.

  8. First-row transition metal hydrogenation and hydrosilylation catalysts

    Trovitch, Ryan J.; Mukhopadhyay, Tufan K.; Pal, Raja; Levin, Hagit Ben-Daat; Porter, Tyler M.; Ghosh, Chandrani

    2017-07-18

    Transition metal compounds, and specifically transition metal compounds having a tetradentate and/or pentadentate supporting ligand are described, together with methods for the preparation thereof and the use of such compounds as hydrogenation and/or hydrosilylation catalysts.

  9. An improved method of preparation of nanoparticular metal oxide catalysts

    2014-01-01

    The present invention concerns an improved method of preparation of nanoparticular vanadium oxide/anatase titania catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular vanadium oxide/anatase titania catalyst precursors comprising...... combustible crystallization seeds upon which the catalyst metal oxide is coprecipitated with the carrier metal oxide, which crystallization seeds are removed by combustion in a final calcining step....

  10. The Metal-Halide Lamp Under Varying Gravity Conditions Measured by Emission and Laser Absorption Spectroscopy

    Flikweert, A. J.; Nimalasuriya, T.; Kroesen, G. M. W.; Haverlag, M.; Stoffels, W. W.

    2009-11-01

    Diffusive and convective processes in the metal-halide lamp cause an unwanted axial colour segregation. Convection is induced by gravity. To understand the flow phenomena in the arc discharge lamp it has been investigated under normal laboratory conditions, micro-gravity (ISS and parabolic flights) and hyper-gravity (parabolic flights 2 g, centrifuge 1 g-10 g). The measurement techniques are webcam imaging, and emission and laser absorption spectroscopy. This paper aims to give an overview of the effect of different artificial gravity conditions on the lamp and compares the results from the three measurement techniques.

  11. Non-destructive measurement of Xe filling pressure in mercury-free metal halide lamp

    Motomura, Hideki; Enoki, Kyosuke; Jinno, Masafumi

    2010-01-01

    Mercury-free metal halide lamps (MHLs) for automotive purposes have been developing in the market. When mercury is not used, the electric and emission characteristics of the lamp strongly depend on the xenon filling pressure. Therefore a non-destructive gas pressure estimation technique is required to obtain stable performance of the lamps as commercial products. The authors have developed an estimation method by which the gas pressure is estimated from the current peak value at the initial stage of ignition under pulsed operation. It is shown that accuracy of the order of ±(0.1-0.3) atm is obtained using an empirical formula.

  12. Application of a mixed metal oxide catalyst to a metallic substrate

    Sevener, Kathleen M. (Inventor); Lohner, Kevin A. (Inventor); Mays, Jeffrey A. (Inventor); Wisner, Daniel L. (Inventor)

    2009-01-01

    A method for applying a mixed metal oxide catalyst to a metallic substrate for the creation of a robust, high temperature catalyst system for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in propulsion systems. The method begins by forming a prepared substrate material consisting of a metallic inner substrate and a bound layer of a noble metal intermediate. Alternatively, a bound ceramic coating, or frit, may be introduced between the metallic inner substrate and noble metal intermediate when the metallic substrate is oxidation resistant. A high-activity catalyst slurry is applied to the surface of the prepared substrate and dried to remove the organic solvent. The catalyst layer is then heat treated to bind the catalyst layer to the surface. The bound catalyst layer is then activated using an activation treatment and calcinations to form the high-activity catalyst system.

  13. Recycling of platinum group metals from the automotive catalysts

    Benevit, Mariana; Petter, Patricia Melo Halmenschlager; Veit, Hugo Marcelo

    2014-01-01

    Currently it is very important to use alternative sources of raw material for obtaining metals, avoiding the traditional mining. This work aims to characterize and evaluate the recoverability of platinum group metals present in automotive catalysts. Thus, the catalysts were divided into two groups: the first was catalysts used in 1.0 cars and the second was catalyst used in 2.0 cars. DRX and FRX techniques and chemical analysis performed by ICP/OES was used to characterized these materials. The results showed that there is a significant amount of platinum group elements in catalyst waste, which can be separated and reused. In the next step, hydro and pyrometallurgical routes, for metals extraction from catalyst waste, will be studied. (author)

  14. Comparative study of energy-efficiency and conservation systems for ceramic metal-halide discharge lamps

    Hermoso Orzáez, Manuel Jesús; Andrés Díaz, José Ramón de

    2013-01-01

    Interest in energy savings in urban lighting is gaining traction and has become a priority for municipal administrations. LED (light-emitting diode) technology appears to be the clear future lighting choice. However, this technology is still rapidly developing and has not been sufficiently tested. As an intermediate step, alternative proposals for energy-saving equipment for traditional discharge lamps are desirable so that the current technologies can coexist with the new LED counterparts for the short and medium term. This article provides a comparative study between two efficiency and energy-saving systems for discharge lamps with metal-halide and ceramic technologies, i.e., a lighting flow dimmer-stabilizer and a double-level electronic ballast. - Highlights: ► It has been demonstrated the possibility of regulating ceramic metal-halide lamps with lighting flow dimmer-stabilizer. ► Electronic ballasts can save approximately double quantity of energy than lighting flow dimmer-stabilizers. ► The use of lighting flow dimmer-stabilizer is more profitable than electronic ballasts due to costs and reliability

  15. Visualizing Carrier Transport in Metal Halide Perovskite Nanoplates via Electric Field Modulated Photoluminescence Imaging.

    Hu, Xuelu; Wang, Xiao; Fan, Peng; Li, Yunyun; Zhang, Xuehong; Liu, Qingbo; Zheng, Weihao; Xu, Gengzhao; Wang, Xiaoxia; Zhu, Xiaoli; Pan, Anlian

    2018-05-09

    Metal halide perovskite nanostructures have recently been the focus of intense research due to their exceptional optoelectronic properties and potential applications in integrated photonics devices. Charge transport in perovskite nanostructure is a crucial process that defines efficiency of optoelectronic devices but still requires a deep understanding. Herein, we report the study of the charge transport, particularly the drift of minority carrier in both all-inorganic CsPbBr 3 and organic-inorganic hybrid CH 3 NH 3 PbBr 3 perovskite nanoplates by electric field modulated photoluminescence (PL) imaging. Bias voltage dependent elongated PL emission patterns were observed due to the carrier drift at external electric fields. By fitting the drift length as a function of electric field, we obtained the carrier mobility of about 28 cm 2 V -1 S -1 in the CsPbBr 3 perovskite nanoplate. The result is consistent with the spatially resolved PL dynamics measurement, confirming the feasibility of the method. Furthermore, the electric field modulated PL imaging is successfully applied to the study of temperature-dependent carrier mobility in CsPbBr 3 nanoplates. This work not only offers insights for the mobile carrier in metal halide perovskite nanostructures, which is essential for optimizing device design and performance prediction, but also provides a novel and simple method to investigate charge transport in many other optoelectronic materials.

  16. Metal-Mediated Halogen Exchange in Aryl and Vinyl Halides: a Review

    Evano, Gwilherm; Nitelet, Antoine; Thilmany, Pierre; Dewez, Damien F.

    2018-04-01

    Halogenated arenes and alkenes are of prime importance in many areas of science, especially in the pharmaceutical, agrochemical and chemical industries. While the simplest ones are commercially available, some of them are still hardly accessible depending on their substitution patterns and the nature of the halogen atom. Reactions enabling the selective and efficient replacement of the halogen atom of an aryl or alkenyl halide by another one, lighter or heavier, are therefore of major importance since they can be used for example to turn a less reactive aryl/alkenyl chloride into the more reactive iodinated derivatives or, in a reversed sense, to block an undesired reactivity, for late-stage modifications or for the introduction of a radionuclide. If some halogen exchange reactions are possible with activated substrates, they usually require catalysis with metal complexes. Remarkably efficient processes have been developed for metal-mediated halogen exchange in aryl and vinyl halides: they are overviewed, in a comprehensive manner, in this review article.

  17. New antipollution processing of a used refining catalyst and complete recovery of the catalyst metallic components

    Trinh Dinh Chan; Llido, E.

    1992-05-15

    The used refining catalyst, containing metals such as vanadium, nickel and iron, is first processed by stripping; it is then calcined in critical conditions and heat processed in the presence of a melted alkaline base; the resulting solid matter is then water processed. The antipollution process can be applied to oil fraction hydroconversion or hydroprocessing catalysts.

  18. Dissolution of Metal Supported Spent Auto Catalysts in Acids

    Fornalczyk A.

    2016-03-01

    Full Text Available Metal supported auto catalysts, have been used in sports and racing cars initially, but nowadays their application systematically increases. In Metal Substrate (supported Converters (MSC, catalytic functions are performed by the Platinum Group Metals (PGM: Pt, Pd, Rh, similarly to the catalysts on ceramic carriers. The contents of these metals make that spent catalytic converters are valuable source of precious metals. All over the world there are many methods for the metals recovery from the ceramic carriers, however, the issue of platinum recovery from metal supported catalysts has not been studied sufficiently yet. The paper presents preliminary results of dissolution of spent automotive catalyst on a metal carrier by means of acids: H2SO4, HCl, HNO3, H3PO4. The main assumption of the research was the dissolution of base metals (Fe, Cr, Al from metallic carrier of catalyst, avoiding dissolution of PGMs. Dissolution was the most effective when concentrated hydrochloric acid, and 2M sulfuric acid (VI was used. It was observed that the dust, remaining after leaching, contained platinum in the level of 0.8% and 0.7%, respectively.

  19. Solid, double-metal cyanide catalysts for synthesis of ...

    Sci. Vol. 126, No. 2, March 2014, pp. 499–509. c Indian Academy of Sciences. Solid, double-metal cyanide catalysts for ... drimers, HPs have a highly branched structural design ... geneous catalysts and corrosion of the reactor lin- ... Carbon dioxide is a greenhouse gas. .... polymer product was reprecipitated from the liquid.

  20. Competition between convection and diffusion in a metal halide lamp, investigated by numerical simulations and imaging laser absorption spectroscopy

    Beks, M.L.; Flikweert, A.J.; Nimalasuriya, T.; Stoffels, W.W.; Mullen, van der J.J.A.M.

    2008-01-01

    The effect of the competition between convection and diffusion on the distribution of metal halide additives in a high pressure mercury lamp has been examined by placing COST reference lamps with mercury fillings of 5 and 10 mg in a centrifuge. By subjecting them to different accelerational

  1. Optical emission spectroscopy of metal-halide lamps: Radially resolved atomic state distribution functions of Dy and Hg

    Nimalasuriya, T.; Flikweert, A.J.; Stoffels, W.W.; Haverlag, M.; Mullen, van der J.J.A.M.; Pupat, N.B.M.

    2006-01-01

    Absolute line intensity measurements are performed on a metal-halide lamp. Several transitions of atomic and ionic Dy and atomic Hg are measured at different radial positions from which we obtain absolute atomic and ionic Dy intensity profiles. From these profiles we construct the radially resolved

  2. Analisa Teknis Pemakaian Kombinasi Lampu Metal Halide Dan Led Sebagai Pemikat Ikan Pada Kapal Pukat Cincin (Purse Seine Dan Pengaruhnya Terhadap Konsumsi Bahan Bakar Genset

    Septian Ragil Wibisono

    2017-01-01

    Full Text Available Saat ini lampu Metal Halide dipakai sebagai pemikat ikan  oleh nelayan Purse Seine. Peggunaan lampu tersebut memerlukan daya Genset yang besar karena satu lampu Metal Halide berdaya 1500 Watt. Semakin banyak lampu Metal Halide yang digunakan semakin besar pula konsumsi bahan bakar Genset. Dalam upaya penghematan energi bahan bakar maka digunakan lampu LED sebagai alternatif pemikat ikan. Lampu LED dikenal sebagai lampu yang hemat energi. Penelitian ini ditujukan untuk mengetahui dan membandingkan konsumsi bahan bakar Genset saat menggunakan kombinasi lampu Metal Halide dan LED. Penelitian ini dilakukan dengan mengambil data konsumsi bahan bakar Genset untuk menyalakan sejumlah lampu Metal Halide dan lampu LED, kemudian dilakukan analisa regresi untuk mendapatkan model persaamaan konsumsi bahan bakar Genset. Selanjutnya dilakukan ekstrapolasi untuk memprediksi konsumsi bahan bakar saat Genset dengan jumlah lampu tertentu. Hasilnya dengan besar fluks cahaya yang hampir sama, saat penggunaan 6 lampu Metal Halide konsumsi bahan bakar sebesar 13.606,03 liter, dan saat menggunakan kombinasi lampu 1 Metal Halide dan 25 lampu LED konsumsi bahan bakar sebesar 13.255,63 liter, yang artinya terjadi penghematan bahan bakar sebesar 2,58%.

  3. 40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

    2010-07-01

    ... Halogen HAP Emissions or HAP Metals Emissions From Process Vents 3 Table 3 to Subpart FFFF of Part 63... to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP... following table that applies to your process vents that contain hydrogen halide and halogen HAP emissions or...

  4. Infrared losses from a Na/Sc metal-halide high intensity discharge arc lamp

    Smith, D J; Bonvallet, G A; Lawler, J E

    2003-01-01

    A study of the near-infrared (IR) emission from the arc of a metal-halide high intensity discharge (MH-HID) lamp with a sodium/scandium chemistry is reported. Radiometrically calibrated spectra from 0.7 to 2.5 μm were recorded as a function of position on the arc tube of a 250 W lamp. These spectra were analysed to determine the relative densities of Na and Sc atoms and the arc temperature as a function of radius. Information from these spectra, combined with absorption measurements in the companion paper (Bonvallet and Lawler 2003), were used to determine the absolute output power in the near-IR from the MH-HID lamp

  5. Double-ended metal halide arc discharge lamp with electrically isolated containment shroud

    Muzeroll, Martin M. (Inventor)

    1994-01-01

    A double-ended arc discharge lamp includes a sealed, light-transmissive outer jacket, a light-transmissive shroud mounted within the outer jacket and directly supported by the outer jacket, and an arc discharge tube mounted within the shroud. The arc tube is typically a metal halide arc discharge tube. In a preferred embodiment, the shroud includes an outwardly flared portion at each end. The outwardly flared portions space the shroud from the outer jacket and support the shroud within the outer jacket. The outwardly flared portions of the shroud can be affixed to the outer jacket by fusing. The outer jacket can be provided with inwardly extending dimples for locating the shroud with respect to the outer jacket. In another embodiment, the outer jacket includes reduced diameter portions near each end which are attached to the shroud.

  6. Radiative properties of ceramic metal-halide high intensity discharge lamps containing additives in argon plasma

    Cressault, Yann; Teulet, Philippe; Zissis, Georges

    2016-07-01

    The lighting represents a consumption of about 19% of the world electricity production. We are thus searching new effective and environment-friendlier light sources. The ceramic metal-halide high intensity lamps (C-MHL) are one of the options for illuminating very high area. The new C-MHL lamps contain additives species that reduce mercury inside and lead to a richer spectrum in specific spectral intervals, a better colour temperature or colour rendering index. This work is particularly focused on the power radiated by these lamps, estimated using the net emission coefficient, and depending on several additives (calcium, sodium, tungsten, dysprosium, and thallium or strontium iodides). The results show the strong influence of the additives on the power radiated despite of their small quantity in the mixtures and the increase of visible radiation portion in presence of dysprosium.

  7. Why does the lumen maintenance of sodium-scandium metal halide lamps improve by VHF operation?

    Van Erk, W; Luijks, G M J F; Hitchcock, W

    2011-01-01

    Lifetime experiments show that sodium-scandium metal halide lamps perform better on very high frequency (VHF) drivers than on low frequency (LF) constant wattage autotransformer (CWA) ballasts. The question why, will be addressed with focus on arc tube aspects. It is argued that at high frequency operation sodium loss is less, and that the absence of thermal fluctuations in the electrode tip causes less damage and cracking to this part of the electrode. Sudden lm W -1 drops, observed with CWA-operated lamps, most probably occur when the arc attaches on such a corroded and cracked surface. Thorium is effective as an emitter both in the CWA and the VHF operation mode, despite the absence of cataphoretic transport to the cathode in the VHF case.

  8. Why does the lumen maintenance of sodium-scandium metal halide lamps improve by VHF operation?

    Van Erk, W [Philips Lighting, Sondervick 47, 5505 NB Veldhoven (Netherlands); Luijks, G M J F [Advanced Development Lighting, Philips Lighting, PO Box 80020, 5600 JM Eindhoven (Netherlands); Hitchcock, W, E-mail: Gerard.luijks@philips.com [Philips Lighting Company, 7265 Route 54, Bath, NY 14810 (United States)

    2011-06-08

    Lifetime experiments show that sodium-scandium metal halide lamps perform better on very high frequency (VHF) drivers than on low frequency (LF) constant wattage autotransformer (CWA) ballasts. The question why, will be addressed with focus on arc tube aspects. It is argued that at high frequency operation sodium loss is less, and that the absence of thermal fluctuations in the electrode tip causes less damage and cracking to this part of the electrode. Sudden lm W{sup -1} drops, observed with CWA-operated lamps, most probably occur when the arc attaches on such a corroded and cracked surface. Thorium is effective as an emitter both in the CWA and the VHF operation mode, despite the absence of cataphoretic transport to the cathode in the VHF case.

  9. Degradation of Highly Alloyed Metal Halide Perovskite Precursor Inks: Mechanism and Storage Solutions

    Dou, Benjia [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Wheeler, Lance M [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Christians, Jeffrey A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Moore, David [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Harvey, Steven P [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Berry, Joseph J [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Van Hest, Marinus F [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Barnes, Frank S. [University of Colorado; Shaheen, Sean E. [University of Colorado

    2018-03-02

    Whereas the promise of metal halide perovskite (MHP) photovoltaics (PV) is that they can combine high efficiency with solution-processability, the chemistry occurring in precursor inks is largely unexplored. Herein, we investigate the degradation of MHP solutions based on the most widely used solvents, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). For the MHP inks studied, which contain formamidinium (FA+), methylammonium (MA+), cesium (Cs+), lead (Pb2+), bromide (Br-), and iodide (I-), dramatic compositional changes are observed following storage of the inks in nitrogen in the dark. We show that hydrolysis of DMF in the precursor solution forms dimethylammonium formate, which subsequently incorporates into the MHP film to compromise the ability of Cs+ and MA+ to stabilize FA+-based MHP. The changes in solution chemistry lead to a modification of the perovskite film stoichiometry, band gap, and structure. The solid precursor salts are stable when ball-milled into a powder, allowing for the storage of large quantities of stoichiometric precursor materials.

  10. The Role of Surface Tension in the Crystallization of Metal Halide Perovskites

    Zhumekenov, Ayan A.

    2017-07-06

    The exciting intrinsic properties discovered in single crystals of metal halide perovskites still await their translation into optoelectronic devices. The poor understanding and control of the crystallization process of these materials are current bottlenecks retarding the shift towards single crystal-based optoelectronics. Here we theoretically and experimentally elucidate the role of surface tension in the rapid synthesis of perovskite single crystals by inverse temperature crystallization (ITC). Understanding the nucleation and growth mechanisms enabled us to exploit surface tension to direct the growth of monocrystalline films of perovskites (AMX3, where A = CH3NH3+ or MA; M = Pb2+, Sn2+; X = Br-, I-) on the solution surface. We achieve up to 1 cm2-sized monocrystalline films with thickness on the order of the charge carrier diffusion length (~5-10 µm). Our work paves the way to control the crystallization process of perovskites, including thin film deposition, which is essential to advance the performance benchmarks of perovskite optoelectronics.

  11. Highly Efficient Light-Emitting Diodes of Colloidal Metal-Halide Perovskite Nanocrystals beyond Quantum Size.

    Kim, Young-Hoon; Wolf, Christoph; Kim, Young-Tae; Cho, Himchan; Kwon, Woosung; Do, Sungan; Sadhanala, Aditya; Park, Chan Gyung; Rhee, Shi-Woo; Im, Sang Hyuk; Friend, Richard H; Lee, Tae-Woo

    2017-07-25

    Colloidal metal-halide perovskite quantum dots (QDs) with a dimension less than the exciton Bohr diameter D B (quantum size regime) emerged as promising light emitters due to their spectrally narrow light, facile color tuning, and high photoluminescence quantum efficiency (PLQE). However, their size-sensitive emission wavelength and color purity and low electroluminescence efficiency are still challenging aspects. Here, we demonstrate highly efficient light-emitting diodes (LEDs) based on the colloidal perovskite nanocrystals (NCs) in a dimension > D B (regime beyond quantum size) by using a multifunctional buffer hole injection layer (Buf-HIL). The perovskite NCs with a dimension greater than D B show a size-irrespective high color purity and PLQE by managing the recombination of excitons occurring at surface traps and inside the NCs. The Buf-HIL composed of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) and perfluorinated ionomer induces uniform perovskite particle films with complete film coverage and prevents exciton quenching at the PEDOT:PSS/perovskite particle film interface. With these strategies, we achieved a very high PLQE (∼60.5%) in compact perovskite particle films without any complex post-treatments and multilayers and a high current efficiency of 15.5 cd/A in the LEDs of colloidal perovskite NCs, even in a simplified structure, which is the highest efficiency to date in green LEDs that use colloidal organic-inorganic metal-halide perovskite nanoparticles including perovskite QDs and NCs. These results can help to guide development of various light-emitting optoelectronic applications based on perovskite NCs.

  12. Heterogeneous Metal Catalysts for Oxidation Reactions

    Md. Eaqub Ali

    2014-01-01

    Full Text Available Oxidation reactions may be considered as the heart of chemical synthesis. However, the indiscriminate uses of harsh and corrosive chemicals in this endeavor are threating to the ecosystems, public health, and terrestrial, aquatic, and aerial flora and fauna. Heterogeneous catalysts with various supports are brought to the spotlight because of their excellent capabilities to accelerate the rate of chemical reactions with low cost. They also minimize the use of chemicals in industries and thus are friendly and green to the environment. However, heterogeneous oxidation catalysis are not comprehensively presented in literature. In this short review, we clearly depicted the current state of catalytic oxidation reactions in chemical industries with specific emphasis on heterogeneous catalysts. We outlined here both the synthesis and applications of important oxidation catalysts. We believe it would serve as a reference guide for the selection of oxidation catalysts for both industries and academics.

  13. Catalytic effect of halide additives ball milled with magnesium hydride

    Malka, I.E.; Bystrzycki, J. [Department of Advanced Materials and Technologies, Military University of Technology, Kaliskiego 2, 00-908 Warsaw (Poland); Czujko, T. [Department of Advanced Materials and Technologies, Military University of Technology, Kaliskiego 2, 00-908 Warsaw (Poland); CanmetENERGY, Hydrogen Fuel Cells and Transportation Energy, Natural Resources (Canada)

    2010-02-15

    The influence of various halide additives milled with magnesium hydride (MgH{sub 2}) on its decomposition temperature was studied. The optimum amount of halide additive and milling conditions were evaluated. The MgH{sub 2} decomposition temperature and energy of activation reduction were measured by temperature programmed desorption (TPD) and differential scanning calorimetry (DSC). The difference in catalytic efficiency between chlorides and fluorides of the various metals studied is presented. The effects of oxidation state, valence and position in the periodic table for selected halides on MgH{sub 2} decomposition temperature were also studied. The best catalysts, from the halides studied, for magnesium hydride decomposition were ZrF{sub 4}, TaF{sub 5}, NbF{sub 5}, VCl{sub 3} and TiCl{sub 3}. (author)

  14. Studies on PEM fuel cell noble metal catalyst dissolution

    Andersen, S. M.; Grahl-Madsen, L.; Skou, E. M.

    2011-01-01

    A combination of electrochemical, spectroscopic and gravimetric methods was carried out on Proton Exchange Membrane (PEM) fuel cell electrodes with the focus on platinum and ruthenium catalysts dissolution, and the membrane degradation. In cyclic voltammetry (CV) experiments, the noble metals were...... found to dissolve in 1 M sulfuric acid solution and the dissolution increased exponentially with the upper potential limit (UPL) between 0.6 and 1.6 vs. RHE. 2-20% of the Pt (depending on the catalyst type) was found to be dissolved during the experiments. Under the same conditions, 30-100% of the Ru...... (depending on the catalyst type) was found to be dissolved. The faster dissolution of ruthenium compared to platinum in the alloy type catalysts was also confirmed by X-ray diffraction measurements. The dissolution of the carbon supported catalyst was found one order of magnitude higher than the unsupported...

  15. Special features of the formation of high-conductivity phases of halides of alkali metals at superhigh pressures

    Babushkin, A.N.; Babushkina, G.V.

    1999-01-01

    The halides of alkali metals are the simplest crystals with the ionic nature of chemical bonds and are used widely as modelling materials in high-pressure physics. As a result of previous theoretical and experimental (optical, structural, electro-physical and shock-waves) investigations it was shown that these materials may be characterised by the overlapping of the valency and conduction bands and by the formation of groups of free charge carriers at pressures of the megabaric level. However, the authors know of no data on the direct investigations of the electrophysical properties of the halides of alkali metals at such high static pressures. The end of this investigation was to examine the temperature dependences of the electrical conductivity and thermal EMF of halides of alkali metals AX (A = Na, K, Rb, Cs, X = Cl, Br, I) in a wide temperature range at pressures from 10 to 50 GPa in order to reveal the general leisure since governing the change of their electronic structures, in particular, the transition to the state with the activation-type or metallic conductivity

  16. EXAFS characterization of supported metal catalysts in chemically dynamic environments

    Robota, H.J.

    1991-01-01

    Characterization of catalysts focuses on the identification of an active site responsible for accelerating desirable chemical reactions. The identification, characterization, and selective modification of such sites is fundamental to the development of structure-function relationships. Unfortunately, this goal is far from realized in nearly all catalysts, and particularly in catalysts comprised of small supported metal particles. X-ray absorption spectroscopy (XAS) has had a dramatic effect on our understanding of supported metal particles in their resting state. However, the performance of a catalyst can not be assessed from such simple resting state measurements. Among the factors which influence catalyst performance are the exact catalyst composition, including the support and any modifiers; particle size; catalyst finishing and pretreatment conditions; pressure, composition, and temperature of the operating environment; time. Gaining an understanding of how the structure of a catalytic site can change with such an array of variables requires that we begin to develop measurement methods which are effective under chemically dynamic conditions. Ideally, it should be possible to obtain a full X-ray absorption spectrum of each element thought to have a causal relationship with observed catalyst properties. From these spectra, we can optimally extract only a relatively limited amount of information which we must then piece together with information derived from other characterization methods and intuition to arrive at a hypothetical structure of the operating catalyst. Information about crystallinity, homogeneity, and general disorder can be obtained from the Debye-Waller factor. Finally, through analogy with known compounds, the electronic structure of the active atoms can be inferred from near edge absorption features

  17. New catalysts for coal processing: Metal carbides and nitrides

    S. Ted Oyama; David F. Cox

    1999-12-03

    The subject of this research project was to investigate the catalytic properties of a new class of materials, transition metal carbides and nitrides, for treatment of coal liquid and petroleum feedstocks. The main objectives were: (1) preparation of catalysts in unsupported and supported form; (2) characterization of the materials; (3) evaluation of their catalytic properties in HDS and HDN; (4) measurement of the surface properties; and (5) observation of adsorbed species. All of the objectives were substantially carried out and the results will be described in detail below. The catalysts were transition metal carbides and nitrides spanning Groups 4--6 in the Periodic Table. They were chosen for study because initial work had shown they were promising materials for hydrotreating. The basic strategy was first to prepare the materials in unsupported form to identify the most promising catalyst, and then to synthesize a supported form of the material. Already work had been carried out on the synthesis of the Group VI compounds Mo{sub 2}C, Mo{sub 2}N, and WC, and new methods were developed for the Group V compounds VC and NbC. All the catalysts were then evaluated in a hydrotreating test at realistic conditions. It was found that the most active catalyst was Mo{sub 2}C, and further investigations of the material were carried out in supported form. A new technique was employed for the study of the bulk and surface properties of the catalysts, near edge x-ray absorption spectroscopy (NEXAFS), that fingerprinted the electronic structure of the materials. Finally, two new research direction were explored. Bimetallic alloys formed between two transition metals were prepared, resulting in catalysts having even higher activity than Mo{sub 2}C. The performance of the catalysts in hydrodechloration was also investigated.

  18. Molecular metal catalysts on supports: organometallic chemistry meets surface science.

    Serna, Pedro; Gates, Bruce C

    2014-08-19

    Recent advances in the synthesis and characterization of small, essentially molecular metal complexes and metal clusters on support surfaces have brought new insights to catalysis and point the way to systematic catalyst design. We summarize recent work unraveling effects of key design variables of site-isolated catalysts: the metal, metal nuclearity, support, and other ligands on the metals, also considering catalysts with separate, complementary functions on supports. The catalysts were synthesized with the goal of structural simplicity and uniformity to facilitate incisive characterization. Thus, they are essentially molecular species bonded to porous supports chosen for their high degree of uniformity; the supports are crystalline aluminosilicates (zeolites) and MgO. The catalytic species are synthesized in reactions of organometallic precursors with the support surfaces; the precursors include M(L)2(acetylacetonate)1-2, with M = Ru, Rh, Ir, or Au and the ligands L = C2H4, CO, or CH3. Os3(CO)12 and Ir4(CO)12 are used as precursors of supported metal clusters, and some such catalysts are made by ship-in-a-bottle syntheses to trap the clusters in zeolite cages. The simplicity and uniformity of the supported catalysts facilitate precise structure determinations, even in reactive atmospheres and during catalysis. The methods of characterizing catalysts in reactive atmospheres include infrared (IR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and nuclear magnetic resonance (NMR) spectroscopies, and complementary methods include density functional theory and atomic-resolution aberration-corrected scanning transmission electron microscopy for imaging of individual metal atoms. IR, NMR, XANES, and microscopy data demonstrate the high degrees of uniformity of well-prepared supported species. The characterizations determine the compositions of surface metal complexes and clusters, including the ligands and the metal

  19. Process for Making a Noble Metal on Tin Oxide Catalyst

    Davis, Patricia; Miller, Irvin; Upchurch, Billy

    2010-01-01

    To produce a noble metal-on-metal oxide catalyst on an inert, high-surface-area support material (that functions as a catalyst at approximately room temperature using chloride-free reagents), for use in a carbon dioxide laser, requires two steps: First, a commercially available, inert, high-surface-area support material (silica spheres) is coated with a thin layer of metal oxide, a monolayer equivalent. Very beneficial results have been obtained using nitric acid as an oxidizing agent because it leaves no residue. It is also helpful if the spheres are first deaerated by boiling in water to allow the entire surface to be coated. A metal, such as tin, is then dissolved in the oxidizing agent/support material mixture to yield, in the case of tin, metastannic acid. Although tin has proven especially beneficial for use in a closed-cycle CO2 laser, in general any metal with two valence states, such as most transition metals and antimony, may be used. The metastannic acid will be adsorbed onto the high-surface-area spheres, coating them. Any excess oxidizing agent is then evaporated, and the resulting metastannic acid-coated spheres are dried and calcined, whereby the metastannic acid becomes tin(IV) oxide. The second step is accomplished by preparing an aqueous mixture of the tin(IV) oxide-coated spheres, and a soluble, chloride-free salt of at least one catalyst metal. The catalyst metal may be selected from the group consisting of platinum, palladium, ruthenium, gold, and rhodium, or other platinum group metals. Extremely beneficial results have been obtained using chloride-free salts of platinum, palladium, or a combination thereof, such as tetraammineplatinum (II) hydroxide ([Pt(NH3)4] (OH)2), or tetraammine palladium nitrate ([Pd(NH3)4](NO3)2).

  20. Application of Metal Catalysts for High Selectivity of Glycerol Conversion to Alcohols

    2010-11-01

    The objective of this project is to determine the applicability of metal-based catalysts and optimize the process conditions for thermochemically producing primary alcohols. Metal catalysts were evaluated for their selectivities for producing alcohol...

  1. Metal-Halide Perovskite Transistors for Printed Electronics: Challenges and Opportunities

    Lin, Yen-Hung

    2017-10-12

    Following the unprecedented rise in photovoltaic power conversion efficiencies during the past five years, metal-halide perovskites (MHPs) have emerged as a new and highly promising class of solar-energy materials. Their extraordinary electrical and optical properties combined with the abundance of the raw materials, the simplicity of synthetic routes, and processing versatility make MHPs ideal for cost-efficient, large-volume manufacturing of a plethora of optoelectronic devices that span far beyond photovoltaics. Herein looks beyond current applications in the field of energy, to the area of large-area electronics using MHPs as the semiconductor material. A comprehensive overview of the relevant fundamental material properties of MHPs, including crystal structure, electronic states, and charge transport, is provided first. Thereafter, recent demonstrations of MHP-based thin-film transistors and their application in logic circuits, as well as bi-functional devices such as light-sensing and light-emitting transistors, are discussed. Finally, the challenges and opportunities in the area of MHPs-based electronics, with particular emphasis on manufacturing, stability, and health and environmental concerns, are highlighted.

  2. Low-Dimensional-Networked Metal Halide Perovskites: The Next Big Thing

    Saidaminov, Makhsud I.

    2017-03-03

    Low-dimensional-networked (low-DN) perovskite derivatives are bulk quantum materials in which charge carriers are localized within ordered metal halide sheets, rods, or clusters that are separated by cationic lattices. After two decades of hibernation, this class of semiconductors reemerged in the past two years, largely catalyzed by the interest in alternative, more stable absorbers to CH3NH3PbI3-type perovskites in photovoltaics. Whether low-DN perovskites will surpass other photovoltaic technologies remains to be seen, but their impressively high photo- and electroluminescence yields have already set new benchmarks in light emission applications. Here we offer our perspective on the most exciting advances in materials design of low-DN perovskites for energy- and optoelectronic-related applications. The next few years will usher in an explosive growth in this tribe of quantum materials, as only a few members have been synthesized, while the potential library of compositions and structures is believed to be much larger and is yet to be discovered.

  3. AB INITIO molecular orbital studies of some high temperature metal halide complexes

    Curtiss, L.A.

    1978-01-01

    The use of ab initio molecular orbital calculations to aid in the characterization, i.e., structures and energies, of metal halide complexes present in high temperature salt vapors has been investigated. Standard LCAO-SCF methods were used and calculations were carried out using the minimal STO-3G basis set. The complexes included in this study were Al 2 F 6 , Al 2 Cl 6 , AlF 3 NH 3 , AlCl 3 NH 3 , and AlF 3 N 2 . The Al 2 X 6 complexes are found to have D/sub 2h/ symmetry in agreement with most experimental results. A planar form was found to be considerably higher in energy. The AlX 3 NH 3 complexes are found to have C/sub 3v/ symmetry with a small barrier to rotation about the Al-N axis. The AlF 3 N 2 complex is found to be weakly bound together with a binding energy of -8.2 kcal/mole at the STO-3G level

  4. A survey of infrared continuum versus line radiation from metal halide lamps

    Kato, M; Herd, M T; Lawler, J E

    2008-01-01

    Near-infrared radiation (near-IR) losses from the arcs of six commercial metal halide high intensity discharge (MH-HID) lamps with various power levels and with both Na/Sc and rare earth doses were surveyed in this paper. A radiometrically calibrated Fourier transform infrared spectrometer was used. Lamps with rare earth doses have appreciably better color rendering indices (CRIs) than lamps with Na/Sc doses. The ratios of near-IR continuum emission over near-IR line emission from these six lamps were compared. The near-IR continuum dominates near-IR losses from lamps with rare earth doses and the continuum is significant, but not dominant, from lamps with Na/Sc doses. There was no strong dependence of this ratio on input power or color temperature (T c ). Total near-IR losses were estimated using absolutely calibrated, horizontal irradiance measurements. Estimated total near-IR losses were correlated with CRI. The lamps with rare earth doses yield the best CRIs, but have appreciably higher near-IR losses due primarily to continuum processes. One of these rare earth MH-HID lamps was used in a more detailed study of the microscopic physics of the continuum mechanism (Herd M T and Lawler E 2007 J. Phys. D: Appl. Phys. 40 3386)

  5. Improving the Stability of Metal Halide Perovskite Materials and Light-Emitting Diodes.

    Cho, Himchan; Kim, Young-Hoon; Wolf, Christoph; Lee, Hyeon-Dong; Lee, Tae-Woo

    2018-01-25

    Metal halide perovskites (MHPs) have numerous advantages as light emitters such as high photoluminescence quantum efficiency with a direct bandgap, very narrow emission linewidth, high charge-carrier mobility, low energetic disorder, solution processability, simple color tuning, and low material cost. Based on these advantages, MHPs have recently shown unprecedented radical progress (maximum current efficiency from 0.3 to 42.9 cd A -1 ) in the field of light-emitting diodes. However, perovskite light-emitting diodes (PeLEDs) suffer from intrinsic instability of MHP materials and instability arising from the operation of the PeLEDs. Recently, many researchers have devoted efforts to overcome these instabilities. Here, the origins of the instability in PeLEDs are reviewed by categorizing it into two types: instability of (i) the MHP materials and (ii) the constituent layers and interfaces in PeLED devices. Then, the strategies to improve the stability of MHP materials and PeLEDs are critically reviewed, such as A-site cation engineering, Ruddlesden-Popper phase, suppression of ion migration with additives and blocking layers, fabrication of uniform bulk polycrystalline MHP layers, and fabrication of stable MHP nanoparticles. Based on this review of recent advances, future research directions and an outlook of PeLEDs for display applications are suggested. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Metal-Halide Perovskite Transistors for Printed Electronics: Challenges and Opportunities.

    Lin, Yen-Hung; Pattanasattayavong, Pichaya; Anthopoulos, Thomas D

    2017-12-01

    Following the unprecedented rise in photovoltaic power conversion efficiencies during the past five years, metal-halide perovskites (MHPs) have emerged as a new and highly promising class of solar-energy materials. Their extraordinary electrical and optical properties combined with the abundance of the raw materials, the simplicity of synthetic routes, and processing versatility make MHPs ideal for cost-efficient, large-volume manufacturing of a plethora of optoelectronic devices that span far beyond photovoltaics. Herein looks beyond current applications in the field of energy, to the area of large-area electronics using MHPs as the semiconductor material. A comprehensive overview of the relevant fundamental material properties of MHPs, including crystal structure, electronic states, and charge transport, is provided first. Thereafter, recent demonstrations of MHP-based thin-film transistors and their application in logic circuits, as well as bi-functional devices such as light-sensing and light-emitting transistors, are discussed. Finally, the challenges and opportunities in the area of MHPs-based electronics, with particular emphasis on manufacturing, stability, and health and environmental concerns, are highlighted. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Prediction of Intrinsic Ferromagnetic Ferroelectricity in a Transition-Metal Halide Monolayer

    Huang, Chengxi; Du, Yongping; Wu, Haiping; Xiang, Hongjun; Deng, Kaiming; Kan, Erjun

    2018-04-01

    The realization of multiferroics in nanostructures, combined with a large electric dipole and ferromagnetic ordering, could lead to new applications, such as high-density multistate data storage. Although multiferroics have been broadly studied for decades, ferromagnetic ferroelectricity is rarely explored, especially in two-dimensional (2D) systems. Here we report the discovery of 2D ferromagnetic ferroelectricity in layered transition-metal halide systems. On the basis of first-principles calculations, we reveal that a charged CrBr3 monolayer exhibits in-plane multiferroicity, which is ensured by the combination of orbital and charge ordering as realized by the asymmetric Jahn-Teller distortions of octahedral Cr - Br6 units. As an example, we further show that (CrBr3)2Li is a ferromagnetic ferroelectric multiferroic. The explored phenomena and mechanism of multiferroics in this 2D system not only are useful for fundamental research in multiferroics but also enable a wide range of applications in nanodevices.

  8. Broadband enhancement of photoluminance from colloidal metal halide perovskite nanocrystals on plasmonic nanostructured surfaces.

    Zhang, Si; Liang, Yuzhang; Jing, Qiang; Lu, Zhenda; Lu, Yanqing; Xu, Ting

    2017-11-07

    Metal halide perovskite nanocrystals (NCs) as a new kind of promising optoelectronic material have attracted wide attention due to their high photoluminescence (PL) quantum yield, narrow emission linewidth and wideband color tunability. Since the PL intensity always has a direct influence on the performance of optoelectronic devices, it is of vital importance to improve the perovskite NCs' fluorescence emission efficiency. Here, we synthesize three inorganic perovskite NCs and experimentally demonstrate a broadband fluorescence enhancement of perovskite NCs by exploiting plasmonic nanostructured surface consisting of nanogrooves array. The strong near-field optical localization associated with surface plasmon polariton-coupled emission effect generated by the nanogrooves array can significantly boost the absorption of perovskite NCs and tailor the fluorescence emissions. As a result, the PL intensities of perovskite NCs are broadband enhanced with a maximum factor higher than 8-fold achieved in experimental demonstration. Moreover, the high efficiency PL of perovskite NCs embedded in the polymer matrix layer on the top of plasmonic nanostructured surface can be maintained for more than three weeks. These results imply that plasmonic nanostructured surface is a good candidate to stably broadband enhance the PL intensity of perovskite NCs and further promote their potentials in the application of visible-light-emitting devices.

  9. Metal Phosphate-Supported Pt Catalysts for CO Oxidation

    Xiaoshuang Qian

    2014-12-01

    Full Text Available Oxides (such as SiO2, TiO2, ZrO2, Al2O3, Fe2O3, CeO2 have often been used to prepare supported Pt catalysts for CO oxidation and other reactions, whereas metal phosphate-supported Pt catalysts for CO oxidation were rarely reported. Metal phosphates are a family of metal salts with high thermal stability and acid-base properties. Hydroxyapatite (Ca10(PO46(OH2, denoted as Ca-P-O here also has rich hydroxyls. Here we report a series of metal phosphate-supported Pt (Pt/M-P-O, M = Mg, Al, Ca, Fe, Co, Zn, La catalysts for CO oxidation. Pt/Ca-P-O shows the highest activity. Relevant characterization was conducted using N2 adsorption-desorption, inductively coupled plasma (ICP atomic emission spectroscopy, X-ray diffraction (XRD, transmission electron microscopy (TEM, CO2 temperature-programmed desorption (CO2-TPD, X-ray photoelectron spectroscopy (XPS, and H2 temperature-programmed reduction (H2-TPR. This work furnishes a new catalyst system for CO oxidation and other possible reactions.

  10. Polymer Catalysts Imprinted with Metal Ions as Biomimics of Metalloenzymes

    Joanna Czulak

    2013-01-01

    Full Text Available This work presents the preparation and properties of molecularly imprinted polymers (MIPs with catalytic centers that mimic the active sites of metalloenzymes. The MIP synthesis was based on suspension polymerization of functional monomers (4-vinylpyridine and acrylonitrile with trimethylolpropane trimethacrylate as a crosslinker in the presence of transition metal ions and 4-methoxybenzyl alcohol as a template. Four metal ions have been chosen for imprinting from among the microelements that are the most essential in the native enzymes: Cu2+, Co2+, Mn2+, and Zn2+. To prepare catalysts, the required loading of metal ions was obtained during sorption process. The catalysts imprinted with Cu2+, Co2+, and Zn2+ were successfully used for hydroquinone oxidation in the presence of hydrogen peroxide. The Mn2+-imprinted catalyst showed no activity due to the insufficient metal loading. Cu2+ MIP showed the highest efficiency. In case of Cu- and Co-MIP catalysts, their activity was additionally increased by the use of surface imprinting technique.

  11. Reactions of synthesis gas on silica supported transition metal catalysts

    Niemelae, M. [VTT Chemical Technology, Espoo (Finland). Lab. of Industrial Chemistry

    1997-12-31

    The effect of catalyst precursor and composition on the activation of CO was investigated using CO hydrogenation as a test reaction. The interrelations of preparation, pretreatment, characteristics and activity were clarified. For Co/SiO{sub 2} catalyst, MgO promotion increased the CO adsorption capacity and the hydrogen uptake, although the extent of reduction for cobalt remained the same or decreased. The conversion per active metallic cobalt site consequently increased in conjunction with MgO promotion, while the effect on overall performance per 1 g of catalyst remained moderate. The precursor affected the performance of Co/SiO{sub 2} considerably. CO was more strongly adsorbed on catalysts of carbonyl origin than on those derived from cobalt nitrate, the activity thus being higher. Although the nitrate derived Co/SiO{sub 2} appeared both to retain its activity and to regain its adsorption capacity better than the catalysts of carbonyl origin, the performance of the latter was superior with time on stream. For tetranuclear cluster based Co-Ru and Co-Rh catalysts, rhodium or ruthenium was in contact with the support and cobalt was enriched on top. On Co-Ru/SiO{sub 2} ruthenium enhanced deactivation, and no benefits in activity or oxygenate selectivity were achieved relative to the monometallic catalysts of cluster origin. The Co-Rh/SiO{sub 2} catalysts were also less active than those derived from monometallic clusters, but they exhibited higher selectivities to oxygenated compounds due to the presence of active sites on the perimeter of the cobalt particles located on rhodium. The highest selectivity to oxygenates was achieved by changing the decomposition atmosphere of Rh{sub 4}(CO){sub 12}/SiO{sub 2} from hydrogen to carbon monoxide. The results also showed two types of active sites to be operative in the formation of oxygenates - one for ethanol and another for aldehydes. (orig.) 69 refs.

  12. A model for additive transport in metal halide lamps containing mercury and dysprosium tri-iodide

    Beks, M L; Haverlag, M; Mullen, J J A M van der

    2008-01-01

    The distribution of additives in a metal halide lamp is examined through numerical modelling. A model for a lamp containing sodium iodide additives has been modified to study a discharge containing dysprosium tri-iodide salts. To study the complex chemistry the method of Gibbs minimization is used to decide which species have to be taken into account and to fill lookup tables with the chemical composition at different combinations of elemental abundance, lamp pressure and temperature. The results from the model with dysprosium additives were compared with earlier results from the lamp containing sodium additives and a simulation of a pure mercury lamp. It was found that radial segregation creates the conditions required for axial segregation. Radial segregation occurs due to the unequal diffusion of atoms and molecules. Under the right conditions convection currents in the lamp can cause axial demixing. These conditions depend on the ratio of axial convection and radial diffusion as expressed by the Peclet number. At a Peclet number of unity axial segregation is most pronounced. At low Peclet numbers radial segregation is at its worst, while axial segregation is not present. At large Peclet numbers the discharge becomes homogeneously mixed. The degree of axial segregation at a Peclet number of unity depends on the temperature at which the additive under consideration fully dissociates. If the molecules dissociate very close to the walls no molecules are transported by the convective currents in the lamp, and hence axial segregation is limited. If they dissociate further away from the walls in the area where the downward convective currents are strongest, more axial segregation is observed

  13. Investigation of the connection between plasma temperature and electrode temperature in metal-halide lamps

    Fromm, D.C.; Gleixner, K.H.; Lieder, G.H.

    2002-01-01

    Spatial profiles of electrode temperatures and plasma temperatures have been measured on 'real' HID lamps filled with a commercial metal-halide compound. The absolute accuracy of pyrometric determination of electrode tip temperatures was ±30 K, while the determination of plasma core temperatures, using a modified Bartels method, has an accuracy of ±100 K. We could deduce a close correlation between the plasma temperature in front of an electrode T p and its tip temperature T t due to the influence of the cataphoresis. If T p is reduced at the cathode the T t value has also lowered, whereas T p at the anode is raised together with its T t data. This correlation disappears at ballast frequencies above 100 Hz, whereas the cataphoresis influence on T p continues up to 500 Hz. Based on the latter limit, a rough estimation of the cataphoresis velocity delivers 700 cm s -1 . As a tentative interpretation, we suggest that the connection between T p and T t is caused by an increase of the ion part of the total current at the cathode due to Na accumulation before it. Thus, the cathode has to emit fewer electrons and works at a lower temperature. Further results are the temporal behaviour of T t depends on the ballast type. For vertical operation the strong influence of convection on T t has also to be taken into account. Above 100 Hz, where only convection plays a role, the upper electrode T t exceeds the T t value of the lower electrode by nearly 400 K. This discrepancy one may explain, tentatively, by convection heating of the upper electrode and convection cooling of the lower one. (author)

  14. Ozone Decomposition on the Surface of Metal Oxide Catalyst

    Batakliev Todor Todorov

    2014-12-01

    Full Text Available The catalytic decomposition of ozone to molecular oxygen over catalytic mixture containing manganese, copper and nickel oxides was investigated in the present work. The catalytic activity was evaluated on the basis of the decomposition coefficient which is proportional to ozone decomposition rate, and it has been already used in other studies for catalytic activity estimation. The reaction was studied in the presence of thermally modified catalytic samples operating at different temperatures and ozone flow rates. The catalyst changes were followed by kinetic methods, surface measurements, temperature programmed reduction and IR-spectroscopy. The phase composition of the metal oxide catalyst was determined by X-ray diffraction. The catalyst mixture has shown high activity in ozone decomposition at wet and dry O3/O2 gas mixtures. The mechanism of catalytic ozone degradation was suggested.

  15. THE THEORY OF DEVELOPMENT OF SUPPORTED METAL-COMPLEX CATALYSTS

    T. L. Rakitskaya

    2015-06-01

    Full Text Available Some results of the investigations for the purpose of development of supported metal-complex catalysts for phosphine and carbon monoxide oxidation as well as for ozone decomposition are summarized. The activity of such catalysts has been found to depend not only on a nature of a central atom and ligands but also on a nature of supports. The theoretical model explaining mechanisms of surface complex formation taking into account the influence of physicochemical and structural-adsorption properties of the supports (SiO2, Al2O3, carbon materials, zeolites, dispersed silicas, lamellar aluminosilicates, etc. has been proposed. For quantitative description of the support effect, such a thermodynamic parameter as the adsorbed water activity assignable with the help of water vapor adsorption isotherms has been introduced. Successive stability constants of the surface metal complexes have been calculated by the kinetic method and, hence, compositions and partial catalytic activity of the latter have been determined. Taking into account the competitive adsorption of metal ions on the supports, some schemes of formation of surface bimetallic complexes have been suggested. The compositions of the supported metal-complex catalysts have been optimized to meet requirements of their use in respirators and plants for air purification from foregoing gaseous toxicants.

  16. Reductive dehalogenation of aryl halides over palladium catalysts deposited on SBA-15 type molecular sieve modified with amine donor groups

    Štěpnička, P.; Semler, M.; Demel, J.; Zukal, Arnošt; Čejka, Jiří

    2011-01-01

    Roč. 341, č. 1-2 (2011), s. 97-102 ISSN 1381-1169 R&D Projects: GA ČR GA104/09/0561 Institutional research plan: CEZ:AV0Z40400503 Keywords : heterogeneous catalysts * supported catalysts * palladium Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.947, year: 2011

  17. Parity-Forbidden Transitions and Their Impact on the Optical Absorption Properties of Lead-Free Metal Halide Perovskites and Double Perovskites.

    Meng, Weiwei; Wang, Xiaoming; Xiao, Zewen; Wang, Jianbo; Mitzi, David B; Yan, Yanfa

    2017-07-06

    Using density functional theory calculations, we analyze the optical absorption properties of lead (Pb)-free metal halide perovskites (AB 2+ X 3 ) and double perovskites (A 2 B + B 3+ X 6 ) (A = Cs or monovalent organic ion, B 2+ = non-Pb divalent metal, B + = monovalent metal, B 3+ = trivalent metal, X = halogen). We show that if B 2+ is not Sn or Ge, Pb-free metal halide perovskites exhibit poor optical absorptions because of their indirect band gap nature. Among the nine possible types of Pb-free metal halide double perovskites, six have direct band gaps. Of these six types, four show inversion symmetry-induced parity-forbidden or weak transitions between band edges, making them not ideal for thin-film solar cell applications. Only one type of Pb-free double perovskite shows optical absorption and electronic properties suitable for solar cell applications, namely, those with B + = In, Tl and B 3+ = Sb, Bi. Our results provide important insights for designing new metal halide perovskites and double perovskites for optoelectronic applications.

  18. COATING OF POLYMERIC SUBSTRATE CATALYSTS ON METALLIC SURFACES

    H. HOSSEINI

    2010-12-01

    Full Text Available This article presents results of a study on coating of a polymeric substrate ca-talyst on metallic surface. Stability of coating on metallic surfaces is a proper specification. Sol-gel technology was used to synthesize adhesion promoters of polysilane compounds that act as a mediator. The intermediate layer was coated by synthesized sulfonated polystyrene-divinylbenzene as a catalyst for production of MTBE in catalytic distillation process. Swelling of catalyst and its separation from the metal surface was improved by i increasing the quantity of divinylbenzene in the resin’s production process and ii applying adhesion pro¬moters based on the sol-gel process. The rate of ethyl silicate hydrolysis was intensified by increasing the concentration of utilized acid while the conden¬sation polymerization was enhanced in the presence of OH–. Sol was formed at pH 2, while the pH should be 8 for the formation of gel. By setting the ratio of the initial concentrations of water to ethyl silicate to 8, the gel formation time was minimized.

  19. Ultrastable Photoelectrodes for Solar Water Splitting Based on Organic Metal Halide Perovskite Fabricated by Lift-Off Process.

    Nam, SeongSik; Mai, Cuc Thi Kim; Oh, Ilwhan

    2018-05-02

    Herein, we report an integrated photoelectrolysis of water employing organic metal halide (OMH) perovskite material. As generic OMH perovskite material and device architecture are highly susceptible to degradation by aqueous electrolytes, we have developed a versatile mold-cast and lift-off process to fabricate and assemble multipurpose metal encapsulation onto perovskite devices. With the metal encapsulation effectively protecting the perovskite cell and also functioning as electrocatalyst, the high-performance perovskite photoelectrodes exhibit high photovoltage and photocurrent that are effectively inherited from the original solid-state solar cell. More importantly, thus-fabricated perovskite photoelectrode demonstrates record-long unprecedented stability even at highly oxidizing potential in strong alkaline electrolyte. We expect that this versatile lift-off process can be adapted in a wide variety of photoelectrochemical devices to protect the material surfaces from corroding electrolyte and facilitate various electrochemical reactions.

  20. Noble metal catalysts in the production of biofuels

    Gutierrez, A.

    2013-11-01

    The energy demand is increasing in the world together with the need to ensure energy security and the desire to decrease greenhouse gas emissions. While several renewable alternatives are available for the production of electricity, e.g. solar energy, wind power, and hydrogen, biomass is the only renewable source that can meet the demand for carbon-based liquid fuels and chemicals. The technology applied in the conversion of biomass depends on the type and complexity of the biomass, and the desired fuel. Hydrogen and hydrogen-rich mixtures (synthesis gas) are promising energy sources as they are more efficient and cleaner than existing fuels, especially when they are used in fuel cells. Hydrotreatment is a catalytic process that can be used in the conversion of biomass or biomass-derived liquids into fuels. In autothermal reforming (ATR), catalysts are used in the production of hydrogen-rich mixtures from conventional fuels or bio-fuels. The different nature of biomass and biomass-derived liquids and mineral oil makes the use of catalysts developed for the petroleum industry challenging. This requires the improvement of available catalysts and the development of new ones. To overcome the limitations of conventional hydrotreatment and ATR catalysts, zirconia-supported mono- and bimetallic rhodium, palladium, and platinum catalysts were developed and tested in the upgrading of model compounds for wood-based pyrolysis oil and in the production of hydrogen, using model compounds for gasoline and diesel. Catalysts were also tested in the ATR of ethanol. For comparative purposes commercial catalysts were tested and the results obtained with model compounds were compared with those obtained with real feedstocks (hydrotreatmet tests with wood-based pyrolysis oil and ATR tests with NExBTL renewable diesel). Noble metal catalysts were active and selective in the hydrotreatment of guaiacol used as the model compound for the lignin fraction of wood-based pyrolysis oil and wood

  1. Merging Metallic Catalysts and Sonication: A Periodic Table Overview

    Claudia E. Domini

    2017-04-01

    Full Text Available This account summarizes and discusses recent examples in which the combination of ultrasonic waves and metal-based reagents, including metal nanoparticles, has proven to be a useful choice in synthetic planning. Not only does sonication often enhance the activity of the metal catalyst/reagent, but it also greatly enhances the synthetic transformation that can be conducted under milder conditions relative to conventional protocols. For the sake of clarity, we have adopted a structure according to the periodic-table elements or families, distinguishing between bulk metal reagents and nanoparticles, as well as the supported variations, thus illustrating the characteristics of the method under consideration in target synthesis. The coverage focuses essentially on the last decade, although the discussion also strikes a comparative balance between the more recent advancements and past literature.

  2. A Study on Organic-Metal Halide Perovskite Film Morphology, Interfacial Layers, Tandem Applications, and Encapsulation

    Fisher, Dallas A.

    Organic-metal halide perovskites have brought about a new wave of research in the photovoltaic community due to their ideally suited optical and electronic parameters. In less than a decade, perovskite solar cell performance has skyrocketed to unprecedented efficiencies with numerous reported methodologies. Perovskites face many challenges with high-quality film morphology, interfacial layers, and long-term stability. In this work, these active areas are explored through a combination of studies. First, the importance of perovskite film precursor ratios is explored with an in-depth study of carrier lifetime and solvent-grain effects. It was found that excess lead iodide precursor greatly improves the film morphology by reducing pinholes in the solar absorber. Dimethyl sulfoxide (DMSO) solvent was found to mend grains, as well as improve carrier lifetime and device performance, possibly by passivation of grain boundary traps. Second, applications of perovskite with tandem cells is investigated, with an emphasis for silicon devices. Perovskites can easily be integrated with silicon, which already has strong market presence. Additionally, both materials' bandgaps are ideally suited for maximum tandem efficiency. The silicon/perovskite tandem device structure necessitated the optimization of inverted (p-i-n) structure devices. PEDOT:PSS, copper oxide, and nickel oxide p-type layers were explored through a combination of photoluminescent, chemical reactivity, and solar simulation results. Results were hindered due to resistive ITO and rough silicon substrates, but tandem devices displayed Voc indicative of proper monolithic performance. Third, replacement of titanium dioxide n-type layer with iron oxide (Fe 2O3, common rust) was studied. Iron oxide experiences less ultraviolet instability than that of titanium dioxide under solar illumination. It was found that current density slightly decreased due to parasitic absorption from the rust, but that open circuit voltage

  3. Electrochemical dopamine sensor based on P-doped graphene: Highly active metal-free catalyst and metal catalyst support.

    Chu, Ke; Wang, Fan; Zhao, Xiao-Lin; Wang, Xin-Wei; Tian, Ye

    2017-12-01

    Heteroatom doping is an effective strategy to enhance the catalytic activity of graphene and its hybrid materials. Despite a growing interest of P-doped graphene (P-G) in energy storage/generation applications, P-G has rarely been investigated for electrochemical sensing. Herein, we reported the employment of P-G as both metal-free catalyst and metal catalyst support for electrochemical detection of dopamine (DA). As a metal-free catalyst, P-G exhibited prominent DA sensing performances due to the important role of P doping in improving the electrocatalytic activity of graphene toward DA oxidation. Furthermore, P-G could be an efficient supporting material for loading Au nanoparticles, and resulting Au/P-G hybrid showed a dramatically enhanced electrocatalytic activity and extraordinary sensing performances with a wide linear range of 0.1-180μM and a low detection limit of 0.002μM. All these results demonstrated that P-G might be a very promising electrode material for electrochemical sensor applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. X-ray induced fluorescence measurement of segregation in a DyI{sub 3}-Hg metal-halide lamp

    Nimalasuriya, T [Department of Applied Physics, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven (Netherlands); Curry, J J [National Institute of Standards and Technology, 100 Bureau Drive, Stop 8422, Gaithersburg, MD 20899-8422 (United States); Sansonetti, C J [National Institute of Standards and Technology, 100 Bureau Drive, Stop 8422, Gaithersburg, MD 20899-8422 (United States); Ridderhof, E J [Department of Applied Physics, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven (Netherlands); Shastri, S D [Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439 (United States); Flikweert, A J [Department of Applied Physics, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven (Netherlands); Stoffels, W W [Department of Applied Physics, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven (Netherlands); Haverlag, M [Department of Applied Physics, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven (Netherlands); Mullen, J J A M van der [Department of Applied Physics, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven (Netherlands)

    2007-05-07

    Segregation of elemental Dy in a DyI{sub 3}-Hg metal-halide high-intensity discharge lamp has been observed with x-ray induced fluorescence. Significant radial and axial Dy segregation are seen, with the axial segregation characterized by a Fischer parameter value of {lambda} = 0.215 {+-} 0.002 mm{sup -1}. This is within 7% of the value ({lambda} = 0.20 {+-} 0.01 mm{sup -1}) obtained by Flikweert et al (2005 J. Appl. Phys. 98 073301) based on laser absorption by neutral Dy atoms. Elemental I is seen to exhibit considerably less axial and radial segregation. Some aspects of the observed radial segregation are compatible with a simplified fluid picture describing two main transition regions in the radial coordinate. The first transition occurs in the region where DyI{sub 3} molecules are in equilibrium with neutral Dy atoms. The second transition occurs where neutral Dy atoms are in equilibrium with ionized Dy. These measurements are part of a larger study on segregation in metal-halide lamps under a variety of conditions.

  5. Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides as Lewis Acidic Heterogeneous Catalysts. Providing Some Context for Nanostructured Metal Fluorides.

    Lennon, David; Winfield, John M

    2017-01-28

    Aspects of the chemistry of selected metal fluorides, which are pertinent to their real or potential use as Lewis acidic, heterogeneous catalysts, are reviewed. Particular attention is paid to β-aluminum trifluoride, aluminum chlorofluoride and aluminas γ and η, whose surfaces become partially fluorinated or chlorinated, through pre-treatment with halogenating reagents or during a catalytic reaction. In these cases, direct comparisons with nanostructured metal fluorides are possible. In the second part of the review, attention is directed to iron(III) and copper(II) metal chlorides, whose Lewis acidity and potential redox function have had important catalytic implications in large-scale chlorohydrocarbons chemistry. Recent work, which highlights the complexity of reactions that can occur in the presence of supported copper(II) chloride as an oxychlorination catalyst, is featured. Although direct comparisons with nanostructured fluorides are not currently possible, the work could be relevant to possible future catalytic developments in nanostructured materials.

  6. Nature of the metal-support interface in supported metal catalysts: results from x-ray absorption spectroscopy

    Koningsberger, D.C.; Gates, B.C.

    1992-01-01

    X-ray absorption spectra characterizing the metal-support interface in supported metal complexes and supported metal catalysts are summarized and evaluated with 29 refs. Mononuclear transition metal complexes on non-reducible metal oxide supports are bonded with metal-oxygen bonds of .apprx.2.15

  7. Origin of vertical orientation in two-dimensional metal halide perovskites and its effect on photovoltaic performance.

    Chen, Alexander Z; Shiu, Michelle; Ma, Jennifer H; Alpert, Matthew R; Zhang, Depei; Foley, Benjamin J; Smilgies, Detlef-M; Lee, Seung-Hun; Choi, Joshua J

    2018-04-06

    Thin films based on two-dimensional metal halide perovskites have achieved exceptional performance and stability in numerous optoelectronic device applications. Simple solution processing of the 2D perovskite provides opportunities for manufacturing devices at drastically lower cost compared to current commercial technologies. A key to high device performance is to align the 2D perovskite layers, during the solution processing, vertical to the electrodes to achieve efficient charge transport. However, it is yet to be understood how the counter-intuitive vertical orientations of 2D perovskite layers on substrates can be obtained. Here we report a formation mechanism of such vertically orientated 2D perovskite in which the nucleation and growth arise from the liquid-air interface. As a consequence, choice of substrates can be liberal from polymers to metal oxides depending on targeted application. We also demonstrate control over the degree of preferential orientation of the 2D perovskite layers and its drastic impact on device performance.

  8. Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

    Wang, Liang

    2018-04-04

    Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.

  9. Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

    Wang, Liang; Guan, Erjia; Zhang, Jian; Yang, Junhao; Zhu, Yihan; Han, Yu; Yang, Ming; Cen, Cheng; Fu, Gang; Gates, Bruce C.; Xiao, Feng-Shou

    2018-01-01

    Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.

  10. Oxide-supported metal clusters: models for heterogeneous catalysts

    Santra, A K; Goodman, D W

    2003-01-01

    Understanding the size-dependent electronic, structural and chemical properties of metal clusters on oxide supports is an important aspect of heterogeneous catalysis. Recently model oxide-supported metal catalysts have been prepared by vapour deposition of catalytically relevant metals onto ultra-thin oxide films grown on a refractory metal substrate. Reactivity and spectroscopic/microscopic studies have shown that these ultra-thin oxide films are excellent models for the corresponding bulk oxides, yet are sufficiently electrically conductive for use with various modern surface probes including scanning tunnelling microscopy (STM). Measurements on metal clusters have revealed a metal to nonmetal transition as well as changes in the crystal and electronic structures (including lattice parameters, band width, band splitting and core-level binding energy shifts) as a function of cluster size. Size-dependent catalytic reactivity studies have been carried out for several important reactions, and time-dependent catalytic deactivation has been shown to arise from sintering of metal particles under elevated gas pressures and/or reactor temperatures. In situ STM methodologies have been developed to follow the growth and sintering kinetics on a cluster-by-cluster basis. Although several critical issues have been addressed by several groups worldwide, much more remains to be done. This article highlights some of these accomplishments and summarizes the challenges that lie ahead. (topical review)

  11. Development of super thin foil metal supported catalyst; Chousuhaku metal tantai shokubai no kaihatsu

    Sanji, F; Takada, T [Toyota Motor Corp., Aichi (Japan)

    1997-10-01

    In order to improve warm-up performance, high heat resistance and long life durability of catalysts, the reduction of the metal support heat capacity has been focused. The effects of both reducing foil thickness and lowering cell density on low heat capacity have been investigated. As a result of engine bench and vehicle test, it was apparent that the reduction of foil thickness has greater effects. Newly developed 30 {mu} m foil thickness metal supported catalyst has quicker warm-up performance, and its structural durability up to 950degC is confirmed. 3 refs., 11 figs., 1 tab.

  12. Effects of preparation method and active metal content on of Ni/kieselguhr catalyst activity

    Galuh Widiyarti; Wuryaningsih Sri Rahayu

    2010-01-01

    The preparation and the active metal content influence the activity of catalyst. Study has been conducted to see the activity of Ni/kieselguhr based on preparation method and Nickel (Ni) contents in the catalyst in the laboratory scale. The Ni/kieselguhr catalyst were prepared by impregnation and precipitation methods, with Ni active contents of 10, 20, and 30 % by weight. The catalysts characterization was analyzed using X-Ray Diffraction (XRD). Catalysts activities were analyzed based on decreasing of iodine number from hydrogenation of crude palm oil for 2 hours. The activity tests results show that precipitation catalysts are more active than impregnation catalysts. The decreasing in iodine number of fatty acid after 2 hours of hydrogenation process using precipitation catalysts and impregnation catalysts are 51.53 and 21.85 %, respectively. In addition, the catalysts are more active with increasing Ni contents. (author)

  13. NANOSTRUCTURED METAL OXIDE CATALYSTS VIA BUILDING BLOCK SYNTHESES

    Craig E. Barnes

    2013-03-05

    A broadly applicable methodology has been developed to prepare new single site catalysts on silica supports. This methodology requires of three critical components: a rigid building block that will be the main structural and compositional component of the support matrix; a family of linking reagents that will be used to insert active metals into the matrix as well as cross link building blocks into a three dimensional matrix; and a clean coupling reaction that will connect building blocks and linking agents together in a controlled fashion. The final piece of conceptual strategy at the center of this methodology involves dosing the building block with known amounts of linking agents so that the targeted connectivity of a linking center to surrounding building blocks is obtained. Achieving targeted connectivities around catalytically active metals in these building block matrices is a critical element of the strategy by which single site catalysts are obtained. This methodology has been demonstrated with a model system involving only silicon and then with two metal-containing systems (titanium and vanadium). The effect that connectivity has on the reactivity of atomically dispersed titanium sites in silica building block matrices has been investigated in the selective oxidation of phenols to benezoquinones. 2-connected titanium sites are found to be five times as active (i.e. initial turnover frequencies) than 4-connected titanium sites (i.e. framework titanium sites).

  14. 3D dysprosium density in the metal-halide lamp measured by emission and laser absorption spectroscopy in a centrifuge at 1-10g

    Flikweert, A.J.; Nimalasuriya, T.; Thubé, G.M.; Kroesen, G.M.W.; Stoffels, W.W.

    2007-01-01

    The metal-halide lamp is a High Intensity Discharge (HID) lamp with a high efficiency. The salt additive (DyI3) acts as prime radiator. The present lamp suffers from non-uniform light output, caused by diffusion and convection processes. To gain a better understanding of the lamp, the convection is

  15. X-ray absorption tomography of a high-pressure metal-halide lamp with a bent arc due to Lorentz-forces

    Denisova, N.; Haverlag, M.; Ridderhof, E.J.; Nimalasuriya, T.; Mullen, van der J.J.A.M.

    2007-01-01

    The arc temperature is one of the most important characteristics which cotrol the emission properties of plasma light sources. X-ray absorption technique has received some attention as a powerful method to determine the temperature in high-pressure metal-halide lamps. An important advantage of x-ray

  16. The Study of Reducing Krypton-85 Activity in Metal Halide Lamp%降低金卤灯内氪-85活度的研究

    叶碧君

    2012-01-01

    通过测试及分析不同氪-85活度填充气体的同规格金卤灯的各项性能参数,研究了在确保金卤灯各项性能的前提下,降低金卤灯中氪-85活度的可行性及金卤灯中氪-85存在的必要性,可以为今后确定金卤灯中需添加的最低氪-85活度提供参考。%By analyzing the parameters of metal halide lamps which are filled with gas with different activity of krypton-85, the paper studies the feasibility of reducing krypton-85 activity in metal halide lamp while ensuring the lamp performance, and proves the necessity of its existence of krypton-85 in metal halide lamp. it can provide us a reference to determine the minimum krypton-85 activity to he added in metal halide lamps.

  17. Preparation and Characterization of Double Metal Cyanide Complex Catalysts

    Weilin Guo

    2003-01-01

    Full Text Available A series of double metal cyanide (DMC complex catalysts were prepared in two different methods by using ß-cyclodextrin, PEG-1000 and Tween-60 as an additional complex ligands respectively. It was showed that a mixture of crystalline and amorphous DMC was synthesized by using traditional method in which the additional complex ligand was added after the precipitation of DMC. Amorphous and dispersed DMC with higher activity could be obtained when the additional complex ligand was added in the reactant solution before reaction. The effect of additional complex ligand and preparation method on the crystalline state and catalytic property of DMC were also investigated.

  18. THE STUDY OF CLINOPTILOLITE MODIFIED WITH3d METALS HALIDES BY IR AND DIFFUSE REFLECTANCE SPECTROSCOPY

    T. L. Rakitskaya

    2015-11-01

    Full Text Available The results of investigation of natural clinoptilolite (N-CLI and that modified with 3d metal halides (MeCl2/N-CLI, where Me are Cu, Co, and Mn by IR and diffuse reflectance spectroscopy are summarized. A band at 3437 cm-1 assigned to stretching vibrations of hydroxyl groups (nOH is found in the IR spectrum of the N-CLI sample. A location of the band was practically the same as for all above MeCl2/N-CLI samples. A band of middle intensity at 1638 cm-1 in the range of deformation vibrations of zeolite water observed in the IR spectrum of N-CLI slightly displays to lower frequencies in the case of the modified samples. An intensive wide band of a complex shape in the range from 1250 to 980 cm-1 assigned to Si–O–Si and Si–O–Al vibrations appears in IR spectra of all samples. A doublet band of middle intensity at 797 and 778 cm-1 is assigned to external symmetric stretching T-O vibrations and a band at 606 cm-1-to vibrations of a double ring. A location of the above bands is the same for all listed samples but their intensity is higher for MnCl2/N-CLI and CoCl2/N-CLI samples. After the reaction with ozone, significant changes in the IR spectra are observed only for MnCl2/N-CLI. They are due to MnO2 formation on the clinoptilolite surface resulting in a high frequency displacement of some bands. Based on UV-vi spectroscopy results, it is reasonable to make conclusions about the coordination and valence state of a central atom in the MeCl2/N-CLI samples under study. A location of charge transfer bands for these samples only slightly differs from that for N-CLI however the intensity of such bands increases for the MeCl2/N-CLI samples. The UV-vis spectrum of MnCl2/N-CLI changes after the reaction with ozone: the appearance of new bands of  charge transfer at 363 and 354 nm and also the two-fold increase in intensity of a charge transfer band at 272 nm in comparison with those of N-CLI and MnCl2/N-CLI are the evidence of change in both the

  19. On halide derivatives of rare-earth metal(III) oxidomolybdates(VI) and -tungstates(VI)

    Schleid, Thomas; Hartenbach, Ingo

    2016-01-01

    Halide derivatives of rare-earth metal(III) oxidomolybdates(VI) have been investigated comprehensively over the last decade comprising the halogens fluorine, chlorine, and bromine. Iodide-containing compounds are so far unknown. The simple composition REXMoO 4 (RE=rare-earth element, X=halogen) is realized for X=F almost throughout the complete lanthanide series as well as for yttrium. While ytterbium and lutetium do not form any fluoride derivative, for lanthanum, only a fluoride-deprived compound with the formula La 3 FMo 4 O 16 is realized. Moreover, molybdenum-rich compounds with the formula REXMo 2 O 7 are also known for yttrium and the smaller lanthanoids. For X=Cl the composition REClMoO 4 is known for yttrium and the whole lanthanide series, although, four different structure types were identified. Almost the same holds for X=Br, however, only two different structure types are realized in this class of compounds. In the case of halide derivatives of rare-earth metal(III) oxidotungstates(VI) the composition REXWO 4 is found for chlorides and bromides only, so far. Due to the similar size of Mo 6+ and W 6+ cations, the structures found for the tungstates are basically the same as for the molybdates. With the larger lanthanides, the representatives for both chloride and bromide derivates exhibit similar structural motifs as seen in the molybdates, however, the crystal structure cannot be determined reliably. In case of the smaller lanthanoids, the chloride derivatives are isostructural with the respective molybdates, although the existence ranges differ slightly. The same is true for rare-earth metal(III) bromide oxidotungstates(VI).

  20. Nano-structured noble metal catalysts based on hexametallate architecture for the reforming of hydrocarbon fuels

    Gardner, Todd H.

    2015-09-15

    Nano-structured noble metal catalysts based on hexametallate lattices, of a spinel block type, and which are resistant to carbon deposition and metal sulfide formation are provided. The catalysts are designed for the reforming of hydrocarbon fuels to synthesis gas. The hexametallate lattices are doped with noble metals (Au, Pt, Rh, Ru) which are atomically dispersed as isolated sites throughout the lattice and take the place of hexametallate metal ions such as Cr, Ga, In, and/or Nb. Mirror cations in the crystal lattice are selected from alkali metals, alkaline earth metals, and the lanthanide metals, so as to reduce the acidity of the catalyst crystal lattice and enhance the desorption of carbon deposit forming moieties such as aromatics. The catalysts can be used at temperatures as high as 1000.degree. C. and pressures up to 30 atmospheres. A method for producing these catalysts and applications of their use also is provided.

  1. Selective propene oxidation on mixed metal oxide catalysts

    James, David William

    2002-01-01

    Selective catalytic oxidation processes represent a large segment of the modern chemical industry and a major application of these is the selective partial oxidation of propene to produce acrolein. Mixed metal oxide catalysts are particularly effective in promoting this reaction, and the two primary candidates for the industrial process are based on iron antimonate and bismuth molybdate. Some debate exists in the literature regarding the operation of these materials and the roles of their catalytic components. In particular, iron antimonate catalysts containing excess antimony are known to be highly selective towards acrolein, and a variety of proposals for the enhanced selectivity of such materials have been given. The aim of this work was to provide a direct comparison between the behaviour of bismuth molybdate and iron antimonate catalysts, with additional emphasis being placed on the component single oxide phases of the latter. Studies were also extended to other antimonate-based catalysts, including cobalt antimonate and vanadium antimonate. Reactivity measurements were made using a continuous flow microreactor, which was used in conjunction with a variety of characterisation techniques to determine relationships between the catalytic behaviour and the properties of the materials. The ratio of Fe/Sb in the iron antimonate catalyst affects the reactivity of the system under steady state conditions, with additional iron beyond the stoichiometric value being detrimental to the acrolein selectivity, while extra antimony provides a means of enhancing the selectivity by decreasing acrolein combustion. Studies on the single antimony oxides of iron antimonate have shown a similarity between the reactivity of 'Sb 2 O 5 ' and FeSbO 4 , and a significant difference between these and the Sb 2 O 3 and Sb 2 O 4 phases, implying that the mixed oxide catalyst has a surface mainly comprised of Sb 5+ . The lack of reactivity of Sb 2 O 4 implies a similarity of the surface with

  2. Platinum group metal recovery and catalyst manufacturing process

    Chung, H. S.; Kim, Y. S.; Yoo, J. H.; Lee, H. S.; Ahn, D. H.; Kim, K. R.; Lee, S. H.; Paek, S. W.; Kang, H. S.

    1998-03-01

    The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metal such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solution was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400 m{sup 2}/g. The content of palladium impregnated on the support was 10 wt.%. Hydrogen isotope exchange efficiency of 93 % to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its actively is unimportant as in nuclear industries. (author). 63 refs., 38 tabs., 36 figs.

  3. Naphthenic acid removal from HVGO by alkaline earth metal catalysts

    Ding, L.; Rahimi, P.; Hawkins, R.; Bhatt, S.; Shi, Y. [National Centre for Upgrading Technology, Devon, AB (Canada); Natural Resources Canada, Devon, AB (Canada). CanmetENERGY

    2009-07-01

    This poster highlighted a study that investigated naphthenic acid removal from bitumen-derived heavy vacuum gas oil (HVGO) by thermal cracking and catalytic decarboxylation over alkaline earth-metal oxides and ZnO catalysts in a batch reactor and a continuous fixed-bed reactor. X-ray diffraction (XRD), thermogravimetric-differential thermal analysis (TG-DTA) temperature-programmed desorption (TPD) of carbon dioxide (CO{sub 2}-TPD), and scanning electron microscopy were used to characterize the fresh and spent catalysts. With MgO and ZnO, naphthenic acid removal proceeded via catalytic decarboxylation. No crystalline phase changes were observed after reaction. With CaO, multiple pathways such as catalytic decarboxylation, neutralization, and thermal cracking were responsible for naphthenic acid conversion. The spent catalysts contained Ca(OH){sub 2} and CaCO{sub 3}. With BaO, naphthenic acid conversion occurred through neutralization. All BaO was converted to Ba(OH){sub 2} during the reaction. tabs., figs.

  4. Method for hydrogen production and metal winning, and a catalyst/cocatalyst composition useful therefor

    Dhooge, Patrick M.

    1987-10-13

    A catalyst/cocatalyst/organics composition of matter is useful in electrolytically producing hydrogen or electrowinning metals. Use of the catalyst/cocatalyst/organics composition causes the anode potential and the energy required for the reaction to decrease. An electrolyte, including the catalyst/cocatalyst composition, and a reaction medium composition further including organic material are also described.

  5. Reuse of Hydrotreating Spent Catalyst

    Habib, A.M.; Menoufy, M.F.; Amhed, S.H.

    2004-01-01

    All hydro treating catalysts used in petroleum refining processes gradually lose activity through coking, poisoning by metal, sulfur or halides or lose surface area from sintering at high process temperatures. Waste hydrotreating catalyst, which have been used in re-refining of waste lube oil at Alexandria Petroleum Company (after 5 years lifetime) compared with the same fresh catalyst were used in the present work. Studies are conducted on partial extraction of the active metals of spent catalyst (Mo and Ni) using three leaching solvents,4% oxidized oxalic acid, 10% aqueous sodium hydroxide and 10% citric acid. The leaching experiments are conducting on the de coked extrude [un crushed] spent catalyst samples. These steps are carried out in order to rejuvenate the spent catalyst to be reused in other reactions. The results indicated that 4% oxidized oxalic acid leaching solution gave total metal removal 45.6 for de coked catalyst samples while NaOH gave 35% and citric acid gave 31.9 % The oxidized leaching agent was the most efficient leaching solvent to facilitate the metal removal, and the rejuvenated catalyst was characterized by the unchanged crystalline phase The rejuvenated catalyst was applied for hydrodesulfurization (HDS) of vacuum gas oil as a feedstock, under different hydrogen pressure 20-80 bar in order to compare its HDS activity

  6. Controlled metal nitrate decomposition for the preparation of supported metal Catalysts

    Wolters, M.

    2010-01-01

    High surface area supported metal (oxide) catalysts are essential for the production of fuels, chemicals, pharmaceuticals and the abatement of environmental pollution. Impregnation of high surface area supports, often silica or alumina, followed by drying, calcination and reduction is one of the

  7. Studies of Immobilized Homogeneous Metal Catalysts on Silica Supports

    Stanger, Keith James [Iowa State Univ., Ames, IA (United States)

    2003-01-01

    The tethered, chiral, chelating diphosphine rhodium complex, which catalyzes the enantioselective hydrogenation of methyl-α-acetamidocinnamate (MAC), has the illustrated structure as established by 31P NMR and IR studies. Spectral and catalytic investigations also suggest that the mechanism of action of the tethered complex is the same as that of the untethered complex in solution. The rhodium complexes, [Rh(COD)H]4, [Rh(COD)2]+BF4-, [Rh(COD)Cl]2, and RhCl3• 3H2O, adsorbed on SiO2 are optimally activated for toluene hydrogenation by pretreatment with H2 at 200 C. The same complexes on Pd-SiO2 are equally active without pretreatments. The active species in all cases is rhodium metal. The catalysts were characterized by XPS, TEM, DRIFTS, and mercury poisoning experiments. Rhodium on silica catalyzes the hydrogenation of fluorobenzene to produce predominantly fluorocyclohexane in heptane and 1,2-dichloroethane solvents. In heptane/methanol and heptane/water solvents, hydrodefluorination to benzene and subsequent hydrogenation to cyclohexane occurs exclusively. Benzene inhibits the hydrodefluorination of fluorobenzene. In DCE or heptane solvents, fluorocyclohexane reacts with hydrogen fluoride to form cyclohexene. Reaction conditions can be chosen to selectively yield fluorocyclohexane, cyclohexene, benzene, or cyclohexane. The oxorhenium(V) dithiolate catalyst [-S(CH2)3s-]Re(O)(Me)(PPh3) was modified by linking it to a tether that could be attached to a silica support. Spectroscopic investigation and catalytic oxidation reactivity showed the heterogenized catalyst's structure and reactivity to be similar to its homogeneous analog. However, the immobilized catalyst offered additional advantages of recyclability, extended stability, and increased resistance to deactivation.

  8. Design of Embedded Metal Catalysts via Reverser Micro-Emulsion System: a Way to Suppress Catalyst Deactivation by Metal Sintering

    AlMana, Noor

    2016-06-19

    The development of highly selective and active, long-lasting, robust, low-cost and environmentally benign catalytic materials is the greatest challenge in the area of catalysis study. In this context, core-shell structures where the active sites are embedded inside the protecting shell have attracted a lot of researchers working in the field of catalysis owing to their enhanced physical and chemical properties suppress catalyst deactivation. Also, a new active site generated at the interface between the core and shell may increases the activity and efficiency of the catalyst in catalytic reactions especially for oxide shells that exhibit redox properties such as TiO2 and CeO2. Moreover, coating oxide layer over metal nanoparticles (NPs) can be designed to provide porosity (micropore/mesopore) that gives selectivity of the various reactants by the different gas diffusion rates. In this thesis, we will discuss the concept of catalyst stabilization against metal sintering by a core-shell system. In particular we will study the mechanistic of forming core-shell particles and the key parameters that can influence the properties and morphology of the Pt metal particle core and SiO2 shell (Pt@SiO2) using the reverse micro-emulsion method. The Pt@SiO2 core-shell catalysts were investigated for low-temperature CO oxidation reaction. The study was further extended to other catalytic applications by varying the composition of the core as well as the chemical nature of the shell material. The Pt NPs were embedded within another oxide matrix such as ZrO2 and TiO2 for CO oxidation reaction. These materials were studied in details to identify the factors governing the coating of the oxide around the metal NPs. Next, a more challenging system, namely, bimetallic Ni9Pt NPs embedded in TiO2 and ZrO2 matrix were investigated for dry reforming of methane reaction at high temperatures. The challenges of designing Ni9Pt@oxide core-shell structure with TiO2 and ZrO2 and their tolerance

  9. Single-Atom Catalysts of Precious Metals for Electrochemical Reactions.

    Kim, Jiwhan; Kim, Hee-Eun; Lee, Hyunjoo

    2018-01-10

    Single-atom catalysts (SACs), in which metal atoms are dispersed on the support without forming nanoparticles, have been used for various heterogeneous reactions and most recently for electrochemical reactions. In this Minireview, recent examples of single-atom electrocatalysts used for the oxygen reduction reaction (ORR), hydrogen oxidation reaction (HOR), hydrogen evolution reaction (HER), formic acid oxidation reaction (FAOR), and methanol oxidation reaction (MOR) are introduced. Many density functional theory (DFT) simulations have predicted that SACs may be effective for CO 2 reduction to methane or methanol production while suppressing H 2 evolution, and those cases are introduced here as well. Single atoms, mainly Pt single atoms, have been deposited on TiN or TiC nanoparticles, defective graphene nanosheets, N-doped covalent triazine frameworks, graphitic carbon nitride, S-doped zeolite-templated carbon, and Sb-doped SnO 2 surfaces. Scanning transmission electron microscopy, extended X-ray absorption fine structure measurement, and in situ infrared spectroscopy have been used to detect the single-atom structure and confirm the absence of nanoparticles. SACs have shown high mass activity, minimizing the use of precious metal, and unique selectivity distinct from nanoparticle catalysts owing to the absence of ensemble sites. Additional features that SACs should possess for effective electrochemical applications were also suggested. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Development of processes for the production of solar grade silicon from halides and alkali metals, phase 1 and phase 2

    Dickson, C. R.; Gould, R. K.; Felder, W.

    1981-01-01

    High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon are described. Product separation and collection processes were evaluated, measure heat release parameters for scaling purposes and effects of reactants and/or products on materials of reactor construction were determined, and preliminary engineering and economic analysis of a scaled up process were made. The feasibility of the basic process to make and collect silicon was demonstrated. The jet impaction/separation process was demonstrated to be a purification process. The rate at which gas phase species from silicon particle precursors, the time required for silane decomposition to produce particles, and the competing rate of growth of silicon seed particles injected into a decomposing silane environment were determined. The extent of silane decomposition as a function of residence time, temperature, and pressure was measured by infrared absorption spectroscopy. A simplistic model is presented to explain the growth of silicon in a decomposing silane enviroment.

  11. Revealing the ultrafast charge carrier dynamics in organo metal halide perovskite solar cell materials using time resolved THz spectroscopy

    Ponseca, C. S., Jr.; Sundström, V.

    2016-03-01

    Ultrafast charge carrier dynamics in organo metal halide perovskite has been probed using time resolved terahertz (THz) spectroscopy (TRTS). Current literature on its early time characteristics is unanimous: sub-ps charge carrier generation, highly mobile charges and very slow recombination rationalizing the exceptionally high power conversion efficiency for a solution processed solar cell material. Electron injection from MAPbI3 to nanoparticles (NP) of TiO2 is found to be sub-ps while Al2O3 NPs do not alter charge dynamics. Charge transfer to organic electrodes, Spiro-OMeTAD and PCBM, is sub-ps and few hundreds of ps respectively, which is influenced by the alignment of energy bands. It is surmised that minimizing defects/trap states is key in optimizing charge carrier extraction from these materials.

  12. Highly aligned vertical GaN nanowires using submonolayer metal catalysts

    Wang, George T [Albuquerque, NM; Li, Qiming [Albuquerque, NM; Creighton, J Randall [Albuquerque, NM

    2010-06-29

    A method for forming vertically oriented, crystallographically aligned nanowires (nanocolumns) using monolayer or submonolayer quantities of metal atoms to form uniformly sized metal islands that serve as catalysts for MOCVD growth of Group III nitride nanowires.

  13. In Situ Preparation of Metal Halide Perovskite Nanocrystal Thin Films for Improved Light-Emitting Devices.

    Zhao, Lianfeng; Yeh, Yao-Wen; Tran, Nhu L; Wu, Fan; Xiao, Zhengguo; Kerner, Ross A; Lin, YunHui L; Scholes, Gregory D; Yao, Nan; Rand, Barry P

    2017-04-25

    Hybrid organic-inorganic halide perovskite semiconductors are attractive candidates for optoelectronic applications, such as photovoltaics, light-emitting diodes, and lasers. Perovskite nanocrystals are of particular interest, where electrons and holes can be confined spatially, promoting radiative recombination. However, nanocrystalline films based on traditional colloidal nanocrystal synthesis strategies suffer from the use of long insulating ligands, low colloidal nanocrystal concentration, and significant aggregation during film formation. Here, we demonstrate a facile method for preparing perovskite nanocrystal films in situ and that the electroluminescence of light-emitting devices can be enhanced up to 40-fold through this nanocrystal film formation strategy. Briefly, the method involves the use of bulky organoammonium halides as additives to confine crystal growth of perovskites during film formation, achieving CH 3 NH 3 PbI 3 and CH 3 NH 3 PbBr 3 perovskite nanocrystals with an average crystal size of 5.4 ± 0.8 nm and 6.4 ± 1.3 nm, respectively, as confirmed through transmission electron microscopy measurements. Additive-confined perovskite nanocrystals show significantly improved photoluminescence quantum yield and decay lifetime. Finally, we demonstrate highly efficient CH 3 NH 3 PbI 3 red/near-infrared LEDs and CH 3 NH 3 PbBr 3 green LEDs based on this strategy, achieving an external quantum efficiency of 7.9% and 7.0%, respectively, which represent a 40-fold and 23-fold improvement over control devices fabricated without the additives.

  14. Methods for producing single crystal mixed halide perovskites

    Zhu, Kai; Zhao, Yixin

    2017-07-11

    An aspect of the present invention is a method that includes contacting a metal halide and a first alkylammonium halide in a solvent to form a solution and maintaining the solution at a first temperature, resulting in the formation of at least one alkylammonium halide perovskite crystal, where the metal halide includes a first halogen and a metal, the first alkylammonium halide includes the first halogen, the at least one alkylammonium halide perovskite crystal includes the metal and the first halogen, and the first temperature is above about 21.degree. C.

  15. Heavy metal ternary halides for room-temperature x-ray and gamma-ray detection

    Liu, Zhifu; Peters, John A.; Stoumpos, Constantinos C.; Sebastian, Maria; Wessels, Bruce W.; Im, Jino; Freeman, Arthur J.; Kanatzidis, Mercouri G.

    2013-09-01

    We report our recent progress on wide bandgap ternary halide compounds CsPbBr3 and CsPbCl3 for room temperature x-ray and gamma-ray detectors. Their bandgaps are measured to be 2.24 eV and 2.86 eV, respectively. The measured mobility-lifetime products of CsPbBr3 are 1.7×10-3, 1.3×10-3 cm2/V, for electron and hole carriers, respectively, comparable to those of CdTe. We measured the room temperature spectral response of CsPbBr3 sample to Ag x-ray radiation. It has a well-resolved spectral response to the 22.4 keV Kα radiation peak and detector efficiency comparable to that of CdZnTe detector at 295 K.

  16. Properties and application of noble metal catalysts for heterogeneous catalytic hydrogenations

    Horn, G; Frohning, C D; Cornils, B [Ruhrchemie A.G., Oberhausen (Germany, F.R.)

    1976-07-01

    The special properties of the six platinum group elements - ruthenium, rhodium, palladium, osmium, iridium, platinum - make them useful as active metals for catalytic reactions. Especially valuable is their property of favouring a single reaction even when the possibility of a number of parallel reactions exists under certain reaction conditions. This selectivity of the noble metal catalyst may be directed or enhanced through appropriate choise of the metal, the reaction conditions, the duration of the reaction, the amount of hydrogen etc. Even the physical state of the catalyst - supported or unsupported - is of influence when using noble metal catalysts as described in this report.

  17. Allotropic Carbon Nanoforms as Advanced Metal-Free Catalysts or as Supports

    Hermenegildo Garcia

    2014-01-01

    Full Text Available This perspective paper summarizes the use of three nanostructured carbon allotropes as metal-free catalysts (“carbocatalysts” or as supports of metal nanoparticles. After an introductory section commenting the interest of developing metal-free catalysts and main features of carbon nanoforms, the main body of this paper is focused on exemplifying the opportunities that carbon nanotubes, graphene, and diamond nanoparticles offer to develop advanced catalysts having active sites based on carbon in the absence of transition metals or as large area supports with special morphology and unique properties. The final section provides my personal view on future developments in this field.

  18. Water Splitting by Thin Film Metal-Oxo Catalysts

    Nocera, Daniel [Harvard Univ., Cambridge, MA (United States)

    2013-03-15

    The dropping price of silicon photovoltaics in the United States is causing load defection to solar supply at an accelerated pace. This conversion to solar and, more generally, other renewable energy sources has accordingly turned the energy research focus from generation to one of storage. Truly disruptive improvements in energy storage technologies are limited by energy density. This limitation, however, does not apply to fuels, which possess the energy density needed for large-scale energy storage. The first step of the basic science needed to drive such historic restructuring of the U.S. energy infrastructure begins with the solar-driven generation of hydrogen and oxygen from water. The solar-produced hydrogen may then be combined with carbon dioxide to deliver any number of fuels. Obviously, light does not directly act on water to engender its splitting into its elemental components. Hence, catalysts are needed to drive the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Of these two reactions, the four-electron, four-proton oxidation of OER is the more kinetically challenging reaction, and therefore the development of energy efficient solar fuels processes demands that OER be accomplished at a minimal overpotential. The research completed in this program developed catalysts that drive OER and at the same time meet the important criteria of (1) using non-critical materials that (2) are easy to assemble and (3) accomplish OER under simple conditions. Research was designed to uncover the chemical principles that underlie the self-assembly of metal oxide oxygen evolving catalysts (M-OEC) from the metals of M = Mn, Co, and Ni. For example, a dogma of heterogeneous catalysis of any sort is that “edges” matter in promoting catalytic transformations. We provided a rationale for such dogma by showing that the OER in Co-OEC occurred at a dimensionally reduced dicobalt edge site. Edge site reactivity was clearly revealed analyzing 18O labeled

  19. Defect-induced local variation of crystal phase transition temperature in metal-halide perovskites.

    Dobrovolsky, Alexander; Merdasa, Aboma; Unger, Eva L; Yartsev, Arkady; Scheblykin, Ivan G

    2017-06-26

    Solution-processed organometal halide perovskites are hybrid crystalline semiconductors highly interesting for low-cost and efficient optoelectronics. Their properties are dependent on the crystal structure. Literature shows a variety of crystal phase transition temperatures and often a spread of the transition over tens of degrees Kelvin. We explain this inconsistency by demonstrating that the temperature of the tetragonal-to-orthorhombic phase transition in methylammonium lead triiodide depends on the concentration and nature of local defects. Phase transition in individual nanowires was studied by photoluminescence microspectroscopy and super-resolution imaging. We propose that upon cooling from 160 to 140 K, domains of the crystal containing fewer defects stay in the tetragonal phase longer than highly defected domains that readily transform to the high bandgap orthorhombic phase at higher temperatures. The existence of relatively pure tetragonal domains during the phase transition leads to drastic photoluminescence enhancement, which is inhomogeneously distributed across perovskite microcrystals.Understanding crystal phase transition in materials is of fundamental importance. Using luminescence spectroscopy and super-resolution imaging, Dobrovolsky et al. study the transition from the tetragonal to orthorhombic crystal phase in methylammonium lead triiodide nanowires at low temperature.

  20. Base metal complexes as homogeneous catalysts and enzyme mimics.

    Hu, Xile

    2011-01-01

    This article is a short overview of some recent research activity in the Laboratory of Inorganic Synthesis and Catalysis (LSCI) at EPFL-ISIC. It summarizes the work on Ni-catalyzed cross-coupling reactions of non-activated alkyl halides. It then describes and discusses the work on the bio-mimetic chemistry of [Fe]-hydrogenase.

  1. Pressure-Induced Metallization of the Halide Perovskite (CH 3 NH 3 )PbI 3

    Jaffe, Adam; Lin, Yu [Photon; Mao, Wendy L. [Photon; Karunadasa, Hemamala I.

    2017-03-10

    We report the metallization of the hybrid perovskite semiconductor (MA)PbI3 (MA = CH3NH3+) with no apparent structural transition. We tracked its bandgap evolution during compression in diamond-anvil cells using absorption spectroscopy and observed strong absorption over both visible and IR wavelengths at pressures above ca. 56 GPa, suggesting the imminent closure of its optical bandgap. The metallic character of (MA)PbI3 above 60 GPa was confirmed using both IR reflectivity and variable-temperature dc conductivity measurements. The impressive semiconductor properties of halide perovskites have recently been exploited in a multitude of optoelectronic applications. Meanwhile, the study of metallic properties in oxide perovskites has revealed diverse electronic phenomena. Importantly, the mild synthetic routes to halide perovskites and the templating effects of the organic cations allow for fine structural control of the inorganic lattice. Pressure-induced closure of the 1.6 eV bandgap in (MA)PbI3 demonstrates the promise of the continued study of halide perovskites under a range of thermodynamic conditions, toward realizing wholly new electronic properties.

  2. Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin (UC)

    2016-08-30

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

  3. Development of Non-Noble Metal Ni-Based Catalysts for Dehydrogenation of Methylcyclohexane

    Al-ShaikhAli, Anaam H.

    2016-11-30

    Liquid organic chemical hydride is a promising candidate for hydrogen storage and transport. Methylcyclohexane (MCH) to toluene (TOL) cycle has been considered as one of the feasible hydrogen carrier systems, but selective dehydrogenation of MCH to TOL has only been achieved using the noble Pt-based catalysts. The aim of this study is to develop non-noble, cost-effective metal catalysts that can show excellent catalytic performance, mainly maintaining high TOL selectivity achievable by Pt based catalysts. Mono-metallic Ni based catalyst is a well-known dehydrogenation catalyst, but the major drawback with Ni is its hydrogenolysis activity to cleave C-C bonds, which leads to inferior selectivity towards dehydrogenation of MCH to TOL. This study elucidate addition of the second metal to Ni based catalyst to improve the TOL selectivity. Herein, ubiquitous bi-metallic nanoparticles catalysts were investigated including (Ni–M, M: Ag, Zn, Sn or In) based catalysts. Among the catalysts investigated, the high TOL selectivity (> 99%) at low conversions was achieved effectively using the supported NiZn catalyst under flow of excess H2. In this work, a combined study of experimental and computational approaches was conducted to determine the main role of Zn over Ni based catalyst in promoting the TOL selectivity. A kinetic study using mono- and bimetallic Ni based catalysts was conducted to elucidate reaction mechanism and site requirement for MCH dehydrogenation reaction. The impact of different reaction conditions (feed compositions, temperature, space velocity and stability) and catalyst properties were evaluated. This study elucidates a distinctive mechanism of MCH dehydrogenation to TOL reaction over the Ni-based catalysts. Distinctive from Pt catalyst, a nearly positive half order with respect to H2 pressure was obtained for mono- and bi-metallic Ni based catalysts. This kinetic data was consistent with rate determining step as (somewhat paradoxically) hydrogenation

  4. A surface science study of model catalysts : II metal-support interactions in Cu/SiO2 model catalysts

    Oetelaar, van den L.C.A.; Partridge, A.; Toussaint, S.L.G.; Flipse, C.F.J.; Brongersma, H.H.

    1998-01-01

    The thermal stability of wet-chemically prepared Cu/SiO2 model catalysts containing nanometer-sized Cu particles on silica model supports was studied upon heating in hydrogen and ultrahigh vacuum. The surface and interface phenomena that occur are determined by the metal-support interactions.

  5. Analysis of noble metal on automotive exhaust catalysts by radioisotope-induce x-ray fluorescence

    Elgart, M.F.

    1976-01-01

    A technique was developed for the in-situ analysis of noble metals deposited on monolithic automotive exhaust catalysts. This technique is based on radioisotope-induced x-ray fluorescence, and provides a detailed picture of the distribution of palladium and platinum on catalyst samples. The experimental results for the cross section of a monolithic exhaust catalyst, analyzed in increments of 0.2 cm 3 , are compared with analyses for palladium and platinum obtained by instrumental neutron activation analysis

  6. Oxidation of tritium in packed bed of noble metal catalyst for detritiation from system gases

    Nishikawa, Masabumi; Takeishi, Toshiharu; Munakata, Kenzo; Kotoh, Kenji; Enoeda, Mikio

    1985-01-01

    Catalytic oxidation rates of tritium in the bed of the noble metal catalysts are obtained and compared with the oxidation rates observed for the packed bed of spongy copper oxide or hopcalites. Use of Pt- or Pd-aluminia catalysts is recommended in this study because they give effective oxidation rates of tritium in the ambient temperature range. The adsorption performance of tritiated water in the catalyst bed is also discussed. (orig.)

  7. Graphene layer encapsulated metal nanoparticles as a new type of non-precious metal catalysts for oxygen reduction

    Hu, Yang; Zhong, Lijie; Jensen, Jens Oluf

    2016-01-01

    Cheap and efficient non-precious metal catalysts for oxygen reduction have been a focus of research in the field of low-temperature fuel cells. This review is devoted to a brief summary of the recent work on a new type of catalysts, i.e., the graphene layer encapsulated metal nanoparticles....... The discussion is focused on the synthesis, structure, mechanism, performance, and further research....

  8. Development of Non-Noble Metal Ni-Based Catalysts for Dehydrogenation of Methylcyclohexane

    Shaikh Ali, Anaam

    2016-01-01

    to TOL has only been achieved using the noble Pt-based catalysts. The aim of this study is to develop non-noble, cost-effective metal catalysts that can show excellent catalytic performance, mainly maintaining high TOL selectivity achievable by Pt based

  9. Exposure of metallic copper surface on Cu-Al2O3-carbon catalysts

    Menon, P.G.; Prasad, J.

    1970-01-01

    The bifunctional nature of Cu---Al2O3-on-carbon catalysts, used in the direct catalytic conversion of ethanol to ethyl acetate, prompted an examination of the dispersion of Cu on the composite catalyst. For this, the N2O-method of Osinga et al. for estimation of bare metallic copper surface on

  10. Impact of various lighting source (incandescent, fluorescent, metal halide and high pressure sodium) on the production performance of chicken broilers

    Guffar, A.; Rahman, K.U.; Siddique, M.; Ahmad, F.

    2009-01-01

    Light is an important aspect of an animal's environment. Avian as well as mammalian species respond to light energy in a variety of ways. Recent research has indicated that light source may affect body weight, immune response, livability and health status. Broiler behavior is strongly affected by light sources. So the present project was designed to study the effect of light sources on the production performance of broilers. For this purpose, 500 day-old broilers purchased from the local market were reared for three days (adaptation period) in one group. Then these were randomly divided into five experimental groups each comprising of 100 birds. Group A was given 25 incandescent light (INC), Group B was given fluorescent light (FC), Group C was given metal halide light (MH), Group D was given high pressure sodium light (HPS) and Group E was given no light source (control). Performance trial in terms of measurement of weekly body weight, weekly feed consumption, feed conversion ratio (FCR), daily water consumption and mortality were checked. Among various lighting sources, MH proved the best light source regarding main parameters of production performance. (author)

  11. Metal Halide Perovskite Supercrystals: Gold-Bromide Complex Triggered Assembly of CsPbBr3 Nanocubes.

    Wang, Kun-Hua; Yang, Jun-Nan; Ni, Qian-Kun; Yao, Hong-Bin; Yu, Shu-Hong

    2018-01-16

    Using nanocrystals as "artificial atoms" to construct supercrystals is an interesting process to explore the stacking style of nanoscale building blocks and corresponding collective properties. Various types of semiconducting supercrystals have been constructed via the assembly of nanocrystals driven by the entropic, electrostatic, or van der Waals interactions. We report a new type of metal halide perovskite supercrystals via the gold-bromide complex triggered assembly of newly emerged attractive CsPbBr 3 nanocubes. Through introducing gold-bromide (Au-Br) complexes into CsPbBr 3 nanocubes suspension, the self-assembly process of CsPbBr 3 nanocubes to form supercrystals was investigated with the different amount of Au-Br complexes added to the suspensions, which indicates that the driven force of the formation of CsPbBr 3 supercrystals included the van der Waals interactions among carbon chains and electrostatic interactions between Au-Br complexes and surfactants. Accordingly, the optical properties change with the assembly of CsPbBr 3 nanocubes and the variation of mesoscale structures of supercrystals with heating treatment was revealed as well, demonstrating the ionic characteristics of CsPbBr 3 nanocrystals. The fabricated CsPbBr 3 supercrystal presents a novel type of semiconducting supercrystals that will open an avenue for the assembly of ionic nanocrystals.

  12. Isotopic exchange of cyclic ethers with deuterium over metal catalysts

    Duchet, J.C.; Cornet, D.

    1976-01-01

    The exchange reaction between deuterium and cyclic ethers (oxolane and α-methyl derivatives) has been investigated using rhodium and palladium catalysts. The first hydrogen undergoing exchange has been found to be located on a β-carbon. This fact, and the poisoning of the exchange of cyclopentane in the presence of ether, suggest that the O atom participates in the exchange mechanism of ethers. It appears, however, that the oxygen--metal bonding occurs only during this simple exchange process; simultaneous adsorption of oxygen and a vicinal carbon causes hydrogenolysis of the O--C bond. In each case multiple exchange is important. In the oxolane molecule two sets of exchangeable hydrogens are distinguished according to their reactivities, as could be expected by analogy with cycloalkanes. However, this distinction is not so clear in the exchange patterns of substituted oxolanes, since intermediate maxima are observed in these cases. It is suggested that the conformational properties of the substituted rings cause a constraint in the formation of 3,4-diadsorbed oxolanes. Thus, multiple exchange, based on α,β-process, and epimerization via the ''roll-over'' mechanism occur preferentially in certain parts of the molecules

  13. Hydrogen production from bio-fuels using precious metal catalysts

    Pasel, Joachim; Wohlrab, Sebastian; Rotov, Mikhail; Löhken, Katrin; Peters, Ralf; Stolten, Detlef

    2017-11-01

    Fuel cell systems with integrated autothermal reforming unit require active and robust catalysts for H2 production. Thus, an experimental screening of catalysts for autothermal reforming of commercial biodiesel fuel was performed. Catalysts consisted of a monolithic cordierite substrate, an oxide support (γ-Al2O3) and Pt, Ru, Ni, PtRh and PtRu as active phase. Experiments were run by widely varying the O2/C and H2O/C molar ratios at different gas hourly space velocities. Fresh and aged catalysts were characterized by temperature programmed methods and thermogravimetry to find correlations with catalytic activity and stability.

  14. Hydrogen production from bio-fuels using precious metal catalysts

    Pasel Joachim

    2017-01-01

    Full Text Available Fuel cell systems with integrated autothermal reforming unit require active and robust catalysts for H2 production. Thus, an experimental screening of catalysts for autothermal reforming of commercial biodiesel fuel was performed. Catalysts consisted of a monolithic cordierite substrate, an oxide support (γ-Al2O3 and Pt, Ru, Ni, PtRh and PtRu as active phase. Experiments were run by widely varying the O2/C and H2O/C molar ratios at different gas hourly space velocities. Fresh and aged catalysts were characterized by temperature programmed methods and thermogravimetry to find correlations with catalytic activity and stability.

  15. Rejuvenation of residual oil hydrotreating catalysts by leaching of foulant metals. Modelling of the metal leaching process

    Marafi, M.; Kam, E.K.T.; Stanislaus, A.; Absi-Halabi, M. [Petroleum Technology Department, Petroleum, Petrochemicals and Materials Division, Kuwait Institute for Scientific Research, Safat (Kuwait)

    1996-11-19

    Increasing emphasis has been paid in recent years on the development of processes for the rejuvenation of spent residual oil hydroprocessing catalysts, which are deactivated by deposition of metals (e.g. vanadium) and coke. As part of a research program on this subject, we have investigated selective removal of the major metal foulant from the spent catalyst by chemical leaching. In the present paper, we report the development of a model for foulant metals leaching from the spent catalyst. The leaching process is considered to involve two consecutive operations: (1) removal of metal foulants along the main mass transfer channels connected to the narrow pores until the pore structure begins to develop and (2) removal of metal foulants from the pore structure. Both kinetic and mass transfer aspects were considered in the model development, and a good agreement was noticed between experimental and simulated results

  16. Oxygen-assisted conversion of propane over metal and metal oxide catalysts

    Laate, Leiv

    2002-07-01

    An experimental set-up has been build and applied in activity/selectivity studies of the oxygen-assisted conversion of propane over metals and metal oxide catalysts. The apparatus has been used in order to achieve an improved understanding of the reactions between alkanes/alkenes and oxygen. Processes that have been studied arc the oxidative dehydrogenation of propane over a VMgO catalyst and the selective combustion of hydrogen in the presence of hydrocarbons over Pt-based catalysts and metal oxide catalysts. From the experiments, the following conclusions are drawn: A study of the oxidative dehydrogenation of propane over a vanadium-magnesium-oxide catalyst confirmed that the main problem with this system is the lack of selectivity due to complete combustion. Selectivity to propene up to about 60% was obtained at 10% conversion at 500{sup o}C, but the selectivity decreased with increasing conversion. No oxygenates were detected, the only by- products were CO and CO{sub 2}. The selectivity to propene is a strong function of the conversion of propane. The reaction rate of propane was found to be 1.0 {+-} 0.1 order in propane and 0.07 {+-} 0.02 order in oxygen. The kinetic results are in agreement with a Mars van Krevelen mechanism with the activation of the hydrocarbons as the slow step. The rate of propene oxidation to CO{sub 2} was studied and found to be significantly higher than that of propane. Another possible process involves the simultaneous equilibrium dehydrogenation of alkanes to alkenes and combustion of the hydrogen formed to shift the equilibrium dehydrogenation reaction further to the product alkenes. A study of the selective combustion of hydrogen in the presence of propane/propene was found to be possible under certain reaction conditions over some metal oxide catalysts. In{sub 2}O{sub 3}/SiO{sub 2}, unsupported Bi{sub 2}O{sub 3} and ZSM-5 show the ability to combust hydrogen in a gas mixture with propane and oxygen with good selectivity. Bi{sub 2

  17. Evaluation of mechanical properties in metal wire mesh supported selective catalytic reduction (SCR) catalyst structures

    Rajath, S.; Siddaraju, C.; Nandakishora, Y.; Roy, Sukumar

    2018-04-01

    The objective of this research is to evaluate certain specific mechanical properties of certain stainless steel wire mesh supported Selective catalytic reduction catalysts structures wherein the physical properties of the metal wire mesh and also its surface treatments played vital role thereby influencing the mechanical properties. As the adhesion between the stainless steel wire mesh and the catalyst material determines the bond strength and the erosion resistance of catalyst structures, surface modifications of the metal- wire mesh structure in order to facilitate the interface bonding is therefore very important to realize enhanced level of mechanical properties. One way to enhance such adhesion properties, the stainless steel wire mesh is treated with the various acids, i.e., chromic acid, phosphoric acid including certain mineral acids and combination of all those in various molar ratios that could generate surface active groups on metal surface that promotes good interface structure between the metal- wire mesh and metal oxide-based catalyst material and then the stainless steel wire mesh is dipped in the glass powder slurry containing some amount of organic binder. As a result of which the said catalyst material adheres to the metal-wire mesh surface more effectively that improves the erosion profile of supported catalysts structure including bond strength.

  18. Recycling of spent noble metal catalysts with emphasis on pyrometallurgical processing

    Hagelueken, C. [Degussa Huels AG, Hanau (Germany)

    1999-09-01

    Precious metal catalysts for catalytic Naphta Reforming, Isomerization, Hydrogenation and other chemical and petrochemical processes are valuable assets for oil refineries and chemical companies. At the end of the service life of a reactor load of catalyst, the efficient and reliable recovery of the precious metals contained in the catalyst is of paramount importance. More than 150 years of technological advances at Degussa-Huels have resulted in refining methods for all kinds of precious metal containing materials which guarantee an optimum technical yield of the precious metals included. The refining of catalysts today is one of the important activities in the precious metals business unit. In the state-of-the-art precious metal refinery at Hanau in the centre of Germany, a wide variety of processes for the recovery of all precious metals is offered. These processes include accurate preparation, sampling and analysis as well as both wet-chemical and pyrometallurgical recovery techniques. Special emphasis in this presentation is laid on the advantages of pyrometallurgical processes for certain kinds of catalysts. To avoid any risks during transport, sampling and treatment of the spent catalyst, all parties involved in the recycling chain strictly have to follow the relevant safety regulations. Under its commitment to 'Responsible Care' standard procedures have been developed which include pre-shipment samples, safety data sheets/questionnaires and inspection of spent catalysts. These measures not only support a safe and environmentally sound catalyst recycling but also enable to determine the most suitable and economic recovery process - for the benefit of the customer. (orig.)

  19. Intermetallic nickel silicide nanocatalyst-A non-noble metal-based general hydrogenation catalyst.

    Ryabchuk, Pavel; Agostini, Giovanni; Pohl, Marga-Martina; Lund, Henrik; Agapova, Anastasiya; Junge, Henrik; Junge, Kathrin; Beller, Matthias

    2018-06-01

    Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds including fine chemicals, agrochemicals, and pharmachemicals. On an industrial scale, hydrogenations are typically performed with precious metal catalysts or with base metal catalysts, such as Raney nickel, which requires special handling due to its pyrophoric nature. We report a stable and highly active intermetallic nickel silicide catalyst that can be used for hydrogenations of a wide range of unsaturated compounds. The catalyst is prepared via a straightforward procedure using SiO 2 as the silicon atom source. The process involves thermal reduction of Si-O bonds in the presence of Ni nanoparticles at temperatures below 1000°C. The presence of silicon as a secondary component in the nickel metal lattice plays the key role in its properties and is of crucial importance for improved catalytic activity. This novel catalyst allows for efficient reduction of nitroarenes, carbonyls, nitriles, N-containing heterocycles, and unsaturated carbon-carbon bonds. Moreover, the reported catalyst can be used for oxidation reactions in the presence of molecular oxygen and is capable of promoting acceptorless dehydrogenation of unsaturated N-containing heterocycles, opening avenues for H 2 storage in organic compounds. The generality of the nickel silicide catalyst is demonstrated in the hydrogenation of over a hundred of structurally diverse unsaturated compounds. The wide application scope and high catalytic activity of this novel catalyst make it a nice alternative to known general hydrogenation catalysts, such as Raney nickel and noble metal-based catalysts.

  20. Catalytic dehydration of ethanol using transition metal oxide catalysts.

    Zaki, T

    2005-04-15

    The aim of this work is to study catalytic ethanol dehydration using different prepared catalysts, which include Fe(2)O(3), Mn(2)O(3), and calcined physical mixtures of both ferric and manganese oxides with alumina and/or silica gel. The physicochemical properties of these catalysts were investigated via X-ray powder diffraction (XRD), acidity measurement, and nitrogen adsorption-desorption at -196 degrees C. The catalytic activities of such catalysts were tested through conversion of ethanol at 200-500 degrees C using a catalytic flow system operated under atmospheric pressure. The results obtained indicated that the dehydration reaction on the catalyst relies on surface acidity, whereas the ethylene production selectivity depends on the catalyst chemical constituents.

  1. Reaction of urea thiourea and their derivatives with tertiary phosphine transition metal halides

    Adam, Eltayeb Mahala

    2000-03-01

    This thesis describes preparation characterization and some properties of a number of new compounds such as (ph 3 p)2 ML where M= cobalt (11), nickel (11), and copper (11), and L= urea, thiourea, phenylthiourea, sym diphenylurea and sym diphenylthiourea.These compounds have been prepared according according to the reaction of dichloro bis (triphenylphosphine) transition metal with urea, thiourea or some of their derivative ligands in 1:1 molar ratio.The work in this thesis is divided into three section firstly:- In the introduction chapter part one includes general definitions of coordination chemistry and related compounds and abroad definition of transition elements.Part two includes the theoretical back ground about transition metal complexes having urea, thiourea or some of their substituted derivative ligands.Part two also discusses the type of bonding between these ligands and the transition metal atom.Secondly: Chapter two describes the general techniques followed in this work such as purification of solvents recrystallization, preparation of starting materials and also gives full detailed procedures of the preparation of a number of new compounds.Thirdly: Discussion with detailed in chapter three, the results of the research are presented the preparation and characterization of a number of new compounds isolated from reaction between urea, thiourea or some of their substituted derivatives and dichloro bis (triphenyl phosphine) transition metal complex giving a general formula (ph 3 )2ML where M=cobalt, nickel, and copper, and urea, thiourea or some of their substituted derivatives ligands. The products of these experiments have been identified using infrared spectra, melting points and molar conductance. The results obtained indicated that all the compounds forming the nitrogen to metal bonds leading to the formation of a four- membered chelate ring, they are relatively thermally stable compounds, and also these compounds are non-electrolytes.(Author)

  2. Development of supported noble metal catalyst for U(VI) to U(IV) reduction

    Tyagi, Deepak; Varma, Salil; Bhattacharyya, K.; Tripathi, A.K.; Bharadwaj, S.R.; Jain, V.K.; Sahu, Avinash; Vincent, Tessy; Jagatap, B.N.; Wattal, P.K.

    2015-01-01

    Uranium-plutonium separation is an essential step in the PUREX process employed in spent nuclear fuel reprocessing. This partitioning in the PUREX process is achieved by selective reduction of Pu(IV) to Pu(III) using uranous nitrate as reductant and hydrazine as stabilizer. Currently in our Indian reprocessing plants, the requirement of uranous nitrate is met by electrolytic reduction of uranyl nitrate. This process, however, suffers from a major drawback of incomplete reduction with a maximum conversion of ~ 60%. Catalytic reduction of U(VI) to U(IV) is being considered as one of the promising alternatives to the electro-reduction process due to fast kinetics and near total conversion. Various catalysts involving noble metals like platinum (Adams catalyst, Pt/Al 2 O 3 , Pt/SiO 2 etc.) have been reported for the reduction. Sustained activity and stability of the catalyst under harsh reaction conditions are still the issues that need to be resolved. We present here the results on zirconia supported noble metal catalyst that is developed in BARC for reduction of uranyl nitrate to uranous nitrate. Supported noble metal catalysts with varying metal loadings (0.5 - 2 wt%) were prepared via support precipitation and noble metal impregnation. The green catalysts were reduced either by chemical reduction using hydrazine hydrate or by heating in hydrogen flow or combination of both the steps. These catalysts were characterized by various techniques such as, XRD, SEM, TEM, N 2 adsorption and H 2 chemisorption. Performance of these catalysts was evaluated for U(VI) to U(IV) reduction with uranyl nitrate feed using hydrazine as reductant. The results with the most active catalyst are named as 'BARC-CAT', which was developed in our lab. (author)

  3. Metal oxides modified NiO catalysts for oxidative dehydrogenation of ethane to ethylene

    Zhu, Haibo

    2014-06-01

    The sol-gel method was applied to the synthesis of Zr, Ti, Mo, W, and V modified NiO based catalysts for the ethane oxidative dehydrogenation reaction. The synthesized catalysts were characterized by XRD, N2 adsorption, SEM and TPR techniques. The results showed that the doping metals could be highly dispersed into NiO domains without the formation of large amount of other bulk metal oxide. The modified NiO materials have small particle size, larger surface area, and higher reduction temperature in contrast to pure NiO. The introduction of group IV, V and VI transition metals into NiO decreases the catalytic activity in ethane ODH. However, the ethylene selectivity is enhanced with the highest level for the Ni-W-O and Ni-Ti-O catalysts. As a result, these two catalysts show improved efficiency of ethylene production in the ethane ODH reaction. © 2014 Elsevier B.V. All rights reserved.

  4. Development of Coke-tolerant Transition Metal Catalysts for Dry Reforming of Methane

    Al-Sabban, Bedour E.

    2016-11-07

    Dry reforming of methane (DRM) is an attractive and promising process for the conversion of methane and carbon dioxide which are the most abundant carbon sources into valuable syngas. The produced syngas, which is a mixture of hydrogen and carbon monoxide, can be used as intermediates in the manufacture of numerous chemicals. To achieve high conversion, DRM reaction is operated at high temperatures (700-900 °C) that can cause major drawbacks of catalyst deactivation by carbon deposition, metal sintering or metal oxidation. Therefore, the primary goal is to develop a metal based catalyst for DRM that can completely suppress carbon formation by designing the catalyst composition. The strategy of this work was to synthesize Ni-based catalysts all of which prepared by homogeneous deposition precipitation method (HDP) to produce nanoparticles with narrow size distribution. In addition, control the reactivity of the metal by finely tuning the bimetallic composition and the reaction conditions in terms of reaction temperature and pressure. The highly endothermic dry reforming of methane proceeds via CH4 decomposition to leave surface carbon species, followed by removal of C with CO2-derived species to give CO. Tuning the reactivity of the active metal towards these reactions during DRM allows in principle the catalyst surface to remain active and clean without carbon deposition for a long-term. The initial attempt was to improve the resistance of Ni catalyst towards carbon deposition, therefore, a series of 5 wt.% bimetallic Ni9Pt1 were supported on various metal oxides (Al2O3, CeO2, and ZrO2). The addition of small amount of noble metal improved the stability of the catalyst compared to their monometallic Ni and Pt catalysts, but still high amount of carbon (> 0.1 wt.%) was formed after 24 h of the reaction. The obtained results showed that the catalytic performance, particle size and amount of deposited carbon depends on the nature of support. Among the tested

  5. Fundamental Studies of the Reforming of Oxygenated Compounds over Supported Metal Catalysts

    Dumesic, James A. [Univ. of Wisconsin, Madison, WI (United States)

    2016-01-04

    The main objective of our research has been to elucidate fundamental concepts associated with controlling the activity, selectivity, and stability of bifunctional, metal-based heterogeneous catalysts for tandem reactions, such as liquid-phase conversion of oxygenated hydrocarbons derived from biomass. We have shown that bimetallic catalysts that combine a highly-reducible metal (e.g., platinum) with an oxygen-containing metal promoter (e.g., molybdenum) are promising materials for conversion of oxygenated hydrocarbons because of their high activity for selective cleavage for carbon-oxygen bonds. We have developed methods to stabilize metal nanoparticles against leaching and sintering under liquid-phase reaction conditions by using atomic layer deposition (ALD) to apply oxide overcoat layers. We have used controlled surface reactions to produce bimetallic catalysts with controlled particle size and controlled composition, with an important application being the selective conversion of biomass-derived molecules. The synthesis of catalysts by traditional methods may produce a wide distribution of metal particle sizes and compositions; and thus, results from spectroscopic and reactions kinetics measurements have contributions from a distribution of active sites, making it difficult to assess how the size and composition of the metal particles affect the nature of the surface, the active sites, and the catalytic behavior. Thus, we have developed methods to synthesize bimetallic nanoparticles with controlled particle size and controlled composition to achieve an effective link between characterization and reactivity, and between theory and experiment. We have also used ALD to modify supported metal catalysts by addition of promoters with atomic-level precision, to produce new bifunctional sites for selective catalytic transformations. We have used a variety of techniques to characterize the metal nanoparticles in our catalysts, including scanning transmission electron

  6. Nitrogen-doped carbon nanotubes as a metal catalyst support

    Mabena, LF

    2011-05-01

    Full Text Available ., which are among the most commonly used heterogeneous catalyst supports (Mart??nez-Me?ndez et al. 2006). Catalyst activity depends on the particle size and appropriate dis- tance between each particle. These catalysts deposited on a support... supported Pt electrodes. Appl Catal B Environ 80:286?295 Maldonado S, Morin S, Stevenson KJ (2006) Structure, composition, and chemical reactivity of carbon nanotubes by selective nitrogen doping. Carbon 44:1429?1437 Mart??nez-Me?ndez S, Henr??quez Y...

  7. Biodiesel production using alkali earth metal oxides catalysts synthesized by sol-gel method

    Majid Mohadesi

    2014-03-01

    Full Text Available Biodiesel fuel is considered as an alternative to diesel fuel. This fuel is produced through transesterification reactions of vegetable oils or animal fat by alcohols in the presence of different catalysts. Recent studies on this process have shown that, basic heterogeneous catalysts have a higher performance than other catalysts. In this study different alkali earth metal oxides (CaO, MgO and BaO doped SiO2 were used as catalyst for the biodiesel production process. These catalysts were synthesis by using the sol-gel method. A transesterification reaction was studied after 8h by mixing corn oil, methanol (methanol to oil molar ratio of 16:1, and 6 wt. % catalyst (based on oil at 60oC and 600rpm. Catalyst loading was studied for different catalysts ranging in amounts from 40, 60 to 80%. The purity and yield of the produced biodiesel for 60% CaO/SiO2 was higher than other catalysts and at 97.3% and 82.1%, respectively.

  8. Studies on PEM Fuel Cell Noble Metal Catalyst Dissolution

    Ma, Shuang; Skou, Eivind Morten

    Incredibly vast advance has been achieved in fuel cell technology regarding to catalyst efficiency, improvement of electrolyte conductivity and optimization of cell system. With breathtakingly accelerating progress, Proton Exchange Membrane Fuel Cells (PEMFC) is the most promising and most widely...

  9. Bioleaching of metals from spent refinery petroleum catalyst using moderately thermophilic bacteria: effect of particle size.

    Srichandan, Haragobinda; Singh, Sradhanjali; Pathak, Ashish; Kim, Dong-Jin; Lee, Seoung-Won; Heyes, Graeme

    2014-01-01

    The present work investigated the leaching potential of moderately thermophilic bacteria in the recovery of metals from spent petroleum catalyst of varying particle sizes. The batch bioleaching experiments were conducted by employing a mixed consortium of moderate thermophilic bacteria at 45°C and by using five different particle sizes (from 45 to >2000 μm) of acetone-washed spent catalyst. The elemental mapping by FESEM confirmed the presence of Al, Ni, V and Mo along with sulfur in the spent catalyst. During bioleaching, Ni (92-97%) and V (81-91%) were leached in higher concentrations, whereas leaching yields of Al (23-38%) were found to be lowest in all particle sizes investigated. Decreasing the particle size from >2000 μm to 45-106 μm caused an increase in leaching yields of metals during initial hours. However, the final metals leaching yields were almost independent of particle sizes of catalyst. Leaching kinetics was observed to follow the diffusion-controlled model showing the linearity more close than the chemical control. The results of the present study suggested that bioleaching using moderate thermophilic bacteria was highly effective in removing the metals from spent catalyst. Moreover, bioleaching can be conducted using spent catalyst of higher particle size (>2000 μm), thus saving the grinding cost and making process attractive for larger scale application.

  10. Chemoselective Oxidation of Bio-Glycerol with Nano-Sized Metal Catalysts

    Li, Hu; Kotni, Ramakrishna; Zhang, Qiuyun

    2015-01-01

    to selectively oxidize glycerol and yield products with good selectivity is the use of nano-sized metal particles as heterogeneous catalysts. In this short review, recent developments in chemoselective oxidation of glycerol to specific products over nano-sized metal catalysts are described. Attention is drawn...... to various reaction parameters such as the type of the support, the size of the metal particles, and the acid/base properties of the reaction medium which were illustrated to largely influence the activity of the nanocatalyst and selectivity to the target product. - See more at: http...

  11. Surface/structure functionalization of copper-based catalysts by metal-support and/or metal-metal interactions

    Konsolakis, Michalis; Ioakeimidis, Zisis

    2014-11-01

    Cu-based catalysts have recently attracted great attention both in catalysis and electro-catalysis fields due to their excellent catalytic performance and low cost. Given that their performance is determined, to a great extent, by Cu sites local environment, considerable efforts have been devoted on the strategic modifications of the electronic and structural properties of Cu sites. In this regard, the feasibility of tuning the local structure of Cu entities by means of metal-support or metal-metal interactions is investigated. More specifically, the physicochemical properties of Cu entities are modified by employing: (i) different oxides (CeO2, La2O3, Sm2O3), or (ii) ceria-based mixed oxides (Ce1-xSmxOδ) as supporting carriers, and (iii) a second metal (Cobalt) adjacent to Cu (bimetallic Cu-Co/CeO2). A characterization study, involving BET, XRD, TPR, and XPS, reveal that significant modifications on structural, redox and electronic properties of Cu sites can be induced by adopting either different oxide carriers or bimetallic complexes. Fundamental insights into the tuning of Cu local environment by metal-support or metal-metal interactions are provided, paving the way for real-life industrial applications.

  12. Optimization of fuel cell membrane electrode assemblies for transition metal ion-chelating ordered mesoporous carbon cathode catalysts

    Johanna K. Dombrovskis

    2014-12-01

    Full Text Available Transition metal ion-chelating ordered mesoporous carbon (TM-OMC materials were recently shown to be efficient polymer electrolyte membrane fuel cell (PEMFC catalysts. The structure and properties of these catalysts are largely different from conventional catalyst materials, thus rendering membrane electrode assembly (MEA preparation parameters developed for conventional catalysts not useful for applications of TM-OMC catalysts. This necessitates development of a methodology to incorporate TM-OMC catalysts in the MEA. Here, an efficient method for MEA preparation using TM-OMC catalyst materials for PEMFC is developed including effects of catalyst/ionomer loading and catalyst/ionomer-mixing and application procedures. An optimized protocol for MEA preparation using TM-OMC catalysts is described.

  13. A study of the convective flow as a function of external parameters in a high-pressure metal halide discharge lamp (HgDyI3)

    Hajji, S.; HadjSalah, S.; Benhalima, A.; Charrada, K.; Zissis, G.

    2016-06-01

    This paper deals with the modelling of the convection processes in metal-halide lamp discharges (HgDyI3). For this, we realized a 3D model, a steady, direct current powered and time-depending model for the solution of conservation equations relative to mass, momentum, and energy. After validation, this model was applied to the study of the effect of some parameters that have appeared on major transport phenomena of mass and energy in studying the lamp. Indeed, the electric current, the atomic ratio (Hg/Dy), and the effect of the convective transport have been studied.

  14. Low temperature incineration of mixed wastes using bulk metal oxide catalysts

    Gordon, M.J.; Gaur, S.; Kelkar, S.; Baldwin, R.M.

    1996-01-01

    Volume reduction of low-level mixed wastes from former nuclear weapons facilities is a significant environmental problem. Processing of these materials presents unique scientific and engineering problems due to the presence of minute quantities of radionuclides which must be contained and concentrated for later safe disposal. Low-temperature catalytic incineration is one option that has been utilized at the Rocky Flats facility for this purpose. This paper presents results of research regarding evaluation of bulk metal oxides as catalysts for low-temperature incineration of carbonaceous residues which are typical by-products of fluidized bed combustion of mixed wastes under oxygen-lean conditions. A series of 14 metal oxides were screened in a thermogravimetric analyzer, using on-line mass spectrometry for speciation of reaction product gases. Catalyst evaluation criteria focused on the thermal-redox activity of the metals using both carbon black and PVC char as surrogate waste materials. Results indicated that metal oxides which were P-type semiconductor materials were suitable as catalysts for this application. Oxides of cobalt, molybdenum, vanadium, and manganese were found to be particularly stable and active catalysts under conditions specific to this process (T<650C, low oxygen partial pressures). Bench-scale evaluation of these metal oxides with respect to stability to chlorine (HCl) attack was carried out at 550C using a TG/MS system. Cobalt oxide was found to be resistant to metal loss in a HCl/He gaseous environment while metal loss from Mo, Mn, and V-based catalysts was moderate to severe. XRD and SEM/EDX analysis of spent Co catalysts indicated the formation of non-stoichiometric cobalt chlorides. Regeneration of chlorinated cobalt was found to successfully restore the low-temperature combustion activity to that of the fresh metal oxide

  15. Acidity, oxophilicity and hydrogen sticking probability of supported metal catalysts for hydrodeoxygenation process

    Lup, A. Ng K.; Abnisa, F.; Daud, W. M. A. W.; Aroua, M. K.

    2018-03-01

    Hydrodeoxygenation is an oxygen removal process that occurs in the presence of hydrogen and catalysts. This study has shown the importance of acidity, oxophilicity and hydrogen sticking probability of supported metal catalysts in having high hydrodeoxygenation activity and selectivity. These properties are required to ensure the catalyst has high affinity for C-O or C=O bonds and the capability for the adsorption and activation of H2 and O-containing compounds. A theoretical framework of temperature programmed desorption technique was also discussed for the quantitative understanding of these properties. By using NH3-TPD, the nature and abundance of acid sites of catalyst can be determined. By using H2-TPD, the nature and abundance of metallic sites can also be determined. The desorption activation energy could also be determined based on the Redhead analysis of TPD spectra with different heating rates.

  16. Stable biexcitons in two-dimensional metal-halide perovskites with strong dynamic lattice disorder

    Thouin, Félix; Neutzner, Stefanie; Cortecchia, Daniele; Dragomir, Vlad Alexandru; Soci, Cesare; Salim, Teddy; Lam, Yeng Ming; Leonelli, Richard; Petrozza, Annamaria; Kandada, Ajay Ram Srimath; Silva, Carlos

    2018-03-01

    With strongly bound and stable excitons at room temperature, single-layer, two-dimensional organic-inorganic hybrid perovskites are viable semiconductors for light-emitting quantum optoelectronics applications. In such a technological context, it is imperative to comprehensively explore all the factors—chemical, electronic, and structural—that govern strong multiexciton correlations. Here, by means of two-dimensional coherent spectroscopy, we examine excitonic many-body effects in pure, single-layer (PEA) 2PbI4 (PEA = phenylethylammonium). We determine the binding energy of biexcitons—correlated two-electron, two-hole quasiparticles—to be 44 ±5 meV at room temperature. The extraordinarily high values are similar to those reported in other strongly excitonic two-dimensional materials such as transition-metal dichalcogenides. Importantly, we show that this binding energy increases by ˜25 % upon cooling to 5 K. Our work highlights the importance of multiexciton correlations in this class of technologically promising, solution-processable materials, in spite of the strong effects of lattice fluctuations and dynamic disorder.

  17. Synthesis, Characterizations, and Applications of Metal-Ions Incorporated High Quality MCM-41 Catalysts

    Lim, Steven S.; Haller, Gary L.

    2013-01-01

    Various metal ions (transition and base metals) incorporated MCM-41 catalysts can be synthesized using colloidal and soluble silica with non-sodium involved process. Transition metal ion-typically V 5+ , Co 2+ , and Ni 2+ -incorporated MCM-41 catalysts were synthesized by isomorphous substitution of Si ions in the framework. Each incorporated metal ion created a single species in the silica framework, single-site solid catalyst, showing a substantial stability in reduction and catalytic activity. Radius of pore curvature effect was investigated with Co-MCM-41 by temperature programmed reduction (TPR). The size of metallic Co clusters, sub-nanometer, could be controlled by a proper reduction treatment of Co-MCM-41 having different pore size and the initial pH adjustment of the Co-MCM-41 synthesis solution. These small metallic clusters showed a high stability under a harsh reaction condition without serious migration, resulting from a direct anchoring of small metallic clusters to the partially or unreduced metal ions on the surface. After a complete reduction, partial occlusion of the metallic cluster surface by amorphous silica stabilized the particles against aggregations. As a probe reaction of particle size sensitivity, carbon single wall nanotubes (SWNT) were synthesized using Co-MCM-41. A metallic cluster stability test was performed by CO methanation using Co- and Ni-MCM-41. Methanol and methane partial oxidations were carried out with V-MCM-41, and the radius of pore curvature effect on the catalytic activity was investigated

  18. Design of Embedded Metal Catalysts via Reverser Micro-Emulsion System: a Way to Suppress Catalyst Deactivation by Metal Sintering

    Al Mana, Noor

    2016-01-01

    are embedded inside the protecting shell have attracted a lot of researchers working in the field of catalysis owing to their enhanced physical and chemical properties suppress catalyst deactivation. Also, a new active site generated at the interface between

  19. Mitigation of hydrogen by oxidation using nitrous oxide and noble metal catalysts

    Britton, M.D.

    1995-01-01

    This test studied the ability of a blend of nuclear-grade, noble-metal catalysts to catalyze a hydrogen/nitrous oxide reaction in an effort to mitigate a potential hydrogen (H 2 ) gas buildup in the Hanford Site Grout Disposal Facility. For gases having H 2 and a stoichiometric excess of either nitrous oxide or oxygen, the catalyst blend can effectively catalyze the H 2 oxidation reaction at a rate exceeding 380 μmoles of H 2 per hour per gram of catalyst (μmol/h/g) and leave the gas with less than a 0.15 residual H 2 Concentration. This holds true in gases with up to 2.25% water vapor and 0.1% methane. This should also hold true for gases with up to 0.1% carbon monoxide (CO) but only until the catalyst is exposed to enough CO to block the catalytic sites and stop the reaction. Gases with ammonia up to 1% may be slightly inhibited but can have reaction rates greater than 250 μmol/h/g with less than a 0.20% residual H 2 concentration. The mechanism for CO poisoning of the catalyst is the chemisorption of CO to the active catalyst sites. The CO sorption capacity (SC) of the catalyst is the total amount of CO that the catalyst will chemisorb. The average SC for virgin catalyst was determined to be 19.3 ± 2.0 μmoles of CO chemisorbed to each gram of catalyst (μmol/g). The average SC for catalyst regenerated with air was 17.3 ± 1.9 μmol/g

  20. Variable Charge and Electrical Double Layer of Mineral-Water Interfaces: Silver Halides versus Metal (Hydr)Oxides

    Hiemstra, T.

    2012-01-01

    Classically, silver (Ag) halides have been used to understand thermodynamic principles of the charging process and the corresponding development of the electrical double layer (EDL). A mechanistic approach to the processes on the molecular level has not yet been carried out using advanced surface

  1. Power generation in microbial fuel cells using platinum group metal-free cathode catalyst: Effect of the catalyst loading on performance and costs.

    Santoro, Carlo; Kodali, Mounika; Herrera, Sergio; Serov, Alexey; Ieropoulos, Ioannis; Atanassov, Plamen

    2018-02-28

    Platinum group metal-free (PGM-free) catalyst with different loadings was investigated in air breathing electrodes microbial fuel cells (MFCs). Firstly, the electrocatalytic activity towards oxygen reduction reaction (ORR) of the catalyst was investigated by rotating ring disk electrode (RRDE) setup with different catalyst loadings. The results showed that higher loading led to an increased in the half wave potential and the limiting current and to a further decrease in the peroxide production. The electrons transferred also slightly increased with the catalyst loading up to the value of ≈3.75. This variation probably indicates that the catalyst investigated follow a 2x2e - transfer mechanism. The catalyst was integrated within activated carbon pellet-like air-breathing cathode in eight different loadings varying between 0.1 mgcm -2 and 10 mgcm -2 . Performance were enhanced gradually with the increase in catalyst content. Power densities varied between 90 ± 9 μWcm -2 and 262 ± 4 μWcm -2 with catalyst loading of 0.1 mgcm -2 and 10 mgcm -2 respectively. Cost assessments related to the catalyst performance are presented. An increase in catalyst utilization led to an increase in power generated with a substantial increase in the whole costs. Also a decrease in performance due to cathode/catalyst deterioration over time led to a further increase in the costs.

  2. Esterification of phenyl acetic acid with p-cresol using metal cation exchanged montmorillonite nanoclay catalysts.

    Bhaskar, M; Surekha, M; Suma, N

    2018-02-01

    The liquid phase esterification of phenyl acetic acid with p -cresol over different metal cation exchanged montmorillonite nanoclays yields p -cresyl phenyl acetate. Different metal cation exchanged montmorillonite nanoclays (M n +  = Al 3+ , Zn 2+ , Mn 2+ , Fe 3+ , Cu 2+ ) were prepared and the catalytic activity was studied. The esterification reaction was conducted by varying molar ratio of the reactants, reaction time and catalyst amount on the yield of the ester. Among the different metal cation exchanged catalysts used, Al 3+ -montmorillonite nanoclay was found to be more active. The characterization of the material used was studied under different techniques, namely X-ray diffraction, scanning electron microscopy and thermogravimetric analysis. The product obtained, p -cresyl phenyl acetate, was identified by thin-layer chromotography and confirmed by Fourier transform infrared, 1 H NMR and 13 C NMR. The regeneration activity of used catalyst was also investigated up to fourth generation.

  3. Modeling of catalytically active metal complex species and intermediates in reactions of organic halides electroreduction.

    Lytvynenko, Anton S; Kolotilov, Sergey V; Kiskin, Mikhail A; Eremenko, Igor L; Novotortsev, Vladimir M

    2015-02-28

    The results of quantum chemical modeling of organic and metal-containing intermediates that occur in electrocatalytic dehalogenation reactions of organic chlorides are presented. Modeling of processes that take place in successive steps of the electrochemical reduction of representative C1 and C2 chlorides - CHCl3 and Freon R113 (1,1,2-trifluoro-1,2,2-trichloroethane) - was carried out by density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2). It was found that taking solvation into account using an implicit solvent model (conductor-like screening model, COSMO) or considering explicit solvent molecules gave similar results. In addition to modeling of simple non-catalytic dehalogenation, processes with a number of complexes and their reduced forms, some of which were catalytically active, were investigated by DFT. Complexes M(L1)2 (M = Fe, Co, Ni, Cu, Zn, L1H = Schiff base from 2-pyridinecarbaldehyde and the hydrazide of 4-pyridinecarboxylic acid), Ni(L2) (H2L2 is the Schiff base from salicylaldehyde and 1,2-ethylenediamine, known as salen) and Co(L3)2Cl2, representing a fragment of a redox-active coordination polymer [Co(L3)Cl2]n (L3 is the dithioamide of 1,3-benzenedicarboxylic acid), were considered. Gradual changes in electronic structure in a series of compounds M(L1)2 were observed, and correlations between [M(L1)2](0) spin-up and spin-down LUMO energies and the relative energies of the corresponding high-spin and low-spin reduced forms, as well as the shape of the orbitals, were proposed. These results can be helpful for determination of the nature of redox-processes in similar systems by DFT. No specific covalent interactions between [M(L1)2](-) and the R113 molecule (M = Fe, Co, Ni, Zn) were found, which indicates that M(L1)2 electrocatalysts act rather like electron transfer mediators via outer-shell electron transfer. A relaxed surface scan of the adducts {M(L1)2·R113}(-) (M = Ni or Co) versus the distance between the

  4. Selective conversion of synthesis gas into C2-oxygenated products using mixed-metal homogeneous catalysts

    Whyman, R.

    1986-01-01

    A feature which is a key to any wider utilization of chemistry based on synthesis gas is an understanding of, and more particularly, an ability to control, those factors which determine the selectivity of the C 1 to C 2 transformation during the hydrogenation of carbon monoxide. With the exception of the rhodium-catalyzed conversion of carbon monoxide and hydrogen into ethylene glycol and methanol, in which molar ethylene glycol/methanol selectivities of ca 2/1 may be achieved, other catalyst systems containing metals such as cobalt or ruthenium exhibit only poor selectivities to ethylene glycol. The initial studies in this area were based on the reasoning that, since the reduction of carbon monoxide to C 2 products is a complex, multi-step process, the use of appropriate combinations of metals could generate synergistic effects which might prove more effective (in terms of both catalytic activity and selectivity) than simply the sum of the individual metal components. In particular, the concept of the combination of a good hydrogenation catalyst with a good carbonylation, or ''CO insertion'', catalyst seemed particularly germane. As a result of this approach the authors discovered an unprecedented example of the effect of catalyst promoters, particularly in the enhancement of C 2 /C 1 selectivity, and one which has led to the development of composite mixed-metal homogeneous catalyst systems for the conversion of CO/H 2 into C 2 -oxygenate esters

  5. Dispersed metal cluster catalysts by design. Synthesis, characterization, structure, and performance

    Arslan, Ilke [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A. [Univ. of Alabama, Tuscaloosa, AL (United States); Gates, Bruce C. [Univ. of California, Davis, CA (United States); Katz, Alexander [Univ. of California, Berkeley, CA (United States)

    2015-09-30

    To understand the class of metal cluster catalysts better and to lay a foundation for the prediction of properties leading to improved catalysts, we have synthesized metal catalysts with well-defined structures and varied the cluster structures and compositions systematically—including the ligands bonded to the metals. These ligands include supports and bulky organics that are being tuned to control both the electron transfer to or from the metal and the accessibility of reactants to influence catalytic properties. We have developed novel syntheses to prepare these well-defined catalysts with atomic-scale control the environment by choice and placement of ligands and applied state-of-the art spectroscopic, microscopic, and computational methods to determine their structures, reactivities, and catalytic properties. The ligands range from nearly flat MgO surfaces to enveloping zeolites to bulky calixarenes to provide controlled coverages of the metal clusters, while also enforcing unprecedented degrees of coordinative unsaturation at the metal site—thereby facilitating bonding and catalysis events at exposed metal atoms. With this wide range of ligand properties and our arsenal of characterization tools, we worked to achieve a deep, fundamental understanding of how to synthesize robust supported and ligand-modified metal clusters with controlled catalytic properties, thereby bridging the gap between active site structure and function in unsupported and supported metal catalysts. We used methods of organometallic and inorganic chemistry combined with surface chemistry for the precise synthesis of metal clusters and nanoparticles, characterizing them at various stages of preparation and under various conditions (including catalytic reaction conditions) and determining their structures and reactivities and how their catalytic properties depend on their compositions and structures. Key characterization methods included IR, NMR, and EXAFS spectroscopies to identify

  6. Carbon Nanofibers as Catalyst Support for Noble Metals

    Toebes, M.L.

    2004-01-01

    In the quest for new and well-defined support materials for heterogeneous catalysts we explored the potential of carbon nanofibers (CNF). CNF belongs to the by now extensive family of synthetic graphite-like carbon materials with advantageous and tunable physico-chemical properties. Aim of the work

  7. Monodisperse metal nanoparticle catalysts on silica mesoporous supports: synthesis, characterizations, and catalytic reactions

    Somorjai, G.A.

    2009-09-14

    The design of high performance catalyst achieving near 100% product selectivity at maximum activity is one of the most important goals in the modern catalytic science research. To this end, the preparation of model catalysts whose catalytic performances can be predicted in a systematic and rational manner is of significant importance, which thereby allows understanding of the molecular ingredients affecting the catalytic performances. We have designed novel 3-dimensional (3D) high surface area model catalysts by the integration of colloidal metal nanoparticles and mesoporous silica supports. Monodisperse colloidal metal NPs with controllable size and shape were synthesized using dendrimers, polymers, or surfactants as the surface stabilizers. The size of Pt, and Rh nanoparticles can be varied from sub 1 nm to 15 nm, while the shape of Pt can be controlled to cube, cuboctahedron, and octahedron. The 3D model catalysts were generated by the incorporation of metal nanoparticles into the pores of mesoporous silica supports via two methods: capillary inclusion (CI) and nanoparticle encapsulation (NE). The former method relies on the sonication-induced inclusion of metal nanoparticles into the pores of mesoporous silica, whereas the latter is performed by the encapsulation of metal nanoparticles during the hydrothermal synthesis of mesoporous silica. The 3D model catalysts were comprehensively characterized by a variety of physical and chemical methods. These catalysts were found to show structure sensitivity in hydrocarbon conversion reactions. The Pt NPs supported on mesoporous SBA-15 silica (Pt/SBA-15) displayed significant particle size sensitivity in ethane hydrogenolysis over the size range of 1-7 nm. The Pt/SBA-15 catalysts also exhibited particle size dependent product selectivity in cyclohexene hydrogenation, crotonaldehyde hydrogenation, and pyrrole hydrogenation. The Rh loaded SBA-15 silica catalyst showed structure sensitivity in CO oxidation reaction. In

  8. Defect formation and desorption of metal atoms from alkali halide crystals under low energy electron bombardment studied by optical absorption and mass spectroscopy

    Seifert, N.R.

    1993-04-01

    This work presents an extensive investigation of electronically induced desorption of ground-state alkali atoms from alkali halides and for the first time correlates directly the desorption with the stability and spatial distribution of the defects formed during bombardment. The electron impact results in the formation of stable F-centers and F-center clusters in the bulk of the crystals. In striking contrast a significant metallization of the surface is observed. Even at temperatures as low as 90 deg C the metallization is achieved within the time resolution of our detection system, which can only be explained by the rapid diffusion of hot holes. Superimposed to the fast and short diffusion of hot holes is the slow F-center diffusion. Measuring the distribution of defects with low energy ion sputtering techniques indicates that at least in the case of LiF the observed diffusion constant of F-centers agrees with values derived by using methods different from that applied here. At low temperatures the formation of F-center clusters and metal on the surface dominates. Colloid formation clearly requires higher temperatures (typically around 200 deg C). This is a strong evidence that efficient F-center diffusion is necessary for the formation of metallic particles (colloids) in the bulk of the crystals. Desorption of alkali atoms from alkali halides at temperatures around room temperature is due to weakly bound alkali atoms. For elevated temperatures the stability of the metallic clusters in the bulk of the crystals (i.e. colloids) are the rate limiting process. (author)

  9. Activity Descriptors for CO2 Electroreduction to Methane on Transition-Metal Catalysts

    Peterson, Andrew; Nørskov, Jens K.

    2012-01-01

    The electrochemical reduction of CO2 into hydrocarbons and alcohols would allow renewable energy sources to be converted into fuels and chemicals. However, no electrode catalysts have been developed that can perform this transformation with a low overpotential at reasonable current densities....... In this work, we compare trends in binding energies for the intermediates in CO2 electrochemical reduction and present an activity “volcano” based on this analysis. This analysis describes the experimentally observed variations in transition-metal catalysts, including why copper is the best-known metal...

  10. Manufacture of highly loaded silica-supported cobalt Fischer–Tropsch catalysts from a metal organic framework

    Sun, Xiaohui; Suarez, Alma I. Olivos; Meijerink, Mark; van Deelen, Tom; Ould-Chikh, Samy; Zečević, Jovana; de Jong, Krijn P.; Kapteijn, Freek; Gascon, Jorge

    2017-01-01

    The development of synthetic protocols for the preparation of highly loaded metal nanoparticle-supported catalysts has received a great deal of attention over the last few decades. Independently controlling metal loading, nanoparticle size

  11. Wire gauze and cordierite supported noble metal catalysts for passive autocatalytic recombiner

    Sanap, Kiran K.; Varma, S.; Waghmode, S.B.; Bharadwaj, S.R.

    2015-01-01

    Highlights: • Synthesis by electroless deposition method and chemical reduction route. • Particle size of 0.1–0.5 μm & 3.5–5 nm for Pt–Pd/Wg & Pt–Pd/Cord catalysts. • Active for H_2 and O_2 reaction with initial H_2 concentration of 1.5 to 7% in air. • Active in presence of different contaminants like CO_2, CH_4, CO & relative humidity. • Enhanced resistance of Pt–Pd/Cord catalyst towards the poisoning of CO. - Abstract: Hydrogen released in nuclear reactor containment under severe accident scenario poses a threat to containment and hence needs to be regulated by catalytic recombination. Mixed noble metal catalysts with platinum–palladium supported on stainless steel wire gauze and cordierite support have been developed for this purpose. The developed catalysts have been found to be highly efficient for removal of hydrogen concentration in the range of 1.5 to 7.0% v/v in air. Though both the catalysts exhibit similar kinetics for lower hydrogen concentration, cordierite supported catalysts exhibits better kinetic rate at higher hydrogen concentration. The performances of these catalysts in presence of various probable catalytic poison like carbon monoxide and catalytic inhibitors like moisture, carbon dioxide, and hydrocarbons provide data for use of these catalysts under the actual scenario. Compared to stainless steel wire gauze supported catalyst, the cordierite based catalyst are found to exhibit enhanced resistance towards carbon monoxide and limited temperature rise for safer application at higher hydrogen concentrations.

  12. Scattering cross section of metal catalyst atoms in silicon nanowires

    Markussen, Troels; Rurali, R.; Cartoixa, X.

    2010-01-01

    A common technique to fabricate silicon nanowires is to use metal particles (e.g., Au, Ag, Cu, Al) to catalyze the growth reaction. As a consequence, the fabricated nanowires contain small concentrations of these metals as impurities. In this work we investigate the effect of the metallic impurit...

  13. Platinum Group Metal-free Catalysts for Hydrogen Evolution Reaction in Microbial Electrolysis Cells.

    Yuan, Heyang; He, Zhen

    2017-07-01

    Hydrogen gas is a green energy carrier with great environmental benefits. Microbial electrolysis cells (MECs) can convert low-grade organic matter to hydrogen gas with low energy consumption and have gained a growing interest in the past decade. Cathode catalysts for the hydrogen evolution reaction (HER) present a major challenge for the development and future applications of MECs. An ideal cathode catalyst should be catalytically active, simple to synthesize, durable in a complex environment, and cost-effective. A variety of noble-metal free catalysts have been developed and investigated for HER in MECs, including Nickel and its alloys, MoS 2 , carbon-based catalysts and biocatalysts. MECs in turn can serve as a research platform to study the durability of the HER catalysts. This personal account has reviewed, analyzed, and discussed those catalysts with an emphasis on synthesis and modification, system performance and potential for practical applications. It is expected to provide insights into the development of HER catalysts towards MEC applications. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Complexes of metal chlorides with proton donors — promising polyfunctional catalysts for electrophilic processes

    Minsker, Karl S.; Ivanova, S. R.; Biglova, Raisa Z.

    1995-05-01

    The Bronsted acids formed as a result of the interaction of aluminium chlorides with Group I and II metal chlorides in the presence of proton-donating compounds are promising polyfunctional catalysts for electrophilic processes (polymerisation, depolymerisation and degradation of macromolecules, alkylation, desulfurisation, and hydrogenation). The factor determing the electrophilic activity and selectivity of the action of the catalysts is their acidity. This makes it possible to predict the direction of the changes in the activity and selectivity of the catalyst in specific chemical processes in conformity with the opposite variation rule: with increase in the acidity of the electrophilic catalyst, their activity increases but the selectivity of their action diminishes. The bibliography includes 72 references.

  15. Precious metal assay analysis of fresh reforming catalyst by x-ray fluorescence spectrometry

    McElroy, F.C.; Mulhall, J.M.

    1991-01-01

    This paper reports that precious metal analysis of fresh reforming catalysts are typically performed by both the catalyst manufacturer and buyer to arrive at a financial settlement on the quantity of metal in each lot of commercial catalyst. Traditional assay methods involve a variety of fire assay or wet chemical acid digestion schemes coupled with gravimetric, colorimetic, or titrimetric measurement for precious metals. Methods must have sufficient precision and accuracy to afford interlaboratory agreement of within one half of one percent relative between the catalyst supplier and purchaser. To meet this requirement many laboratories rely on classical methods. Unfortunately these proceeders are labor intensive and time consuming. X-ray fluorescence has the inherent instrument precision to achieve typical intralaboratory precision of 0.5% RSD on a wide variety of elements and numerous sample types. We have developed an X-ray fluorescence method for the assay quality analysis of fresh reforming catalyst containing platinum, rhenium, and iridium. This method was applied to numerous samples over the past five years

  16. Dehalogenation of aromatic halides by polyaniline/zero-valent iron composite nanofiber: Kinetics and mechanisms

    Giri, S

    2016-03-01

    Full Text Available Dehalogenation of aryl halides was demonstrated using polyaniline/zero valent iron composite nanofiber (termed as PANI/Fe0) as a cheap, efficient and environmentally friendly heterogeneous catalyst. The catalyst was prepared via rapid mixing...

  17. Designing Multifunctionality into Single Phase and Multiphase Metal-Oxide-Selective Propylene Ammoxidation Catalysts

    James F. Brazdil

    2018-03-01

    Full Text Available Multifunctionality is the hallmark of most modern commercial heterogeneous catalyst systems in use today, including those used for the selective ammoxidation of propylene to acrylonitrile. It is the quintessential principle underlying commercial catalyst design efforts since petrochemical process development is invariably driven by the need to reduce manufacturing costs. This is in large part achieved through new and improved catalysts that increase selectivity and productivity. In addition, the future feedstocks for chemical processes will be invariably more refractory than those currently in use (e.g., replacing alkenes with alkanes or using CO2, thus requiring a disparate combination of chemical functions in order to effect multiple chemical transformations with the fewest separate process steps. This review summarizes the key chemical phenomena behind achieving the successful integration of multiple functions into a mixed-metal-oxide-selective ammoxidation catalyst. An experiential and functional catalyst design model is presented that consists of one or both of the following components: (1 a mixed-metal-oxide–solid solution where the individual metal components serve separate and necessary functions in the reaction mechanism through their atomic level interaction in the context of a single crystallographic structure; (2 the required elemental components and their catalytic function existing in separate phases, where these phases are able to interact for the purposes of electron and lattice oxygen transfer through the formation of a structurally coherent interface (i.e., epitaxy between the separate crystal structures. Examples are provided from the literature and explained in the context of this catalyst design model. The extension of the model concepts to the design of heterogeneous catalysts in general is also discussed.

  18. Combinatorial computational chemistry approach to the design of metal catalysts for deNOx

    Endou, Akira; Jung, Changho; Kusagaya, Tomonori; Kubo, Momoji; Selvam, Parasuraman; Miyamoto, Akira

    2004-01-01

    Combinatorial chemistry is an efficient technique for the synthesis and screening of a large number of compounds. Recently, we introduced the combinatorial approach to computational chemistry for catalyst design and proposed a new method called ''combinatorial computational chemistry''. In the present study, we have applied this combinatorial computational chemistry approach to the design of precious metal catalysts for deNO x . As the first step of the screening of the metal catalysts, we studied Rh, Pd, Ag, Ir, Pt, and Au clusters regarding the adsorption properties towards NO molecule. It was demonstrated that the energetically most stable adsorption state of NO on Ir model cluster, which was irrespective of both the shape and number of atoms including the model clusters

  19. Nano Transition Metal Sulfide Catalyst for Solvolysis Liquefaction of Soda Lignin

    Fei-Ling, P.; Chin-Hua, C.; Sarani Zakaria; Soon-Keong, N.; Tze-Khong, L.

    2011-01-01

    Solvolysis liquefaction of soda lignin in the presence of various transition metal sulfide catalysts was studied to investigate the catalyst effects on the oil and gas yields, conversion rate and higher heating value (HHV) of oil. Nano sized copper sulfide, iron sulfide and molybdenum sulfide were successfully synthesized via a simple hydrothermal method under reaction temperature 200 degree Celsius for 90 min. The addition of transition metal sulfide based catalysts (CuS, MoS 2 and FeS 2 ) enhanced both production of the oils and gas and the higher heating value (HHV) of oil products. A high oil and gas yields of 82.1 % and 2890 cm 3 was obtained with MoS 2 at 250 degree Celsius for 60 min. Elemental analyses for the oils revealed that the liquid products have much higher heating values than the crude soda lignin powder. (author)

  20. Efficient selective catalytic reduction of NO by novel carbon-doped metal catalysts made from electroplating sludge.

    Zhang, Jia; Zhang, Jingyi; Xu, Yunfeng; Su, Huimin; Li, Xiaoman; Zhou, Ji Zhi; Qian, Guangren; Li, Li; Xu, Zhi Ping

    2014-10-07

    Electroplating sludges, once regarded as industrial wastes, are precious resources of various transition metals. This research has thus investigated the recycling of an electroplating sludge as a novel carbon-doped metal (Fe, Ni, Mg, Cu, and Zn) catalyst, which was different from a traditional carbon-supported metal catalyst, for effective NO selective catalytic reduction (SCR). This catalyst removed >99.7% NO at a temperature as low as 300 °C. It also removed NO steadily (>99%) with a maximum specific accumulative reduced amount (MSARA) of 3.4 mmol/g. Gas species analyses showed that NO removal was accompanied by evolving N2 and CO2. Moreover, in a wide temperature window, the sludge catalyst showed a higher CO2 selectivity (>99%) than an activated carbon-supported metal catalyst. Structure characterizations revealed that carbon-doped metal was transformed to metal oxide in the sludge catalyst after the catalytic test, with most carbon (2.33 wt %) being consumed. These observations suggest that NO removal over the sludge catalyst is a typical SCR where metals/metal oxides act as the catalytic center and carbon as the reducing reagent. Therefore, our report probably provides an opportunity for high value-added utilizations of heavy-metal wastes in mitigating atmospheric pollutions.

  1. Metal-phthalocyanine functionalized carbon nanotubes as catalyst for the oxygen reduction reaction: A theoretical study

    Orellana, Walter

    2012-07-01

    The covalent functionalization of metallic single-walled carbon nanotubes (CNTs) with transition metal phthalocyanines (MPc, with M = Mn, Fe and Co) are addressed by density functional calculations. The CNT-MPc catalytic activity toward the oxygen reduction reaction (ORR) is investigated through the O2 stretching frequency adsorbed on the phthalocyanine metal center. We find better reduction abilities when the CNT functionalization occurs through sp2-like bonds. Multiple stable-spin states for the M-O2 adduct are also found for M = Mn and Fe, suggesting higher ORR rates. The CNT-MPc complexes show metallic characteristics, suggesting favorable conditions to work as ORR cathode catalysts in fuel cells.

  2. Separation of Metals From Spent Catalysts Waste by Bioleaching Process

    Sirin Fairus, Tria Liliandini, M.Febrian, Ronny Kurniawan

    2010-01-01

    A kind of waste that hard to be treated is a metal containing solid waste. Leaching method is one thealternative waste treatment. But there still left an obstacle on this method, it is the difficulty to find theselective solvent for the type of certain metal that will separated. Bioleaching is one of the carry ablealternative waste treatments to overcome that obstacle. Bioleaching is a metal dissolving process orextraction from a sediment become dissolve form using microorganisms. On this met...

  3. Recycling of platinum group metals from the automotive catalysts; Reciclagem de metais do grupo da platina proveniente de catalisadores automotivos

    Benevit, Mariana; Petter, Patricia Melo Halmenschlager; Veit, Hugo Marcelo, E-mail: patymhp@yahoo.com.br [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Faculdade de Engenharia. Departamento de Materiais

    2014-07-01

    Currently it is very important to use alternative sources of raw material for obtaining metals, avoiding the traditional mining. This work aims to characterize and evaluate the recoverability of platinum group metals present in automotive catalysts. Thus, the catalysts were divided into two groups: the first was catalysts used in 1.0 cars and the second was catalyst used in 2.0 cars. DRX and FRX techniques and chemical analysis performed by ICP/OES was used to characterized these materials. The results showed that there is a significant amount of platinum group elements in catalyst waste, which can be separated and reused. In the next step, hydro and pyrometallurgical routes, for metals extraction from catalyst waste, will be studied. (author)

  4. Core-shell composite metal catalysts incased into natural ceramic nanotubes

    Vinokurov, V; Berberov, A; Afonin, D; Borzaev, H; Ivanov, E; Gushchin, P; Lvov, Y

    2014-01-01

    The bimetallic halloysite nanotubes were prepared by the injection of halloysite- containing aerosols into the microwave plasma reactor. Nanotubes contain metal nanoparticles formed from the metal salt solution in the lumen of nanotubes and the iron oxide nanoparticles at the outer surface of nanotubes. Such halloysite composites may be sputtered onto the surface of the porous carrier forming the nanostructured catalyst, as was shown by the pure halloysite sputtering onto the model porous ceramic surface

  5. Metal oxides modified NiO catalysts for oxidative dehydrogenation of ethane to ethylene

    Zhu, Haibo; Dong, Hailin; Laveille, Paco; Saih, Youssef; Caps, Valerie; Basset, Jean-Marie

    2014-01-01

    in contrast to pure NiO. The introduction of group IV, V and VI transition metals into NiO decreases the catalytic activity in ethane ODH. However, the ethylene selectivity is enhanced with the highest level for the Ni-W-O and Ni-Ti-O catalysts. As a result

  6. Direct observation of surface reconstruction and termination on a complex metal oxide catalyst by electron microscopy

    Zhu, Yihan

    2012-03-19

    On the surface: The surface reconstruction of an MoVTeO complex metal oxide catalyst was observed directly by various electron microscopic techniques and the results explain the puzzling catalytic behavior. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Synthesis of Single-Walled Carbon Nanotubes: Effects of Active Metals, Catalyst Supports, and Metal Loading Percentage

    Wei-Wen Liu

    2013-01-01

    Full Text Available The effects of active metals, catalyst supports, and metal loading percentage on the formation of single-walled carbon nanotubes (SWNTs were studied. In particular, iron, cobalt, and nickel were investigated for SWNTs synthesis. Iron was found to grow better-quality SWNTs compared to cobalt and nickel. To study the effect of catalyst supports, magnesium oxide, silicon oxide, and aluminium oxide were chosen for iron. Among the studied supports, MgO was identified to be a suitable support for iron as it produced SWNTs with better graphitisation determined by Raman analysis. Increasing the iron loading decreased the quality of SWNTs due to extensive agglomeration of the iron particles. Thus, lower metal loading percentage is preferred to grow better-quality SWNTs with uniform diameters.

  8. Pt-based Bi-metallic Monolith Catalysts for Partial Upgrading of Microalgae Oil

    Lawal, Adeniyi [Stevens Inst. of Technology, Hoboken, NJ (United States); Manganaro, James [Anasyn LLC, Princeton, NJ (United States); Goodall, Brian [Valicor Renewables LLC, Dexter, MI (United States); Farrauto, Robert [Columbia Univ., New York, NY (United States)

    2015-03-24

    Valicor’s proprietary wet extraction process in conjunction with thermochemical pre-treatment was performed on algal biomass from two different algae strains, Nannochloropsis Salina (N.S.) and Chlorella to produce algae oils. Polar lipids such as phospholipids were hydrolyzed, and metals and metalloids, known catalyst poisons, were separated into the aqueous phase, creating an attractive “pre-refined” oil for hydrodeoxygenation (HDO) upgrading by Stevens. Oil content and oil extraction efficiency of approximately 30 and 90% respectively were achieved. At Stevens, we formulated a Pt-based bi-metallic catalyst which was demonstrated to be effective in the hydro-treating of the algae oils to produce ‘green’ diesel. The bi-metallic catalyst was wash-coated on a monolith, and in conjunction with a high throughput high pressure (pilot plant) reactor system, was used in hydrotreating algae oils from N.S. and Chlorella. Mixtures of these algae oils and refinery light atmospheric gas oil (LAGO) supplied by our petroleum refiner partner, Marathon Petroleum Corporation, were co-processed in the pilot plant reactor system using the Pt-based bi-metallic monolith catalyst. A 26 wt% N.S. algae oil/74 wt % LAGO mixture hydrotreated in the reactor system was subjected to the ASTM D975 Diesel Fuel Specification Test and it met all the important requirements, including a cetane index of 50.5. An elemental oxygen analysis performed by an independent and reputable lab reported an oxygen content of trace to none found. The successful co-processing of a mixture of algae oil and LAGO will enable integration of algae oil as a refinery feedstock which is one of the goals of DOE-BETO. We have presented experimental data that show that our precious metal-based catalysts consume less hydrogen than the conventional hydrotreating catalyst NiMo Precious metal catalysts favor the hydrodecarbonylation/hydrodecarboxylation route of HDO over the dehydration route preferred by base metal

  9. Activity Tests of Macro-Meso Porous Catalysts over Metal Foam Plate for Steam Reforming of Bio-Ethanol.

    Park, No-Kuk; Jeong, Yong Han; Kang, Misook; Lee, Tae Jin

    2018-09-01

    The catalytic activity of a macro-mesoporous catalyst coated on a metal foam plate in the reforming of bio-ethanol to synthesis gas was investigated. The catalysts were prepared by coating a support with a noble metal and transition metal. The catalytic activity for the production of synthetic gas by the reforming of bio-ethanol was compared according to the support material, reaction temperature, and steam/carbon ratio. The catalysts coated on the metal foams were prepared using a template method, in which macro-pores and meso-pores were formed by mixing polymer beads. In particular, the thermodynamic equilibrium composition of bio-ethanol reforming with the reaction temperature and steam/carbon ratio to produce synthetic gas was examined using the HSC (Enthalpy-Entropy-Heat capacity) chemistry program in this study. The composition of hydrogen and carbon monoxide in the reformate gas produced by steam reforming over the Rh/Ni-Ce-Zr/Al2O3-based pellet type catalysts and metal foam catalysts that had been coated with the Rh/Al-Ce-Zr-based catalysts was investigated by experimental activity tests. The activity of the metal foam catalyst was higher than that of the pellet type catalyst.

  10. A review of metal recovery from spent petroleum catalysts and ash.

    Akcil, Ata; Vegliò, Francesco; Ferella, Francesco; Okudan, Mediha Demet; Tuncuk, Aysenur

    2015-11-01

    With the increase in environmental awareness, the disposal of any form of hazardous waste has become a great concern for the industrial sector. Spent catalysts contribute to a significant amount of the solid waste generated by the petrochemical and petroleum refining industry. Hydro-cracking and hydrodesulfurization (HDS) catalysts are extensively used in the petroleum refining and petrochemical industries. The catalysts used in the refining processes lose their effectiveness over time. When the activity of catalysts decline below the acceptable level, they are usually regenerated and reused but regeneration is not possible every time. Recycling of some industrial waste containing base metals (such as V, Ni, Co, Mo) is estimated as an economical opportunity in the exploitation of these wastes. Alkali roasted catalysts can be leached in water to get the Mo and V in solution (in which temperature plays an important role during leaching). Several techniques are possible to separate the different metals, among those selective precipitation and solvent extraction are the most used. Pyrometallurgical treatment and bio-hydrometallurgical leaching were also proposed in the scientific literature but up to now they did not have any industrial application. An overview on patented and commercial processes was also presented. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Ultrahigh figure-of-merit for hydrogen generation from sodium borohydride using ternary metal catalysts

    Hu, Lunghao; Ceccato, R.; Raj, R.

    We report further increase in the figure-of-merit (FOM) for hydrogen generation from NaBH 4 than reported in an earlier paper [1], where a sub-nanometer layer of metal catalysts are deposited on carbon nanotube paper (CNT paper) that has been functionalized with polymer-derived silicon carbonitride (SiCN) ceramic film. Ternary, Ru-Pd-Pt, instead of the binary Pd-Pt catalyst used earlier, together with a thinner CNT paper is shown to increase the figure-of-merit by up to a factor of six, putting is above any other known catalyst for hydrogen generation from NaBH 4. The catalysts are prepared by first impregnating the functionalized CNT-paper with solutions of the metal salts, followed by reduction in a sodium borohydride solution. The reaction mechanism and the catalyst efficiency are described in terms of an electric charge transfer, whereby the negative charge on the BH 4 - ion is exchanged with hydrogen via the electronically conducting SiCN/CNT substrate [1].

  12. Metal Chlorides Supported Solid Catalysts for F-C Acylations of Arenes

    李阳; 刘云龙; 穆曼曼; 陈立功

    2015-01-01

    A series of metal chlorides supported solid catalysts were prepared by simple wet impregnation method. Their catalytic performances for Friedel-Crafts acylation of toluene with benzoyl chloride were evaluated and the excellent results were obtained over FeCl3/SiO2. These catalysts were characterized by BET, NH3-TPD and FT-IR of pyridine adsorption to clarify the structure-activity relationship. It was found that FeCl3/SiO2 has larger pore size and pore volume than other catalysts, which increased the accessibility of the catalyst. In addition, FeCl3/SiO2 ex-hibited higher molar ratio of Lewis acid sites and Brφnsted acid sites, which might be another reason for the in-crease of toluene conversion. Furthermore, the reaction parameters, including temperature, time and molar ratio, were optimized. Under the optimized conditions, 91.2%, conversion and 82.0%, selectivity were obtained. Mean-while, the generality of the catalyst was demonstrated by the acylations of alkyl substituted aromatics. Finally, the catalyst was reused for four runs with slight loss in catalytic activity, which attributed to the drain of the active component.

  13. Coupled Metal/Oxide Catalysts with Tunable Product Selectivity for Electrocatalytic CO2 Reduction.

    Huo, Shengjuan; Weng, Zhe; Wu, Zishan; Zhong, Yiren; Wu, Yueshen; Fang, Jianhui; Wang, Hailiang

    2017-08-30

    One major challenge to the electrochemical conversion of CO 2 to useful fuels and chemical products is the lack of efficient catalysts that can selectively direct the reaction to one desirable product and avoid the other possible side products. Making use of strong metal/oxide interactions has recently been demonstrated to be effective in enhancing electrocatalysis in the liquid phase. Here, we report one of the first systematic studies on composition-dependent influences of metal/oxide interactions on electrocatalytic CO 2 reduction, utilizing Cu/SnO x heterostructured nanoparticles supported on carbon nanotubes (CNTs) as a model catalyst system. By adjusting the Cu/Sn ratio in the catalyst material structure, we can tune the products of the CO 2 electrocatalytic reduction reaction from hydrocarbon-favorable to CO-selective to formic acid-dominant. In the Cu-rich regime, SnO x dramatically alters the catalytic behavior of Cu. The Cu/SnO x -CNT catalyst containing 6.2% of SnO x converts CO 2 to CO with a high faradaic efficiency (FE) of 89% and a j CO of 11.3 mA·cm -2 at -0.99 V versus reversible hydrogen electrode, in stark contrast to the Cu-CNT catalyst on which ethylene and methane are the main products for CO 2 reduction. In the Sn-rich regime, Cu modifies the catalytic properties of SnO x . The Cu/SnO x -CNT catalyst containing 30.2% of SnO x reduces CO 2 to formic acid with an FE of 77% and a j HCOOH of 4.0 mA·cm -2 at -0.99 V, outperforming the SnO x -CNT catalyst which only converts CO 2 to formic acid in an FE of 48%.

  14. Metal recovery from spent refinery catalysts by means of biotechnological strategies

    Beolchini, F.; Fonti, V.; Ferella, F.; Veglio, F.

    2010-01-01

    A bioleaching study aimed at recovering metals from hazardous spent hydroprocessing catalysts was carried out. The exhaust catalyst was rich in nickel (4.5 mg/g), vanadium (9.4 mg/g) and molybdenum (4.4 mg/g). Involved microorganisms were iron/sulphur oxidizing bacteria. Investigated factors were elemental sulphur addition, ferrous iron addition and actions contrasting a possible metal toxicity (either adding powdered activated charcoal or simulating a cross current process by means of periodical filtration). Ferrous iron resulted to be essential for metal extraction: nickel and vanadium extraction yields were 83% and 90%, respectively, while about 50% with no iron. The observed values for molybdenum extraction yields were not as high as Ni and V ones (the highest values were around 30-40%). The investigated actions aimed at contrasting a possible metal toxicity resulted not to be effective; in contrast, sequential filtration of the liquor leach had a significant negative effect on metals extraction. Nickel and vanadium dissolution kinetics resulted to be significantly faster than molybdenum dissolution ones. Furthermore, a simple first order kinetic model was successfully fitted to experimental data. All the observed results supported the important role of the indirect mechanism in bioleaching of LC-Finer catalysts.

  15. Metal recovery from spent refinery catalysts by means of biotechnological strategies

    Beolchini, F., E-mail: f.beolchini@univpm.it [Department of Marine Sciences, Polytechnic University of Marche, Via Brecce Bianche, 60131 Ancona (Italy); Fonti, V. [Department of Marine Sciences, Polytechnic University of Marche, Via Brecce Bianche, 60131 Ancona (Italy); Ferella, F.; Veglio, F. [Department of Chemistry, Chemical Engineering and Materials, University of L' Aquila, Monteluco di Roio, 67040 L' Aquila (Italy)

    2010-06-15

    A bioleaching study aimed at recovering metals from hazardous spent hydroprocessing catalysts was carried out. The exhaust catalyst was rich in nickel (4.5 mg/g), vanadium (9.4 mg/g) and molybdenum (4.4 mg/g). Involved microorganisms were iron/sulphur oxidizing bacteria. Investigated factors were elemental sulphur addition, ferrous iron addition and actions contrasting a possible metal toxicity (either adding powdered activated charcoal or simulating a cross current process by means of periodical filtration). Ferrous iron resulted to be essential for metal extraction: nickel and vanadium extraction yields were 83% and 90%, respectively, while about 50% with no iron. The observed values for molybdenum extraction yields were not as high as Ni and V ones (the highest values were around 30-40%). The investigated actions aimed at contrasting a possible metal toxicity resulted not to be effective; in contrast, sequential filtration of the liquor leach had a significant negative effect on metals extraction. Nickel and vanadium dissolution kinetics resulted to be significantly faster than molybdenum dissolution ones. Furthermore, a simple first order kinetic model was successfully fitted to experimental data. All the observed results supported the important role of the indirect mechanism in bioleaching of LC-Finer catalysts.

  16. Ultrafast Transient Absorption Spectroscopy of Polymer-Based Organophotoredox Catalysts Mimicking Transition-Metal Complexes

    Jamhawi, Abdelqader; Paul, Anam C.; Smith, Justin D.; Handa, Sachin; Liu, Jinjun

    2017-06-01

    Transition-metal complexes of rare earth metals including ruthenium and iridium are most commonly employed as visible-light photocatalysts. Despite their highly important and broad applications, they have many disadvantages including high cost associated with low abundance in earth crust, potential toxicity, requirement of specialized ligands for desired activity, and difficulty in recycling of metal contents as well as associated ligands. Polymer-based organophotoredox catalysts are promising alternatives and possess unique advantages such as easier synthesis from inexpensive starting material, longer excited state life time, broad range of activity, sustainability, and recyclability. In this research talk, time-resolved photoluminescence and femtosecond transient absorption (TA) spectroscopy measurements of three novel polymer-based organophotoredox catalysts will be presented. By our synthetic team, their catalytic activity has been proven in some highly valuable chemical transformations, that otherwise require transition metal complexes. Time-resolved spectroscopic investigations have demonstrated that photoinduced processes in these catalysts are similar to the transition metal complexes. Especially, intramolecular vibrational relaxation, internal conversion, and intersystem crossing from the S1 state to the T1 state all occur on a sub-picosecond timescale. The long lifetime of the T1 state ( 2-3 microsecond) renders these polymers potent oxidizing and reducing agents. A spectroscopic and kinetic model has been developed for global fitting of TA spectra in both the frequency and time domains. Implication of the current ultrafast spectroscopy studies of these novel molecules to their roles in photocatalysis will be discussed.

  17. Tailoring the synthesis of supported Pd catalysts towards desired structure and size of metal particles.

    Suresh, Gatla; Radnik, Jörg; Kalevaru, Venkata Narayana; Pohl, Marga-Martina; Schneider, Matthias; Lücke, Bernhard; Martin, Andreas; Madaan, Neetika; Brückner, Angelika

    2010-05-14

    In a systematic study, the influence of different preparation parameters on phase composition and size of metal crystallites and particles in Pd-Cu/TiO(2) and Pd-Sb/TiO(2) catalyst materials has been explored. Temperature and atmosphere of thermal pretreatment (pure He or 10% H(2)/He), nature of metal precursors (chlorides, nitrates or acetates) as well as of ammonium additives (ammonium sulfate, nitrate, carbonate) and urea were varied with the aim of tailoring the synthesis procedure for the preferential formation of metal particles with similar size and structure as observed recently in active catalysts after long-term equilibration under catalytic reaction conditions in acetoxylation of toluene to benzylacetate. Among the metal precursors and additives, the chloride metal precursors and (NH(4))(2)SO(4) were most suitable. Upon thermal pretreatment of Pd-Sb or Pd-Cu precursors, chloroamine complexes of Pd and Cu are formed, which decompose above 220 degrees C to metallic phases independent of the atmosphere. In He, metallic Pd particles were formed with both the co-components. In H(2)/He flow, Pd-Cu precursors were converted to core-shell particles with a Cu shell and a Pd core, while Sb(1)Pd(1) and Sb(7)Pd(20) alloy phases were formed in the presence of Sb. Metal crystallites of about 40 nm agglomerate to particles of up to 150 nm in He and to even larger size in H(2)/He.

  18. Patterned forests of vertically-aligned multiwalled carbon nanotubes using metal salt catalyst solutions.

    Garrett, David J; Flavel, Benjamin S; Baronian, Keith H R; Downard, Alison J

    2013-01-01

    A simple method for producing patterned forests of multiwalled carbon nanotubes (MWCNTs) is described. An aqueous metal salt solution is spin-coated onto a substrate patterned with photoresist by standard methods. The photoresist is removed by acetone washing leaving the acetone-insoluble catalyst pattern on the substrate. Dense forests of vertically aligned (VA) MWCNTs are grown on the patterned catalyst layers by chemical vapour deposition. The procedures have been demonstrated by growing MWCNT forests on two substrates: silicon and conducting graphitic carbon films. The forests adhere strongly to the substrates and when grown directly on carbon film, offer a simple method of preparing MWCNT electrodes.

  19. Studies on mixed metal oxides solid solutions as heterogeneous catalysts

    H. R. Arandiyan

    2009-03-01

    Full Text Available In this work, a series of perovskite-type mixed oxide LaMo xV1-xO3+δ powder catalysts (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, and 1.0, with 0.5 < δ < 1.5, prepared by the sol-gel process and calcined at 750ºC, provide an attractive and effective alternative means of synthesizing materials with better control of morphology. Structures of resins obtained during the gel formation process by FT-IR spectroscopy and XRD analysis showed that all the LaMo xV1-xO3+δ samples are single phase perovskite-type solid solutions. The surface area (BET between 2.5 - 5.0 m²/g (x = 0.1 and 1.0 respectively increases with increasing Mo ratio in the samples. They show high purity, good chemical homogeneity, and lower calcinations temperatures as compared with the solid-state chemistry route. SEM coupled to EDS and thermogravimetric analysis/differential thermal analyses (TGA/DTA have been carried out in order to evaluate the homogeneity of the catalyst. Finally, the experimental studies show that the calcination temperature and Mo content exhibited a significant influence on catalytic activity. Among the LaMo xV1-xO3+δ samples, LaMo0.7V0.3O4.2 showed the best catalytic activity for the topic reaction and the best activity and stability for ethane reforming at 850ºC under 8 bar.

  20. Magnesium oxide prepared via metal-chitosan complexation method: Application as catalyst for transesterification of soybean oil and catalyst deactivation studies

    Almerindo, Gizelle I.; Probst, Luiz F. D.; Campos, Carlos E. M.; de Almeida, Rusiene M.; Meneghetti, Simoni M. P.; Meneghetti, Mario R.; Clacens, Jean-Marc; Fajardo, Humberto V.

    2011-10-01

    A simple method to prepare magnesium oxide catalysts for biodiesel production by transesterification reaction of soybean oil with ethanol is proposed. The method was developed using a metal-chitosan complex. Compared to the commercial oxide, the proposed catalysts displayed higher surface area and basicity values, leading to higher yield in terms of fatty acid ethyl esters (biodiesel). The deactivation of the catalyst due to contact with CO2 and H2O present in the ambient air was verified. It was confirmed that the active catalytic site is a hydrogenocarbonate adsorption site.

  1. Studies on unusually reactive metal powders. Preparation of new organometallic and organic compounds including potential new catalysts. Final report, July 1, 1980-December 31, 1984

    Rieke, R.D.

    1985-06-01

    This research project was involved with the preparation and study of highly reactive metal powders prepared by the reduction of metal salts with alkali metals. Studies concentrated on nickel, copper, cadmium, uranium, iron, and magnesium. The nickel powders have been found to react rapidly with benzylic halides, and the resulting organonickel complexes yield dibenzyl. Aryl halides react rapidly with the nickel powders to produce biaryl compounds in high yields. Benzylic halides react with the nickel powders in the presence of acylhalides to produce benzyl ketones in high yields. Reactions of ROCOCOC1 and benzylic halides with nickel powders yield benzyl ketones. These reactions proceed with a wide variety of substituents on the phenyl ring of the benzylic halides. Highly reactive uranium has been prepared, and found to react with a variety of oxygen containing substrates, such as nitrobenzene to yield azo benzene. Highly reactive magnesium has opened up a totally new area of low temperature Grignard chemistry. The preparation of highly reactive copper has allowed the direct preparation of organocopper species directly from organic halides. 16 refs., 6 tabs

  2. Surface/structure functionalization of copper-based catalysts by metal-support and/or metal–metal interactions

    Konsolakis, Michalis, E-mail: mkonsol@science.tuc.gr [School of Production Engineering and Management, Technical University of Crete, GR-73100 Chania, Crete (Greece); Ioakeimidis, Zisis [Department of Mechanical Engineering, University of Western Macedonia, Bakola and Sialvera, GR-50100 Kozani (Greece)

    2014-11-30

    Highlights: • The surface chemistry of Cu-based catalysts is adjusted by metal-support or metal–metal interactions. • Three series of catalysts, i.e., Cu/REOs, Cu/Ce{sub 1−x}Sm{sub x}O{sub δ} and Cu–Co/CeO{sub 2} were prepared. • The local structure of Cu sites is remarkably affected by support or active phase modification. • Useful insights toward the fundamental understanding of Cu-catalyzed reactions are provided. - Abstract: Cu-based catalysts have recently attracted great attention both in catalysis and electro-catalysis fields due to their excellent catalytic performance and low cost. Given that their performance is determined, to a great extent, by Cu sites local environment, considerable efforts have been devoted on the strategic modifications of the electronic and structural properties of Cu sites. In this regard, the feasibility of tuning the local structure of Cu entities by means of metal-support or metal–metal interactions is investigated. More specifically, the physicochemical properties of Cu entities are modified by employing: (i) different oxides (CeO{sub 2}, La{sub 2}O{sub 3}, Sm{sub 2}O{sub 3}), or (ii) ceria-based mixed oxides (Ce{sub 1−x}Sm{sub x}O{sub δ}) as supporting carriers, and (iii) a second metal (Cobalt) adjacent to Cu (bimetallic Cu–Co/CeO{sub 2}). A characterization study, involving BET, XRD, TPR, and XPS, reveal that significant modifications on structural, redox and electronic properties of Cu sites can be induced by adopting either different oxide carriers or bimetallic complexes. Fundamental insights into the tuning of Cu local environment by metal-support or metal–metal interactions are provided, paving the way for real-life industrial applications.

  3. Predicting catalyst-support interactions between metal nanoparticles and amorphous silica supports

    Ewing, Christopher S.; Veser, Götz; McCarthy, Joseph J.; Lambrecht, Daniel S.; Johnson, J. Karl

    2016-10-01

    Metal-support interactions significantly affect the stability and activity of supported catalytic nanoparticles (NPs), yet there is no simple and reliable method for estimating NP-support interactions, especially for amorphous supports. We present an approach for rapid prediction of catalyst-support interactions between Pt NPs and amorphous silica supports for NPs of various sizes and shapes. We use density functional theory calculations of 13 atom Pt clusters on model amorphous silica supports to determine linear correlations relating catalyst properties to NP-support interactions. We show that these correlations can be combined with fast discrete element method simulations to predict adhesion energy and NP net charge for NPs of larger sizes and different shapes. Furthermore, we demonstrate that this approach can be successfully transferred to Pd, Au, Ni, and Fe NPs. This approach can be used to quickly screen stability and net charge transfer and leads to a better fundamental understanding of catalyst-support interactions.

  4. Transition metal oxide loaded MCM catalysts for photocatalytic ...

    Transition metal oxide (TiO2, Fe2O3, CoO) loaded MCM-41 and MCM-48 were synthesized by a two-step .... washed consecutively with water and ethanol, and cal- cined at 823 K for 5 .... conversion was observed in 1 h when the reaction was.

  5. Ultrasound-driven design of new mesoporous metal catalysts

    Schaeferhans, Jana; Pazos Perez, Nicolas; Andreeva, Daria [Physikalische Chemie II, Univ. Bayreuth (Germany); Skorb, Ekaterina [Max-Planck-Institut fuer Kolloid- und Grenzflaechenforschung, Golm (Germany)

    2011-07-01

    Mesoporous metal nanocomposites were formed by a ''green chemistry'' method with ultrasound irradiation. The sonication technique combines the fabrication of a mesoporous support consisting of metallic particles (Al, Mg) several tens of micrometers in size and the subsequent incorporation of metal (Ag, Au, Pt etc.) nanoparticles into its pores. Next to filling the mesoporous support with particles we are also able to form mesoporous alloys e.g. AlNi or CoAlFe. The resulting material is analyzed by transmission electron microscopy, powder X-ray diffraction, small-angle neutron scattering and the Brunauer-Emmett-Teller and the Barrett-Joyner-Halenda method. Surface areas up to 200 m{sup 2}/g with a narrow pore size distribution around 3 nm can be achieved. The mesoporous structures are analyzed by confocal light microscopy after coloring the particles with dye. We explain the formation of the mesoporous inner structures by the following mechanism: Thermal etching and recrystallization of metals by ultrasound-stimulated high-speed jets of liquid form the porous structure that is stabilized by surface oxidation through free radicals generated during cavitation. We expect this approach to be universal and opening perspectives for a whole new class of catalytic materials that can be prepared in a fairly easy and cost effective way.

  6. Reactivity of halide and pseudohalide ligands

    Kukushkin, Yu.N.

    1987-01-01

    Reactivity of halide and pseudohalide (cyanide, azide, thiocyanate, cyanate) ligands tending to form bridge bonds in transition metal (Re, Mo, W) complexes is considered. Complexes where transition metal salts are ligands of other, complex-forming ion, are described. Transformation of innerspheric pseudohalide ligands is an important way of directed synthesis of these metal coordination compounds

  7. Ethanol tolerant precious metal free cathode catalyst for alkaline direct ethanol fuel cells

    Grimmer, Ilena; Zorn, Paul; Weinberger, Stephan; Grimmer, Christoph; Pichler, Birgit; Cermenek, Bernd; Gebetsroither, Florian; Schenk, Alexander; Mautner, Franz-Andreas

    2017-01-01

    Highlights: • Selective ORR catalysts are presented for alkaline direct ethanol fuel cells. • Perovskite based cathode catalysts show high tolerance toward ethanol. • A membrane-free alkaline direct ethanol fuel cell is presented. - Abstract: La 0.7 Sr 0.3 (Fe 0.2 Co 0.8 )O 3 and La 0.7 Sr 0.3 MnO 3 −based cathode catalysts are synthesized by the sol-gel method. These perovskite cathode catalysts are tested in half cell configuration and compared to MnO 2 as reference material in alkaline direct ethanol fuel cells (ADEFCs). The best performing cathode is tested in single cell setup using a standard carbon supported Pt 0.4 Ru 0.2 based anode. A backside Luggin capillary is used in order to register the anode potential during all measurements. Characteristic processes of the electrodes are investigated using electrochemical impedance spectroscopy. Physical characterizations of the perovskite based cathode catalysts are performed with a scanning electron microscope (SEM) and by X-ray diffraction showing phase pure materials. In half cell setup, La 0.7 Sr 0.3 MnO 3 shows the highest tolerance toward ethanol with a performance of 614 mA cm −2 at 0.65 V vs. RHE in 6 M KOH and 1 M EtOH at RT. This catalyst outperforms the state-of-the-art precious metal-free MnO 2 catalyst in presence of ethanol. In fuel cell setup, the peak power density is 27.6 mW cm −2 at a cell voltage of 0.345 V and a cathode potential of 0.873 V vs. RHE.

  8. Nanosheet Supported Single-Metal Atom Bifunctional Catalyst for Overall Water Splitting.

    Ling, Chongyi; Shi, Li; Ouyang, Yixin; Zeng, Xiao Cheng; Wang, Jinlan

    2017-08-09

    Nanosheet supported single-atom catalysts (SACs) can make full use of metal atoms and yet entail high selectivity and activity, and bifunctional catalysts can enable higher performance while lowering the cost than two separate unifunctional catalysts. Supported single-atom bifunctional catalysts are therefore of great economic interest and scientific importance. Here, on the basis of first-principles computations, we report a design of the first single-atom bifunctional eletrocatalyst, namely, isolated nickel atom supported on β 12 boron monolayer (Ni 1 /β 12 -BM), to achieve overall water splitting. This nanosheet supported SAC exhibits remarkable electrocatalytic performance with the computed overpotential for oxygen/hydrogen evolution reaction being just 0.40/0.06 V. The ab initio molecular dynamics simulation shows that the SAC can survive up to 800 K elevated temperature, while enacting a high energy barrier of 1.68 eV to prevent isolated Ni atoms from clustering. A viable experimental route for the synthesis of Ni 1 /β 12 -BM SAC is demonstrated from computer simulation. The desired nanosheet supported single-atom bifunctional catalysts not only show great potential for achieving overall water splitting but also offer cost-effective opportunities for advancing clean energy technology.

  9. Recovery of Platinum Group Metals from Spent Catalysts Using Iron Chloride Vapor Treatment

    Taninouchi, Yu-ki; Okabe, Toru H.

    2018-05-01

    The recovery of platinum group metals (PGMs) from spent automobile catalysts is a difficult process because of their relatively low contents in the scrap. In this study, to improve the efficiency of the existing recycling techniques, a novel physical concentration method involving treatment with FeCl2 vapor has been examined. The reactions occurring between typical catalyst components and FeCl2 vapor are discussed from the thermodynamic point of view, and the validity of the proposed technique was experimentally verified. The obtained results indicate that the vapor treatment at around 1200 K (927 °C) can effectively alloy PGMs (Pt, Pd, and Rh) with Fe, resulting in the formation of a ferromagnetic alloy. It was also confirmed that cordierite and alumina (the major catalyst components) remained unreacted after the vapor treatment, while ceria species were converted into oxychlorides. The samples simulating the automobile catalyst were also subjected to magnetic separation after the treatment with FeCl2 vapor; as a result, PGMs were successfully extracted and concentrated in the form of a magnetic powder. Thus, the FeCl2 vapor treatment followed by magnetic separation can be utilized for recovering PGMs directly from spent catalysts as an effective pretreatment for the currently used recycling methods.

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

    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.

  11. Mono-, bi-, and tri-metallic Ni-based catalysts for the catalytic hydrotreatment of pyrolysis liquids

    Yin, Wang; Venderbosch, Robbie H.; He, Songbo; Bykova, Maria V.; Khromova, Sofia A.; Yakovlev, Vadim A.; Heeres, Hero J.

    Catalytic hydrotreatment is a promising technology to convert pyrolysis liquids into intermediates with improved properties. Here, we report a catalyst screening study on the catalytic hydrotreatment of pyrolysis liquids using bi- and tri-metallic nickel-based catalysts in a batch autoclave (initial

  12. Evaluation of functionalized silica's for the adsorptive recovery of homogeneous catalysts through interaction with the metal centre

    Djekic, T.; Ham, van der A.G.J.; Haan, de A.B.

    2007-01-01

    The goal of this paper is the evaluation of functionalized silica's for the recovery of homogeneous catalysts by adsorption via its metal centre. As model catalysts, we selected bis(triphenylphosphine)cobalt(II)dichloride (CoCl2(PPh3)2), bis(triphenylphosphine)palladium(II)dichloride (PdCl2(PPh3)2)

  13. Evaluation of functionalized silica¿s for the adsorptive recovery of homogenous catalysts through interaction with the metal centre

    Djekic, T.; van der Ham, Aloysius G.J.; de Haan, A.B.

    2007-01-01

    The goal of this paper is the evaluation of functionalized silica's for the recovery of homogeneous catalysts by adsorption via its metal centre. As model catalysts, we selected bis(triphenylphosphine)cobalt(II)dichloride (CoCl2(PPh3)2), bis(triphenylphosphine)palladium(II)dichloride (PdCl2(PPh3)2)

  14. KF-loaded mesoporous Mg-Fe bi-metal oxides: high performance transesterification catalysts for biodiesel production.

    Tao, Guiju; Hua, Zile; Gao, Zhe; Zhu, Yan; Zhu, Yan; Chen, Yu; Shu, Zhu; Zhang, Lingxia; Shi, Jianlin

    2013-09-21

    Using newly developed mesoporous Mg-Fe bi-metal oxides as supports, a novel kind of high performance transesterification catalysts for biodiesel production has been synthesized. More importantly, the impregnation solvent was for the first time found to substantially affect the structures and catalytic performances of the resultant transesterification catalysts.

  15. Biogenic metallic nanoparticles as catalyst for bioelectricity production: A novel approach in microbial fuel cells

    Saravanakumar, Kandasamy, E-mail: saravana732@gmail.com [School of Agriculture and Biology, Shanghai Jiao Tong University, Shanghai (China); State Key Laboratory of Microbial Metabolism, Shanghai Jiao Tong University, Shanghai (China); Key Laboratory of Urban Agriculture (South), Ministry of Agriculture, Shanghai (China); MubarakAli, Davoodbasha [Microbial Genetic Engineering Laboratory, Division of Bioengineering, College of Life Science and Bioengineering, Incheon National University, Songdo 406772, Incheon (Korea, Republic of); Department of Microbiology, School of Lifesciences, Bharathidasan University, Tiruchirappalli 620024 (India); Kathiresan, Kandasamy [Centre of Advanced Study in Marine Biology, Faculty of Marine Sciences, Annamalai University, Parangipettai 608 502, Tamil Nadu (India); Thajuddin, Nooruddin [Department of Microbiology, School of Lifesciences, Bharathidasan University, Tiruchirappalli 620024 (India); Department of Botany and Microbiology, College of Science, King Saud University, Riyadh 11451 (Saudi Arabia); Alharbi, Naiyf S. [Department of Botany and Microbiology, College of Science, King Saud University, Riyadh 11451 (Saudi Arabia); Chen, Jie, E-mail: jiechen59@sjtu.edu.cn [School of Agriculture and Biology, Shanghai Jiao Tong University, Shanghai (China); State Key Laboratory of Microbial Metabolism, Shanghai Jiao Tong University, Shanghai (China); Key Laboratory of Urban Agriculture (South), Ministry of Agriculture, Shanghai (China)

    2016-01-15

    Highlights: • Trichoderma sp., showed an abilities to synthesis of AgNPs and AuNPs with an excellent stability. • AuNPs significantly enhanced the bioelectricity production by MFC of anaerobic fermentation as catalyst. • Maximum bioelectricity production was optimized and obtained the voltage of 432.80 mA using RSM. - Abstract: The present work aimed to use the biogenic metallic nanoparticles as catalyst for bioelectricity production in microbial fuel cell (MFC) approach under anaerobic condition. Silver and gold nanoparticles (AuNPs) were synthesized using Trichoderma sp. Particle size and cystallinity were measured by X-ray diffraction revealed the crystalline structure with average size of 36.17 nm. Electron microscopic studies showed spherical shaped silver nanoparticles (AgNPs) and cubical shaped AuNPs with size ranges from 50 to 150 nm. The concentration of biogenic metallic nanoparticles as catalyst for enhanced bioelectricity generations and estimated by response surface methodology (RSM) and found at the greatest of 342.80 mA under optimized conditions are time interval, temperature, nanoparticles used as 63 h, 28 ± 2.0 °C, 22.54 mg l{sup −1} (AgNPs) and 25.62 mg l{sup −1} (AuNPs) in a batch reactor. AuNPs acted as an excellent catalyst to enhance the bioelectricity production. This novel technique could be used for eco-friendly, economically feasible and facile electricity production.

  16. Biogenic metallic nanoparticles as catalyst for bioelectricity production: A novel approach in microbial fuel cells

    Saravanakumar, Kandasamy; MubarakAli, Davoodbasha; Kathiresan, Kandasamy; Thajuddin, Nooruddin; Alharbi, Naiyf S.; Chen, Jie

    2016-01-01

    Highlights: • Trichoderma sp., showed an abilities to synthesis of AgNPs and AuNPs with an excellent stability. • AuNPs significantly enhanced the bioelectricity production by MFC of anaerobic fermentation as catalyst. • Maximum bioelectricity production was optimized and obtained the voltage of 432.80 mA using RSM. - Abstract: The present work aimed to use the biogenic metallic nanoparticles as catalyst for bioelectricity production in microbial fuel cell (MFC) approach under anaerobic condition. Silver and gold nanoparticles (AuNPs) were synthesized using Trichoderma sp. Particle size and cystallinity were measured by X-ray diffraction revealed the crystalline structure with average size of 36.17 nm. Electron microscopic studies showed spherical shaped silver nanoparticles (AgNPs) and cubical shaped AuNPs with size ranges from 50 to 150 nm. The concentration of biogenic metallic nanoparticles as catalyst for enhanced bioelectricity generations and estimated by response surface methodology (RSM) and found at the greatest of 342.80 mA under optimized conditions are time interval, temperature, nanoparticles used as 63 h, 28 ± 2.0 °C, 22.54 mg l"−"1 (AgNPs) and 25.62 mg l"−"1 (AuNPs) in a batch reactor. AuNPs acted as an excellent catalyst to enhance the bioelectricity production. This novel technique could be used for eco-friendly, economically feasible and facile electricity production.

  17. Rapid Microwave-Assisted Copper-Catalyzed Nitration of Aromatic Halides with Nitrite Salts

    Paik, Seung Uk; Jung, Myoung Geun

    2012-01-01

    A rapid and efficient copper-catalyzed nitration of aryl halides has been established under microwave irradiation. The catalytic systems were found to be the most effective with 4-substituted aryl iodides leading to nearly complete conversions. Nitration of aromatic compounds is one of the important industrial processes as underlying intermediates in the manufacture of a wide range of chemicals such as dyes, pharmaceuticals, agrochemicals and explosives. General methods for the nitration of aromatic compounds utilize strongly acidic conditions employing nitric acid or a mixture of nitric and sulfuric acids, sometimes leading to problems with poor regioselectivity, overnitration, oxidized byproducts and excess acid waste in many cases of functionalized aromatic compounds. Several other nitrating agents or methods avoiding harsh reaction conditions have been explored using metal nitrates, nitrite salts, and ionic liquid-mediated or microwave-assisted nitrations. Recently, copper or palladium compounds have been successfully used as efficient catalysts for the arylation of amines with aryl halides under mild conditions

  18. Rapid Microwave-Assisted Copper-Catalyzed Nitration of Aromatic Halides with Nitrite Salts

    Paik, Seung Uk; Jung, Myoung Geun [Keimyung University, Daegu (Korea, Republic of)

    2012-02-15

    A rapid and efficient copper-catalyzed nitration of aryl halides has been established under microwave irradiation. The catalytic systems were found to be the most effective with 4-substituted aryl iodides leading to nearly complete conversions. Nitration of aromatic compounds is one of the important industrial processes as underlying intermediates in the manufacture of a wide range of chemicals such as dyes, pharmaceuticals, agrochemicals and explosives. General methods for the nitration of aromatic compounds utilize strongly acidic conditions employing nitric acid or a mixture of nitric and sulfuric acids, sometimes leading to problems with poor regioselectivity, overnitration, oxidized byproducts and excess acid waste in many cases of functionalized aromatic compounds. Several other nitrating agents or methods avoiding harsh reaction conditions have been explored using metal nitrates, nitrite salts, and ionic liquid-mediated or microwave-assisted nitrations. Recently, copper or palladium compounds have been successfully used as efficient catalysts for the arylation of amines with aryl halides under mild conditions.

  19. Growth of carbon nanocone arrays on a metal catalyst: The effect of carbon flux ionization

    Levchenko, I.; Khachan, J.; Vladimirov, S. V.; Ostrikov, K.

    2008-01-01

    The growth of carbon nanocone arrays on metal catalyst particles by deposition from a low-temperature plasma is studied by multiscale Monte Carlo/surface diffusion numerical simulation. It is demonstrated that the variation in the degree of ionization of the carbon flux provides an effective control of the growth kinetics of the carbon nanocones, and leads to the formation of more uniform arrays of nanostructures. In the case of zero degree of ionization (neutral gas process), a width of the distribution of nanocone heights reaches 360 nm with the nanocone mean height of 150 nm. When the carbon flux of 75% ionization is used, the width of the distribution of nanocone heights decreases to 100 nm, i.e., by a factor of 3.6. A higher degree of ionization leads to a better uniformity of the metal catalyst saturation and the nanocone growth, thus contributing to the formation of more height-uniform arrays of carbon nanostructures.

  20. Transition metal sulfide promoted molybdenum or tungsten sulfide catalysts and their uses for hydroprocessing

    Jacobson, A.J.; Chianelli, R.R.; Pecoraro, T.A.

    1987-01-01

    A process is described for hydrorefining a hydrocarbon feed which comprises contacting the feed at a temperature of at least about 150 0 C and in the presence of hydrogen with a catalyst obtained by heating one or more precursor salts at elevated temperature of at least about 150 0 C, in the presence of sulfur or one or more sulfur-bearing compounds and under oxygen-free conditions for a time sufficient to form the catalyst. The precursor salt contains a tetrathiometallate anion of Mo, W or mixture thereof and a cation comprising one or more divalent promoter metals which are chelated by at least one neutral, nitrogen-containing polydentate ligand. The divalent promoter metal is selected from the group consisting of Ni, Co, Zn, Cu and mixture thereof. The contacting occurs for a time sufficient to hydrorefine at least a portion of the feed

  1. Atomic Resolution Imaging of Nanoscale Structural Ordering in a Complex Metal Oxide Catalyst

    Zhu, Yihan

    2012-08-28

    The determination of the atomic structure of a functional material is crucial to understanding its "structure-to-property" relationship (e.g., the active sites in a catalyst), which is however challenging if the structure possesses complex inhomogeneities. Here, we report an atomic structure study of an important MoVTeO complex metal oxide catalyst that is potentially useful for the industrially relevant propane-based BP/SOHIO process. We combined aberration-corrected scanning transmission electron microscopy with synchrotron powder X-ray crystallography to explore the structure at both nanoscopic and macroscopic scales. At the nanoscopic scale, this material exhibits structural and compositional order within nanosized "domains", while the domains show disordered distribution at the macroscopic scale. We proposed that the intradomain compositional ordering and the interdomain electric dipolar interaction synergistically induce the displacement of Te atoms in the Mo-V-O channels, which determines the geometry of the multifunctional metal oxo-active sites.

  2. Methane oxidation over noble metal catalysts as related to controlling natural gas vehicle exhaust emissions

    Oh, S.H.; Mitchell, P.J.; Siewert, R.M.

    1992-01-01

    Natural gas has considerable potential as an alternative automotive fuel. This paper reports on methane, the principal hydrocarbon species in natural-gas engine exhaust, which has extremely low photochemical reactivity but is a powerful greenhouse gas. Therefore, exhaust emissions of unburned methane from natural-gas vehicles are of particular concern. This laboratory reactor study evaluates noble metal catalysts for their potential in the catalytic removal of methane from natural-gas vehicle exhaust. Temperature run-up experiments show that the methane oxidation activity decreases in the order Pd/Al 2 O 3 > Rh/Al 2 O 3 > Pt/Al 2 O 3 . Also, for all the noble metal catalysts studied, methane conversion can be maximized by controlling the O 2 concentration of the feedstream at a point somewhat rich (reducing) of stoichiometry

  3. Methane coupling reaction in an oxy-steam stream through an OH radical pathway by using supported alkali metal catalysts

    Liang, Yin; Li, Zhikao; Nourdine, Mohamed; Shahid, Salman; Takanabe, Kazuhiro

    2014-01-01

    A universal reaction mechanism involved in the oxidative coupling of methane (OCM) is demonstrated under oxy-steam conditions using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH

  4. Nature of the activates places of the acid solid catalysts of the sulphated metallic oxides type

    Gomez, Miguel A; Fontalvo Javier

    1998-01-01

    In this revision the state of the knowledge is presented with respect to the understanding of the nature of the active places for the strongly acid solid catalysts of the type sulphated metallic oxides. The results presented by means of models are based on the characterization of the properties physicochemical carried out by means of technical as XPS, to GO, NMR etc., and the evaluation of the catalytic activity in different applications

  5. Industrial biotemplating saves precious metals in catalysts; Industrielles Biotemplating zur Einsparung von Edelmetallen in Katalysatoren

    Hofinger, Juergen; Roos, Steffen; Zirpel, Kevin; Wengrzik, Stefanie [Namos GmbH, Dresden (Germany)

    2009-07-15

    Modern molecular biology provides the tools to design surfaces on the nanometer scale. This opens the way to a breakthrough innovation, which can optimize many industrial processes. In a proof-of-concept study, scientists were able to successfully reduce the amount of precious metals required for a diesel oxidation catalyst. This was the first successful application, and right now the biotemplating technology awaits further development for other applications involving catalytic processes or specifically designed surfaces for industrial processes. (orig.)

  6. Suitable alkaline for graphene peeling grown on metallic catalysts using chemical vapor deposition

    Karamat, S.; Sonuşen, S.; Çelik, Ü.; Uysallı, Y.; Oral, A.

    2016-04-01

    In chemical vapor deposition, the higher growth temperature roughens the surface of the metal catalyst and a delicate method is necessary for the transfer of graphene from metal catalyst to the desired substrates. In this work, we grow graphene on Pt and Cu foil via ambient pressure chemical vapor deposition (AP-CVD) method and further alkaline water electrolysis was used to peel off graphene from the metallic catalyst. We used different electrolytes i.e., sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH) and barium hydroxide Ba(OH)2 for electrolysis, hydrogen bubbles evolved at the Pt cathode (graphene/Pt/PMMA stack) and as a result graphene layer peeled off from the substrate without damage. The peeling time for KOH and LiOH was ∼6 min and for NaOH and Ba(OH)2 it was ∼15 min. KOH and LiOH peeled off graphene very efficiently as compared to NaOH and Ba(OH)2 from the Pt electrode. In case of copper, the peeling time is ∼3-5 min. Different characterizations like optical microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy were done to analyze the as grown and transferred graphene samples.

  7. Oxidation of ethoxylated fatty alcohols to alkylpolyglycol carboxylic acids using noble metals as catalysts

    Sagredos, Angelos

    2009-09-01

    Full Text Available The conversion of ethoxylated fatty alcohols to the corresponding carboxylic acids through dehydrogenation/ oxidation using noble-metal catalysts has been studied. Ethoxylated primary aliphatic alcohols, ethoxylated random secondary aliphatic alcohols and ethoxylated alkylphenols have been converted to the corresponding acids in the presence of a base. The noble metal catalysts Palladium and Platinum were used without significant degradation of the ethoxyl chain in yields that exceeded 90%. On the other hand, the catalysts Rhodium and Ruthenium gave yields of about 80% and 60% respectively.La conversión de alcoholes grasos etoxilados a los correspondientes ácidos carboxílicos por deshidrogenación/ oxidación con metales nobles como catalizador ha sido estudiada. Alcoholes primarios alifáticos etoxilados, alcoholes alifáticos secundarios etoxilados al azar y alquilfenoles etoxilados han sido convertidos a los correspondientes ácidos en presencia de base. Los catalizadores paladio y platino fueron usados sin degradación significativa de las cadenas etoxiladas con un rendimiento que excedió del 90%. Por otra parte catalizadores de rodio y rutenio produjeron rendimientos del 80 y 60%, respectivamente.

  8. Revisiting the electrochemical oxidation of ammonia on carbon-supported metal nanoparticle catalysts

    Li, Zhe-Fei; Wang, Yuxuan; Botte, Gerardine G.

    2017-01-01

    Highlights: • A procedure to pretreat electrocatalysts to study the ammonia oxidation is provided. • N ads and O/OH ads were identified as the major deactivation species that prevent ammonia oxidatoin. • The electrocatalytic activity, thermodynamics, and possible deactivation mechanisms for ammonia oxidation were elucidated. • The onset potential for ammonia oxidation is related to the hydrogen binding energy of the catalyst. • Ammonia electro-oxidation involves a complex decoupled electron and proton transfer process. - Abstract: The ammonia electro-oxidation reaction (AOR) has been studied due to its promising applications in ammonia electrolysis, wastewater remediation, direct ammonia fuel cells, and sensors. However, it is difficult to compare and analyze the reported electrocatalytic activity of AOR reliably, likely due to the variation in catalyst synthesis, electrode composition, electrode morphology, and testing protocol. In this paper, the electro-oxidation of ammonia on different carbon-supported precious metal nanoparticle catalysts was revisited. The effect of experimental conditions, electrochemical test parameters, electrocatalytic activity, thermodynamics, and possible deactivation mechanism of the catalysts were investigated. Pt/C catalyst possesses the highest electrocatalytic activity, while Ir/C and Rh/C show lower overpotential. The onset potential of the AOR is related to the hydrogen binding energy of the catalyst. N ads is one major cause of deactivation accompanied with the formation of surface O/OH ads at high potentials. The coulombic efficiency of N ads formation on Pt is about 1% initially and gradually decreases with reaction time. Increase in ammonia concentration leads to increase in current density, while increase in hydroxyl ions concentration can enhance the current density and reduce the overpotential simultaneously. The slopes of AOR onset potential and hydrogen adsorption/desorption potential of Pt/C as a function of p

  9. Transesterification of jatropha oil with methanol over Mg–Zn mixed metal oxide catalysts

    Lee, H.V.; Taufiq-Yap, Y.H.; Hussein, M.Z.; Yunus, R.

    2013-01-01

    A design was developed for the transesterification reaction of non-edible Jatropha Curcas oil using a heterogeneous catalysis system to replace the use of a homogeneous catalytic reaction. Investigations were conducted on solid MgO–ZnO mixed metal oxide catalyst bases with different atomic ratios of magnesium to zinc (Mg/Zn). These catalysts were characterized by BET (Brunauer–Emmer–Teller) surface area analysis, X-ray Diffraction (XRD), and Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray Spectroscopy (EDS), and the alkalinity of the catalysts was studied by Temperature Programmed Desorption of carbon dioxide (TPD-CO 2 ). The physicochemical properties of the MgO–ZnO binary system were superior to those of the individual bulk oxides of MgO and ZnO. In addition, the formation of a binary system between MgO and ZnO established an effective method for transesterification processes. In this study, the effects of stoichiometric composition and surface characteristics on the transesterification activity of MgO–ZnO were investigated. The catalysts exhibited high catalytic activity (∼80%) with reliable reusability for biodiesel production. -- Highlights: ► Transesterification reaction of non-edible jatropha oil using solid base catalyst. ► MgO–ZnO binary system showed superior effect than the individual MgO and ZnO. ► More than 80% of FAME yield was achieved under mild condition. ► MgO–ZnO catalyst showed reliable reusability throughout 5 runs. ► Fuel properties of prepared biodiesel were complying with the biodiesel standards.

  10. Silica Supported Platinum Catalysts for Total Oxidation of the Polyaromatic Hydrocarbon Naphthalene: An Investigation of Metal Loading and Calcination Temperature

    David R. Sellick

    2015-04-01

    Full Text Available A range of catalysts comprising of platinum supported on silica, prepared by an impregnation method, have been studied for the total oxidation of naphthalene, which is a representative Polycyclic Aromatic Hydrocarbon. The influence of platinum loading and calcination temperature on oxidation activity was evaluated. Increasing the platinum loading up to 2.5 wt.% increased the catalyst activity, whilst a 5.0 wt.% catalyst was slightly less active. The catalyst containing the optimum 2.5 wt.% loading was most active after calcination in air at 550 °C. Characterisation by carbon monoxide chemisorption and X-ray photoelectron spectroscopy showed that low platinum dispersion to form large platinum particles, in combination with platinum in metallic and oxidised states was important for high catalyst activity. Catalyst performance improved after initial use in repeat cycles, whilst there was slight deactivation after prolonged time-on-stream.

  11. The gas phase emitter effect of lanthanum within ceramic metal halide lamps and its dependence on the La vapor pressure and operating frequency

    Ruhrmann, C.; Hoebing, T.; Bergner, A.; Groeger, S.; Awakowicz, P.; Mentel, J. [Electrical Engineering and Plasma Technology, Ruhr University Bochum, D-44780 Bochum (Germany); Denissen, C.; Suijker, J. [Philips Lighting, Category Professional Lamps, P.O. Box 80020, NL-5600JM Eindhoven (Netherlands)

    2015-08-07

    The gas phase emitter effect increases the lamp lifetime by lowering the work function and, with it, the temperature of the tungsten electrodes of metal halide lamps especially for lamps in ceramic vessels due to their high rare earth pressures. It is generated by a monolayer on the electrode surface of electropositive atoms of certain emitter elements, which are inserted into the lamp bulb by metal iodide salts. They are vaporized, dissociated, ionized, and deposited by an emitter ion current onto the electrode surface within the cathodic phase of lamp operation with a switched-dc or ac-current. The gas phase emitter effect of La and the influence of Na on the emitter effect of La are studied by spatially and phase-resolved pyrometric measurements of the electrode tip temperature, La atom, and ion densities by optical emission spectroscopy as well as optical broadband absorption spectroscopy and arc attachment images by short time photography. An addition of Na to the lamp filling increases the La vapor pressure within the lamp considerably, resulting in an improved gas phase emitter effect of La. Furthermore, the La vapor pressure is raised by a heating of the cold spot. In this way, conditions depending on the La vapor pressure and operating frequency are identified, at which the temperature of the electrodes becomes a minimum.

  12. Doped Graphene as Non-Metallic Catalyst for Fuel Cells

    Adriana MARINOIU

    2017-08-01

    Full Text Available Aiming a commercial development of proton exchange membrane fuel cells (PEMFC, a low cost, sustainable and high performance electrocatalyst for oxygen reduction reaction (ORR with capability to replace/reduce rare metals, are high desirable. In this paper, we present a class of doped graphene, namely iodinated graphene with highly ORR electrochemical performances, synthesized by using the electrophilic substitution method. The prepared samples were characterized by different techniques, including Scanning Electron Microscopy SEM, X-ray photoelectron spectroscopy XPS, Raman spectroscopy, surface area measurement by BET method, that revealed the structure and morphology. The most highly iodinated graphene was tested in a single cell by measuring the cyclic voltammetry. The electrochemical performances were evaluated and compared with a typical PEMFC configuration, when a single cathodic peak at 0.2 V with a current density of – 3.67 mA cm-2 for the Pt/C electrode was obtained. The best electrochemical performances in terms of electrochemical active area, was obtained for a new concept of cathode composed from Pt/C – iodine doped graphene, when a well-defined peak centred at 0.23 V with a current density of approx. – 9.1 mA cm-2 was obtained, indicating a high catalytic activity for ORR.DOI: http://dx.doi.org/10.5755/j01.ms.23.2.16216

  13. Vapor phase carbonylation of dimethyl ether and methyl acetate with supported transition metal catalysts

    Shikada, T.; Fujimoto, K.; Tominaga, H.O.

    1986-01-01

    The synthesis of acetic acid (AcOH) from methanol (MeOH) and carbon monoxide has been performed industrially in the liquid phase using a rhodium complex catalyst and an iodide promoter. The selectivity to AcOH is more than 99% under mild conditions (175 0 C, 28 atm). The homogeneous rhodium catalyst has been also effective for the synthesis of acetic anhydride (Ac 2 O) by carbonylation of dimethyl ether (DME) or methyl acetate (AcOMe). However, rhodium is one of the most expensive metals and its proved reserves are quite limited. It is highly desired, therefore, to develop a new catalyst as a substitute for rhodium. The authors have already reported that nickel supported on active carbon exhibits an excellent activity for the vapor phase carbonylation of MeOh in the presence of iodide promoter and under moderately pressurized conditions. In addition, corrosive attack on reactors by iodide compounds is expected to be negligible in the vapor phase system. In the present work, vapor phase carbonylation of DME and AcOMe on nickel-active carbon (Ni/A.C.) and molybdenum-active carbon (Mo/A.C.) catalysts was studied

  14. NMR evidence of metal-support interaction in syngas conversion catalyst Co-TiO2

    Murty, A.N.; Seamster, M.; Thorpe, A.N.; Obermyer, R.T.; Rao, V.U.S.

    1990-01-01

    To examine the relation between catalytic and magnetic properties, the zero-field NMR spectra and hysteresis loops of cobalt supported on silica, alumina, magnesia, titania, and ZSM-5 with and without the promoter thoria were investigated. Cobalt was incorporated on the support by simple physical admixture of precipitated cobalt and support, and by aqueous impregnation technique. Our studies indicate that the particle sizes are consistently lower in the presence of thoria. Of all the catalysts examined, the Co/Th/TiO 2 catalyst exhibits a high saturation magnetization value---about 20% higher than pure cobalt. In addition, the NMR spectrum of the aqueous impregnation Co/TiO 2 catalyst is distinctly different from the rest. All the NMR lines are shifted to a higher frequency by about 4 MHz. These two features---enhancement of the magnetic moment of cobalt atoms and increases in the hyperfine field at the Co nucleus---clearly indicate that there occurs strong metal-support interaction between cobalt and titania support. The higher hydrocarbon yields observed by the earlier investigators with Co/TiO 2 catalysts might be related to this phenomenon

  15. Catalytic incineration of CO and VOC emissions over supported metal oxide catalysts

    Larsson, Per-Olof

    1999-05-01

    Catalytic incineration is one of the methods to reduce the emissions of CO and VOCs. Low operation temperature and low catalyst cost are essential parameters for catalytic incinerators. Pt/Al{sub 2}O{sub 3} catalysts are frequently used today, but the cheaper metal oxide catalysts can be very competitive if comparable overall activity is obtained. This thesis concerns how it is possible to decrease the operation temperature for supported metal oxide catalysts by using different supports, active metal oxides and additives. In the thesis it is demonstrated that different copper oxide based catalysts have the best activity and durability for complete oxidation among several tested metal oxide catalysts. CuO{sub x} supported on TiO{sub 2} and Al{sub 2}O{sub 3} showed increased activity with the CuO{sub x} loading up to the threshold coverage for formation of crystalline CuO particles, which is 12 {mu}mol/m{sup 2} on TiO{sub 2} and 6 {mu}mol/m{sup 2} on Al{sub 2}O{sub 3}. Up to the threshold coverage for CuO formation, well dispersed copper oxide species were formed on TiO{sub 2}, and a dispersed copper aluminate surface phase was formed on Al{sub 2}O{sub 3}. Durability tests showed accelerated sintering of TiO{sub 2} by copper, but stabilisation was possible by modification of the TiO{sub 2} with CeO{sub x} before the deposition of CuO{sub x}. The stabilisation was obtained by formation of a Ce-O-Ti surface phase. Addition of CeO{sub x} also enhanced the activity of the copper oxide species thanks to favourable interaction between the active copper oxide species and the CeO{sub x} on the support, which could be seen as increased reducibility in TPR experiments. The increased activity and reducibility was also observed for CuO{sub x} supported on ceria modified Al{sub 2}O{sub 3}. In this regard it was shown that CuO{sub x} deposited on CeO{sub 2}(001) surfaces was substantially more active for CO oxidation than copper oxide deposited on CeO{sub 2}(111) Surfaces. This

  16. Bio-oil Stabilization by Hydrogenation over Reduced Metal Catalysts at Low Temperatures

    Wang, Huamin; Lee, Suh-Jane; Olarte, Mariefel V.; Zacher, Alan H.

    2016-08-30

    Biomass fast pyrolysis integrated with bio-oil upgrading represents a very attractive approach for converting biomass to hydrocarbon transportation fuels. However, the thermal and chemical instability of bio-oils presents significant problems when they are being upgraded, and development of effective approaches for stabilizing bio-oils is critical to the success of the technology. Catalytic hydrogenation to remove reactive species in bio-oil has been considered as one of the most efficient ways to stabilize bio-oil. This paper provides a fundamental understanding of hydrogenation of actual bio-oils over a Ru/TiO2 catalyst under conditions relevant to practical bio-oil hydrotreating processes. Bio-oil feed stocks, bio-oils hydrogenated to different extents, and catalysts have been characterized to provide insights into the chemical and physical properties of these samples and to understand the correlation of the properties with the composition of the bio-oil and catalysts. The results indicated hydrogenation of various components of the bio-oil, including sugars, aldehydes, ketones, alkenes, aromatics, and carboxylic acids, over the Ru/TiO2 catalyst and 120 to 160oC. Hydrogenation of these species significantly changed the chemical and physical properties of the bio-oil and overall improved its thermal stability, especially by reducing the carbonyl content, which represented the content of the most reactive species (i.e., sugar, aldehydes, and ketones). The change of content of each component in response to increasing hydrogen additions suggests the following bio-oil hydrogenation reaction sequence: sugar conversion to sugar alcohols, followed by ketone and aldehyde conversion to alcohols, followed by alkene and aromatic hydrogenation, and then followed by carboxylic acid hydrogenation to alcohols. Hydrogenation of bio-oil samples with different sulfur contents or inorganic material contents suggested that sulfur poisoning of the reduced Ru metal catalysts was

  17. Highly Active Non-PGM Catalysts Prepared from Metal Organic Frameworks

    Heather M. Barkholtz

    2015-06-01

    Full Text Available Finding inexpensive alternatives to platinum group metals (PGMs is essential for reducing the cost of proton exchange membrane fuel cells (PEMFCs. Numerous materials have been investigated as potential replacements of Pt, of which the transition metal and nitrogen-doped carbon composites (TM/Nx/C prepared from iron doped zeolitic imidazolate frameworks (ZIFs are among the most active ones in catalyzing the oxygen reduction reaction based on recent studies. In this report, we demonstrate that the catalytic activity of ZIF-based TM/Nx/C composites can be substantially improved through optimization of synthesis and post-treatment processing conditions. Ultimately, oxygen reduction reaction (ORR electrocatalytic activity must be demonstrated in membrane-electrode assemblies (MEAs of fuel cells. The process of preparing MEAs using ZIF-based non-PGM electrocatalysts involves many additional factors which may influence the overall catalytic activity at the fuel cell level. Evaluation of parameters such as catalyst loading and perfluorosulfonic acid ionomer to catalyst ratio were optimized. Our overall efforts to optimize both the catalyst and MEA construction process have yielded impressive ORR activity when tested in a fuel cell system.

  18. Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

    Jernigan, Glenn Geoffrey [California Univ., Berkeley, CA (United States). Dept. of Chemistry

    1994-10-01

    Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu2O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu2O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu2O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N2 and CO2. At the end of each reaction, the catalyst was found to be Cu2O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

  19. Hydrogen-water deuterium exchange over metal oxide promoted nickel catalysts

    Sagert, N H; Shaw-Wood, P E; Pouteau, R M.L. [Atomic Energy of Canada Ltd., Pinawa, Manitoba. Whiteshell Nuclear Research Establishment

    1975-11-01

    Specific rates have been measured for hydrogen-water deuterium isotope exchange over unsupported nickel promoted with about 20% of various metal oxides. The oxides used were Cr/sub 2/O/sub 3/, MoO/sub 2/, MnO, WO/sub 2/-WO/sub 3/, and UO/sub 2/. Nickel surface areas, which are required to measure the specific rates, were determined by hydrogen chemisorption. Specific rates were measured as a function of temperature in the range 353 to 573 K and as a function of the partial pressure of hydrogen and water over a 10-fold range of partial pressure. The molybdenum and tungsten oxides gave the highest specific rates, and manganese and uranium oxides the lowest. Chromium oxide was intermediate, although it gave the highest rate per gram of catalyst. The orders with respect to hydrogen and water over molybdenum oxide and tungsten oxide promoted nickel were consistent with a mechanism in which nickel oxide is formed from the reaction of water with the catalyst, and then is reduced by hydrogen. Over manganese and uranium oxide promoted catalysts, these orders are consistent with a mechanism in which adsorbed water exchanges with chemisorbed hydrogen atoms on the nickel surface. Chromium oxide is intermediate. It was noted that those oxides which favored the nickel oxide route had electronic work functions closest to those of metallic nickel and nickel oxide.

  20. Experimental observations on the competing effect of tetrahydrofuran and an electrolyte and the strength of hydrate inhibition among metal halides in mixed CO{sub 2} hydrate equilibria

    Sabil, Khalik M., E-mail: khalik_msabil@petronas.com.m [Delft University of Technology, Laboratory of Process Equipment, Mechanical, Maritime and Materials Engineering, Leeghwaterstraat 44, 2628 CA Delft (Netherlands); Universiti Teknologi PETRONAS, Chemical Engineering Programme, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Roman, Vicente R.; Witkamp, Geert-Jan [Delft University of Technology, Laboratory of Process Equipment, Mechanical, Maritime and Materials Engineering, Leeghwaterstraat 44, 2628 CA Delft (Netherlands); Peters, Cor J., E-mail: C.J.Peters@tudelft.n [Delft University of Technology, Laboratory of Process Equipment, Mechanical, Maritime and Materials Engineering, Leeghwaterstraat 44, 2628 CA Delft (Netherlands); Petroleum Institute, Chemical Engineering Program, Bu Hasa Building, Room 2207A, P.O. Box 2533, Abu Dhabi (United Arab Emirates)

    2010-03-15

    In the present work, experimental data on the equilibrium conditions of mixed CO{sub 2} and THF hydrates in aqueous electrolyte solutions are reported. Seven different electrolytes (metal halides) were used in this work namely sodium chloride (NaCl), calcium chloride (CaCl{sub 2}), magnesium chloride (MgCl{sub 2}), potassium bromide (KBr), sodium fluoride (NaF), potassium chloride (KCl), and sodium bromide (NaBr). All equilibrium data were measured by using Cailletet apparatus. Throughout this work, the overall concentration of CO{sub 2} and THF were kept constant at (0.04 and 0.05) mol fraction, respectively, while the concentration of electrolytes were varied. The experimental temperature ranged from (275 to 305) K and pressure up 7.10 MPa had been applied. From the experimental results, it is concluded that THF, which is soluble in water is able to suppress the salt inhibiting effect in the range studied. In all quaternary systems studied, a four-phase hydrate equilibrium line was observed where hydrate (H), liquid water (L{sub W}), liquid organic (L{sub V}), and vapour (V) exist simultaneously at specific pressure and temperature. The formation of this four-phase equilibrium line is mainly due to a liquid-liquid phase split of (water + THF) mixture when pressurized with CO{sub 2} and the split is enhanced by the salting-out effect of the electrolytes in the quaternary system. The strength of hydrate inhibition effect among the electrolytes was compared. The results shows the hydrate inhibiting effect of the metal halides is increasing in the order NaF < KBr < NaCl < NaBr < CaCl{sub 2} < MgCl{sub 2}. Among the cations studied, the strength of hydrate inhibition increases in the following order: K{sup +} < Na{sup +} < Ca{sup 2+} < Mg{sup 2+}. Meanwhile, the strength of hydrate inhibition among the halogen anion studied decreases in the following order: Br{sup -} > Cl{sup -} > F{sup -}. Based on the results, it is suggested that the probability of formation and

  1. Experimental observations on the competing effect of tetrahydrofuran and an electrolyte and the strength of hydrate inhibition among metal halides in mixed CO2 hydrate equilibria

    Sabil, Khalik M.; Roman, Vicente R.; Witkamp, Geert-Jan; Peters, Cor J.

    2010-01-01

    In the present work, experimental data on the equilibrium conditions of mixed CO 2 and THF hydrates in aqueous electrolyte solutions are reported. Seven different electrolytes (metal halides) were used in this work namely sodium chloride (NaCl), calcium chloride (CaCl 2 ), magnesium chloride (MgCl 2 ), potassium bromide (KBr), sodium fluoride (NaF), potassium chloride (KCl), and sodium bromide (NaBr). All equilibrium data were measured by using Cailletet apparatus. Throughout this work, the overall concentration of CO 2 and THF were kept constant at (0.04 and 0.05) mol fraction, respectively, while the concentration of electrolytes were varied. The experimental temperature ranged from (275 to 305) K and pressure up 7.10 MPa had been applied. From the experimental results, it is concluded that THF, which is soluble in water is able to suppress the salt inhibiting effect in the range studied. In all quaternary systems studied, a four-phase hydrate equilibrium line was observed where hydrate (H), liquid water (L W ), liquid organic (L V ), and vapour (V) exist simultaneously at specific pressure and temperature. The formation of this four-phase equilibrium line is mainly due to a liquid-liquid phase split of (water + THF) mixture when pressurized with CO 2 and the split is enhanced by the salting-out effect of the electrolytes in the quaternary system. The strength of hydrate inhibition effect among the electrolytes was compared. The results shows the hydrate inhibiting effect of the metal halides is increasing in the order NaF 2 2 . Among the cations studied, the strength of hydrate inhibition increases in the following order: K + + 2+ 2+ . Meanwhile, the strength of hydrate inhibition among the halogen anion studied decreases in the following order: Br - > Cl - > F - . Based on the results, it is suggested that the probability of formation and the strength of ionic-hydrogen bond between an ion and water molecule and the effects of this bond on the ambient water

  2. Thermodynamics of Small Alkali Metal Halide Cluster Ions: Comparison of Classical Molecular Simulations with Experiment and Quantum Chemistry

    Vlcek, Lukas [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Uhlik, Filip [Charles Univ., Prague (Czech Republic); Moucka, Filip [Purkinje Univ. (Czech Republic); Nezbeda, Ivo [Purkinje Univ. (Czech Republic); Academy of Sciences of the Czech Republic (ASCR), Prague (Czech Republic); Chialvo, Ariel A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2015-12-16

    We evaluate the ability of selected classical molecular models to describe the thermodynamic and structural aspects of gas-phase hydration of alkali halide ions and the formation of small water clusters. To understand the effect of many-body interactions (polarization) and charge penetration effects on the accuracy of a force field, we perform Monte Carlo simulations with three rigid water models using different functional forms to account for these effects: (i) point charge non-polarizable SPC/E, (ii) Drude point charge polarizable SWM4- DP, and (iii) Drude Gaussian charge polarizable BK3. Model predictions are compared with experimental Gibbs free energies and enthalpies of ion hydration, and with microscopic structural properties obtained from quantum DFT calculations. We find that all three models provide comparable predictions for pure water clusters and cation hydration, but differ significantly in their description of anion hydration. None of the investigated classical force fields can consistently and quantitatively reproduce the experimental gas phase hydration thermodynamics. The outcome of this study highlights the relation between the functional form that describes the effective intermolecular interactions and the accuracy of the resulting ion hydration properties.

  3. Supported palladium nanoparticles synthesized by living plants as a catalyst for Suzuki-Miyaura reactions.

    Helen L Parker

    Full Text Available The metal accumulating ability of plants has previously been used to capture metal contaminants from the environment; however, the full potential of this process is yet to be realized. Herein, the first use of living plants to recover palladium and produce catalytically active palladium nanoparticles is reported. This process eliminates the necessity for nanoparticle extraction from the plant and reduces the number of production steps compared to traditional catalyst palladium on carbon. These heterogeneous plant catalysts have demonstrated high catalytic activity in Suzuki coupling reactions between phenylboronic acid and a range of aryl halides containing iodo-, bromo- and chloro- moieties.

  4. Suitable alkaline for graphene peeling grown on metallic catalysts using chemical vapor deposition

    Karamat, S., E-mail: shumailakaramat@gmail.com [Department of Physics, Middle East Technical University, Ankara 06800 (Turkey); COMSATS Institute of Information Technology, Islamabad 54000 (Pakistan); Sonuşen, S. [Sabancı Üniversitesi (SUNUM), İstanbul 34956 (Turkey); Çelik, Ü. [Nanomagnetics Instruments, Ankara (Turkey); Uysallı, Y. [Department of Physics, Middle East Technical University, Ankara 06800 (Turkey); Oral, A., E-mail: orahmet@metu.edu.tr [Department of Physics, Middle East Technical University, Ankara 06800 (Turkey)

    2016-04-15

    Graphical abstract: - Highlights: • Graphene layers were grown on Pt and Cu foil via ambient pressure chemical vapor deposition method and for the delicate removal of graphene from metal catalysts, electrolysis method was used by using different alkaline (sodium hydroxide, potassium hydroxide, lithium hydroxide and barium hydroxide). • The delamination speed of PMMA/graphene stack was higher during the KOH and LiOH electrolysis as compare to NaOH and Ba(OH){sub 2}. Ba(OH){sub 2} is not advisable because of the residues left on the graphene surface which would further trapped in between graphene and SiO{sub 2}/Si surface after transfer. The average peeling time in case of Pt electrode is ∼6 min for KOH and LiOH and ∼15 min for NaOH and Ba(OH){sub 2}. • Electrolysis method also works for the Cu catalyst. The peeling of graphene was faster in the case of Cu foil due to small size of bubbles which moves faster between the stack and the electrode surface. The average peeling time was ∼3–5 min. • XPS analysis clearly showed that the Pt substrates can be re-used again. Graphene layer was transferred to SiO{sub 2}/Si substrates and to the flexible substrate by using the same peeling method. - Abstract: In chemical vapor deposition, the higher growth temperature roughens the surface of the metal catalyst and a delicate method is necessary for the transfer of graphene from metal catalyst to the desired substrates. In this work, we grow graphene on Pt and Cu foil via ambient pressure chemical vapor deposition (AP-CVD) method and further alkaline water electrolysis was used to peel off graphene from the metallic catalyst. We used different electrolytes i.e., sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH) and barium hydroxide Ba(OH){sub 2} for electrolysis, hydrogen bubbles evolved at the Pt cathode (graphene/Pt/PMMA stack) and as a result graphene layer peeled off from the substrate without damage. The peeling time for KOH and Li

  5. Suitable alkaline for graphene peeling grown on metallic catalysts using chemical vapor deposition

    Karamat, S.; Sonuşen, S.; Çelik, Ü.; Uysallı, Y.; Oral, A.

    2016-01-01

    Graphical abstract: - Highlights: • Graphene layers were grown on Pt and Cu foil via ambient pressure chemical vapor deposition method and for the delicate removal of graphene from metal catalysts, electrolysis method was used by using different alkaline (sodium hydroxide, potassium hydroxide, lithium hydroxide and barium hydroxide). • The delamination speed of PMMA/graphene stack was higher during the KOH and LiOH electrolysis as compare to NaOH and Ba(OH)_2. Ba(OH)_2 is not advisable because of the residues left on the graphene surface which would further trapped in between graphene and SiO_2/Si surface after transfer. The average peeling time in case of Pt electrode is ∼6 min for KOH and LiOH and ∼15 min for NaOH and Ba(OH)_2. • Electrolysis method also works for the Cu catalyst. The peeling of graphene was faster in the case of Cu foil due to small size of bubbles which moves faster between the stack and the electrode surface. The average peeling time was ∼3–5 min. • XPS analysis clearly showed that the Pt substrates can be re-used again. Graphene layer was transferred to SiO_2/Si substrates and to the flexible substrate by using the same peeling method. - Abstract: In chemical vapor deposition, the higher growth temperature roughens the surface of the metal catalyst and a delicate method is necessary for the transfer of graphene from metal catalyst to the desired substrates. In this work, we grow graphene on Pt and Cu foil via ambient pressure chemical vapor deposition (AP-CVD) method and further alkaline water electrolysis was used to peel off graphene from the metallic catalyst. We used different electrolytes i.e., sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH) and barium hydroxide Ba(OH)_2 for electrolysis, hydrogen bubbles evolved at the Pt cathode (graphene/Pt/PMMA stack) and as a result graphene layer peeled off from the substrate without damage. The peeling time for KOH and LiOH was ∼6 min and for NaOH and

  6. Minimizing Isolate Catalyst Motion in Metal-Assisted Chemical Etching for Deep Trenching of Silicon Nanohole Array.

    Kong, Lingyu; Zhao, Yunshan; Dasgupta, Binayak; Ren, Yi; Hippalgaonkar, Kedar; Li, Xiuling; Chim, Wai Kin; Chiam, Sing Yang

    2017-06-21

    The instability of isolate catalysts during metal-assisted chemical etching is a major hindrance to achieve high aspect ratio structures in the vertical and directional etching of silicon (Si). In this work, we discussed and showed how isolate catalyst motion can be influenced and controlled by the semiconductor doping type and the oxidant concentration ratio. We propose that the triggering event in deviating isolate catalyst motion is brought about by unequal etch rates across the isolate catalyst. This triggering event is indirectly affected by the oxidant concentration ratio through the etching rates. While the triggering events are stochastic, the doping concentration of silicon offers a good control in minimizing isolate catalyst motion. The doping concentration affects the porosity at the etching front, and this directly affects the van der Waals (vdWs) forces between the metal catalyst and Si during etching. A reduction in the vdWs forces resulted in a lower bending torque that can prevent the straying of the isolate catalyst from its directional etching, in the event of unequal etch rates. The key understandings in isolate catalyst motion derived from this work allowed us to demonstrate the fabrication of large area and uniformly ordered sub-500 nm nanoholes array with an unprecedented high aspect ratio of ∼12.

  7. The importance of pre-treatment of spent hydrotreating catalysts on metals recovery

    Alexandre Luiz de Souza Pereira

    2011-01-01

    Full Text Available This work describes a three-step pre-treatment route for processing spent commercial NiMo/Al2O3 catalysts. Extraction of soluble coke with n-hexane and/or leaching of foulant elements with oxalic acid were performed before burning insoluble coke under air. Oxidized catalysts were leached with 9 mol L-1 sulfuric acid. Iron was the only foulant element partially leached by oxalic acid. The amount of insoluble matter in sulfuric acid was drastically reduced when iron and/or soluble coke were previously removed. Losses of active phase metals (Ni, Mo during leaching with oxalic acid were compensated by the increase of their recovery in the sulfuric acid leachate.

  8. The importance of pre-treatment of spent hydrotreating catalysts on metals recovery

    Pereira, Alexandre Luiz de Souza; Silva, Cristiano Nunes da; Afonso, Julio Carlos, E-mail: julio@iq.ufrj.b [Universidade Federal do Rio de Janeiro (IQ/UFRJ), RJ (Brazil). Inst. de Quimica. Dept. de Quimica Analitica; Mantovano, Jose Luiz [Instituto de Engenharia Nuclear (CNEN/IEN-RJ), Rio de Janeiro, RJ (Brazil). Dept. de Quimica e Materiais Nucleares

    2011-07-01

    This work describes a three-step pre-treatment route for processing spent commercial Ni Mo/Al{sub 2}O{sub 3} catalysts. Extraction of soluble coke with n-hexane and/or leaching of foulant elements with oxalic acid were performed before burning insoluble coke under air. Oxidized catalysts were leached with 9 mol L{sup -1} sulfuric acid. Iron was the only foulant element partially leached by oxalic acid. The amount of insoluble matter in sulfuric acid was drastically reduced when iron and/or soluble coke were previously removed. Losses of active phase metals (Ni, Mo) during leaching with oxalic acid were compensated by the increase of their recovery in the sulfuric acid leachate. (author)

  9. Patterned growth of carbon nanotubes on Si substrates without predeposition of metal catalysts

    Chen, Y.; Yu, J.

    2005-07-01

    Aligned carbon nanotubes (CNTs) can be readily synthesized on quartz or silicon-oxide-coated Si substrates using a chemical vapor deposition method, but it is difficult to grow them on pure Si substrates without predeposition of metal catalysts. We report that aligned CNTs were grown by pyrolysis of iron phthalocyanine at 1000°C on the templates created on Si substrates with simple mechanical scratching. Scanning electron microscopy and x-ray energy spectroscopy analysis revealed that the trenches and patterns created on the surface of Si substrates were preferred nucleation sites for nanotube growth due to a high surface energy, metastable surface structure, and possible capillarity effect. A two-step pyrolysis process maintained Fe as an active catalyst.

  10. Metal-mediated aminocatalysis provides mild conditions: Enantioselective Michael addition mediated by primary amino catalysts and alkali-metal ions

    Matthias Leven

    2013-01-01

    Full Text Available Four catalysts based on new amides of chiral 1,2-diamines and 2-sulfobenzoic acid have been developed. The alkali-metal salts of these betaine-like amides are able to form imines with enones, which are activated by Lewis acid interaction for nucleophilic attack by 4-hydroxycoumarin. The addition of 4-hydroxycoumarin to enones gives ee’s up to 83% and almost quantitative yields in many cases. This novel type of catalysis provides an effective alternative to conventional primary amino catalysis were strong acid additives are essential components.

  11. Multi-metallic oxides as catalysts for light alcohols and hydrocarbons from synthesis gas

    Perez, Miguel [Instituto Mexicano del Petroleo, Mexico, D.F. (Mexico); Diaz, L; Galindo, H de J; Dominguez, J. M; Salmon, Manuel [Universidad Nacional Autonoma de Mexico, Mexico, D.F. (Mexico)

    1999-08-01

    A series of Cu-Co-Cr oxides doped with alkaline metals (M), were prepared by the coprecipitation method with metal nitrates (Cu{sup I}I, CO{sup I}I, CR{sup I}II) and (M{sub 2})CO{sub 3} in aqueous solution. The calcined products were used as catalysts for the Fisher-Tropsch synthesis in a stainless-steel fixed bed microreactor. The material was characterized by x-ray diffraction, and the specific surface area, pore size and nitrogen adsorption-desorption properties were also determined. The alkaline metals favored the methanol synthesis and prevent the dehydration reactions whereas the hydrocarbon formation is independent to these metals. [Spanish] Una serie de oxidos Cu-Co-Cr soportados con metales alcalinos (M), fueron preparados por el metodo con nitratos metalicos (Cu{sup I}I, CO{sup I}I, CR{sup I}II) y (M{sub 2})CO{sub 3} en soluciones acuosas. Los productos calcinados fueron usados como catalizadores para la sintesis de Fisher-tropsch en la superficie fija de un microreactor de acero inoxidable. El material fue caracterizado por difraccion de rayos X y el area de superficie especifica, el tamano de poro y propiedades de absorcion-desorcion de nitrogeno fueron determinadas. Los metales alcalinos favorecieron la sintesis de metanol y previnieron las reacciones de deshidratacion, mientras que la formacion de hidrocarburos es independiente de estos metales.

  12. Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts.

    Cheng, Fangyi; Chen, Jun

    2012-03-21

    Because of the remarkably high theoretical energy output, metal-air batteries represent one class of promising power sources for applications in next-generation electronics, electrified transportation and energy storage of smart grids. The most prominent feature of a metal-air battery is the combination of a metal anode with high energy density and an air electrode with open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we present the fundamentals and recent advances related to the fields of metal-air batteries, with a focus on the electrochemistry and materials chemistry of air electrodes. The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials (e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and inorganic-organic composites (e.g., metal macrocycle derivatives). The design and optimization of air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of metal-air batteries (219 references).

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

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

    2001-01-01

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

  14. Semiconductor-metal transition of Se in Ru-Se Catalyst Nanoparticles

    Babu, P. K.; Lewera, Adam; Oldfield, Eric; Wieckowski, Andrzej

    2009-03-01

    Ru-Se composite nanoparticles are promising catalysts for the oxygen reduction reaction (ORR) in fuel cells. Though the role of Se in enhancing the chemical stability of Ru nanoparticles is well established, the microscopic nature of Ru-Se interaction was not clearly understood. We carried out a combined investigation of ^77Se NMR and XPS on Ru-Se nanoparticles and our results indicate that Se, a semiconductor in elemental form, becomes metallic when interacting with Ru. ^77Se spin-lattice relaxation rates are found to be proportional to T, the well-known Korringa behavior characteristic of metals. The NMR results are supported by the XPS binding energy shifts which suggest that a possible Ru->Se charge transfer could be responsible for the semiconductor->metal transition of Se which also makes Ru less susceptible to oxidation during ORR.

  15. Graphene hydrogels with embedded metal nanoparticles as efficient catalysts in 4-nitrophenol reduction and methylene blue decolorization

    Żelechowska Kamila

    2016-12-01

    Full Text Available Synthesis and characterization of the graphene hydrogels with three different metallic nanoparticles, that is Au, Ag and Cu, respectively is presented. Synthesized in a one-pot approach graphene hydrogels with embedded metallic nanoparticles were tested as heterogeneous catalysts in a model reaction of 4-nitrophenol reduction. The highest activity was obtained for graphene hydrogel with Cu nanoparticles and additional reaction of methylene blued degradation was evaluated using this system. The obtained outstanding catalytic activity arises from the synergistic effect of graphene and metallic nanoparticles. The hydrogel form of the catalyst benefits in the easiness in separation from the reaction mixture (for example using tweezers and reusability.

  16. Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles.

    Liu, Lichen; Corma, Avelino

    2018-05-23

    Metal species with different size (single atoms, nanoclusters, and nanoparticles) show different catalytic behavior for various heterogeneous catalytic reactions. It has been shown in the literature that many factors including the particle size, shape, chemical composition, metal-support interaction, and metal-reactant/solvent interaction can have significant influences on the catalytic properties of metal catalysts. The recent developments of well-controlled synthesis methodologies and advanced characterization tools allow one to correlate the relationships at the molecular level. In this Review, the electronic and geometric structures of single atoms, nanoclusters, and nanoparticles will be discussed. Furthermore, we will summarize the catalytic applications of single atoms, nanoclusters, and nanoparticles for different types of reactions, including CO oxidation, selective oxidation, selective hydrogenation, organic reactions, electrocatalytic, and photocatalytic reactions. We will compare the results obtained from different systems and try to give a picture on how different types of metal species work in different reactions and give perspectives on the future directions toward better understanding of the catalytic behavior of different metal entities (single atoms, nanoclusters, and nanoparticles) in a unifying manner.

  17. On the metal-support synergy for selective gas-phase ethanol oxidation over MgCuCr2O4 supported metal nanoparticle catalysts

    Liu, P.; Zhu, X.; Yang, S.; Li, T.; Hensen, E.J.M.

    2015-01-01

    Achieving high yields in the production of bulk chemicals is an important goal for the chemical industry. We investigated the influence of the metal on the catalytic performance of M/MgCuCr2O4 (M = Cu, Ag, Pd, Pt, Au) catalysts to better understand the metal-support synergy for the aerobic oxidation

  18. Surface noble metal modified PdM/C (M = Ru, Pt, Au) as anode catalysts for direct ethanol fuel cells

    Mao, Han; Huang, Tao; Yu, Aishui

    2016-01-01

    In this article, we studied the surface noble metal modification on Pd nanoparticles, other than the homogeneous or core-shell structure. The surface modification will lead to the uneven constitution within the nanoparticles and thus more obvious optimization effect toward the catalyst brought by the lattice deformation. The surface of the as-prepared Pd nanoparticles was modified with Ru, Pt or Au by a moderate and green approach, respectively. XPS results confirm the interactive electron effects between Pd and the modified noble metal. Electrochemical measurements show that the surface noble metal modified catalysts not only show higher catalytic activity, but also better stability and durability. The PdM/C catalysts all exhibit good dispersion and very little agglomeration after long-term potential cycles toward ethanol oxidation. With only 10% metallic atomic ratio of Au, PdAu/C catalyst shows extraordinary catalytic activity and stability, the peak current reaches 1700 mA mg"−"1 Pd, about 2.5 times that of Pd/C. Moreover, the PdAu/C maintains 40% of the catalytic activity after 4500 potential cycles. - Highlights: • Pd-based catalysts with complicated exposed facets. • Much enhanced electrocatalytic activity and stability with about 10% noble metal M (M = Ru, Pt, Au) on Pd nanoparticles. • The outstanding electrocatalytic performance of PdAu/C towards ethanol oxidation after the Au modification.

  19. Surface noble metal modified PdM/C (M = Ru, Pt, Au) as anode catalysts for direct ethanol fuel cells

    Mao, Han; Huang, Tao, E-mail: huangt@fudan.edu.cn; Yu, Aishui, E-mail: asyu@fudan.edu.cn

    2016-08-15

    In this article, we studied the surface noble metal modification on Pd nanoparticles, other than the homogeneous or core-shell structure. The surface modification will lead to the uneven constitution within the nanoparticles and thus more obvious optimization effect toward the catalyst brought by the lattice deformation. The surface of the as-prepared Pd nanoparticles was modified with Ru, Pt or Au by a moderate and green approach, respectively. XPS results confirm the interactive electron effects between Pd and the modified noble metal. Electrochemical measurements show that the surface noble metal modified catalysts not only show higher catalytic activity, but also better stability and durability. The PdM/C catalysts all exhibit good dispersion and very little agglomeration after long-term potential cycles toward ethanol oxidation. With only 10% metallic atomic ratio of Au, PdAu/C catalyst shows extraordinary catalytic activity and stability, the peak current reaches 1700 mA mg{sup −1} Pd, about 2.5 times that of Pd/C. Moreover, the PdAu/C maintains 40% of the catalytic activity after 4500 potential cycles. - Highlights: • Pd-based catalysts with complicated exposed facets. • Much enhanced electrocatalytic activity and stability with about 10% noble metal M (M = Ru, Pt, Au) on Pd nanoparticles. • The outstanding electrocatalytic performance of PdAu/C towards ethanol oxidation after the Au modification.

  20. APPARATUS FOR THE PRODUCTION OF LITHIUM METAL

    Baker, P.S.; Duncan, F.R.; Greene, H.B.

    1961-08-22

    Methods and apparatus for the production of high-purity lithium from lithium halides are described. The apparatus is provided for continuously contacting a molten lithium halide with molten barium, thereby forming lithium metal and a barium halide, establishing separate layers of these reaction products and unreacted barium and lithium halide, and continuously withdrawing lithium and barium halide from the reaction zone. (AEC)

  1. Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells

    Setzler, Brian P.; Zhuang, Zhongbin; Wittkopf, Jarrid A.; Yan, Yushan

    2016-12-01

    Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW-1 in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

  2. Preparation and characterization of bi-metallic nanoparticle catalyst having better anti-coking properties using reverse micelle technique

    Zacharia, Thomas

    Energy needs are rising on an exponential basis. The mammoth energy sources like coal, natural gas and petroleum are the cause of pollution. The large outcry for an alternate energy source which is environmentally friendly and energy efficient is heard during the past few years. This is where “Clean-Fuel” like hydrogen gained its ground. Hydrogen is mainly produced by steam methane reforming (SMR). An alternate sustainable process which can reduce the cost as well as eliminate the waste products is Tri-reforming. In both these reforming processes nickel is used as catalyst. However as the process goes on the catalyst gets deactivated due to coking on the catalytic surface. This goal of this thesis work was to develop a bi-metallic catalyst which has better anti-coking properties compared to the conventional nickel catalyst. Tin was used to dope nickel. It was found that Ni3Sn complex around a core of Ni is coking resistant compared to pure nickel catalyst. Reverse micelle synthesis of catalyst preparation was used to control the size and shape of catalytic particles. These studies will benefit researches on hydrogen production and catalyst manufactures who work on different bi-metallic combinations.

  3. PYROLYSIS OF ISOCHRYSIS MICROALGAE WITH METAL OXIDE CATALYSTS FOR BIO-OIL PRODUCTION

    TEVFİK AYSU

    2016-12-01

    Full Text Available Pyrolysis of Isochrysis microalgae was carried out in a fixed-bed reactor without and with metal oxide catalysts (CeO2, TiO2, Al2O3 at the temperatures of 450, 500 and 550 oC with a constant heating rate of 40 oC/min. The pyrolysis conditions including catalyst and temperature were studied in terms of their effects on the yields of pyrolysis products and quality. The amount of bio-char, bio-oil and gas products was calculated. The composition of the produced bio-oils was determined by Elemental analysis (EA, Fourier transform infrared spectroscopy (FT-IR, proton nuclear magnetic resonance (1H NMR and Gas chromatography/mass spectrometry (GC–MS techniques. As a result of the pyrolysis experiments, it is shown that there have been significant effects of both catalyst and temperature on the conversion of Isochrysis microalgae into solid, liquid (bio-oil and gas products. The highest bio-oil yield (24.30 % including aqueous phase was obtained in the presence of TiO2 (50% as catalyst at 500 °C. 98 different compounds were identified by GC-MS in bio-oils obtained at 500 oC. According to 1H NMR analysis, bio-oils contained ∼60-64 % aliphatic and ∼17-19 % aromatic structural units. EA showed that the bio-oils contained ∼66-69 % C and having 31-34 MJ/kg higher heating values.

  4. Structural characterization of dispersed metal catalysts. Progress report, September 1, 1982-August 31, 1983

    Reucroft, P.J.; De Angelis, R.J.; Bentley, J.

    1983-01-01

    Analytical electron microscopy characterization techniques have been developed to investigate the structural features of small metal particles (50 to 100 angstroms) in porous media. In the first phase of the project, bright and dark field imaging techniques have been emphasized with EDAX characterization. High quality images have been obtained in both bright field and dark field and earlier characterization studies on three catalyst systems have been confirmed and extended. Particle size growth (sintering) at low temperatures is much greater in the Au/SiO 2 system, indicating a weak metal-support interaction. A more uniform and generally smaller particle size distribution is observed in Ni/MgSiO 3 compared to Ni/SiO 2 . The nickel particles in Ni/SiO 2 show contrast effects which indicate that the particles contain faults or twins

  5. Supported transition metal sulfide promoted molybdenum or tungsten sulfide catalysts and their uses for hydroprocessing

    Ho, T.C.; Chianelli, R.R.; Jacobson, A.J.; Young, A.R.

    1987-01-01

    A process is described for hydrotreating a hydrocarbon feed which comprises contacting the feed at a temperature of at least about 150 0 C and heating the composite at elevated temperature of at least about 150 0 C, in the presence of sulfur and under oxygen-free conditions for a time sufficient to form the catalyst. The precursor salt contains a tetrathiometallate anion of Mo, W or mixture thereof and a cation comprising one or more divalent promoter metals which are chelated by at least one neutral, nitrogen-containing polydentate ligand L. The divalent promoter metal is selected from the group consisting of Ni, Co, Zn, Cu and mixture thereof. The contacting occurs for a time sufficient to hydrotreat at least a portion of the feed

  6. Enhancement of isotope exchange reactions over ceramic breeder material by deposition of catalyst metal

    Narisato, Y.; Munakata, K.; Koga, A.; Yokoyama, Y.; Takata, T.; Okabe, H.

    2004-01-01

    The deposition of catalyst metals in ceramic breeders could enhance the release rate of tritium due to the promotion of isotope exchange reactions taking place at the interface of the breeder surface and the sweep gas. In this work, the authors examined the effects of catalytic active metal deposited on lithium titanate on the isotope exchange reactions. With respect to the virgin lithium titanate, it was found that the rate of the isotope exchange reactions taking place on the surface is quite low. However, the deposition of palladium greatly increased the exchange reaction rate. The effect of the amounts of deposited palladium on the isotope exchange reaction rate was also investigated. The results indicate that the exchange reactions are still enhanced even if the amounts of deposited palladium are as low as 0.04%

  7. Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework

    Kim, In Soo [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Nanophotonics Center, Korea Institute of Science and Technology, Seoul 02792 South Korea; Li, Zhanyong [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Zheng, Jian [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Platero-Prats, Ana E. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Mavrandonakis, Andreas [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Pellizzeri, Steven [Chemical and Biomolecular Engineering, Clemson University, 205 Earle Hall Clemson SC 29634 USA; Ferrandon, Magali [Chemical Sciences and Engineering Division, Argonne National Lab, 9700 S. Cass Ave. Argonne IL 60439 USA; Vjunov, Aleksei [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Gallington, Leighanne C. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Webber, Thomas E. [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Vermeulen, Nicolaas A. [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Penn, R. Lee [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Getman, Rachel B. [Chemical and Biomolecular Engineering, Clemson University, 205 Earle Hall Clemson SC 29634 USA; Cramer, Christopher J. [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Chapman, Karena W. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Camaioni, Donald M. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Fulton, John L. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Lercher, Johannes A. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Department of Chemistry and Catalysis Research Institute, Technische Universität München, Lichtenbergstrasse 4 85748 Garching Germany; Farha, Omar K. [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Hupp, Joseph T. [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Martinson, Alex B. F. [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA

    2018-01-02

    Installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 degrees C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and Xray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support.

  8. Metal Oxide Supported Vanadium Substituted Keggin Type Polyoxometalates as Catalyst For Oxidation of Dibenzothiophene

    Lesbani, Aldes; Novri Meilyana, Sarah; Karim, Nofi; Hidayati, Nurlisa; Said, Muhammad; Mohadi, Risfidian; Miksusanti

    2018-01-01

    Supported polyoxometalatate H4[γ-H2SiV2W10O40]·nH2O with metal oxide i.e. silica, titanium, and tantalum was successfully synthesized via wet impregnation method to form H4[γ-H2SiV2W10O40]·nH2O-Si, H4[γ-H2SiV2W10O40]·nH2O-Ti, and H4[γ-H2SiV2W10O40]·nH2O-Ta. Characterization was performed using FTIR spectroscopy, X-Ray analyses, and morphology analyses using SEM. All compounds were used as the catalyst for desulfurization of dibenzothiophene (DBT). Silica and titanium supported polyoxometalate H4[γ-H2SiV2W10O40]·nH2O better than tantalum due to retaining crystallinity after impregnation process. On the other hand, compound H H4[γ-H2SiV2W10O40]·nH2O-Ta showed high catalytic activity than other supported metal oxides for desulfurization of DBT. Optimization desulfurization process resulted in 99% conversion of DBT under a mild condition at 70 °C, 0.1 g catalyst, and reaction for 3 hours. Regeneration studies showed catalyst H4[γ-H2SiV2W10O40]·nH2O-Ti was remaining catalytic activity for desulfurization of DBT.

  9. Light alkane (mixed feed selective dehydrogenation using bi-metallic zeolite supported catalyst

    Zeeshan Nawaz

    2009-12-01

    Full Text Available Light alkanes are the important intermediates of many refinery processes and their catalytic dehydrogenation gives corresponding alkenes. The aim behind this experimentation is to investigate reaction behavior of mixed alkanes during direct catalytic dehydrogenation and emphasis has been given to enhance propene. Bi-metallic zeolite supported catalyst Pt-Sn/ZSM-5 was prepared by sequentional impregnation method and characterized by BET, EDS and XRD. Direct dehydrogenation reaction is highly endothermic and its conversion is thermodynamically limited. Results showed that the increase in temperature increases the conversion to some extent but there is no overall effect on selectivity of propene. Increase in time-on-stream (TOS remarkably improves propene selectivity at the expense of lower conversion. The performances of bi-metallic zeolite based catalyst largely affected by coke deposition. The presence of butane and ethane adversely affected propane conversion. Optimum propene selectivity is about 48 %, obtained at 600 oC and time-on-stream 10 h.

  10. Large-scale synthesis of coiled-like shaped carbon nanotubes using bi-metal catalyst

    Krishna, Vemula Mohana; Somanathan, T.; Manikandan, E.; Umar, Ahmad; Maaza, M.

    2018-02-01

    Carbon nanomaterials (CNMs), especially carbon nanotubes (CNTs) with coiled structure exhibit scientifically fascinating. They may be projected as an innovative preference to future technological materials. Coiled carbon nanotubes (c-CNTs) on a large-scale were successfully synthesized with the help of bi-metal substituted α-alumina nanoparticles catalyst via chemical vapor deposition (CVD) technique. Highly spring-like carbon nanostructures were observed by field emission scanning electron microscope (FESEM) examination. Furthermore, the obtained material has high purity, which correlates the X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX) analysis. Raman spectroscopy reveals that the carbon multi layers are well graphitized and crystalline, even if they have defects in its structure due to coiled morphology. High-resolution transmission electron microscope (HRTEM) describes internal structure and dia of the product. Ultimately, results support the activity of bi-metal impregnated α-alumina nanoparticles catalyst to determine the high yield, graphitization and internal structure of the material. We have also studied the purified c-CNTs magnetic properties at room temperature and will be an added advantage in several applications.

  11. Influence of platinum group metal-free catalyst synthesis on microbial fuel cell performance

    Santoro, Carlo; Rojas-Carbonell, Santiago; Awais, Roxanne; Gokhale, Rohan; Kodali, Mounika; Serov, Alexey; Artyushkova, Kateryna; Atanassov, Plamen

    2018-01-01

    Platinum group metal-free (PGM-free) ORR catalysts from the Fe-N-C family were synthesized using sacrificial support method (SSM) technique. Six experimental steps were used during the synthesis: 1) mixing the precursor, the metal salt, and the silica template; 2) first pyrolysis in hydrogen rich atmosphere; 3) ball milling; 4) etching the silica template using harsh acids environment; 5) the second pyrolysis in ammonia rich atmosphere; 6) final ball milling. Three independent batches were fabricated following the same procedure. The effect of each synthetic parameters on the surface chemistry and the electrocatalytic performance in neutral media was studied. Rotating ring disk electrode (RRDE) experiment showed an increase in half wave potential and limiting current after the pyrolysis steps. The additional improvement was observed after etching and performing the second pyrolysis. A similar trend was seen in microbial fuel cells (MFCs), in which the power output increased from 167 ± 2 μW cm-2 to 214 ± 5 μW cm-2. X-ray Photoelectron Spectroscopy (XPS) was used to evaluate surface chemistry of catalysts obtained after each synthetic step. The changes in chemical composition were directly correlated with the improvements in performance. We report outstanding reproducibility in both composition and performance among the three different batches.

  12. Organic-inorganic perovskites containing trivalent metal halide layers: the templating influence of the organic cation layer.

    Mitzi, D B

    2000-12-25

    Thin sheetlike crystals of the metal-deficient perovskites (H2AEQT)M2/3I4 [M = Bi or Sb; AEQT = 5,5"'-bis-(aminoethyl)-2,2':5',2'':5'',2'''-quaterthiophene] were formed from slowly cooled ethylene glycol/2-butanol solutions containing the bismuth(III) or antimony(III) iodide and AEQT.2HI salts. Each structure was refined in a monoclinic (C2/m) subcell, with the lattice parameters a = 39.712(13) A, b = 5.976(2) A, c = 6.043(2) A, beta = 92.238(5) degrees, and Z = 2 for M = Bi and a = 39.439(7) A, b = 5.952(1) A, c = 6.031(1) A, beta = 92.245(3) degrees, and Z = 2 for M = Sb. The trivalent metal cations locally adopt a distorted octahedral coordination, with M-I bond lengths ranging from 3.046(1) to 3.218(3) A (3.114 A average) for M = Bi and 3.012(1) to 3.153(2) A (3.073 A average) for M = Sb. The new organic-inorganic hybrids are the first members of a metal-deficient perovskite family consisting of (Mn+)2/nV(n-2)/nX4(2-) sheets, where V represents a vacancy (generally left out of the formula) and the metal cation valence, n, is greater than 2. The organic layers in the AEQT-based organic-inorganic hybrids feature edge-to-face aromatic interactions among the rigid, rodlike quaterthiophene moieties, which may help to stabilize the unusual metal-deficient layered structures.

  13. Selective catalytic reduction of nitric oxide by ethylene over metal-modified ZSM-5- and {gamma}-Al{sub 2}O{sub 3}-catalysts

    Eraenen, K; Kumar, N; Lindfors, L E [Aabo Akademi, Turku (Finland). Lab. of Industrial Chemistry

    1997-12-31

    Metal-modified ZSM-5 and {gamma}-Al{sub 2}O{sub 3} catalysts were tested in reduction of nitric oxide by ethylene. Different metals were introduced into the ZSM-5 catalyst by ion-exchange and by introduction of metals during the zeolite synthesis. To prepare bimetallic catalysts a combination of these methods was used. The {gamma}-Al{sub 2}O{sub 3} was impregnated with different metals by the incipient wetness technique and by adsorption. Activity measurements showed that the ZSM-5 based catalysts were more active than the {gamma}-Al{sub 2}O{sub 3} based catalysts. The highest conversion was obtained over a ZSM-5 catalyst prepared by introduction of Pd during synthesis of the zeolite and subsequently ion-exchanged with copper. (author)

  14. Selective catalytic reduction of nitric oxide by ethylene over metal-modified ZSM-5- and {gamma}-Al{sub 2}O{sub 3}-catalysts

    Eraenen, K.; Kumar, N.; Lindfors, L.E. [Aabo Akademi, Turku (Finland). Lab. of Industrial Chemistry

    1996-12-31

    Metal-modified ZSM-5 and {gamma}-Al{sub 2}O{sub 3} catalysts were tested in reduction of nitric oxide by ethylene. Different metals were introduced into the ZSM-5 catalyst by ion-exchange and by introduction of metals during the zeolite synthesis. To prepare bimetallic catalysts a combination of these methods was used. The {gamma}-Al{sub 2}O{sub 3} was impregnated with different metals by the incipient wetness technique and by adsorption. Activity measurements showed that the ZSM-5 based catalysts were more active than the {gamma}-Al{sub 2}O{sub 3} based catalysts. The highest conversion was obtained over a ZSM-5 catalyst prepared by introduction of Pd during synthesis of the zeolite and subsequently ion-exchanged with copper. (author)

  15. Growth of vertically aligned single-walled carbon nanotubes with metallic chirality through faceted FePt-Au catalysts

    Ohashi, Toshiyuki; Iwama, Hiroki; Shima, Toshiyuki

    2016-02-01

    Direct synthesis of vertically aligned metallic single-walled carbon nanotubes (m-SWCNT forests) is a difficult challenge. We have successfully synthesized m-SWCNT forests using faceted iron platinum-gold catalysts epitaxially grown on a single crystalline magnesium oxide substrate. The metallic content of the forests estimated by Raman spectroscopy reaches 90%. From the standpoint of growth rate of the forests, the growth mechanism is probably based on the catalyst of solid state. It is suggested that preferential growth of m-SWCNTs is achieved when both factors are satisfied, namely, {111} dominant octahedral facet and ideal size (fine particles) of FePt particles.

  16. Catalyst and processing effects on metal-assisted chemical etching for the production of highly porous GaN

    Geng, Xuewen; Grismer, Dane A; Bohn, Paul W; Duan, Barrett K; Zhao, Liancheng

    2013-01-01

    Metal-assisted chemical etching is a facile method to produce micro-/nanostructures in the near-surface region of gallium nitride (GaN) and other semiconductors. Detailed studies of the production of porous GaN (PGaN) using different metal catalysts and GaN doping conditions have been performed in order to understand the mechanism by which metal-assisted chemical etching is accomplished in GaN. Patterned catalysts show increasing metal-assisted chemical etching activity to n-GaN in the order Ag < Au < Ir < Pt. In addition, the catalytic behavior of continuous films is compared to discontinuous island films. Continuous metal films strongly shield the surface, hindering metal-assisted chemical etching, an effect which can be overcome by using discontinuous films or increasing the irradiance of the light source. With increasing etch time or irradiance, PGaN morphologies change from uniform porous structures to ridge and valley structures. The doping type plays an important role, with metal-assisted chemical etching activity increasing in the order p-GaN < intrinsic GaN < n-GaN. Both the catalyst identity and the doping type effects are explained by the work functions and the related band offsets that affect the metal-assisted chemical etching process through a combination of different barriers to hole injection and the formation of hole accumulation/depletion layers at the metal–semiconductor interface. (paper)

  17. Environmental Friendly Azide-Alkyne Cycloaddition Reaction of Azides, Alkynes, and Organic Halides or Epoxides in Water: Efficient "Click" Synthesis of 1,2,3-Triazole Derivatives by Cu Catalyst

    刘建明; 刘慕文; 岳园园; 姚美焕; 卓克垒

    2012-01-01

    An efficient click synthesis of 1,2,3-triazole derivatives from benzyl halides or alkyl halides, epoxides, terminal alkynes, and sodium azides in the presence of copper salts and relative benzimidazole salts have been developed. This procedure eliminates the need to handle potentially organic azides, which are generated in situ. A broad spec- trum of substrates can participate in the process effectively to produce the desired products in good yields.

  18. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts.

    Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P; Yang, Bin

    2018-01-10

    Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al 2 O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf) 4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote deoxygenation reactions catalyzed by super Lewis acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

    Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P.; Yang, Bin

    2017-01-01

    Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.

  20. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

    Wang, Hongliang [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Current address: Center of Biomass Engineering/College of Agronomy and Biotechnology, China Agricultural University, Beijing 100193 PR China; Wang, Huamin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Kuhn, Eric [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Tucker, Melvin P. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Yang, Bin [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA

    2017-11-14

    Super Lewis acids containing the triflate anion (e.g. Hf(OTf)4, Ln(OTf)3, Al(OTf)3) and noble metal catalysts (e.g. Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage via selective bonding to etheric oxygens while the noble metal catalysed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt% of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates via protonating hydroxyls and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalysed by super Lewis acids.

  1. Amino-functionalized metal-organic frameworks as tunable heterogeneous basic catalysts

    Fischer, M.; Hartmann, M. [Erlangen-Nuernberg Univ., Erlangen (Germany). Erlangen Catalysis Resource Center

    2011-07-01

    Metal-organic framework (MOF) materials have been explored for applications in heterogeneous catalysis in recent years. In addition to the use of MOFs as supports for the deposition of highly dispersed metal particles, the incorporation of active centers such as coordinatively unsaturated metal sites and the functionalization of the organic linkers with acidic or basic groups seems to be most promising. In our contribution, three different MOFs carrying amino groups at their organic linkers, namely Fe-MIL-101-NH{sub 2} (S{sub BET} = 3438 m{sup 2}g{sup -1}), Al-MIL-101-NH{sub 2} (S{sub BET} = 3099 m{sup 2}g{sup -1}) and CAU-1 (S{sub BET} = 1492 m{sup 2}g{sup -1}), were synthesized and tested in the Knoevenagel condensation of benzaldehyde with malononitrile and with ethyl cyanoacetate, respectively. It is shown that the expected products benzylidenemalononitrile (BzMN) and ethyl a-cyanocinnamate (EtCC) are formed with selectivities of more than 99 % and yields of 90 to 95 % after 3 h (for BzMN). Due to the very small pore windows of CAU-1 (0.3 to 0.4 nm) the reaction proceeds much slower over this catalyst in comparison to the amino-MIL-101 derivatives, which possess open pore windows of up to 1.6 nm. Finally, leaching tests confirm that the reaction is heterogeneously catalyzed. Moreover, the catalysts are recyclable without significant loss of activity. (orig.)

  2. Dislocation unpinning model of acoustic emission from alkali halide ...

    The present paper reports the dislocation unpinning model of acoustic emis- sion (AE) from ... Acoustic emission; dislocation; alkali halide crystals; plastic deformation. ..... [5] T Nishimura, A Tahara and T Kolama, Jpn. Metal Inst. 64, 339 (2000).

  3. Transition Metal Phosphide Nanoparticles Supported on SBA-15 as Highly Selective Hydrodeoxygenation Catalysts for the Production of Advanced Biofuels.

    Yang, Yongxing; Ochoa-Hernández, Cristina; de la Peña O'Shea, Víctor A; Pizarro, Patricia; Coronado, Juan M; Serrano, David P

    2015-09-01

    A series of catalysts constituted by nanoparticles of transition metal (M = Fe, Co, Ni and Mo) phosphides (TMP) dispersed on SBA-15 were synthesized by reduction of the corresponding metal phosphate precursors previously impregnated on the mesostructured support. All the samples contained a metal-loading of 20 wt% and with an initial M/P mole ratio of 1, and they were characterized by X-ray diffraction (XRD), N2 sorption, H2-TPR and transmission electron microscopy (TEM). Metal phosphide nanocatalysts were tested in a high pressure continuous flow reactor for the hydrodeoxygenation (HDO) of a methyl ester blend containing methyl oleate (C17H33-COO-CH3) as main component (70%). This mixture constitutes a convenient surrogate of triglycerides present in vegetable oils, and following catalytic hydrotreating yields mainly n-alkanes. The results of the catalytic assays indicate that Ni2P/SBA-15 catalyst presents the highest ester conversion, whereas the transformation rate is about 20% lower for MoP/SBA-15. In contrast, catalysts based on Fe and Co phosphides show a rather limited activity. Hydrocarbon distribution in the liquid product suggests that both hydrodeoxygenation and decarboxylation/decarbonylation reactions occur simultaneously over the different catalysts, although MoP/SBA-15 possess a selectivity towards hydrodeoxygenation exceeding 90%. Accordingly, the catalyst based on MoP affords the highest yield of n-octadecane, which is the preferred product in terms of carbon atom economy. Subsequently, in order to conjugate the advantages of both Ni and Mo phosphides, a series of catalysts containing variable proportions of both metals were prepared. The obtained results reveal that the mixed phosphides catalysts present a catalytic behavior intermediate between those of the monometallic phosphides. Accordingly, only marginal enhancement of the yield of n-octadecane is obtained for the catalysts with a Mo/Ni ratio of 3. Nevertheless, owing to this high selectivity

  4. Metal-polypyridyl catalysts for electro- and photochemical reduction of water to hydrogen.

    Zee, David Z; Chantarojsiri, Teera; Long, Jeffrey R; Chang, Christopher J

    2015-07-21

    Climate change, rising global energy demand, and energy security concerns motivate research into alternative, sustainable energy sources. In principle, solar energy can meet the world's energy needs, but the intermittent nature of solar illumination means that it is temporally and spatially separated from its consumption. Developing systems that promote solar-to-fuel conversion, such as via reduction of protons to hydrogen, could bridge this production-consumption gap, but this effort requires invention of catalysts that are cheap, robust, and efficient and that use earth-abundant elements. In this context, catalysts that utilize water as both an earth-abundant, environmentally benign substrate and a solvent for proton reduction are highly desirable. This Account summarizes our studies of molecular metal-polypyridyl catalysts for electrochemical and photochemical reduction of protons to hydrogen. Inspired by concept transfer from biological and materials catalysts, these scaffolds are remarkably resistant to decomposition in water, with fast and selective electrocatalytic and photocatalytic conversions that are sustainable for several days. Their modular nature offers a broad range of opportunities for tuning reactivity by molecular design, including altering ancillary ligand electronics, denticity, and/or incorporating redox-active elements. Our first-generation complex, [(PY4)Co(CH3CN)2](2+), catalyzes the reduction of protons from a strong organic acid to hydrogen in 50% water. Subsequent investigations with the pentapyridyl ligand PY5Me2 furnished molybdenum and cobalt complexes capable of catalyzing the reduction of water in fully aqueous electrolyte with 100% Faradaic efficiency. Of particular note, the complex [(PY5Me2)MoO](2+) possesses extremely high activity and durability in neutral water, with turnover frequencies at least 8500 mol of H2 per mole of catalyst per hour and turnover numbers over 600 000 mol of H2 per mole of catalyst over 3 days at an

  5. Structure-Reactivity Relationships in Multi-Component Transition Metal Oxide Catalysts FINAL Report

    Altman, Eric I. [Yale Univ., New Haven, CT (United States)

    2015-10-06

    The focus of the project was on developing an atomic-level understanding of how transition metal oxide catalysts function. Over the course of several renewals the specific emphases shifted from understanding how local structure and oxidation state affect how molecules adsorb and react on the surfaces of binary oxide crystals to more complex systems where interactions between different transition metal oxide cations in an oxide catalyst can affect reactivity, and finally to the impact of cluster size on oxide stability and reactivity. Hallmarks of the work were the use of epitaxial growth methods to create surfaces relevant to catalysis yet tractable for fundamental surface science approaches, and the use of scanning tunneling microscopy to follow structural changes induced by reactions and to pinpoint adsorption sites. Key early findings included the identification of oxidation and reduction mechanisms on a tungsten oxide catalyst surface that determine the sites available for reaction, identification of C-O bond cleavage as the rate limiting step in alcohol dehydration reactions on the tungsten oxide surface, and demonstration that reduction does not change the favored reaction pathway but rather eases C-O bond cleavage and thus reduces the reaction barrier. Subsequently, a new reconstruction on the anatase phase of TiO2 relevant to catalysis was discovered and shown to create sites with distinct reactivity compared to other TiO2 surfaces. Building on this work on anatase, the mechanism by which TiO2 enhances the reactivity of vanadium oxide layers was characterized and it was found that the TiO2 substrate can force thin vanadia layers to adopt structures they would not ordinarily form in the bulk which in turn creates differences in reactivity between supported layers and bulk samples. From there, the work progressed to studying well-defined ternary oxides where synergistic effects between the two cations can induce

  6. Isotope exchange reaction of tritium on precious metal catalyst based on cation-exchanged mordenite for blanket tritium recovery

    Kawamura, Yoshinori, E-mail: kawamura.yoshinori@jaea.go.jp [Japan Atomic Energy Agency, 801-1 Mukoyama, Naka, Ibaraki 311-0193 (Japan); Hayashi, Takumi [Japan Atomic Energy Agency, 2-4 Shirane Shirakata, Tokai, Ibaraki 319-1195 (Japan); Yamanishi, Toshihiko [Japan Atomic Energy Agency, 2-166 Omotedate Obuchi, Rokkasho, Aomori 039-3212 (Japan)

    2016-11-01

    Highlights: • Precious metal catalyst based on cation-exchanged mordenite was prepared. • Isotope exchange reaction between H{sub 2} and HTO on the catalyst was investigated. • The order of entire reaction is not clear, but it is the first-order reaction as for HTO. • Effect of exchanged cation may appear as the difference of the surface area of catalyst. - Abstract: It is known that the chemical forms of tritium released from a ceramic breeder blanket are hydrogen form and water form. To recover tritiated water vapor, adoption of dryer that is packed column of synthetic zeolite has been proposed. On the other hand, synthetic zeolite is often used as a support of precious metal catalyst. Such catalysts usually have a capability of hydrogen isotope exchange between gas and water vapor. If this catalyst is used to dryer, the dryer may obtain a preferable function for tritium recovery by isotopic exchange reaction. To assess such functions, reaction rate should be estimated. The results of water adsorption experiment on cation-exchanged mordenite-type zeolite suggested the possibility that state of adsorbed water varied by exchanged cation. So, in this work, precious metal catalyst based on cation-exchanged mordenite was prepared, and the reaction rate of chemical exchange between hydrogen and tritiated water was investigated under temperature range between 30 °C and 80 °C by the steady-state approximation. In the case of platinum on Na-mordenite, the reaction between gaseous hydrogen and tritiated water vapor was almost expressed as first-order reaction concerning tritiated water vapor concentration.

  7. Effect of Metal Addition and Silica/Alumina Ratio of Zeolite on the Ethanol-to-Aromatics by Using Metal Supported ZSM-5 Catalyst

    Kim, Han-Gyu; Yang, Yoon-Cheol; Jeong, Kwang-Eun; Kim, Tae-Wan; Jeong, Soon-Yong; Kim, Chul-Ung; Jhung, Sung Hwa; Lee, Kwan-Young

    2013-01-01

    The catalytic conversion of ethanol to aromatic compounds ETA was studied over ZSM-5 heterogeneous catalysts. The effect of reaction temperature, weight hourly space velocity (WHSV), and addition of water and methanol, which are the potential impurities of bio-ethanol, on the catalytic performance was investigated in a fixed bed reactor. Commercial ZSM-5 catalysts having different Si/Al 2 ratios of 23 to 280 and modified ZSM-5 catalysts by addition of metal (Zn, La, Cu, and Ga) were used for the activity and stability tests in ETA reaction. The catalysts were characterized with ammonia temperature programmed desorption (NH3-TPD) and nitrogen adsorption-desorption techniques. The results of catalytic performance revealed that the optimal Si/Al 2 ratio of ZSM-5 is about 50-80 and the selectivity to aromatic compounds decreases in the order of Zn/La > Zn > La > Cu > Ga for the modified ZSM-5 catalysts. Among these catalysts from the ETA reaction, Zn-La/ZSM-5 showed the best catalytic performance for the ETA reaction. The selectivity to aromatic compounds was 72% initially and 56% after 30 h over the catalysts at reaction temperature of 437 .deg. C and WHSV of 0.8 h −1

  8. Understanding of catalysis on early transition metal oxide-based catalysts through exploration of surface structure and chemistry during catalysis using in-situ approaches

    Tao, Franklin [Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering. Dept. of Chemistry

    2015-09-14

    Two main categories of heterogeneous catalysts are metal and metal oxide which catalyze 80% chemical reactions at solid-gas and solid-liquid interfaces. Metal oxide catalysts are much more complicated than metal catalysts. The reason is that the cations of the metal atoms could exhibit a few different oxidation states on surface of the same catalyst particle such as Co3O4 or change of their oxidation states under different reactive environments. For a metal catalyst, there is only one oxidation state typically. In addition, surface of a metal oxide can be terminated with multiple surface functionalities including O atoms with different binding configurations and OH group. For metal, only metal atoms are exposed typically. Obviously, the complication of surface chemistry and structure of a metal oxide makes studies of surface of an oxide catalyst very challenging. Due to the complication of surface of a meal oxide, the electronic and geometric structures of surface of a metal oxide and the exposed species have received enormous attention since oxide catalysts catalyze at least 1/3 chemical reactions in chemical and energy industries. Understanding of catalytic reactions on early transition metal oxide-based catalysts is fundamentally intriguing and of great practical interest in energy- and environment-related catalysis. Exploration of surface chemistry of oxide-based catalysts at molecular level during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide-based catalysts and developing oxide-based catalysts with high activity and selectivity. Thus, the overall objective of this project is to explore surface chemistry and structure of early transition metal oxide-based catalysts through in-situ characterization of surface of catalysts, measurements of catalytic performances, and then build an intrinsic correlation of surface chemistry and structure with their catalytic performances in a few

  9. A Novel Synthesis of Gold Nanoparticles Supported on Hybrid Polymer/Metal Oxide as Catalysts for p-Chloronitrobenzene Hydrogenation

    Cristian H. Campos

    2017-01-01

    Full Text Available This contribution reports a novel preparation of gold nanoparticles on polymer/metal oxide hybrid materials (Au/P[VBTACl]-M metal: Al, Ti or Zr and their use as heterogeneous catalysts in liquid phase hydrogenation of p-chloronitrobenzene. The support was prepared by in situ radical polymerization/sol gel process of (4-vinyl-benzyltrimethylammonium chloride and 3-(trimethoxysilylpropyl methacrylate in conjunction with metal-alkoxides as metal oxide precursors. The supported catalyst was prepared by an ion exchange process using chloroauric acid (HAuCl4 as gold precursor. The support provided the appropriate environment to induce the spontaneous reduction and deposition of gold nanoparticles. The hybrid material was characterized. TEM and DRUV-vis results indicated that the gold forms spherical metallic nanoparticles and that their mean diameter increases in the sequence, Au/P[VBTACl]-Zr > Au/P[VBTACl]-Al > Au/P[VBTACl]-Ti. The reactivity of the Au catalysts toward the p-CNB hydrogenation reaction is attributed to the different particle size distributions of gold nanoparticles in the hybrid supports. The kinetic pseudo-first-order constant values for the catalysts in the hydrogenation reaction increases in the order, Au/P[VBTACl]-Al > Au/P[VBTACl]-Zr > Au/P[VBTACl]-Ti. The selectivity for all the catalytic systems was greater than 99% toward the chloroaniline target product. Finally the catalyst supported on the hybrid with Al as metal oxide could be reused at least four times without loss in activity or selectivity for the hydrogenation of p-CNB in ethanol as solvent.

  10. Recovery of Ni Metal from Spent Catalyst with Emulsion Liquid Membrane Using Cyanex 272 as Extractant

    Yuliusman; Huda, M.; Ramadhan, I. T.; Farry, A. R.; Wulandari, P. T.; Alfia, R.

    2018-03-01

    In this study was conducted to recover nickel metal from spent nickel catalyst resulting from hydrotreating process in petroleum industry. The nickel extraction study with the emulsion liquid membrane using Cyanex 272 as an extractant to extract and separate nickel from the feed phase solution. Feed phase solution was preapred from spent catalyst using sulphuric acid. Liquid membrane consists of a kerosene as diluent, a Span 80 as surfactant, a Cyanex 272 as carrier and sulphuric acid solutions have been used as the stripping solution. The important parameters governing the permeation of nickel and their effect on the separation process have been studied. These parameters are surfactant concentration, extractant concentration feed phase pH. The optimum conditions of the emulsion membrane making process is using 0.06 M Cyanex 272, 8% w/v SPAN 80, 0.05 M H2SO4, internal phase extractant / phase volume ratio: 1/1, and stirring speed 1150 rpm for 60 Minute that can produce emulsion membrane with stability level above 90% after 4 hours. In the extraction process with optimum condition pH 6 for feed phase, ratio of phase emulsion/phase of feed: 1/2, and stirring speed 175 rpm for 15 minutes with result 81.51% nickel was extracted.

  11. Photo-electrocatalytic hydrogen generation at dye-sensitised electrodes functionalised with a heterogeneous metal catalyst

    Hoogeveen, Dijon A.; Fournier, Maxime; Bonke, Shannon A.; Fang, Xi-Ya; Mozer, Attila J.; Mishra, Amaresh; Bäuerle, Peter; Simonov, Alexandr N.; Spiccia, Leone

    2016-01-01

    Dye-sensitised photocathodes promoting hydrogen evolution are usually coupled to a catalyst to improve the reaction rate. Herein, we report on the first successful integration of a heterogeneous metal particulate catalyst, viz., Pt aggregates electrodeposited from acidic solutions on the surface of a NiO-based photocathode sensitised with a p-type perylenemonoimid-sexithiophene-triphenylamine dye (PMI-6T-TPA). The platinised dye-NiO electrodes generate photocurrent density of ca −0.03 mA cm −2 (geom.) with 100% faradaic efficiency for the H 2 evolution at 0.059 V vs. reversible hydrogen electrode under 1 sun visible light irradiation (AM1.5G, 100 mW cm −2 , λ > 400 nm) for more than 10 hours in 0.1 M H 2 SO 4 (aq.). The Pt-free dye-NiO and dye-free Pt-modified NiO cathodes show no photo-electrocatalytic hydrogen evolution under these conditions. The performance of these Pt-modified PMI-6T-TPA-based photoelectrodes compares well to that of previously reported dye-sensitised photocathodes for H 2 evolution.

  12. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

    Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

    2015-01-01

    Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanof...

  13. Airborne concentrations of metals and total dust during solid catalyst loading and unloading operations at a petroleum refinery.

    Lewis, Ryan C; Gaffney, Shannon H; Le, Matthew H; Unice, Ken M; Paustenbach, Dennis J

    2012-09-01

    Workers handle catalysts extensively at petroleum refineries throughout the world each year; however, little information is available regarding the airborne concentrations and plausible exposures during this type of work. In this paper, we evaluated the airborne concentrations of 15 metals and total dust generated during solid catalyst loading and unloading operations at one of the largest petroleum refineries in the world using historical industrial hygiene samples collected between 1989 and 2006. The total dust and metals, which included aluminum, cadmium, chromium, cobalt, copper, iron, lead, manganese, molybdenum, nickel, platinum, silicon, silver, vanadium, and zinc, were evaluated in relation to the handling of four different types of solid catalysts associated with three major types of catalytic processes. Consideration was given to the known components of the solid catalysts and any metals that were likely deposited onto them during use. A total of 180 analytical results were included in this analysis, representing 13 personal and 54 area samples. Of the long-term personal samples, airborne concentrations of metals ranged from refinery and perhaps other modern refineries during the timeframe examined. Copyright © 2011 Elsevier GmbH. All rights reserved.

  14. Application of Two Cobalt-Based Metal-Organic Frameworks as Oxidative Desulfurization Catalysts.

    Masoomi, Mohammad Yaser; Bagheri, Minoo; Morsali, Ali

    2015-12-07

    Two new porous cobalt-based metal-organic frameworks, [Co6(oba)5(OH)2(H2O)2(DMF)4]n · 5DMF (TMU-10) and [Co3(oba)3(O) (Py)0.5] n · 4DMF · Py (TMU-12) have been synthesized by solvothermal method using a nonlinear dicarboxylate ligand. Under mild reaction conditions, these compounds exhibited good catalytic activity and reusability in oxidative desulfurization (ODS) reaction of model oil which was prepared by dissolving dibenzothiophene (DBT) in n-hexane. FT-IR and Mass analysis showed that the main product of DBT oxidation is its corresponding sulfone, which was adsorbed on the surfaces of catalysts. The activation energy was obtained as 13.4 kJ/mol.

  15. Catalyst-free growth of InN nanorods by metal-organic chemical vapor deposition

    Kim, Min Hwa; Moon, Dae Young; Park, Jinsub; Nanishi, Yasushi; Yi, Gyu-Chul; Yoon, Euijoon

    2012-01-01

    We demonstrated the growth of catalyst-free InN nanostructures including nanorods on (0001) Al 2 O 3 substrates using metal-organic chemical vapor deposition. As the growth time increased, growth rate along c-direction increased superlinearly with decreasing c-plane area fractions and increasing side wall areas. It was also found that desorption from the sidewalls of InN nanostructures during the InN nanorods formation was one of essential key parameters of the growth mechanism. We propose a growth model to explain the InN nanostructure evolution by considering the side wall desorption and re-deposition of indium at top c-plane surfaces. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. Applications of Immobilized Bio-Catalyst in Metal-Organic Frameworks

    Qi Wang

    2018-04-01

    Full Text Available Immobilization of bio-catalysts in solid porous materials has attracted much attention in the last few decades due to its vast application potential in ex vivo catalysis. Despite the high efficiency and selectivity of enzymatic catalytic processes, enzymes may suffer from denaturation under industrial production conditions, which, in turn, diminish their catalytic performances and long-term recyclability. Metal-organic frameworks (MOFs, as a growing type of hybrid materials, have been identified as promising platforms for enzyme immobilization owing to their enormous structural and functional tunability, and extraordinary porosity. This review mainly focuses on the applications of enzyme@MOFs hybrid materials in catalysis, sensing, and detection. The improvements of catalytic activity and robustness of encapsulated enzymes over the free counterpart are discussed in detail.

  17. Influence of Multi-Valency, Electrostatics and Molecular Recognition on the Adsorption of Transition Metal Complexes on Metal Oxides: A Molecular Approach to Catalyst Synthesis

    Rioux, Robert M. [Pennsylvania State Univ., University Park, PA (United States)

    2017-03-31

    In this work, we have primarily utilized isothermal titration calorimetry (ITC) and complimentary catalyst characterization techniques to study and assess the impact of solution conditions (i.e., solid-liquid) interface on the synthesis of heterogeneous and electro-catalysts. Isothermal titration calorimetry is well-known technique from biochemistry/physics, but has been applied to a far lesser extent to characterize buried solid-liquid interfaces in materials science. We demonstrate the utility and unique information provided by ITC for two distinct catalytic systems. We explored the thermodynamics associated catalyst synthesis for two systems: (i) ion-exchange or strong electrostatic adsorption for Pt and Pd salts on silica and alumina materials (ii) adsorption to provide covalent attachment of metal and metal-oxo clusters to Dion-Jacobsen perovskite materials.

  18. C-H functionalization: thoroughly tuning ligands at a metal ion, a chemist can greatly enhance catalyst's activity and selectivity.

    Shul'pin, Georgiy B

    2013-09-28

    This brief essay consists of a few "exciting stories" devoted to relations within a metal-complex catalyst between a metal ion and a coordinated ligand. When, as in the case of a human couple, the rapport of the partners is cordial and a love cements these relations, a chemist finds an ideal married couple, in other words he obtains a catalyst of choice which allows him to functionalize C-H bonds very efficiently and selectively. Examples of such lucky marriages in the catalytic world of ions and ligands are discussed here. Activity of the catalyst is characterized by turnover number (TON) or turnover frequency (TOF) as well as by yield of a target product. Introducing a chelating N,N- or N,O-ligand to the catalyst molecule (this can be an iron or manganese derivative) sharply enhances its activity. However, the activity of vanadium derivatives (with additionally added to the solution pyrazinecarboxylic acid, PCA) as well as of various osmium complexes does not dramatically depend on the nature of ligands surrounding metal ions. Complexes of these metals are very efficient catalysts in oxidations with H2O2. Osmium derivatives are record-holders exhibiting extremely high TONs whereas vanadium complexes are on the second position. Finally, elegant examples of alkane functionalization on the ions of non-transition metals (aluminium, gallium etc.) are described when one ligand within the metal complex (namely, hydroperoxyl ligand HOO(-)) helps other ligand of this complex (H2O2 molecule coordinated to the metal) to disintegrate into two species, generating very reactive hydroxyl radical. Hydrogen peroxide molecule, even ligated to the metal ion, is perfectly stable without the assistance of the neighboring HOO(-) ligand. This ligand can be easily oxidized donating an electron to its partner ligand (H2O2). In an analogous case, when the central ion in the catalyst is a transition metal, this ion changing its oxidation state can donate an electron to the coordinated H2O2

  19. Structural and Dynamical Properties of Alkaline Earth Metal Halides in Supercritical Water: Effect of Ion Size and Concentration.

    Keshri, Sonanki; Tembe, B L

    2017-11-22

    Constant temperature-constant pressure molecular dynamics simulations have been performed for aqueous alkaline earth metal chloride [M 2+ -Cl - (M = Mg, Ca, Sr, and Ba)] solutions over a wide range of concentrations (0.27-5.55 m) in supercritical (SC) and ambient conditions to investigate their structural and dynamical properties. A strong influence of the salt concentration is observed on the ion-ion pair correlation functions in both ambient and SC conditions. In SC conditions, significant clustering is observed in the 0.27 m solution, whereas the reverse situation is observed at room temperature and this is also supported by the residence times of the clusters. The concentration and ion size (cation size) seem to have opposite effects on the average number of hydrogen bonds. The simulation results show that the self-diffusion coefficients of water, cations, and the chloride ion increase with increasing temperature, whereas they decrease with increasing salt concentration. The cluster size distribution shows a strong density dependence in both ambient and SC conditions. In SC conditions, cluster sizes display a near-Gaussian distribution, whereas the distribution decays monotonically in ambient conditions.

  20. Entropy in halide perovskites

    Katan, Claudine; Mohite, Aditya D.; Even, Jacky

    2018-05-01

    Claudine Katan, Aditya D. Mohite and Jacky Even discuss the possible impact of various entropy contributions (stochastic structural fluctuations, anharmonicity and lattice softness) on the optoelectronic properties of halide perovskite materials and devices.

  1. Mechanochemical synthesis of graphene oxide-supported transition metal catalysts for the oxidation of isoeugenol to vanillin.

    Franco, Ana; De, Sudipta; Balu, Alina M; Garcia, Araceli; Luque, Rafael

    2017-01-01

    Vanillin is one of the most commonly used natural products, which can also be produced from lignin-derived feedstocks. The chemical synthesis of vanillin is well-established in large-scale production from petrochemical-based starting materials. To overcome this problem, lignin-derived monomers (such as eugenol, isoeugenol, ferulic acid etc.) have been effectively used in the past few years. However, selective and efficient production of vanillin from these feedstocks still remains an issue to replace the existing process. In this work, new transition metal-based catalysts were proposed to investigate their efficiency in vanillin production. Reduced graphene oxide supported Fe and Co catalysts showed high conversion of isoeugenol under mild reaction conditions using H 2 O 2 as oxidizing agent. Fe catalysts were more selective as compared to Co catalysts, providing a 63% vanillin selectivity at 61% conversion in 2 h. The mechanochemical process was demonstrated as an effective approach to prepare supported metal catalysts that exhibited high activity for the production of vanillin from isoeugenol.

  2. Mechanochemical synthesis of graphene oxide-supported transition metal catalysts for the oxidation of isoeugenol to vanillin

    Ana Franco

    2017-07-01

    Full Text Available Vanillin is one of the most commonly used natural products, which can also be produced from lignin-derived feedstocks. The chemical synthesis of vanillin is well-established in large-scale production from petrochemical-based starting materials. To overcome this problem, lignin-derived monomers (such as eugenol, isoeugenol, ferulic acid etc. have been effectively used in the past few years. However, selective and efficient production of vanillin from these feedstocks still remains an issue to replace the existing process. In this work, new transition metal-based catalysts were proposed to investigate their efficiency in vanillin production. Reduced graphene oxide supported Fe and Co catalysts showed high conversion of isoeugenol under mild reaction conditions using H2O2 as oxidizing agent. Fe catalysts were more selective as compared to Co catalysts, providing a 63% vanillin selectivity at 61% conversion in 2 h. The mechanochemical process was demonstrated as an effective approach to prepare supported metal catalysts that exhibited high activity for the production of vanillin from isoeugenol.

  3. Low-temperature conversion of ammonia to nitrogen in water with ozone over composite metal oxide catalyst.

    Chen, Yunnen; Wu, Ye; Liu, Chen; Guo, Lin; Nie, Jinxia; Chen, Yu; Qiu, Tingsheng

    2018-04-01

    As one of the most important water pollutants, ammonia nitrogen emissions have increased year by year, which has attracted people's attention. Catalytic ozonation technology, which involves production of ·OH radical with strong oxidation ability, is widely used in the treatment of organic-containing wastewater. In this work, MgO-Co 3 O 4 composite metal oxide catalysts prepared with different fabrication conditions have been systematically evaluated and compared in the catalytic ozonation of ammonia (50mg/L) in water. In terms of high catalytic activity in ammonia decomposition and high selectivity for gaseous nitrogen, the catalyst with MgO-Co 3 O 4 molar ratio 8:2, calcined at 500°C for 3hr, was the best one among the catalysts we tested, with an ammonia nitrogen removal rate of 85.2% and gaseous nitrogen selectivity of 44.8%. In addition, the reaction mechanism of ozonation oxidative decomposition of ammonia nitrogen in water with the metal oxide catalysts was discussed. Moreover, the effect of coexisting anions on the degradation of ammonia was studied, finding that SO 4 2- and HCO 3 - could inhibit the catalytic activity while CO 3 2- and Br - could promote it. The presence of coexisting cations had very little effect on the catalytic ozonation of ammonia nitrogen. After five successive reuses, the catalyst remained stable in the catalytic ozonation of ammonia. Copyright © 2017. Published by Elsevier B.V.

  4. Electrical enhancement of direct methanol fuel cells by metal-plasma ion implantation Pt-Ru/C multilayer catalysts.

    Weng, Ko-Wei; Chen, Yung-Lin; Chen, Ya-Chi; Lin, Tai-Nan

    2009-02-01

    Direct methanol fuel cells (DMFC) have been widely studied owing to their simple cell configuration, high volume energy density, short start-up time, high operational reliability and other favorable characteristics. However, major limitations include high production cost, poisoning of the catalyst and methanol crossover. This study adopts a simple technique for preparing Pt-Ru/C multilayer catalysts, including magnetron sputtering (MS) and metal-plasma ion implantation (MPII). The Pt catalysts were sputtered onto the gas diffusion layer (GDL), followed by the implantation of Ru catalysts using MPII (at an accelerating voltage of 20 kV and an implantation dose of 1 x 10(16) ions/cm2). Pt-Ru is repeatedly processed to prepare Pt-Ru/C multilayer catalysts. The catalyst film structure and microstructure were analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electronic microscopy (SEM), respectively. The cell performance was tested using a potential stat/galvano-stat. The results reveal that the membrane electrode assembly (MEA) of four multilayer structures enhances the cell performance of DMFC. The measured power density is 2.2 mW/cm2 at a methanol concentration of 2 M, with an OCV of 0.493 V.

  5. Methane coupling reaction in an oxy-steam stream through an OH radical pathway by using supported alkali metal catalysts

    Liang, Yin

    2014-03-24

    A universal reaction mechanism involved in the oxidative coupling of methane (OCM) is demonstrated under oxy-steam conditions using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from a H 2O-O2 reaction followed by C-H activation in CH 4 with an OH radical. Thus, the presence of water enhances both the CH4 conversion rate and the C2 selectivity. This OH radical pathway that is selective for the OCM was observed for the catalyst without Mn, which suggests clearly that Mn is not the essential component in a selective OCM catalyst. The experiments with different catalyst compositions revealed that the OH.-mediated pathway proceeded in the presence of catalysts with different alkali metals (Na, K) and different oxo anions (W, Mo). This difference in catalytic activity for OH radical generation accounts for the different OCM selectivities. As a result, a high C2 yield is achievable by using Na2WO4/SiO2, which catalyzes the OH.-mediated pathway selectively. Make it methane: A universal reaction mechanism involved in the oxidative coupling of methane is demonstrated under oxy-stream conditions by using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from an H2O-O2 reaction, followed by C-H activation in CH4 with an OH radical. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Investigating the gas phase emitter effect of caesium and cerium in ceramic metal halide lamps in dependence on the operating frequency

    Ruhrmann, C; Westermeier, M; Bergner, A; Awakowicz, P; Mentel, J [Ruhr University Bochum, Electrical Engineering and Plasma Technology, D-44780 Bochum (Germany); Luijks, G M J F, E-mail: juergen.mentel@ruhr-uni-bochum.de [Philips Lighting, GBU HID, PO box 80020, 5600JM Eindhoven (Netherlands)

    2011-09-07

    The work function and with it the temperature of tungsten electrodes in HID lamps can be lowered and the lifetime of lamps increased by the gas phase emitter effect. A determination of the emitter effect of Cs and Ce is performed by phase resolved measurements of the electrode tip temperature T{sub tip}({psi}), plasma temperature T{sub pl}({psi}) and particle densities N({psi}) by means of pyrometric, optical emission and broadband absorption spectroscopy in dependence on the operating frequency. The investigated HID lamps are ceramic metal halide lamps with transparent discharge vessels made of YAG, filled with a buffer gas consisting of Ar, Kr and predominantly Hg and seeded with CsI or CeI{sub 3}. In the YAG lamp seeded with CsI and CeI{sub 3} as well as in a YAG lamp seeded with DyI{sub 3} (corresponding results can be found in a preceding paper) a gas phase emitter effect is observed in the cathodic phase due to a Cs, Ce or Dy ion current. In the YAG lamp seeded with CsI the phase averaged coverage of the electrode surface with emitter atoms decreases and the electrode temperature rises with increasing frequency, whereas the emitter effect of Ce and Dy is extended to the anodic phase, which leads to a decreased average temperature T{sub tip}({psi}) with increasing frequency. This different behaviour of the averaged values of T{sub tip}({psi}) for increasing frequency is caused by the differing adsorption energies E{sub a} of the respective emitter materials. In spite of the influence of E{sub a} on the coverage of the electrode with emitter atoms, the cathodic gas phase emitter effect produces in the YAG lamps seeded with CsI, CeI{sub 3} and DyI{sub 3} a general reduction in the electrode tip temperature T{sub tip}({psi}) in comparison with a YAG lamp with Hg filling only.

  7. Metal-Exchanged β Zeolites as Catalysts for the Conversion of Acetone to Hydrocarbons

    Aurora J. Cruz-Cabeza

    2012-01-01

    Full Text Available Various metal-β zeolites have been synthesized under similar ion-exchange conditions. During the exchange process, the nature and acid strength of the used cations modified the composition and textural properties as well as the Brönsted and Lewis acidity of the final materials. Zeolites exchanged with divalent cations showed a clear decrease of their surface Brönsted acidity and an increase of their Lewis acidity. All materials were active as catalysts for the transformation of acetone into hydrocarbons. Although the protonic zeolite was the most active in the acetone conversion (96.8% conversion, the metal-exchanged zeolites showed varied selectivities towards different products of the reaction. In particular, we found the Cu-β to have a considerable selectivity towards the production of isobutene from acetone (over 31% yield compared to 7.5% of the protonic zeolite. We propose different reactions mechanisms in order to explain the final product distributions.

  8. Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework.

    Kim, In Soo; Li, Zhanyong; Zheng, Jian; Platero-Prats, Ana E; Mavrandonakis, Andreas; Pellizzeri, Steven; Ferrandon, Magali; Vjunov, Aleksei; Gallington, Leighanne C; Webber, Thomas E; Vermeulen, Nicolaas A; Penn, R Lee; Getman, Rachel B; Cramer, Christopher J; Chapman, Karena W; Camaioni, Donald M; Fulton, John L; Lercher, Johannes A; Farha, Omar K; Hupp, Joseph T; Martinson, Alex B F

    2018-01-22

    Single atoms and few-atom clusters of platinum are uniformly installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and X-ray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Recycling CO 2 ? Computational Considerations of the Activation of CO 2 with Homogeneous Transition Metal Catalysts

    Drees, Markus

    2012-08-10

    Faced with depleting fossil carbon sources, the search for alternative energy carriers and energy storage possibilities has become an important issue. Nature utilizes carbon dioxide as starting material for storing sun energy in plant hydrocarbons. A similar approach, storing energy from renewable sources in chemical bonds with CO 2 as starting material, may lead to partial recycling of CO 2 created by human industrial activities. Unfortunately, currently available routes for the transformation of CO 2 involve high temperatures and are often not selective. With the development of more sophisticated methods and better software, theoretical studies have become both increasingly widespread and useful. This concept article summarizes theoretical investigations of the current state of the feasibility of CO 2 activation with molecular transition metal catalysts, highlighting the most promising reactions of CO 2 with olefins to industrially relevant acrylic acid/acrylates, and the insertion of CO 2 into metal-element bonds, particularly for the synthesis of cyclic carbonates and polymers. Rapidly improving computational power and methods help to increase the importance and accuracy of calculations continuously and make computational chemistry a useful tool helping to solve some of the most important questions for the future. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Interações hiperfinas em catalisadores metálicos Hyperfine interactions in metallic catalysts

    Henrique Saitovitch; Paulo R. J. Silva; Fabio B. Passos

    2005-01-01

    Heterogeneous catalysts are of fundamental importance in several modern chemical processes. The characterization of catalysts is an issue of very present interest as it can provide a better understanding of the fundamental aspects of the catalytic phenomena, thus helping in the development of more efficient catalysts. In order to extend and improve the characterization of catalysts, new and less conventional methods are being applied, such as nuclear spectroscopies. In this paper we focus on ...

  11. Metal-Organic-Framework mediated supported-cobalt catalysts in multiphase hydrogenation reactions

    Sun, X.

    2017-01-01

    The production of most industrially important chemicals involves catalysis. Depending on the difference in phases between the catalysts and reactants, one distinguishes homogenous catalysis and heterogeneous catalysis, with the latter being more attractive in real applications, due to the easy separation of products from catalysts and reusing the latter. In spite of the research and development of heterogeneous catalysts for decades, the exploration for catalysts system with outstanding activ...

  12. Photodynamic therapy using a novel irradiation source, LED lamp, is similarly effective to photodynamic therapy using diode laser or metal-halide lamp on DMBA- and TPA-induced mouse skin papillomas.

    Takahashi, Hidetoshi; Nakajima, Susumu; Ogasawara, Koji; Asano, Ryuji; Nakae, Yoshinori; Sakata, Isao; Iizuka, Hajime

    2014-08-01

    Photodynamic therapy (PDT) is useful for superficial skin tumors such as actinic keratosis and Bowen disease. Although PDT is non-surgical and easily-performed treatment modality, irradiation apparatus is large and expensive. Using 7, 12-dimethylbenz[a]anthracene (DMBA) and 12-ο-tetradecanoylphorbol-13-acetate (TPA)-induced mouse skin papilloma model, we compared the efficacy of TONS501- and ALA-PDT with a LED lamp, a diode laser lamp or a metal-halide lamp on the skin tumor regression. TONS501-PDT using 660 nm LED lamp showed anti-tumor effect at 1 day following the irradiation and the maximal anti-tumor effect was observed at 3 days following the irradiation. There was no significant difference in the anti-tumor effects among TONS501-PDT using LED, TONS501-PDT using diode laser, and 5-aminolevulinic acid hydrochloride (ALA)-PDT using metal-halide lamp. Potent anti-tumor effect on DMBA- and TPA-induced mouse skin papilloma was observed by TONS501-PDT using 660 nm LED, which might be more useful for clinical applications. © 2014 Japanese Dermatological Association.

  13. Niobium-based catalysts prepared by reactive radio-frequency magnetron sputtering and arc plasma methods as non-noble metal cathode catalysts for polymer electrolyte fuel cells

    Ohnishi, Ryohji; Katayama, Masao; Takanabe, Kazuhiro; Kubota, Jun; Domen, Kazunari

    2010-01-01

    Two vacuum methods, reactive radio-frequency (RF) magnetron sputtering and arc plasma deposition, were used to prepare niobium-based catalysts for an oxygen reduction reaction (ORR) as non-noble metal cathodes for polymer electrode fuel cells (PEFCs). Thin films with various N and O contents, denoted as NbO x and Nb-O-N, were prepared on glassy carbon plates by RF magnetron sputtering with controlled partial pressures of oxygen and nitrogen. Electrochemical measurements indicated that the introduction of the nitrogen species into the thin film resulted in improved ORR activity compared to the oxide-only film. Using an arc plasma method, niobium was deposited on highly oriented pyrolytic graphite (HOPG) substrates, and the sub-nanoscale surface morphology of the deposited particles was investigated using scanning tunneling microscopy (STM). To prepare practical cathode catalysts, niobium was deposited on carbon black (CB) powders by arc plasma method. STM and transmission electron microscopy observations of samples on HOPG and CB indicated that the prepared catalysts were highly dispersed at the atomic level. The onset potential of oxygen reduction on Nb-O-N/CB was 0.86 V vs. a reversible hydrogen electrode, and the apparent current density was drastically improved by the introduction of nitrogen.

  14. Controllable synthesis of metal selenide heterostructures mediated by Ag2Se nanocrystals acting as catalysts

    Zhou, Jiangcong; Huang, Feng; Xu, Ju; Wang, Yuansheng

    2013-09-01

    Ag2Se nanocrystals were demonstrated to be novel semiconductor mediators, or in other word catalysts, for the growth of semiconductor heterostructures in solution. This is a result of the unique feature of Ag2Se as a fast ion conductor, allowing foreign cations to dissolve and then to heterogrow the second phase. Using Ag2Se nanocrystals as catalysts, dimeric metal selenide heterostructures such as Ag2Se-CdSe and Ag2Se-ZnSe, and even multi-segment heterostructures such as Ag2Se-CdSe-ZnSe and Ag2Se-ZnSe-CdSe, were successfully synthesized. Several interesting features were found in the Ag2Se based heterogrowth. At the initial stage of heterogrowth, a layer of the second phase forms on the surface of an Ag2Se nanosphere, with a curved junction interface between the two phases. With further growth of the second phase, the Ag2Se nanosphere tends to flatten the junction surface by modifying its shape from sphere to hemisphere in order to minimize the conjunct area and thus the interfacial energy. Notably, the crystallographic relationship of the two phases in the heterostructure varies with the lattice parameters of the second phase, in order to reduce the lattice mismatch at the interface. Furthermore, a small lattice mismatch at the interface results in a straight rod-like second phase, while a large lattice mismatch would induce a tortuous product. The reported results may provide a new route for developing novel selenide semiconductor heterostructures which are potentially applicable in optoelectronic, biomedical, photovoltaic and catalytic fields.Ag2Se nanocrystals were demonstrated to be novel semiconductor mediators, or in other word catalysts, for the growth of semiconductor heterostructures in solution. This is a result of the unique feature of Ag2Se as a fast ion conductor, allowing foreign cations to dissolve and then to heterogrow the second phase. Using Ag2Se nanocrystals as catalysts, dimeric metal selenide heterostructures such as Ag2Se-CdSe and Ag2Se

  15. Synthesis and characterization of group V metal carbide and nitride catalysts

    Kwon, Heock-Hoi

    1998-11-01

    Group V transition metal carbides and nitrides were prepared via the temperature programmed reaction (TPR) of corresponding oxides with NHsb3 or a CHsb4/Hsb2 mixture. Except for the tantalum compounds, phase-pure carbides and nitrides were prepared. The vanadium carbides and nitrides were the most active and selective catalysts. Therefore the principal focus of the research was the preparation, characterization, and evaluation of high surface area vanadium nitride catalysts. A series of vanadium nitrides with surface areas up to 60 msp2/g was prepared. Thermal gravimetric analysis coupled with x-ray diffraction and scanning electron microscopy indicated that the solid-state reaction proceeded by the sequential reduction of Vsb2Osb5 to VOsb{0.9} and concluded with the topotactic substitution of nitrogen for oxygen in VOsb{0.9}. The transformation of Vsb2Osb5 to VN was pseudomorphic. An experimental design was executed to determine effects of the heating rates and space velocities on the VN microstructures. The heating rates had minor effects on the surface areas and pore size distributions; however, increasing the space velocity significantly increased the surface area. The materials were mostly mesoporous. Oxygen chemisorption on the vanadium nitrides scaled linearly with the surface area. The corresponding O/Vsbsurface ratio was ≈0.6. The vanadium nitrides were active for butane activation and pyridine hydrodenitrogenation. During butane activation, their selectivities towards dehydrogenation products were as high as 98%. The major product in pyridine hydrodenitrogenation was pentane. The reaction rates increased almost linearly with the surface area suggesting that these reactions were structure insensitive. The vanadium nitrides were not active for crotonaldehyde hydrogenation; however, they catalyzed an interesting ring formation reaction that produced methylbenzaldehyde and xylene from crotonaldehyde. A new method was demonstrated for the production of very

  16. Carbon nanotubes and other nanostructures as support material for nanoparticulate noble-metal catalysts in fuel cells

    Veltzé, Sune; Larsen, Mikkel Juul; Elina, Yli-Rantala

    or platinum-alloy catalysts in the electrodes are required. To maximize the utilization of the noble metal it is frequently deposited as nanoparticles (1–5 nm) on a stabilizing support of carbon black. Carbon black provides good anchoring of the catalyst particles, but is prone to severe destructive oxidation...... at high electrical potentials encountered occasionally in fuel cells. Other nanostructures of carbon are being investigated as alternatives to carbon black as they have several beneficial properties. Multi-walled carbon nanotubes (MW-CNT) are an example of one type of these promising materials. Like...... of the fuel-cell electrodes. However, the low concentration of structural defects also poses challenges with regard to anchoring of the catalyst particles on the CNT surface. Thus, activation treatments introducing surface functional groups may be necessary. Also, the surface properties are responsible...

  17. Palladium Loaded on Magnetic Nanoparticles as Efficient and Recyclable Catalyst for the Suzuki- Miyaura Reaction

    H. Khojasteh

    2015-07-01

    Full Text Available Palladium is the best metal catalyst for Suzuki cross coupling reaction for synthesize of unsymmetrical biaryl compounds. But its high cost limits its application in wide scale. Using of nanoscale particles as active catalytic cites is a good approach for reducing needed noble metal. By loading precious nanoparticles on magnetic nanocores as a support, recycling and reusing of catalyst will be possible. Magnetic nanoparticles have super paramagnetic feature and applying an external magnetic field can collect the supported catalyst from reaction milieu simply. In this work new palladium catalyst immobilized on modified magnetic nanoparticles containing NNO donor atoms were synthesized. Then the catalyst characterized by FT-IR spectroscopy, thermogravimetric analysis, X-ray diffraction and ICP. Prepared catalyst showed high activity in the Suzuki– Miyaura cross-coupling reaction of phenylboronic acid with aryl halides. Activity, Pd loading, reusability and Pd leaching of catalyst were studied. Results showed that the supported catalyst has the advantage to be completely recoverable with the simple application of an external magnetic field.

  18. NO reduction by CO over noble-metal catalysts under cycled feedstreams

    Muraki, H.; Fujitani, Y.

    1986-01-01

    The reduction of NO with CO was studied over α-Al/sub 2/O/sub 3/-supported Pt, Pd, Rh, Ru, and Ir catalysts. The activities were measured by using cycled feeds and steady noncycled feed. The activity sequence of the catalysts tested was Rh > Ru > Ir > Pd > Pt. The activities of Pt and Pd catalysts were increased under the cycled feed. The periodic operation effect on the Pt catalyst was more predominant than that on the Pd catalyst. The order of periodic operation effect corresponded to the order of their susceptibility to CO self-poisoning

  19. One step bioconversion of waste precious metals into Serratia biofilm-immobilized catalyst for Cr(VI) reduction.

    Yong, P; Liu, W; Zhang, Z; Beauregard, D; Johns, M L; Macaskie, L E

    2015-11-01

    For reduction of Cr(VI) the Pd-catalyst is excellent but costly. The objectives were to prove the robustness of a Serratia biofilm as a support for biogenic Pd-nanoparticles and to fabricate effective catalyst from precious metal waste. Nanoparticles (NPs) of palladium were immobilized on polyurethane reticulated foam and polypropylene supports via adhesive biofilm of a Serratia sp. The biofilm adhesion and cohesion strength were unaffected by palladization and catalytic biofilm integrity was also shown by magnetic resonance imaging. Biofilm-Pd and mixed precious metals on biofilm (biofilm-PM) reduced 5 mM Cr(VI) to Cr(III) when immobilized in a flow-through column reactor, at respective flow rates of 9 and 6 ml/h. The lower activity of the latter was attributed to fewer, larger, metal deposits on the bacteria. Activity was lost in each case at pH 7 but was restored by washing with 5 mM citrate solution or by exposure of columns to solution at pH 2, suggesting fouling by Cr(III) hydroxide product at neutral pH. A 'one pot' conversion of precious metal waste into new catalyst for waste decontamination was shown in a continuous flow system based on the use of Serratia biofilm to manufacture and support catalytic Pd-nanoparticles.

  20. A Comparative Study of Mn/Co Binary Metal Catalysts Supported on Two Commercial Diatomaceous Earths for Oxidation of Benzene

    Marco Tomatis

    2018-03-01

    Full Text Available Two commercial diatomaceous earths were used as supports for the preparation of Mn/Co binary metal catalysts at different metal loads (5 to 10 wt % Mn and 5 to 15 wt % Co by incipient wetness deposition. The activity of the prepared catalysts towards the complete oxidation of benzene to CO2 and water was investigated between 100 and 400 °C. Raw supports and synthesized catalysts were characterized by XRD, N2 physisorption, SEM-EDS, H2-TPR, and TPD. The purification treatment of food-grade diatomite significantly affected the crystallinity of this support while reducing its specific surface area (SSA. A loss of SSA, associated with the increase in the metal load, was observed on samples prepared on natural diatomite, while the opposite trend occurred with food-grade diatomite-supported catalysts. Metal nanoparticles of around 50 nm diameter were observed on the catalysts’ surface by SEM analysis. EDS analysis confirmed the uniform deposition of the active phases on the support’s surface. A larger H2 consumption was found by TPR analysis of natural diatomite-based samples in comparison to those prepared at the same metal load on food-grade diatomite. During the catalytic oxidation experiment, over 90% conversion of benzene were achieved at a reaction temperature of 225 °C by all of the prepared samples. In addition, the formation of coke during the oxidation tests was demonstrated by TGA analysis and the soluble fraction of the produced coke was characterized by GC-MS.

  1. Effects of particulates, heavy metals and acid gas on the removals of NO and PAHs by V2O5-WO3 catalysts in waste incineration system

    Chang, Feng-Yim; Chen, Jyh-Cherng; Wey, Ming-Yen; Tsai, Shih-An

    2009-01-01

    This study investigated the activities of prepared and commercial V 2 O 5 -WO 3 catalysts for simultaneous removals of NO and polycyclic aromatic hydrocarbons (PAHs) and the influences of particulates, heavy metals, SO 2 , and HCl on the performances of catalysts. The experiments were carried out in a laboratory-scale waste incineration system equipped with a catalyst reactor. The DREs of PAHs by prepared and commercial V 2 O 5 -WO 3 catalysts were 64% and 72%, respectively. Increasing the particulate concentrations in flue gas suppressed the DRE of PAHs, but increasing the carbon content on surface of catalysts promotes the NO conversions. The DRE of PAHs by the catalysts was significantly decreased by the increased concentrations of heavy metal Cd, but was promoted by high concentration of Pb. The influence level of SO 2 was higher than HCl on the performances of V 2 O 5 -WO 3 catalysts for PAHs removal, but was lower than HCl for NO removal. Prepared and commercial V 2 O 5 -WO 3 catalysts have similar trends on the effects of particulates, heavy metals, SO 2 , and HCl. The results of ESCA analysis reveal that the presences of these pollutants on the surface of catalysts did not change the chemical state of V and W.

  2. Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network

    Shui, Jianglan; Chen, Chen; Grabstanowicz, Lauren; Zhao, Dan; Liu, Di-Jia

    2015-01-01

    Fuel cell vehicles, the only all-electric technology with a demonstrated >300 miles per fill travel range, use Pt as the electrode catalyst. The high price of Pt creates a major cost barrier for large-scale implementation of polymer electrolyte membrane fuel cells. Nonprecious metal catalysts (NPMCs) represent attractive low-cost alternatives. However, a significantly lower turnover frequency at the individual catalytic site renders the traditional carbon-supported NPMCs inadequate in reaching the desired performance afforded by Pt. Unconventional catalyst design aiming at maximizing the active site density at much improved mass and charge transports is essential for the next-generation NPMC. We report here a method of preparing highly efficient, nanofibrous NPMC for cathodic oxygen reduction reaction by electrospinning a polymer solution containing ferrous organometallics and zeolitic imidazolate framework followed by thermal activation. The catalyst offers a carbon nanonetwork architecture made of microporous nanofibers decorated by uniformly distributed high-density active sites. In a single-cell test, the membrane electrode containing such a catalyst delivered unprecedented volumetric activities of 3.3 A⋅cm−3 at 0.9 V or 450 A⋅cm−3 extrapolated at 0.8 V, representing the highest reported value in the literature. Improved fuel cell durability was also observed. PMID:26261338

  3. Chromium-based metal-organic framework MIL-101 as a highly effective catalyst in plasma for toluene removal

    Wu, Junliang; Xia, Qibin; Xiao, Jing; Li, Zhong

    2017-11-01

    Catalytic performance of MIL-101—a type of chromium-based metal-organic frameworks (MOFs)—in a plasma catalysis system for toluene removal was experimentally studied. The MIL-101 was synthesized using a hydrothermal method, and its catalytic performance was compared to two other catalysts, Cr2O3/γ-Al2O3 and γ-Al2O3, in a dielectric barrier discharge (DBD) reactor. Results showed that the presence of a catalyst in plasma changed the voltage and current characteristic substantially, and promoted the performance of the plasma reactor. Among the catalysts, the MIL-101 exhibited a significantly high toluene conversion, which was 20% and 35% higher than Cr2O3/γ-Al2O3 and γ-Al2O3, respectively, under the same testing conditions, as well as higher carbon balance and CO2 selectivity. The analysis of by-products on the surfaces of the catalysts before and after reaction demonstrated that MIL-101 had better resistance towards by-products accumulation compared to Cr2O3/γ-Al2O3 and γ-Al2O3. The loading of MnO x on MIL-101 further promoted its catalytic performance. MIL-101 exhibits attractive catalytic properties as a catalyst in a plasma catalysis system for the decomposition of volatile organic compounds.

  4. Chromium-based metal-organic framework MIL-101 as a highly effective catalyst in plasma for toluene removal

    Wu, Junliang; Xia, Qibin; Xiao, Jing; Li, Zhong

    2017-01-01

    Catalytic performance of MIL-101—a type of chromium-based metal-organic frameworks (MOFs)—in a plasma catalysis system for toluene removal was experimentally studied. The MIL-101 was synthesized using a hydrothermal method, and its catalytic performance was compared to two other catalysts, Cr 2 O 3 / γ -Al 2 O 3 and γ -Al 2 O 3 , in a dielectric barrier discharge (DBD) reactor. Results showed that the presence of a catalyst in plasma changed the voltage and current characteristic substantially, and promoted the performance of the plasma reactor. Among the catalysts, the MIL-101 exhibited a significantly high toluene conversion, which was 20% and 35% higher than Cr 2 O 3 / γ -Al 2 O 3 and γ -Al 2 O 3 , respectively, under the same testing conditions, as well as higher carbon balance and CO 2 selectivity. The analysis of by-products on the surfaces of the catalysts before and after reaction demonstrated that MIL-101 had better resistance towards by-products accumulation compared to Cr 2 O 3 / γ -Al 2 O 3 and γ -Al 2 O 3 . The loading of MnO x on MIL-101 further promoted its catalytic performance. MIL-101 exhibits attractive catalytic properties as a catalyst in a plasma catalysis system for the decomposition of volatile organic compounds. (paper)

  5. Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts.

    Murahashi, Shun-Ichi

    2011-01-01

    This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. (Communicated by Ryoji Noyori, M.J.A.).

  6. Aromatic hydrocarbon production via eucalyptus urophylla pyrolysis over several metal modified ZSM-5 catalysts – an analysis by py-GC/MS

    Metal modified HZSM-5 catalysts were prepared by ion exchange of NH4ZSM-5 (SIO2/Al2O3 = 23) using gallium, molybdenum, nickel and zinc, and their combinations thereof. The prepared catalysts were used to evaluate catalytic pyrolysis for the conversion of Eucalyptus urophylla to fuels and chemicals, ...

  7. Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts

    MURAHASHI, Shun-Ichi

    2011-01-01

    This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. PMID:21558760

  8. Hydrolysis in the organic phase during the extraction of alkali metal halides and water by copper bis(2-ethylhexyl)phosphate

    Golovanov, V.I.; Kuznetsov, S.M.

    2001-01-01

    Experimental data on extraction of halides, among which are LiCl and CsCl, and water by copper di-(2-ethylhexyl)phosphate solutions in respect to hydrolysis mechanism of reaction are generalized. Copper di-(2-ethylhexyl)phosphate manifests properties of ionogen colloidal surfactant in water. Extraction of halides by copper di-(2-ethylhexyl)phosphate was shown to be visualized by the process of capsule formation in MHal molecules, as well as in hydrolyzed MOH and HHal forms of electrolyte by Cu 4 (D2EHF) 8 · hH 2 O clathrate-like micellar associates. The model of hydrolysis mechanism is not different from proposed earlier model of electrolyte extraction with their partial dissociation in organic phase [ru

  9. Non-noble metal based electro-catalyst compositions for proton exchange membrane based water electrolysis and methods of making

    Kumta, Prashant N.; Kadakia, Karan Sandeep; Datta, Moni Kanchan; Velikokhatnyi, Oleg

    2017-02-07

    The invention provides electro-catalyst compositions for an anode electrode of a proton exchange membrane-based water electrolysis system. The compositions include a noble metal component selected from the group consisting of iridium oxide, ruthenium oxide, rhenium oxide and mixtures thereof, and a non-noble metal component selected from the group consisting of tantalum oxide, tin oxide, niobium oxide, titanium oxide, tungsten oxide, molybdenum oxide, yttrium oxide, scandium oxide, cooper oxide, zirconium oxide, nickel oxide and mixtures thereof. Further, the non-noble metal component can include a dopant. The dopant can be at least one element selected from Groups III, V, VI and VII of the Periodic Table. The compositions can be prepared using a surfactant approach or a sol gel approach. Further, the compositions are prepared using noble metal and non-noble metal precursors. Furthermore, a thin film containing the compositions can be deposited onto a substrate to form the anode electrode.

  10. Systemic analysis of thermodynamic properties of lanthanide halides

    Mirsaidov, U.; Badalov, A.; Marufi, V.K.

    1992-01-01

    System analysis of thermodynamic characteristics of lanthanide halides was carried out. A method making allowances for the influence of spin and orbital moments of momentum of the main states of lanthanide trivalent ions in their natural series was employed. Unknown in literature thermodynamic values were calculated and corrected for certain compounds. The character of lanthanide halide thermodynamic parameter change depending on ordinal number of the metals was ascertained. Pronouncement of tetrad-effect in series of compounds considered was pointed out

  11. An introduction to catalyst

    Jeon, Hak Je

    1988-11-01

    This book explains basic conception of catalyst such as definition, velocity of chemical reaction and velocity of catalyst reaction, absorption with absorption energy and chemical absorption, pore structure with the role of pore and measurement of pore structure, catalyst activity on solid structure, electrical property on catalyst activity, choice and design of catalyst, catalytic reaction with reaction velocity and chemical equilibrium and reaction velocity model, measurement of reaction velocity and material analysis, catalyst for mixed compound, catalyst for solid acid and catalyst for supported metal.

  12. Potential of Transition Metal Atoms Embedded in Buckled Monolayer g-C3N4 as Single-Atom Catalysts

    Li, Shu-Long

    2017-10-27

    We use first-principles calculations to systematically explore the potential of transition metal atoms (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) embedded in buckled monolayer g-C3N4 as single-atom catalysts. We show that clustering of Sc and Ti on g-C3N4 is thermodynamically impeded and that V, Cr, Mn, and Cu are much less susceptible to clustering than the other TM atoms under investigation. Strong bonding of the transition metal atoms in the cavities of g-C3N4 and high diffusion barriers together are responsible for single-atom fixation. Analysis of the CO oxidation process indicates that embedding of Cr and Mn in g-C3N4 gives rise to promising single-atom catalysts at low temperature.

  13. Potential of Transition Metal Atoms Embedded in Buckled Monolayer g-C3N4 as Single-Atom Catalysts

    Li, Shu-Long; Kan, Xiang; Yin, Hui; Gan, Li-Yong; Schwingenschlö gl, Udo; Zhao, Yong

    2017-01-01

    We use first-principles calculations to systematically explore the potential of transition metal atoms (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) embedded in buckled monolayer g-C3N4 as single-atom catalysts. We show that clustering of Sc and Ti on g-C3N4 is thermodynamically impeded and that V, Cr, Mn, and Cu are much less susceptible to clustering than the other TM atoms under investigation. Strong bonding of the transition metal atoms in the cavities of g-C3N4 and high diffusion barriers together are responsible for single-atom fixation. Analysis of the CO oxidation process indicates that embedding of Cr and Mn in g-C3N4 gives rise to promising single-atom catalysts at low temperature.

  14. Correction: A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

    Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

    2016-12-22

    Correction for 'A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide' by Chee Koon Ng et al., Chem. Commun., 2016, 52, 11842-11845.

  15. Preparation of Cyclic Urethanes from Amino Alcohols and Carbon Dioxide Using Ionic Liquid Catalysts with Alkali Metal Promoters

    Masahiko Arai; Hisanori Senboku; Hiroshi Kanamaru; Shin-ichiro Fujita

    2006-01-01

    Several ionic liquids were applied as catalysts for the synthesis of cyclic urethanes from amino alcohols and pressurized CO2 in the presence of alkali metal compounds as promoters. A comparative study was made for the catalytic performance using different ionic liquids, substrates, promoters, and pressures. The optimum catalytic system was BMIM-Br promoted by K2CO3, which, for 1-amino-2-propanol, produced cyclic urethane in 40% yield with a smaller yield of substituted cyclic ...

  16. On possibility of preparation of catalysts for ammonia synthesis based on cyanocomplexes of some d-metals

    Sergeeva, A.N.; Dovgej, V.V.; Pavlenko, L.I.; Zubritskaya, D.I.; Tkachenko, Zh.I.; Okorskaya, A.P.; Lyubchenko, Yu.A.

    1983-01-01

    The catalytic properties of the systems prepared on the basis of coordination cyanides of iron, ruthenium, osmium, rhenium, molydenum, vanadium and other d-metals in the ammonia synthesis reaction are studied. It has been found that thermal stability of catalytic systems containing vanadium and molybdenum is considerably higher than that of the industrial sample of similar type containing aluminium. The systems prepared on the basis of hexacyanoferrates, ruthenates and osmates can be referred to low-temperature type catalysts

  17. Recovery of platinum-group metals (PGMS from spent automotive catalysts: Part II: Automotive catalysts: Structures and principle of operation

    Dimitrijević Mile D.

    2015-01-01

    Full Text Available Catalytic converters are incorporated into motor vehicle emission systems (passenger cars, trucks and other motor vehicles, as well as civil and agricultural machines, as of lately to reduce air pollution as well as to meet the emission standards. Their purpose is to convert toxic emissions generated by combustion of liquid fossil fuels into less harmful products. In catalytic converters, rhodium is used for the reduction of gasses, whereas platinum and palladium are used for the oxidation of gasses. This paper presents the structure and operating principle of automotive catalysts in view of the fact that cars are the most prevalent motor vehicles worldwide and due to the fact that the production of cars with gasoline and diesel engines will dominate until at least 2020.

  18. Evaluation of potential for reuse of industrial wastewater using metal-immobilized catalysts and reverse osmosis.

    Choi, Jeongyun; Chung, Jinwook

    2015-04-01

    This report describes a novel technology of reusing the wastewater discharged from the display manufacturing industry through an advanced oxidation process (AOP) with a metal-immobilized catalyst and reverse osmosis (RO) in the pilot scale. The reclaimed water generated from the etching and cleaning processes in display manufacturing facilities was low-strength organic wastewater and was required to be recycled to secure a water source. For the reuse of reclaimed water to ultrapure water (UPW), a combination of solid-phase AOP and RO was implemented. The removal efficiency of TOC by solid-phase AOP and RO was 92%. Specifically, the optimal acid, pH, and H2O2 concentrations in the solid-phase AOP were determined. With regard to water quality and operating costs, the combination of solid-phase AOP and RO was superior to activated carbon/RO and ultraviolet AOP/anion polisher/coal carbon. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. A polyoxometalate-encapsulating cationic metal-organic framework as a heterogeneous catalyst for desulfurization.

    Hao, Xiu-Li; Ma, Yuan-Yuan; Zang, Hong-Ying; Wang, Yong-Hui; Li, Yang-Guang; Wang, En-Bo

    2015-02-23

    A new cationic triazole-based metal-organic framework encapsulating Keggin-type polyoxometalates, with the molecular formula [Co(BBPTZ)3][HPMo12O40]⋅24 H2O [compound 1; BBPTZ = 4,4'-bis(1,2,4-triazol-1-ylmethyl)biphenyl] is hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The structure of compound 1 contains a non-interpenetrated 3D CdSO4 (cds)-type framework with two types of channels that are interconnected with each other; straight channels that are occupied by the Keggin-type POM anions, and wavelike channels that contain lattice water molecules. The catalytic activity of compound 1 in the oxidative desulfurization reaction indicates that it is not only an effective and size-selective heterogeneous catalyst, but it also exhibits distinct structural stability in the catalytic reaction system. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Development of metal catalyst impregnation technology for membrane-based oxygen removal system

    Kim, Mun Soo; Lee, Doo Ho; Kang, Duk Won

    2005-01-01

    Dissolved oxygen(DO) is a primary cause of PWSCC and its content in reactor coolant system in NPPs has been strictly controlled by various DO removal methods. There are several removal methods of DO, such as vacuum degasification, thermal deaeration, and reductive removal by oxygen scavengers. Although the operation principles of vacuum degasification and thermal deaeration are simple, these methods require a lot of energy for operation and show lower efficiency. And these methods have a few handicaps such as temperature, pH, toxicity, high cost of installation and so on. For the purpose of developing the best method for DO removal from make-up water storage tank, it is necessary to overcome the disadvantages of hydrazine treatment. From this point of view, membrane-based oxygen removal system (MORS) has many advantages than other methods for example, friendly environmental process, versatility of operation conditions with high temperature and low pressure, small space, low cost, etc. Recently de-gassing membrane is widely used in power plant's feed water system for DO removal. De-gassing membrane has some advantages; it removes other dissolved gases such as CO2, N2, as well as O2, and is more economical than Catalytic resin-based Oxygen Removal System. In this study, to obtain better efficiency of MORS, we modified the polypropylene (PP) hollow fiber membrane by plasma treatment and ion beam irradiation supported platinum(Pt), palladium(Pd) as metal catalyst on the surface of the membrane

  1. A New Energy-Saving Catalytic System: Carbon Dioxide Activation by a Metal/Carbon Catalyst.

    Yun, Danim; Park, Dae Sung; Lee, Kyung Rok; Yun, Yang Sik; Kim, Tae Yong; Park, Hongseok; Lee, Hyunjoo; Yi, Jongheop

    2017-09-22

    The conversion of CO 2 into useful chemicals is an attractive method to reduce greenhouse gas emissions and to produce sustainable chemicals. However, the thermodynamic stability of CO 2 means that a lot of energy is required for its conversion into chemicals. Here, we suggest a new catalytic system with an alternative heating system that allows minimal energy consumption during CO 2 conversion. In this system, electrical energy is transferred as heat energy to the carbon-supported metal catalyst. Fast ramping rates allow high operating temperatures (T app =250 °C) to be reached within 5 min, which leads to an 80-fold decrease of energy consumption in methane reforming using CO 2 (DRM). In addition, the consumed energy normalized by time during the DRM reaction in this current-assisted catalysis is sixfold lower (11.0 kJ min -1 ) than that in conventional heating systems (68.4 kJ min -1 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Metal-Catalyst-Free Synthesis and Characterization of Single-Crystalline Silicon Oxynitride Nanowires

    Shuang Xi

    2012-01-01

    Full Text Available Large quantities of single-crystal silicon oxynitride nanowires with high N concentration have been synthesized directly on silicon substrate at 1200°C without using any metal catalyst. The diameter of these ternary nanowires is ranging from 10 to 180 nm with log-normal distribution, and the length of these nanowires varies from a few hundreds of micrometers to several millimeters. A vapor-solid mechanism was proposed to explain the growth of the nanowires. These nanowires are grown to form a disordered mat with an ultrabright white nonspecular appearance. The mat demonstrates highly diffusive reflectivity with the optical reflectivity of around 80% over the whole visible wavelength, which is comparable to the most brilliant white beetle scales found in nature. The whiteness might be resulted from the strong multiscattering of a large fraction of incident light on the disordered nanowire mat. These ultra-bright white nanowires could form as reflecting surface to meet the stringent requirements of bright-white light-emitting-diode lighting for higher optical efficiency. They can also find applications in diverse fields such as sensors, cosmetics, paints, and tooth whitening.

  3. Catalysts prepared by interaction of transition metal organometallic compounds with the surface of supporters

    Ryndin, Yu.A.; Kuznetsov, B.N.; Moroz, Eh.M.; Tripol'skij, A.A.; Ermakov, Yu.I.

    1977-01-01

    The phase composition and dispersion of the catalyst (W + Pt)/SiO 2 , subjected to oxidation and reduction at an elevated temperature was investigated by roentgenographic methods (radial distribution of atoms and broadening of X-ray lines). The X-ray data are compared with the results of chemisorption measurements of platinum dispersion in the specimens and their activity in reactions of benzene hydration and ethane hydrogenolysis. It has been established that catalysts reduced at 600 deg C and not subjected to oxidation, as well as catalysts oxidized at 200 deg C and then reduced at 600 deg C are characterized by a high platinum dispersion. The dispersion catalysts are noted for their activity in the reaction of benzene hydration and ethane hydrogenolysis. On the other hand, the activity of catalysts oxidized and reduced in rigid conditions (600 deg C, air) is much lower and is close to the activity of the coarsely dispersed PtSiO 2 catalyst

  4. Effect of plasma treatments to graphite nanofibers supports on electrochemical behaviors of metal catalyst electrodes.

    Lee, Hochun; Jung, Yongju; Kim, Seok

    2012-02-01

    In the present work, we had studied the graphite nanofibers as catalyst supports after a plasma treatment for studying the effect of surface modification. By controlling the plasma intensity, a surface functional group concentration was changed. The nanoparticle size, loading efficiency, and catalytic activity were studied, after Pt-Ru deposition by a chemical reduction. Pt-Ru catalysts deposited on the plasma-treated GNFs showed the smaller size, 3.58 nm than the pristine GNFs. The catalyst loading contents were enhanced with plasma power and duration time increase, meaning an enhanced catalyst deposition efficiency. Accordingly, cyclic voltammetry result showed that the specific current density was increased proportionally till 200 W and then the value was decreased. Enhanced activity of 40 (mA mg(-1)-catalyst) was accomplished at 200 W and 180 sec duration time. Consequently, it was found that the improved electroactivity was originated from the change of size or morphology of catalysts by controlling the plasma intensity.

  5. Bulk-surface relationship of an electronic structure for high-throughput screening of metal oxide catalysts

    Kweun, Joshua Minwoo; Li, Chenzhe; Zheng, Yongping; Cho, Maenghyo; Kim, Yoon Young; Cho, Kyeongjae

    2016-01-01

    Graphical abstract: - Highlights: • Bulk-surface relationship was predicted by the ligand field nature of metal oxides. • Antibonding and bonding d-bands occupancy clarified the bulk-surface relationship. • Different surface relaxations were explained by the bulk electronic structures. • Transition from the bulk to the surface state was simulated by oxygen adsorption. - Abstract: Designing metal-oxides consisting of earth-abundant elements has been a crucial issue to replace precious metal catalysts. To achieve efficient screening of metal-oxide catalysts via bulk descriptors rather than surface descriptors, we investigated the relationship between the electronic structure of bulk and that of the surface for lanthanum-based perovskite oxides, LaMO_3 (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu). Through density functional theory calculations, we examined the d-band occupancy of the bulk and surface transition-metal atoms (n_B_u_l_k and n_S_u_r_f) and the adsorption energy of an oxygen atom (E_a_d_s) on (001), (110), and (111) surfaces. For the (001) surface, we observed strong correlation between the n_B_u_l_k and n_S_u_r_f with an R-squared value over 94%, and the result was interpreted in terms of ligand field splitting and antibonding/bonding level splitting. Moreover, the E_a_d_s on the surfaces was highly correlated with the n_B_u_l_k with an R-squared value of more than 94%, and different surface relaxations could be explained by the bulk electronic structure (e.g., LaMnO_3 vs. LaTiO_3). These results suggest that a bulk-derived descriptor such as n_B_u_l_k can be used to screen metal-oxide catalysts.

  6. Metal-free carbon materials-catalyzed sulfate radical-based advanced oxidation processes: A review on heterogeneous catalysts and applications.

    Zhao, Qingxia; Mao, Qiming; Zhou, Yaoyu; Wei, Jianhong; Liu, Xiaocheng; Yang, Junying; Luo, Lin; Zhang, Jiachao; Chen, Hong; Chen, Hongbo; Tang, Lin

    2017-12-01

    In recent years, advanced oxidation processes (AOPs), especially sulfate radical based AOPs have been widely used in various fields of wastewater treatment due to their capability and adaptability in decontamination. Recently, metal-free carbon materials catalysts in sulfate radical production has been more and more concerned because these materials have been demonstrated to be promising alternatives to conventional metal-based catalysts, but the review of metal-free catalysts is rare. The present review outlines the current state of knowledge on the generation of sulfate radical using metal-free catalysts including carbon nanotubes, graphene, mesoporous carbon, activated carbon, activated carbon fiber, nanodiamond. The mechanism such as the radical pathway and non-radical pathway, and factors influencing of the activation of sulfate radical was also be revealed. Knowledge gaps and research needs have been identified, which include the perspectives on challenges related to metal-free catalyst, heterogeneous metal-free catalyst/persulfate systems and their potential in practical environmental remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Effect of impregnation protocol in the metallic sites of Pt–Ag/activated carbon catalysts for water denitration

    Aristizábal, A. [Departament d’Enginyeria Química, Universitat Rovira i Virgili, Campus Sescelades, Av. Països Catalans 26, 43007 Tarragona (Spain); Contreras, S., E-mail: sandra.contreras@urv.cat [Departament d’Enginyeria Química, Universitat Rovira i Virgili, Campus Sescelades, Av. Països Catalans 26, 43007 Tarragona (Spain); Divins, N.J.; Llorca, J. [Institut de Tècniques Energètiques i Centre de Recerca en Nanoenginyeria, Universitat Politècnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain); Medina, F. [Departament d’Enginyeria Química, Universitat Rovira i Virgili, Campus Sescelades, Av. Països Catalans 26, 43007 Tarragona (Spain)

    2014-04-01

    Highlights: • Mean particle size is tuned by the Pt precursor. H{sub 2}PtCl{sub 6} leads to smaller size. • H{sub 2}PtCl{sub 6} leads to higher extent of Pt–Ag particles with a composition richer in silver. • Pt(NH{sub 3}){sub 4}(NO{sub 3}){sub 2} leads to Ag{sup 0} particles and some Pt–Ag ensembles in less extent. • Nitrate and nitrite rates are linearly related to mean metal particle size. • Physical mixture of catalysts enhances N{sub 2} selectivities. - Abstract: The influence of the Pt precursor and the impregnation protocol in the catalytic behavior of 3%Pt–1.5%Ag supported on activated carbon for water denitration in a continuous reactor was studied. Pt(NH{sub 3}){sub 4}(NO{sub 3}){sub 2} and H{sub 2}PtCl{sub 6} were selected as Pt precursors. Five protocols were investigated: sequential impregnations (both sequences), co-impregnation, physical mixture of monometallic catalysts, and physical mixture of a bimetallic catalyst with a Pt monometallic catalyst. The samples were characterized by XRD, XPS, TPR, HRTEM and physisorption. It was found that the catalytic activity strongly depends on the synthesis protocol and the Pt precursor, which modify the particle size. Higher nitrate rates are achieved using H{sub 2}PtCl{sub 6} than Pt(NH{sub 3}){sub 4}(NO{sub 3}){sub 2}; this is mainly related to the smaller metal particle size of the former, evidenced by HRTEM. Nitrate consumption rate is directly related with the mean particle size. The physical mixture of monometallic catalysts resulted in the highest nitrogen rate.

  8. Pyrolysis of marine biomass to produce bio-oil and its upgrading using a novel multi-metal catalyst prepared from the spent car catalytic converter.

    Sabegh, Mahzad Yaghmaei; Norouzi, Omid; Jafarian, Sajedeh; Khosh, Akram Ghanbari; Tavasoli, Ahmad

    2018-02-01

    In order to reduce the economic and environmental consequences caused by spent car catalyst, we herein report for the first time a novel promising multi-metal catalyst prepared from spent car catalytic converters to upgrade the pyrolysis bio-oils. The physico-chemical properties of prepared catalyst were characterized by XRD, EDS, FESEM, and FT-IR analyses. The thermal stability of the multi-metal catalyst was studied with TGA. To investigate the activity of the catalyst, Conversion of Cladophora glomerata (C. glomerata) into bio-products was carried out via a fixed bed reactor with and without catalyst at the temperature of 500°C. Although the catalyst didn't catalyze the gasification reaction, bio-oil was upgraded over the catalyst. The main effect of the catalyst on the bio-oil components is deoxygenating of nitrogen compounds and promotion the ketonization reaction, which converts acid to ketone and declines the corrosive nature of bio-oil. Copyright © 2017. Published by Elsevier Ltd.

  9. N, S co-doped carbon spheres with highly dispersed CoO as non-precious metal catalyst for oxygen reduction reaction

    Chen, Linlin; Guo, Xingpeng; Zhang, Guoan

    2017-08-01

    It is still a great challenge in preparing non-precious metal catalysts with high activity and long-term stability to substitute for precious metal catalysts for oxygen reduction reaction (ORR) in fuel cells. Herein, we report a novel and facile catalyst-N, S co-doped carbon spheres with highly dispersed CoO (CoO@NS-CSs), where biomass glucose spheres act as carbon precursor and H2S, NH3 derived from the decomposition of thiourea not only provide N, S sources but also can etch carbon spheres to produce nanoporous structure. CoO@NS-CSs catalyst exhibits excellent ORR activity with a high onset potential of 0.946 V vs. RHE (reversible hydrogen electrode) and a half-wave potential of 0.821 V vs. RHE through a four-electron pathway in alkaline solution, which is comparable to commercial Pt/C catalyst (onset potential: 0.926 V vs. RHE, half-wave potential: 0.827 V vs. RHE). Furthermore, both the long-term stability and methanol-tolerance of CoO@NS-CSs catalyst are superior to those of commercial Pt/C catalyst. The excellent ORR performance of CoO@NS-CSs catalyst can be attributed to its micro-mesopore structure, high specific surface area (667 m2 g-1), and highly dispersed CoO. This work manifests that the obtained CoO@NS-CSs catalyst is promising to be applied to fuel cells.

  10. The effect of noble metals on catalytic methanation reaction over supported Mn/Ni oxide based catalysts

    Wan Azelee Wan Abu Bakar

    2015-09-01

    Full Text Available Carbon dioxide (CO2 in sour natural gas can be removed using green technology via catalytic methanation reaction by converting CO2 to methane (CH4 gas. Using waste to wealth concept, production of CH4 would increase as well as creating environmental friendly approach for the purification of natural gas. In this research, a series of alumina supported manganese–nickel oxide based catalysts doped with noble metals such as ruthenium and palladium were prepared by wetness impregnation method. The prepared catalysts were run catalytic screening process using in-house built micro reactor coupled with Fourier Transform Infra Red (FTIR spectroscopy to study the percentage CO2 conversion and CH4 formation analyzed by GC. Ru/Mn/Ni(5:35:60/Al2O3 calcined at 1000 °C was found to be the potential catalyst which gave 99.74% of CO2 conversion and 72.36% of CH4 formation at 400 °C reaction temperature. XRD diffractogram illustrated that the supported catalyst was in polycrystalline with some amorphous state at 1000 °C calcination temperature with the presence of NiO as active site. According to FESEM micrographs, both fresh and used catalysts displayed spherical shape with small particle sizes in agglomerated and aggregated mixture. Nitrogen Adsorption analysis revealed that both catalysts were in mesoporous structures with BET surface area in the range of 46–60 m2/g. All the impurities have been removed at 1000 °C calcination temperature as presented by FTIR, TGA–DTA and EDX data.

  11. Effect of the relationship between particle size, inter-particle distance, and metal loading of carbon supported fuel cell catalysts on their catalytic activity

    Corradini, Patricia Gon; Pires, Felipe I.; Paganin, Valdecir A.; Perez, Joelma; Antolini, Ermete

    2012-09-01

    The effect of the relationship between particle size ( d), inter-particle distance ( x i ), and metal loading ( y) of carbon supported fuel cell Pt or PtRu catalysts on their catalytic activity, based on the optimum d (2.5-3 nm) and x i / d (>5) values, was evaluated. It was found that for y fuel cell electrode than that using catalysts with y ethanol oxidation on PtRu/C catalysts with same particle size and same degree of alloying but different metal loading. Tests in direct ethanol fuel cells showed that, compared to 20 wt% PtRu/C, the negative effect of the lower x i / d on the catalytic activity of 30 and 40 wt% PtRu/C catalysts was superior to the positive effect of the thinner catalyst layer.

  12. Manufacture of highly loaded silica-supported cobalt Fischer–Tropsch catalysts from a metal organic framework

    Sun, Xiaohui

    2017-11-16

    The development of synthetic protocols for the preparation of highly loaded metal nanoparticle-supported catalysts has received a great deal of attention over the last few decades. Independently controlling metal loading, nanoparticle size, distribution, and accessibility has proven challenging because of the clear interdependence between these crucial performance parameters. Here we present a stepwise methodology that, making use of a cobalt-containing metal organic framework as hard template (ZIF-67), allows addressing this long-standing challenge. Condensation of silica in the Co-metal organic framework pore space followed by pyrolysis and subsequent calcination of these composites renders highly loaded cobalt nanocomposites (~ 50 wt.% Co), with cobalt oxide reducibility in the order of 80% and a good particle dispersion, that exhibit high activity, C5 + selectivity and stability in Fischer-Tropsch synthesis.

  13. Spray pyrolysis synthesis of γ-Al_2O_3 supported metal and metal phosphide catalysts and their activity in the hydrodeoxygenation of a bio-oil model compound

    Ly, Hoang Vu; Im, Kyungmin; Go, Youngchae; Galiwango, Emmanuel; Kim, Seung-Soo; Kim, Jinsoo; Choi, Jae Hyung; Woo, Hee Chul

    2016-01-01

    Highlights: • Spherical γ-Al_2O_3 supported metal and metal phosphide catalysts were synthesized by spray pyrolysis method. • Hydrodeoxygenation (HDO) of 2-furyl methyl ketone (FMK) was conducted using metal/metal phosphide catalysts. • FMK was converted into 2-allyl furan and methyl cyclohexane. • The highest FMK conversion of 83% was achieved over 10 wt% Ni/γ-Al_2O_3 catalysts at reaction temperature of 400 °C. - Abstract: In this study, spherical γ-Al_2O_3 supported metal and metal phosphide (Ni, Co, Ni_2P and CoP) catalysts were successfully prepared by combining sol-gel and spray pyrolysis methods. First boehmite sol was prepared based on the Yoldas process and then the corresponding metal salts were added to the sol at the desired concentration, followed by spray pyrolysis of the mixed solution. As the well-mixed solution was transformed to spherical γ-Al_2O_3 supported metal and metal phosphide catalysts during spray pyrolysis process, the metal species were uniformly distributed in the mesoporous γ-Al_2O_3 supports. The product catalysts were investigated under different conditions for hydrodeoxygenation of bio-oil model compound, 2-furyl methyl ketone (FMK), which is the main component of the bio-oil product from pyrolysis of Saccharina japonica. Among the investigated catalysts, the 10 wt% Ni/γ-Al_2O_3 catalyst after calcination at 800 °C showed the highest FMK conversion of 83.02% at the reaction temperature of 400 °C. The gas and liquid products were analyzed by gas chromatography (GC) with TCD/FID detectors and GC–MS, respectively, to determine the product compositions.

  14. Determination of platinum group metal catalyst residues in active pharmaceutical ingredients by means of total reflection X-ray spectrometry

    Marguí, Eva; Queralt, Ignasi; Hidalgo, Manuela

    2013-01-01

    The control of metal catalyst residues (i.e., platinum group metals (PGMs)) in different stages of the manufacturing processes of the active pharmaceutical ingredients (APIs) and, especially, in the final product is crucial. For API specimens, there are strict guidelines to limit the levels of metal residues based on their individual levels of safety concern. For PGMs the concentration limit has been established at 10 mg/kg in the API. Therefore great effort is currently being devoted to the development of new and simple procedures to control metals in pharmaceuticals. In the present work, an analytical methodology based on benchtop total reflection X-ray fluorescence spectrometry (TXRF) has been developed for the rapid and simple determination of some PGM catalyst impurities (Rh, Pd, Ir and Pt) in different types of API samples. An evaluation of different sample treatments (dissolution and digestion of the solid pharmaceutical samples) has been carried out and the developed methodologies have been validated according to the analytical parameters to be considered and acceptance criteria for PGM determination according to the United States Pharmacopeia (USP). Limits of quantification obtained for PGM metals were in the range of 2–4 mg/kg which are satisfactory according to current legislation. From the obtained results it is shown that the developed TXRF method can be implemented in the pharmaceutical industries to increase productivity of the laboratory; offering an interesting and complementary analytical tool to other atomic spectroscopic methods. - Highlights: • A TXRF method for PGM catalyst residue determination in API samples is presented. • Analysis can be performed using 10 μL of the internal standardized dissolved API. • The method is rapid, simple and suitable according to the USP requirements

  15. Recent progress of ordered mesoporous silica-supported chiral metallic catalysts

    LIU Rui

    2013-02-01

    Full Text Available Recently,ordered silica-based mesoporous chiral organometallics-functionalized heterogeneous catalysts have attracted extensive research interest due to their excellent properties,such as easy preparation,high activity and convenient recycle.This review mainly summarizesthe generally prepared strategy and the silica-based organometallics-functionalized heterogeneous catalysts reported in the literatures.

  16. Carbon Nanofiber Supported Transition-Metal Carbide Catalysts for the Hydrodeoxygenation of Guaiacol

    Jongerius, A.; Gosselink, R.W.; Dijkstra, J.; Bitter, J.H.; Bruijnincx, P.C.A.; Weckhuysen, B.M.

    2013-01-01

    Hydrodeoxygenation (HDO) studies over carbon nanofiber-supported (CNF) W2C and Mo2C catalysts were performed on guaiacol, a prototypical substrate to evaluate the potential of a catalyst for valorization of depolymerized lignin streams. Typical reactions were executed at 55 bar hydrogen pressure

  17. Catalysts, methods of making catalysts, and methods of use

    Renard, Laetitia; El Eter, Mohamad; Caps, Valerie; Basset, Jean-Marie

    2014-01-01

    Embodiments of the present disclosure provide for catalysts, methods of making catalysts, methods of using catalysts, and the like. In an embodiment, the method of making the catalysts can be performed in a single step with a metal nanoparticle precursor and a metal oxide precursor, where a separate stabilizing agent is not needed.

  18. Catalysts, methods of making catalysts, and methods of use

    Renard, Laetitia

    2014-03-06

    Embodiments of the present disclosure provide for catalysts, methods of making catalysts, methods of using catalysts, and the like. In an embodiment, the method of making the catalysts can be performed in a single step with a metal nanoparticle precursor and a metal oxide precursor, where a separate stabilizing agent is not needed.

  19. Catalyst of a metal heteropoly acid salt that is insoluble in a polar solvent on a non-metallic porous support and method of making

    Wang, Yong [Richland, WA; Peden, Charles H. F. [West Richland, WA; Choi, Saemin [Richland, WA

    2002-10-29

    The present invention includes a catalyst having (a) a non-metallic support having a plurality of pores; (b) a metal heteropoly acid salt that is insoluble in a polar solvent on the non-metallic support; wherein at least a portion of the metal heteropoly acid salt is dispersed within said plurality of pores. The present invention also includes a method of depositing a metal heteropoly acid salt that is insoluble in a polar solvent onto a non-metallic support having a plurality of pores. The method has the steps of: (a) obtaining a first solution containing a first precursor of a metal salt cation; (b) obtaining a second solution containing a second precursor of a heteropoly acid anion in a solvent having a limited dissolution potential for said first precursor; (c) impregnating the non-metallic support with the first precursor forming a first precursor deposit within the plurality of pores, forming a first precursor impregnated support; (d) heating said first precursor impregnated support forming a bonded first precursor impregnated support; (e) impregnating the second precursor that reacts with the precursor deposit and forms the metal heteropoly acid salt.

  20. Plasma-chemical production of metal-polypyrrole-catalysts for the reduction of oxygen in fuel cells. Precious-metal-free catalysts for fuel cells.; Plasmachemische Erzeugung von Metall-Polypyrrol-Katalysatoren fuer die Sauerstoffreduktion in Brennstoffzellen. Edelmetallfreie Katalysatoren fuer Brennstoffzellen

    Walter, Christian

    2013-07-01

    This thesis is about the production of non noble metal catalysts for the oxygen reduction reaction in fuel cells. Therefore, a novel dual plasma process is developed, constructed and the so-produced films are analysed by various electrochemical (CV, RDE and RRDE) and structural methods (SEM, EDX, IR, XPS, conductivity, XRD, NEXAFS, EXAFS and TEM). It is shown, that by doing this, non noble metal catalysts could be produced without the need of a high temperature treatment. Furthermore, the catalytic activity obtained is superior to that of chemically produced metal-polypyrrole films.

  1. A study of the convective flow as a function of external parameters in a high-pressure metal halide discharge lamp (HgDyI{sub 3})

    Hajji, S.; HadjSalah, S.; Benhalima, A.; Charrada, K. [Unité d' Etude des Milieux Ionisés et Réactifs, IPEIM, 5019 route de Kairouan Monastir, Université de Monastir (Tunisia); Zissis, G. [Laboratoire Plasma et Conversion d' Énergie, 118 rte Narbonne, Bât3R2, 31062 Toulouse (France)

    2016-06-15

    This paper deals with the modelling of the convection processes in metal–halide lamp discharges (HgDyI{sub 3}). For this, we realized a 3D model, a steady, direct current powered and time-depending model for the solution of conservation equations relative to mass, momentum, and energy. After validation, this model was applied to the study of the effect of some parameters that have appeared on major transport phenomena of mass and energy in studying the lamp. Indeed, the electric current, the atomic ratio (Hg/Dy), and the effect of the convective transport have been studied.

  2. Associated equilibria with participatian of single and mixed silver, lead and cadmium halide complexes in mixtures of molten alkali and alkaline earth metal nitrates

    Gouk, Kh.S.; Gupta, R.K.; Vekma, K.V.

    1983-01-01

    Associated equilibria in the systems, which contain single and mixed silver, cadmium and lead halide complexes in the KNO 3 -Ba(N0 3 ) 2 (87.6:12.4 and 89:11 mol.%) and NaNO 3 -Ba(NO 3 ) 2 (94.2-5.8 mol%) melts in the temperature range from 568.2 up to 698.2 K are investigated. Applicability of equations derivated on the base of quasi-lattice model to description of temperature coefficients of association constants is analized

  3. Methods of making textured catalysts

    Werpy, Todd [West Richland, WA; Frye, Jr., John G.; Wang, Yong [Richland, WA; Zacher, Alan H [Kennewick, WA

    2010-08-17

    A textured catalyst having a hydrothermally-stable support, a metal oxide and a catalyst component is described. Methods of conducting aqueous phase reactions that are catalyzed by a textured catalyst are also described. The invention also provides methods of making textured catalysts and methods of making chemical products using a textured catalyst.

  4. Advanced cathode materials for polymer electrolyte fuel cells based on pt/ metal oxides: from model electrodes to catalyst systems.

    Fabbri, Emiliana; Pătru, Alexandra; Rabis, Annett; Kötz, Rüdiger; Schmidt, Thomas J

    2014-01-01

    The development of stable catalyst systems for application at the cathode side of polymer electrolyte fuel cells (PEFCs) requires the substitution of the state-of-the-art carbon supports with materials showing high corrosion resistance in a strongly oxidizing environment. Metal oxides in their highest oxidation state can represent viable support materials for the next generation PEFC cathodes. In the present work a multilevel approach has been adopted to investigate the kinetics and the activity of Pt nanoparticles supported on SnO2-based metal oxides. Particularly, model electrodes made of SnO2 thin films supporting Pt nanoparticles, and porous catalyst systems made of Pt nanoparticles supported on Sb-doped SnO2 high surface area powders have been investigated. The present results indicate that SnO2-based supports do not modify the oxygen reduction reaction mechanism on the Pt nanoparticle surface, but rather lead to catalysts with enhanced specific activity compared to Pt/carbon systems. Different reasons for the enhancement in the specific activity are considered and discussed.

  5. Metallic oxides for desulphurization catalyst reaction; Oxidos metalicos mistos como catalisadores para reacoes de dessulfurizacao

    Medeiros, R.L.B.A.; Melo, D.M.A.; Melo, M.A.F. [Universidade Federal do Rio Grande do Norte, Natal, RN (Brazil); Souza, K.S.G.M. [Universidade Federal da Paraiba - Departamento de Engenharia Quimica, PB (Brazil); Barros, J.M.F. [Universidade Federal de Campina Grande - Campos Cuite, PB (Brazil)

    2010-07-01

    The mixed metal oxides constitute an important class of catalytic materials widely investigated in different fields of applications. Studies of rare earth nickelates have been carried by several researchers in order to investigate the structural stability afforded by oxide formed and the existence of catalytic properties at room temperature. So, this study aims synthesize the nano sized catalyst of nickelate of lanthanum doped with strontium (La(1- x)Sr{sub x}NiO4-{sigma}; x = 0,2 and 0,3), through the Pechini method and your characterization for subsequent application in the desulfurization of thiophene reaction. The precursor solutions were calcined at 300 degree C/2h for pyrolysis of polyester and later calcinations occurred at temperatures of 500 - 1000 degree C. The resulting powders were characterized by thermogravimetric analysis (TG / DTG), surface area for adsorption of N{sub 2} by BET method, Xray diffraction (XRD), scanning electron microscopy (HR{sub S}EM) and spectrometry dispersive energy (EDS). The results of XRD had show that the perovskites obtained consist of two phases (LSN and NiO) and from 700 degree C have crystalline structure. The results of SEM evidenced the obtainment of nano metric powders. The results of BET show that the powders have surface area within the range used in catalysis (5-50m{sup 2}/g). The characterization of active sites was performed by reaction of desulfurization of thiophene at room temperature and 200 degree C, the relation F/W equal to 0,7 mol h{sup -1}m{sub c}at {sup -1}. The products of the reaction were separated by gas chromatography and identified by the selective detection PFPD sulfur. All samples had presented conversion above 95%. (author)

  6. Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

    Bory, Benjamin F.; Wang, Jingxin; Janssen, René A. J.; Meskers, Stefan C. J.; Gomes, Henrique L.; De Leeuw, Dago M.

    2014-01-01

    Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10 25 /m 3 . The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics

  7. Transfer Hydro-dehalogenation of Organic Halides Catalyzed by Ruthenium(II) Complex.

    You, Tingjie; Wang, Zhenrong; Chen, Jiajia; Xia, Yuanzhi

    2017-02-03

    A simple and efficient Ru(II)-catalyzed transfer hydro-dehalogenation of organic halides using 2-propanol solvent as the hydride source was reported. This methodology is applicable for hydro-dehalogenation of a variety of aromatic halides and α-haloesters and amides without additional ligand, and quantitative yields were achieved in many cases. The potential synthetic application of this method was demonstrated by efficient gram-scale transformation with catalyst loading as low as 0.5 mol %.

  8. A "catalyst switch" Strategy for the sequential metal-free polymerization of epoxides and cyclic Esters/Carbonate

    Zhao, Junpeng

    2014-06-24

    A "catalyst switch" strategy was used to synthesize well-defined polyether-polyester/polycarbonate block copolymers. Epoxides (ethylene oxide and/or 1,2-butylene oxide) were first polymerized from a monoalcohol in the presence of a strong phosphazene base promoter (t-BuP4). Then an excess of diphenyl phosphate (DPP) was introduced, followed by the addition and polymerization of a cyclic ester (ε-caprolactone or δ-valerolactone) or a cyclic carbonate (trimethylene carbonate), where DPP acted as both the neutralizer of phosphazenium alkoxide (polyether chain end) and the activator of cyclic ester/carbonate. This work has provided a one-pot sequential polymerization method for the metal-free synthesis of block copolymers from monomers which are suited for different types of organic catalysts. © 2014 American Chemical Society.

  9. A "catalyst switch" Strategy for the sequential metal-free polymerization of epoxides and cyclic Esters/Carbonate

    Zhao, Junpeng; Pahovnik, David; Gnanou, Yves; Hadjichristidis, Nikolaos

    2014-01-01

    A "catalyst switch" strategy was used to synthesize well-defined polyether-polyester/polycarbonate block copolymers. Epoxides (ethylene oxide and/or 1,2-butylene oxide) were first polymerized from a monoalcohol in the presence of a strong phosphazene base promoter (t-BuP4). Then an excess of diphenyl phosphate (DPP) was introduced, followed by the addition and polymerization of a cyclic ester (ε-caprolactone or δ-valerolactone) or a cyclic carbonate (trimethylene carbonate), where DPP acted as both the neutralizer of phosphazenium alkoxide (polyether chain end) and the activator of cyclic ester/carbonate. This work has provided a one-pot sequential polymerization method for the metal-free synthesis of block copolymers from monomers which are suited for different types of organic catalysts. © 2014 American Chemical Society.

  10. Dual-Function Metal-Organic Framework as a Versatile Catalyst for Detoxifying Chemical Warfare Agent Simulants.

    Liu, Yangyang; Moon, Su-Young; Hupp, Joseph T; Farha, Omar K

    2015-12-22

    The nanocrystals of a porphyrin-based zirconium(IV) metal-organic framework (MOF) are used as a dual-function catalyst for the simultaneous detoxification of two chemical warfare agent simulants at room temperature. Simulants of nerve agent (such as GD, VX) and mustard gas, dimethyl 4-nitrophenyl phosphate and 2-chloroethyl ethyl sulfide, have been hydrolyzed and oxidized, respectively, to nontoxic products via a pair of pathways catalyzed by the same MOF. Phosphotriesterase-like activity of the Zr6-containing node combined with photoactivity of the porphyrin linker gives rise to a versatile MOF catalyst. In addition, bringing the MOF crystals down to the nanoregime leads to acceleration of the catalysis.

  11. Hydrodeoxygenation of mono- and dimeric lignin model compounds on noble metal catalysts

    Guvenatam, Burcu; Kursun, Osman; Heeres, Hero; Pidko, Evgeny A.; Hensen, Emiel J. M.

    2014-01-01

    The influence of reaction conditions (temperature, acidity) on the catalytic performance of supported Pt, Pd and Ru catalysts for the aqueous phase hydrodeoxygenation (HDO) of lignin model compounds was systematically investigated. Phenol conversion proceeds via hydrogenation of the aromatic ring

  12. Atomic Resolution Imaging of Nanoscale Structural Ordering in a Complex Metal Oxide Catalyst

    Zhu, Yihan; Wang, Qingxiao; Zhao, Lan; Teng, Baiyang; Lu, Weimin; Han, Yu

    2012-01-01

    The determination of the atomic structure of a functional material is crucial to understanding its "structure-to-property" relationship (e.g., the active sites in a catalyst), which is however challenging if the structure possesses complex

  13. Ni-Based Catalysts for Low Temperature Methane Steam Reforming: Recent Results on Ni-Au and Comparison with Other Bi-Metallic Systems

    Anna M. Venezia

    2013-06-01

    Full Text Available Steam reforming of light hydrocarbons provides a promising method for hydrogen production. Ni-based catalysts are so far the best and the most commonly used catalysts for steam reforming because of their acceptably high activity and significantly lower cost in comparison with alternative precious metal-based catalysts. However, nickel catalysts are susceptible to deactivation from the deposition of carbon, even when operating at steam-to-carbon ratios predicted to be thermodynamically outside of the carbon-forming regime. Reactivity and deactivation by carbon formation can be tuned by modifying Ni surfaces with a second metal, such as Au through alloy formation. In the present review, we summarize the very recent progress in the design, synthesis, and characterization of supported bimetallic Ni-based catalysts for steam reforming. The progress in the modification of Ni with noble metals (such as Au and Ag is discussed in terms of preparation, characterization and pretreatment methods. Moreover, the comparison with the effects of other metals (such as Sn, Cu, Co, Mo, Fe, Gd and B is addressed. The differences of catalytic activity, thermal stability and carbon species between bimetallic and monometallic Ni-based catalysts are also briefly shown.

  14. Survey on synthesis and reaction of environmentally benign water-soluble metal complex catalysts; Kankyo chowagata suiyosei sakutai shokubai no gosei hanno no chosa

    NONE

    1997-03-01

    This report describes the research trend survey results on the synthesis and reaction of water-soluble metal complexes which are regarded as environmentally benign catalysts. For the synthesis and catalysis of water-soluble complexes, synthetic methods of water-soluble phosphines, such as sulfonated TPPMS and TPPTS, are described in detail. Synthesis and reactivity of hydroxymethylphosphines are introduced, and the application of electrospray mass spectroscopy is elucidated as a tool for the analysis of them. Changes of the application of transition metal complexes with water-soluble phosphines to catalysis are described. Dual catalysts which have both functions of phase transfer catalysts and homogeneous catalysts are introduced. Concept of counter phase transfer catalysts is also introduced, and some catalytic reactions are described. In addition, this report introduces catalysis of water-soluble polymer-supported metal complexes, immobilization of metal colloids with water-soluble ligands and their analysis, and water-soluble complexes as hybrid catalysts. 144 refs., 94 figs., 10 tabs.

  15. Metal-​based catalysts for controlled ring-​opening polymerization of macrolactones : high molecular weight and well-​defined copolymer architectures

    Bouyahyi, M.; Duchateau, R.

    2014-01-01

    This contribution describes our recent results regarding the metal-¿catalyzed ring-¿opening polymn. of pentadecalactone and its copolymn. with e-¿caprolactone involving single-¿site metal complexes based on aluminum, zinc, and calcium. Under the right conditions (i.e., monomer concn., catalyst type,

  16. 4,6-Dimethyl-dibenzothiophene conversion over Al{sub 2}O{sub 3}-TiO{sub 2}-supported noble metal catalysts

    Nunez, Sara [Departamento de Ingenieria de Procesos e Hidraulica, Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Vicentina, Iztapalapa, 09340, Mexico, D.F. (Mexico); Escobar, Jose, E-mail: jeaguila@imp.mx [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, San Bartolo Atepehuacan, Gustavo A. Madero, 07730, Mexico, D.F. (Mexico); Vazquez, Armando; Reyes, Jose Antonio de los [Departamento de Ingenieria de Procesos e Hidraulica, Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Vicentina, Iztapalapa, 09340, Mexico, D.F. (Mexico); Hernandez-Barrera, Melissa [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, San Bartolo Atepehuacan, Gustavo A. Madero, 07730, Mexico, D.F. (Mexico)

    2011-03-15

    Research highlights: {yields} Al{sub 2}O{sub 3} and Al{sub 2}O{sub 3}-TiO{sub 2} (molar ratio Al/Ti = 2, AT2) mixed oxides were pore-filling impregnated to obtain Pd, Pt and Pd-Pt catalysts with {approx}1 wt% nominal metal loading. {yields} Reduced catalysts were tested in the 4,6-dimethyl-dibenzothiophene hydrodesulfurization (HDS). {yields} In Pd-containing materials, TiO{sub 2} incorporation into the alumina support was favorable to the catalytic activity of noble metal catalysts. {yields} Enhanced intrinsic activity (per exposed metallic site) was obtained in Pt-containing catalysts supported on the AT2 mixed oxide. {yields} Yield to different products over various catalysts seemed to be strongly influenced by metallic particles dispersion. - Abstract: Al{sub 2}O{sub 3} and Al{sub 2}O{sub 3}-TiO{sub 2} (molar ratio Al/Ti = 2, AT2) mixed oxides were synthesized using a low-temperature sol-gel method and were further pore-filling impregnated to obtain Pd and Pt catalysts with {approx}1 wt% nominal metal loading. Simultaneous impregnation was used to prepare bimetallic materials at Pd:Pt = 80:20. Solids characterization was carried out by N{sub 2}-physisorption, high-resolution transmission electron microscopy (HR-TEM and E-FTEM), X-ray diffraction, temperature-programmed reduction and CO-chemisorption. Reduced (350 deg. C, H{sub 2} flow) catalysts were tested in the 4,6-dimethyl-dibenzothiophene hydrodesulfurization (HDS) (in n-dodecane, at 300 deg. C and 5.5 MPa, batch reactor). In Pd-containing materials, TiO{sub 2} incorporation into the alumina support was favorable to the catalytic activity of noble metal catalysts, where bimetallic Pd-Pt with AT2 carrier had the highest organo-S compound conversion. Enhanced intrinsic activity (per exposed metallic site) was obtained in Pt-containing catalysts supported on the AT2 mixed oxide (as compared to alumina-supported ones). Yield to different products over various catalysts seemed to be strongly influenced by

  17. Reducible oxide based catalysts

    Thompson, Levi T.; Kim, Chang Hwan; Bej, Shyamal K.

    2010-04-06

    A catalyst is disclosed herein. The catalyst includes a reducible oxide support and at least one noble metal fixed on the reducible oxide support. The noble metal(s) is loaded on the support at a substantially constant temperature and pH.

  18. Adsorption of heavy metal ion from aqueous solution by nickel oxide nano catalyst prepared by different methods

    Amira M. Mahmoud

    2015-03-01

    Full Text Available Environmental pollution by heavy metal is arising as the most endangering tasks to both water sources and atmosphere quality today. The treatment of heavy metals is of special concern due to their recalcitrance and persistence in the environment. To limit the spread of the heavy metals within water sources, nickel oxide nanoparticles adsorbents were synthesized and characterized with the aim of removal of one of the aggressive heavy elements, namely; lead ions. Nano nickel oxide adsorbents were prepared using NaOH and oxalic acid dissolved in ethanol as precursors. The results indicated that adsorption capacity of Pb(II ion by NiO-org catalyst is favored than that prepared using NaOH as a precipitant. Nickel oxide nanoparticles prepared by the two methods were characterized structurally and chemically through XRD, DTA, TGA, BET and FT-IR. Affinity and efficiency sorption parameters of the solid nano NiO particles, such as; contact time, initial concentration of lead ions and the dosage of NiO nano catalyst and competitive adsorption behaviors were studied. The results showed that the first-order reaction law fit the reduction of lead ion, also showed good linear relationship with a correlation coefficient (R2 larger than 0.9.

  19. Unsupported NiPt alloy metal catalysts prepared by water-in-oil (W/O) microemulsion method for methane cracking

    Zhou, Lu

    2016-05-18

    Unsupported NiPt metal catalyst with Ni/Pt molar ratio of 88/12 is prepared by water-in-oil (W/O) microemulsion method in this study. Compared to monometallic Ni and Pt catalysts, the NiPt catalyst exhibits superior activity and stability for methane cracking. By XRD (X-ray powder diffraction), XPS (X-ray photoelectron spectroscopy) and TEM (Transmission electron microscopy) analyses, the formation of Ni(0)Pt(0) alloy is believed to be the main reason for the reactivity improvement of this catalyst. Carbon nano tube (CNT) with Ni(0)Pt(0) particles anchored on the top of tube are found for the NiPt catalyst. © 2016 Elsevier Ltd.

  20. Transition-Metal-Controlled Inorganic Ligand-Supported Non-Precious Metal Catalysts for the Aerobic Oxidation of Amines to Imines.

    Yu, Han; Zhai, Yongyan; Dai, Guoyong; Ru, Shi; Han, Sheng; Wei, Yongge

    2017-10-09

    Most state-of-art transition-metal catalysts usually require organic ligands, which are essential for controlling the reactivity and selectivity of reactions catalyzed by transition metals. However, organic ligands often suffer from severe problems including cost, toxicity, air/moisture sensitivity, and being commercially unavailable. Herein, we show a simple, mild, and efficient aerobic oxidation procedure of amines using inorganic ligand-supported non-precious metal catalysts 1, (NH 4 ) n [MMo 6 O 18 (OH) 6 ] (M=Cu 2+ ; Fe 3+ ; Co 3+ ; Ni 2+ ; Zn 2+ , n=3 or 4), synthesized by a simple one-step method in water at 100 °C, demonstrating that the catalytic activity and selectivity can be significantly improved by changing the central metal atom. In the presence of these catalysts, the catalytic oxidation of primary and secondary amines, as well as the coupling of alcohols and amines, can smoothly proceed to afford various imines with O 2 (1 atm) as the sole oxidant. In particular, the catalysts 1 have transition-metal ion core, and the planar arrangement of the six Mo VI centers at their highest oxidation states around the central heterometal can greatly enhance the Lewis acidity of catalytically active sites, and also enable the electrons in the center to delocalize onto the six edge-sharing MO 6 units, in the same way as ligands in traditional organometallic complexes. The versatility of this methodology maybe opens a path to catalytic oxidation through inorganic ligand-coordinated metal catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Modification of the performance of WO3-ZrO2 catalysts by metal addition in hydrocarbon reactions

    Gerardo Carlos Torres

    2012-01-01

    Full Text Available A study of the different hydrocarbon reactions over Ni doped WO3-ZrO2 catalysts was performed. Ni was found as NiO at low Ni concentration while at high Ni concentrations a small fraction was present as a metal. For both cases, Ni strongly modified total acidity and concentration of strong acid sites. In the cyclohexane dehydrogenation reaction, Ni addition promotes both benzene and methyl cyclopentane production. The hydroconversion activity (n-butane and n-octane increases with the augment of total acidity produced by Ni. The selectivity to reaction products is modified according to the acid strength distribution changes produced by Ni addition.

  2. Bipolarons in metal-metal halide solutions

    Fois, E.S.; Selloni, A.; Parrinello, M.; Car, R.

    1988-06-02

    A novel molecular dynamics method is used to follow the adiabatic dynamics of two electrons solvated in molten KCl. The electrons are treated quantum mechanically within the local spin density approximation. A coupled set of Newtonian and time-dependent Schroedinger-like equations is used to describe the evolution of the ions and of the Kohn-Sham orbitals. The authors find that parallel spin electrons repel each other and form separate F-center-like states. Antiparallel spin electrons, instead, attract each other and coalesce into a single bipolaronic complex. The electrons sit mostly in an ionic cavity which is surrounded by cations. The diffusion of the bipolaron, while bound, occurs on an ionic time scale. However, dissociation processes occur during which the electrons can acquire a high mobility leading on average to a large electronic diffusion.

  3. Evaluation of air jet erosion profiles in metal mesh supported SCR plate catalyst based on glass fiber concentrations

    Rajath, S.; Nandakishora, Y.; Siddaraju, C.; Roy, Sukumar

    2018-04-01

    This paper explains the evaluation of erosion profiles in metal mesh supported SCR plate catalyst structures in which the glass fibers concentration in the catalyst material is considered as prime factor for erosion resistance and mechanical strength. The samples are prepared and tested at the specified and constant conditions like velocity as 30m/s, sand flow rate as 2g/min, average particle diameter 300 µm and all these samples were tested at different angles at impact preferably 15°,30°,45°,60°,75°,and 90° as per ASTM G76 standards. Say, if 5% glass fibers are present in catalyst material, then erosion resistance increases, but the density of glass fibers is very less because each glass fiber is approximately 20 microns in diameter and weight of individual is negligible. The composition in which 2% fiber is present has slightly higher erosion comparatively, but 3% glass fibers or more foreign inclusion like excessive binders can be eliminated that contributes much for the conversion of NOx. So 2% -3% glass fibers are preferred and optimized based on NOx conversion and erosion resistance property.

  4. Statistical Optimization for Acid Hydrolysis of Microcrystalline Cellulose and Its Physiochemical Characterization by Using Metal Ion Catalyst

    Md. Ziaul Karim

    2014-10-01

    Full Text Available Hydrolyzing the amorphous region while keeping the crystalline region unaltered is the key technology for producing nanocellulose. This study investigated if the dissolution properties of the amorphous region of microcrystalline cellulose can be enhanced in the presence of Fe3+ salt in acidic medium. The process parameters, including temperature, time and the concentration of metal chloride catalyst (FeCl3, were optimized by using the response surface methodology (RSM. The experimental observation demonstrated that temperature and time play vital roles in hydrolyzing the amorphous sections of cellulose. This would yield hydrocellulose with higher crystallinity. The factors that were varied for the production of hydrocellulose were the temperature (x1, time (x2 and FeCl3 catalyst concentration (x3. Responses were measured in terms of percentage of crystallinity (y1 and the yield (y2 of the prepared hydrocellulose. Relevant mathematical models were developed. Analysis of variance (ANOVA was carried out to obtain the most significant factors influencing the responses of the percentage of crystallinity and yield. Under optimum conditions, the percentage of crystallinity and yield were 83.46% and 86.98% respectively, at 90.95 °C, 6 h, with a catalyst concentration of 1 M. The physiochemical characteristics of the prepared hydrocellulose were determined in terms of XRD, SEM, TGA and FTIR analyses. The addition of FeCl3 salt in acid hydrolyzing medium is a novel technique for substantially increasing crystallinity with a significant morphological change.

  5. A hard X-ray study of a manganese-terpyridine catalyst in a chromium-based Metal Organic Framework

    Ramsey, Alexandra V. [SLAC National Accelerator Lab., Menlo Park, CA (United States)

    2015-08-28

    Hydrogen produced from water splitting is a promising source of clean energy. However, a robust catalyst is necessary to carry out the water oxidation step of water splitting. In this study, the catalyst studied was [(terpy)Mn(μ-O)2Mn(terpy)]3+ (MnTD) synthesized in the Metal Organic Framework (MOF) MIL-101(Cr), and the method used for analysis was hard X-ray powder diffraction. The diffraction data was used to detect the presence of MOF in different catalytic stages, and lattice parameters were assigned to the samples containing MOF. Fourier maps were constructed with GSAS II to determine the contents of the MOF as preliminary studies suggested that MnTD may not be present. Results showed that MOF is present before catalysis occurs but disappears by the time 45 minutes of catalysis has ensued. Changes in the MOF’s lattice parameters and location of electron density in the Fourier maps suggest attractions between the MOF and catalyst that may lead to MOF degradation. Fourier maps also revealed limited, if any, amounts of MnTD, even before catalysis occurred. Molecular manganese oxide may be the source of the high rate of water oxidation catalysis in the studied system.

  6. Photocatalytic carbon dioxide reduction with rhodium-based catalysts in solution and heterogenized within metal-organic frameworks.

    Chambers, Matthew B; Wang, Xia; Elgrishi, Noémie; Hendon, Christopher H; Walsh, Aron; Bonnefoy, Jonathan; Canivet, Jérôme; Quadrelli, Elsje Alessandra; Farrusseng, David; Mellot-Draznieks, Caroline; Fontecave, Marc

    2015-02-01

    The first photosensitization of a rhodium-based catalytic system for CO2 reduction is reported, with formate as the sole carbon-containing product. Formate has wide industrial applications and is seen as valuable within fuel cell technologies as well as an interesting H2 -storage compound. Heterogenization of molecular rhodium catalysts is accomplished via the synthesis, post-synthetic linker exchange, and characterization of a new metal-organic framework (MOF) Cp*Rh@UiO-67. While the catalytic activities of the homogeneous and heterogeneous systems are found to be comparable, the MOF-based system is more stable and selective. Furthermore it can be recycled without loss of activity. For formate production, an optimal catalyst loading of ∼10 % molar Rh incorporation is determined. Increased incorporation of rhodium catalyst favors thermal decomposition of formate into H2 . There is no precedent for a MOF catalyzing the latter reaction so far. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. SBA-15-functionalized 3-oxo-ABNO as recyclable catalyst for aerobic oxidation of alcohols under metal-free conditions.

    Karimi, Babak; Farhangi, Elham; Vali, Hojatollah; Vahdati, Saleh

    2014-09-01

    The nitroxyl radical 3-oxo-9-azabicyclo [3.3.1]nonane-N-oxyl (3-oxo-ABNO) has been prepared using a simple protocol. This organocatalyst is found to be an efficient catalyst for the aerobic oxidation of a wide variety of alcohols under metal-free conditions. In addition, the preparation and characterization of a supported version of 3-oxo-ABNO on ordered mesoporous silica SBA-15 (SABNO) is described for the first time. The catalyst has been characterized using several techniques including simultaneous thermal analysis (STA), transmission electron microscopy (TEM), and nitrogen sorption analysis. This catalyst exhibits catalytic performance comparable to its homogeneous analogue and much superior catalytic activity in comparison with (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO) for the aerobic oxidation of almost the same range of alcohols under identical reaction conditions. It is also found that SABNO can be conveniently recovered and reused at least 12 times without significant effect on its catalytic efficiency. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Effect of the relationship between particle size, inter-particle distance, and metal loading of carbon supported fuel cell catalysts on their catalytic activity

    Gon Corradini, Patricia; Pires, Felipe I.; Paganin, Valdecir A.; Perez, Joelma, E-mail: jperez@iqsc.usp.br [Instituto de Quimica de Sao Carlos, USP (Brazil); Antolini, Ermete [Scuola di Scienza dei Materiali (Italy)

    2012-09-15

    The effect of the relationship between particle size (d), inter-particle distance (x{sub i}), and metal loading (y) of carbon supported fuel cell Pt or PtRu catalysts on their catalytic activity, based on the optimum d (2.5-3 nm) and x{sub i}/d (>5) values, was evaluated. It was found that for y < 30 wt%, the optimum values of both d and x{sub i}/d can be always obtained. For y {>=} 30 wt%, instead, the positive effect of a thinner catalyst layer of the fuel cell electrode than that using catalysts with y < 30 wt% is concomitant to a decrease of the effective catalyst surface area due to an increase of d and/or a decrease of x{sub i}/d compared to their optimum values, with in turns gives rise to a decrease in the catalytic activity. The effect of the x{sub i}/d ratio has been successfully verified by experimental results on ethanol oxidation on PtRu/C catalysts with same particle size and same degree of alloying but different metal loading. Tests in direct ethanol fuel cells showed that, compared to 20 wt% PtRu/C, the negative effect of the lower x{sub i}/d on the catalytic activity of 30 and 40 wt% PtRu/C catalysts was superior to the positive effect of the thinner catalyst layer.

  9. Heterometallic metal-organic framework-templated synthesis of porous Co3O4/ZnO nanocage catalysts for the carbonylation of glycerol

    Lü, Yinyun; Jiang, Yating; Zhou, Qi; Li, Yunmei; Chen, Luning; Kuang, Qin; Xie, Zhaoxiong; Zheng, Lansun

    2017-12-01

    The efficient synthesis of glycerol carbonate (GLC) has recently received great attention due to its significance in reducing excess glycerol in biodiesel production as well as its promising applications in several industrial fields. However, the achievement of high conversion and high selectivity of GLC from glycerol in heterogeneous catalytic processes remains a challenge due to the absence of high-performance solid catalysts. Herein, highly porous nanocage catalysts composed of well-mixed Co3O4 and ZnO nanocrystals were successfully fabricated via a facile heterometallic metal-organic framework (MOF)-templated synthetic route. Benefiting from a high porosity and the synergistic effect between Co3O4 and ZnO, the as-prepared composite catalysts exhibited a significantly enhanced production efficiency of GLC in the carbonylation reaction of glycerol with urea compared to the single-component counterparts. The yield of GLC over the Co50Zn50-350 catalyst reached 85.2%, with 93.3% conversion and near 91% GLC selectivity, and this catalytic performance was superior to that over most heterogeneous catalysts. More importantly, the proposed templated synthetic strategy of heterometallic MOFs facilitates the regulation of catalyst composition and surface structure and can therefore be potentially extended in the tailoring of other metal oxide composite catalysts.

  10. Selective Synthesis of Gasoline-Ranged Hydrocarbons from Syngas over Hybrid Catalyst Consisting of Metal-Loaded ZSM-5 Coupled with Copper-Zinc Oxide

    Ting Ma

    2014-04-01

    Full Text Available The conversion of syngas (CO + H2 to gasoline-ranged hydrocarbons was carried out using a hybrid catalyst consisting of metal-loaded ZSM-5 coupled with Cu-ZnO in a near-critical n-hexane solvent. Methanol was synthesized from syngas over Cu-ZnO; subsequently, was converted to hydrocarbons through the formation of dimethyl ether (DME over the metal-loaded ZSM-5. When 0.5 wt% Pd/ZSM-5 and 5 wt% Cu/ZSM-5 among the metal-loaded ZSM-5 catalysts with Pd, Co, Fe or Cu were employed as a portion of the hybrid catalyst, the gasoline-ranged hydrocarbons were selectively produced (the gasoline-ranged hydrocarbons in all hydrocarbons: 59% for the hybrid catalyst with Pd/ZSM-5 and 64% for that with Cu/ZSM-5 with a similar CO conversion during the reaction. An increase in the Cu loading on ZSM-5 resulted in increasing the yield of the gasoline-ranged hydrocarbons, and in decreasing the yield of DME. Furthermore, the hybrid catalyst with Cu/ZSM-5 exhibited no deactivation for 30 h of the reaction. It was revealed that a hybrid catalyst containing Cu/ZSM-5 was efficient in the selective synthesis of gasoline-ranged hydrocarbons from syngas via methanol in the near-critical n-hexane fluid.

  11. DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

    Branko N. Popov

    2009-02-20

    The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst shows the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable

  12. DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

    Branko N. Popov

    2009-03-03

    The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst shows the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable

  13. Hybrid lead halide perovskites for light energy conversion: Excited state properties and photovoltaic applications

    Manser, Joseph S.

    travel 220 nm over the course of 2 ns after photoexcitation, with an extrapolated diffusion length greater than one micrometer over the full excited state lifetime. The solution-processability of metal halide perovskites necessarily raises questions as to the properties of the solvated precursors and their connection to the final solid-state perovskite phase. Through structural and steady-state and time-resolved absorption studies, the important link between the excited state properties of the precursor components, composed of solvated and solid-state halometallate complexes, and CH3NH3PbI3 is evinced. This connection provides insight into optical nonlinearities and electronic properties of the perovskite phase. Fundamental studies of CH 3NH3PbI3 ultimately serve as a foundation for application of this and other related materials in high-performance devices. In the final chapter, the operation of CH3NH3PbI 3 solar cells in a tandem architecture is presented. The quest for economic, large scale hydrogen production has motivated the search for new materials and device designs capable of splitting water using only energy from the sun. In light of this, we introduce an all solution-processed tandem water splitting assembly composed of a BiVO4 photoanode and a single-junction CH3NH3PbI3 hybrid perovskite solar cell. This unique configuration allows efficient solar photon management, with the metal oxide photoanode selectively harvesting high energy visible photons and the underlying perovskite solar cell capturing lower energy visible-near IR wavelengths in a single-pass excitation. Operating without external bias under standard terrestrial one sun illumination, the photoanode-photovoltaic architecture, in conjunction with an earthabundant cobalt phosphate catalyst, exhibits a solar-to-hydrogen conversion efficiency of 2.5% at neutral pH. The design of low-cost tandem water splitting assemblies employing single-junction hybrid perovskite materials establishes a potentially

  14. Effects of metal salt catalysts on yeast cell growth in ethanol conversion

    Chung-Yun Hse; Yin Lin

    2009-01-01

    The effects of the addition of metal salts and metal salt-catalyzed hydrolyzates on yeast cell growth in ethanol fermentation were investigated. Four yeast strains (Saccharomyces cerevisiae WT1, Saccharomyces cerevisiae MT81, Candida sp. 1779, and Klumaromyces fragilis), four metal salts (CuCl2, FeCl3, AgNO3, and I2), two metal salt-catalyzed hydrolyzates (...

  15. VUV photo-oxidation of gaseous benzene combined with ozone-assisted catalytic oxidation: Effect on transition metal catalyst

    Huang, Haibao; Lu, Haoxian; Zhan, Yujie; Liu, Gaoyuan; Feng, Qiuyu; Huang, Huiling; Wu, Muyan; Ye, Xinguo

    2017-01-01

    Volatile organic compounds (VOCs) cause the major air pollution concern. In this study, a series of ZSM-5 supported transition metals were prepared by impregnation method. They were combined with vacuum UV (VUV) photo-oxidation in a continuous-flow packed-bed reactor and used for the degradation of benzene, a typical toxic VOCs. Compared with VUV photo-oxidation alone, the introduction of catalysts can greatly enhance benzene oxidation under the help of O3, the by-products from VUV irradiation, via ozone-assisted catalytic oxidation (OZCO). The catalytic activity of transition metals towards benzene oxidation followed the order: Mn > Co > Cu > Ni > Fe. Mn achieved the best catalytic activity due to the strongest capability for O3 catalytic decomposition and utilization. Benzene and O3 removal efficiency reached as high as 97% and 100% after 360 min, respectively. O3 was catalytically decomposed, generating highly reactive oxidants such as rad OH and rad O for benzene oxidation.

  16. Influences of species of metals and supports on the hydrogenation activity of carbon-supported metal sulfides catalysts; Tanso biryushi tanji shokubai no suisoka kassei ni taisuru kassei kinzoku oyobi tantaishu no eikyo

    Sakanishi, K.; Hasuo, H.; Taniguchi, H.; Nagamatsu, T.; Mochida, I. [Kyushu University, Fukuoka (Japan). Institute of Advanced Material Study

    1996-10-28

    In order to design catalysts suitable for primary liquefaction stage and secondary upgrading stage respectively in the multi-stage liquefaction process, various carbon-supported catalysts were prepared. Catalytic activities of them were investigated for the hydrogenation of 1-methylnaphthalene, to discuss the influences of metals and carbon species on the catalytic activity. Various water soluble and oil soluble Mo and Ni salts were used for NiMo supported catalysts. Among various carbon supports, Ketjen Black (KB) was effective for preparing the catalyst showing the most excellent hydrogenation activity. The KB and Black Pearl 2000 (BP2000) showing high hydrogenation activity were fine particles having high specific surface area more than 1000 m{sup 2}/g and primary particle diameter around 30 nm. This was inferred to contribute to the high dispersion support of active metals. Since such fine particles of carbon exhibited hydrophobic surface, they were suitable for preparing catalysts from the methanol-soluble metals. Although Ni and Mo added iron-based catalysts provided lower aromatic hydrogenation activity, they exhibited liquefaction activity competing with the NiMo/KB catalyst. 3 refs., 1 fig., 3 tabs.

  17. Fluorine-doped carbon nanotubes as an efficient metal-free catalyst for destruction of organic pollutants in catalytic ozonation.

    Wang, Jing; Chen, Shuo; Quan, Xie; Yu, Hongtao

    2018-01-01

    Metal-free carbon materials have been presented to be potential alternatives to metal-based catalysts for heterogeneous catalytic ozonation, yet the catalytic performance still needs to be enhanced. Doping carbon with non-metallic heteroatoms (e.g., N, B, and F) could alter the electronic structure and electrochemical properties of original carbon materials, has been considered to be an effective method for improving the catalytic activity of carbon materials. Herein, fluorine-doped carbon nanotubes (F-CNTs) were synthesized via a facile method and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The as-synthesized F-CNTs exhibited notably enhanced catalytic activity towards catalytic ozonation for the degradation of organic pollutants. The oxalic acid removal efficiency of optimized F-CNTs was approximately two times as much as that of pristine CNTs, and even exceeded those of four conventional metal-based catalysts (ZnO, Al 2 O 3 , Fe 2 O 3 , and MnO 2 ). The XPS and Raman studies confirmed that the covalent CF bonds were formed at the sp 3 C sites instead of sp 2 C sites on CNTs, not only resulting in high positive charge density of C atoms adjacent to F atoms, but remaining the delocalized π-system with intact carbon structure of F-CNTs, which then favored the conversion of ozone molecules (O 3 ) into reactive oxygen species (ROS) and contributed to the high oxalic acid removal efficiency. Furthermore, electron spin resonance (ESR) studies revealed that superoxide radicals (O 2 - ) and singlet oxygen ( 1 O 2 ) might be the dominant ROS that responsible for the degradation of oxalic acid in these catalytic systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Metal-Doped Nitrogenated Carbon as an Efficient Catalyst for Direct CO2 Electroreduction to CO and Hydrocarbons.

    Varela, Ana Sofia; Ranjbar Sahraie, Nastaran; Steinberg, Julian; Ju, Wen; Oh, Hyung-Suk; Strasser, Peter

    2015-09-07

    This study explores the kinetics, mechanism, and active sites of the CO2 electroreduction reaction (CO2RR) to syngas and hydrocarbons on a class of functionalized solid carbon-based catalysts. Commercial carbon blacks were functionalized with nitrogen and Fe and/or Mn ions using pyrolysis and acid leaching. The resulting solid powder catalysts were found to be active and highly CO selective electrocatalysts in the electroreduction of CO2 to CO/H2 mixtures outperforming a low-area polycrystalline gold benchmark. Unspecific with respect to the nature of the metal, CO production is believed to occur on nitrogen functionalities in competition with hydrogen evolution. Evidence is provided that sufficiently strong interaction between CO and the metal enables the protonation of CO and the formation of hydrocarbons. Our results highlight a promising new class of low-cost, abundant electrocatalysts for synthetic fuel production from CO2 . © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. High-temperature catalytic reforming of n-hexane over supported and core-shell Pt nanoparticle catalysts: role of oxide-metal interface and thermal stability.

    An, Kwangjin; Zhang, Qiao; Alayoglu, Selim; Musselwhite, Nathan; Shin, Jae-Youn; Somorjai, Gabor A

    2014-08-13

    Designing catalysts with high thermal stability and resistance to deactivation while simultaneously maintaining their catalytic activity and selectivity is of key importance in high-temperature reforming reactions. We prepared Pt nanoparticle catalysts supported on either mesoporous SiO2 or TiO2. Sandwich-type Pt core@shell catalysts (SiO2@Pt@SiO2 and SiO2@Pt@TiO2) were also synthesized from Pt nanoparticles deposited on SiO2 spheres, which were encapsulated by either mesoporous SiO2 or TiO2 shells. n-Hexane reforming was carried out over these four catalysts at 240-500 °C with a hexane/H2 ratio of 1:5 to investigate thermal stability and the role of the support. For the production of high-octane gasoline, branched C6 isomers are more highly desired than other cyclic, aromatic, and cracking products. Over Pt/TiO2 catalyst, production of 2-methylpentane and 3-methylpentane via isomerization was increased selectively up to 420 °C by charge transfer at Pt-TiO2 interfaces, as compared to Pt/SiO2. When thermal stability was compared between supported catalysts and sandwich-type core@shell catalysts, the Pt/SiO2 catalyst suffered sintering above 400 °C, whereas the SiO2@Pt@SiO2 catalyst preserved the Pt nanoparticle size and shape up to 500 °C. The SiO2@Pt@TiO2 catalyst led to Pt nanoparticle sintering due to incomplete protection of the TiO2 shells during the reaction at 500 °C. Interestingly, over the Pt/TiO2 catalyst, the average size of Pt nanoparticles was maintained even after 500 °C without sintering. In situ ambient pressure X-ray photoelectron spectroscopy demonstrated that the Pt/TiO2 catalyst did not exhibit TiO2 overgrowth on the Pt surface or deactivation by Pt sintering up to 600 °C. The extraordinarily high stability of the Pt/TiO2 catalyst promoted high reaction rates (2.0 μmol · g(-1) · s(-1)), which was 8 times greater than other catalysts and high isomer selectivity (53.0% of C6 isomers at 440 °C). By the strong metal-support interaction

  20. Electrochemistry of plutonium in molten halides

    McCurry, L.E.; Moy, G.M.M.; Bowersox, D.F.

    1987-01-01

    The electrochemistry of plutonium in molten halides is of technological importance as a method of purification of plutonium. Previous authors have reported that plutonium can be purified by electrorefining impure plutonium in various molten haldies. Work to eluciate the mechanism of the plutonium reduction in molten halides has been limited to a chronopotentiometric study in LiCl-KCl. Potentiometric studies have been carried out to determine the standard reduction potential for the plutonium (III) couple in various molten alkali metal halides. Initial cyclic voltammetric experiments were performed in molten KCL at 1100 K. A silver/silver chloride (10 mole %) in equimolar NaCl-KCl was used as a reference electrode. Working and counter electrodes were tungsten. The cell components and melt were contained in a quartz crucible. Background cyclic voltammograms of the KCl melt at the tungsten electrode showed no evidence of electroactive impurities in the melt. Plutonium was added to the melt as PuCl/sub 3/, which was prepared by chlorination of the oxide. At low concentrations of PuCl/sub 3/ in the melt (0.01-0.03 molar), no reduction wave due to the reduction of Pu(III) was observed in the voltammograms up to the potassium reduction limit of the melt. However on scan reversal after scanning into the potassium reduction limit a new oxidation wave was observed

  1. Hydrodeoxygenation and coupling of aqueous phenolics over bifunctional zeolite-supported metal catalysts.

    Hong, Do-Young; Miller, Stephen J; Agrawal, Pradeep K; Jones, Christopher W

    2010-02-21

    Pt supported on HY zeolite is successfully used as a bifunctional catalyst for phenol hydrodeoxygenation in a fixed-bed configuration at elevated hydrogen pressures, leading to hydrogenation-hydrogenolysis ring-coupling reactions producing hydrocarbons, some with enhanced molecular weight.

  2. Studies in transition metal chemistry ; V. Soluble Ziegler-type catalysts based on vanadium, part 1

    Liefde Meijer, H.J. de; Hurk, J.W.G. van den; Kerk, G.J.M. van der

    1966-01-01

    Experiments are described aiming at a simplification of the catalyst system originally consisting of a mixture of tetraphenyltin, aluminium bromide and vanadium tetrachloride (or vanadium oxytrichloride). It is shown that tetraphenyltin merely acts as a phenylating agent for the aluminium bromide

  3. Polymeric carbon nitride nanomesh as an efficient and durable metal-free catalyst for oxidative desulfurization.

    Shen, Lijuan; Lei, Ganchang; Fang, Yuanxing; Cao, Yanning; Wang, Xinchen; Jiang, Lilong

    2018-03-06

    We report the first use of polymeric carbon nitride (CN) for the catalytic selective oxidation of H 2 S. The as-prepared CN with unique ultrathin "nanomeshes" structure exhibits excellent H 2 S conversion and high S selectivity. In particular, the CN nanomesh also displays better durability in the desulfurization reaction than traditional catalysts, such as carbon- and iron-based materials.

  4. Rapid accurate analysis of metal (oxide)-on-silica catalysts by atomic absorption spectrometry

    Jütte, B.A.H.G.; Heikamp, A.; Agterdenbos, J.

    1979-01-01

    The catalysts, which contain 10–60% copper, chromium, nickel and silicon, are decomposed in sealed Teflon-lined vessels and analyzed by atomic absorption spectrometry. Matrix matching and bracketing standards are applied. The RSD of a single determination is about 1% for all components.

  5. Oxidative coupling of 1-naphthols over noble and base metal catalysts

    Maphoru, MV

    2014-01-01

    Full Text Available Bismuth-promoted platinum catalysts were tested for the oxidative coupling of 2- and 4-substituted 1-naphthols at different temperatures and ambient pressure. The principal final products are the 3,3'-substituted 1,1'-binaphthalenylidene-4,4'-diones...

  6. Resonant halide perovskite nanoparticles

    Tiguntseva, Ekaterina Y.; Ishteev, Arthur R.; Komissarenko, Filipp E.; Zuev, Dmitry A.; Ushakova, Elena V.; Milichko, Valentin A.; Nesterov-Mueller, Alexander; Makarov, Sergey V.; Zakhidov, Anvar A.

    2017-09-01

    The hybrid halide perovskites is a prospective material for fabrication of cost-effective optical devices. Unique perovskites properties are used for solar cells and different photonic applications. Recently, perovskite-based nanophotonics has emerged. Here, we consider perovskite like a high-refractive index dielectric material, which can be considered to be a basis for nanoparticles fabrication with Mie resonances. As a result, we fabricate and study resonant perovskite nanoparticles with different sizes. We reveal, that spherical nanoparticles show enhanced photoluminescence signal. The achieved results lay a cornerstone in the field of novel types of organic-inorganic nanophotonics devices with optical properties improved by Mie resonances.

  7. Efficient hydrogenation of biomass-derived furfural and levulinic acid on the facilely synthesized noble-metal-free Cu–Cr catalyst

    Yan, Kai; Chen, Aicheng

    2013-01-01

    Biomass-derived platform intermediate furfural and levulinic acid were efficiently hydrogenated to the value-added furfuryl alcohol and promising biofuel γ-valerolactone, respectively, using a noble-metal-free Cu–Cr catalyst, which was facilely and successfully synthesized by a modified co-precipitation method using the cheap metal nitrates. In the first hydrogenation of furfural, 95% yield of furfuryl alcohol was highly selectively produced at 99% conversion of furfural under the mild conditions. For the hydrogenation of levulinic acid, 90% yield of γ-valerolactone was highly selectively produced at 97.8% conversion. Besides, the physical properties of the resulting Cu–Cr catalysts were studied by XRD (X-ray diffraction), EDX (Energy-dispersive X-ray), TEM (Transmission electron microscopy) and XPS (X-ray photoelectron spectroscopy) to reveal their influence on the catalytic performance. Subsequently, different reaction parameters were studied and it was found that Cu 2+ /Cr 3+ ratios (0.5, 1 and 2), reaction temperature (120–220 °C) and hydrogen pressure (35–70 bar) presented important influence on the catalytic activities. In the end, the stability of the Cu–Cr catalysts was also studied. - Highlights: • A noble-metal-free Cu–Cr catalyst was successfully synthesized using metal nitrates. • Cu–Cr catalysts were highly selective hydrogenation of biomass-derived furfural to FA. • Cu–Cr catalysts were efficient for hydrogenation of biomass-derived LA to biofuel GVL. • The physical properties of the resulting Cu–Cr catalysts were systematically studied. • Reaction parameters and stability in the hydrogenation of furfural were studied in details

  8. Topotactic Transformation of Metal-Organic Frameworks to Graphene-Encapsulated Transition-Metal Nitrides as Efficient Fenton-like Catalysts.

    Li, Xuning; Ao, Zhimin; Liu, Jiayi; Sun, Hongqi; Rykov, Alexandre I; Wang, Junhu

    2016-12-27

    Innovation in transition-metal nitride (TMN) preparation is highly desired for realization of various functionalities. Herein, series of graphene-encapsulated TMNs (Fe x Mn 6-x Co 4 -N@C) with well-controlled morphology have been synthesized through topotactic transformation of metal-organic frameworks in an N 2 atmosphere. The as-synthesized Fe x Mn 6-x Co 4 -N@C nanodices were systematically characterized and functionalized as Fenton-like catalysts for catalytic bisphenol A (BPA) oxidation by activation of peroxymonosulfate (PMS). The catalytic performance of Fe x Mn 6-x Co 4 -N@C was found to be largely enhanced with increasing Mn content. Theoretical calculations illustrated that the dramatically reduced adsorption energy and facilitated electron transfer for PMS activation catalyzed by Mn 4 N are the main factors for the excellent activity. Both sulfate and hydroxyl radicals were identified during the PMS activation, and the BPA degradation pathway mainly through hydroxylation, oxidation, and decarboxylation was investigated. Based on the systematic characterization of the catalyst before and after the reaction, the overall PMS activation mechanism over Fe x Mn 6-x Co 4 -N@C was proposed. This study details the insights into versatile TMNs for sustainable remediation by activation of PMS.

  9. The physical and chemical properties of nanostructured mixed-metal catalysts

    Liu, Li [Texas A & M Univ., College Station, TX (United States); Goodman, David Wayne [Texas A & M Univ., College Station, TX (United States)

    2016-04-21

    The main targets of this study has been to synthesize well-defined nanoclusters of Ni, Co, Pt, Rh and Pd as well as mixed-metal nanoclusters on ultrathin oxide surfaces and to characterize their detailed morphology using scanning probe techniques. The focus of the research is an understanding of the effects of metal-substrate interactions and overall composition on the structure/stability of single metal and mixed-metal nanoclusters and their catalytic activity.

  10. Nickel oxide and carbon nanotube composite (NiO/CNT) as a novel cathode non-precious metal catalyst in microbial fuel cells.

    Huang, Jianjian; Zhu, Nengwu; Yang, Tingting; Zhang, Taiping; Wu, Pingxiao; Dang, Zhi

    2015-10-15

    Comparing with the precious metal catalysts, non-precious metal catalysts were preferred to use in microbial fuel cells (MFCs) due to the low cost and high oxygen reduction reaction (ORR) efficiency. In this study, the transmission electron microscope and X-ray diffraction as well as Raman investigation revealed that the prepared nanoscale NiO was attached on the surface of CNT. Cyclic voltammogram and rotating ring-disk electrode tests showed that the NiO/CNT composite catalyst had an apparent oxygen reduction peak and 3.5 electron transfer pathway was acquired under oxygen atmosphere. The catalyst performance was highly dependent on the percentage of NiO in the CNT nanocomposites. When 77% NiO/CNT nano-sized composite was applied as cathode catalyst in membrane free single-chamber air cathode MFC, a maximum power density of 670 mW/m(2) and 0.772 V of OCV was obtained. Moreover, the MFC with pure NiO (control) could not achieve more than 0.1 V. All findings suggested that NiO/CNT could be a potential cathode catalyst for ORR in MFCs. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Effect of the relationship between particle size, inter-particle distance, and metal loading of carbon supported fuel cell catalysts on their catalytic activity

    Gon Corradini, Patricia; Pires, Felipe I.; Paganin, Valdecir A.; Perez, Joelma; Antolini, Ermete

    2012-01-01

    The effect of the relationship between particle size (d), inter-particle distance (x i ), and metal loading (y) of carbon supported fuel cell Pt or PtRu catalysts on their catalytic activity, based on the optimum d (2.5–3 nm) and x i /d (>5) values, was evaluated. It was found that for y i /d can be always obtained. For y ≥ 30 wt%, instead, the positive effect of a thinner catalyst layer of the fuel cell electrode than that using catalysts with y i /d compared to their optimum values, with in turns gives rise to a decrease in the catalytic activity. The effect of the x i /d ratio has been successfully verified by experimental results on ethanol oxidation on PtRu/C catalysts with same particle size and same degree of alloying but different metal loading. Tests in direct ethanol fuel cells showed that, compared to 20 wt% PtRu/C, the negative effect of the lower x i /d on the catalytic activity of 30 and 40 wt% PtRu/C catalysts was superior to the positive effect of the thinner catalyst layer.

  12. Crystal growth, structure and phase studies on gold halides

    Janssen, Eugenius Maria Wilhelmus Janssen

    1977-01-01

    Only very corrosive substances attack gold, the most noble metal. In this study the reactivity and the phase diagrams of gold with the halogens chlorine, bromine and iodine have been investigated. owing to the noble behaviour of gold, its halides are sensitive to heat; on heating they decompose into

  13. Highly reusability surface loaded metal particles magnetic catalyst microspheres (MCM-MPs) for treatment of dye-contaminated water

    Liu, Ying; Zhang, Kun; Yin, Xiaoshuang; Yang, Wenzhong; Zhu, Hongjun

    2016-01-01

    The metal-deposited magnetic catalyst microspheres (MCM-MPs) were successfully synthesized by one facile, high yield and controllable approach. Here, the bare magnetic microspheres were firstly synthesized according to the solvothermal method. Then silica shell were coated on the surface of the magnetic microspheres via sol–gel method, and subsequently with surface modifying with amino in the purpose to form SiO_2–NH_2 shell. Thus, metal particles were easily adsorbed into the SiO_2–NH_2 shell and in-situ reduced by NaBH_4 solution. All the obtained products (MCM-Cu, MCM-Ag, MCM-Pd) which were monodisperse and constitutionally stable were exhibited high magnetization and excellent catalytic activity towards dyes solution reduction. The catalytic rate ratio of MCM-Pd: MCM-Cu: MCM-Ag could be 10:3:1. Besides, some special coordination compound Cu_2(OH)_3Br had been generated in the in-situ reduced process of MCM-Cu, which produced superior cyclical stability (>20 times) than that of MCM-Ag and MCM-Pd. In all, those highly reusability and great catalytic efficiency of MCM-MPs show promising and great potential for treatment of dye-contaminated water. - Graphical abstract: Surface loaded metal particles magnetic catalyst microspheres MCM-MPs for rapid decolorizing dye-contaminated water: Synthesis, characterization and possible mechanisms. - Highlights: • A simple and high yield synthetic method for fabricate multi MCM-MPs is proposed with adequately optimize. • The highest reusability of MCM-Cu is attribute to the coordination compounds Cu_2(OH)_3Br. • MCM-MPs show excellent catalytic properties under different situations for various dyes • The catalytic mechanism of MCM-MPs is presented.

  14. Highly reusability surface loaded metal particles magnetic catalyst microspheres (MCM-MPs) for treatment of dye-contaminated water

    Liu, Ying; Zhang, Kun, E-mail: kun4219@njtech.edu.cn; Yin, Xiaoshuang; Yang, Wenzhong; Zhu, Hongjun

    2016-04-01

    The metal-deposited magnetic catalyst microspheres (MCM-MPs) were successfully synthesized by one facile, high yield and controllable approach. Here, the bare magnetic microspheres were firstly synthesized according to the solvothermal method. Then silica shell were coated on the surface of the magnetic microspheres via sol–gel method, and subsequently with surface modifying with amino in the purpose to form SiO{sub 2}–NH{sub 2} shell. Thus, metal particles were easily adsorbed into the SiO{sub 2}–NH{sub 2} shell and in-situ reduced by NaBH{sub 4} solution. All the obtained products (MCM-Cu, MCM-Ag, MCM-Pd) which were monodisperse and constitutionally stable were exhibited high magnetization and excellent catalytic activity towards dyes solution reduction. The catalytic rate ratio of MCM-Pd: MCM-Cu: MCM-Ag could be 10:3:1. Besides, some special coordination compound Cu{sub 2}(OH){sub 3}Br had been generated in the in-situ reduced process of MCM-Cu, which produced superior cyclical stability (>20 times) than that of MCM-Ag and MCM-Pd. In all, those highly reusability and great catalytic efficiency of MCM-MPs show promising and great potential for treatment of dye-contaminated water. - Graphical abstract: Surface loaded metal particles magnetic catalyst microspheres MCM-MPs for rapid decolorizing dye-contaminated water: Synthesis, characterization and possible mechanisms. - Highlights: • A simple and high yield synthetic method for fabricate multi MCM-MPs is proposed with adequately optimize. • The highest reusability of MCM-Cu is attribute to the coordination compounds Cu{sub 2}(OH){sub 3}Br. • MCM-MPs show excellent catalytic properties under different situations for various dyes • The catalytic mechanism of MCM-MPs is presented.

  15. In situ Generated Ruthenium Catalyst Systems Bearing Diverse N-Heterocyclic Carbene Precursors for Atom-Economic Amide Synthesis from Alcohols and Amines.

    Cheng, Hua; Xiong, Mao-Qian; Cheng, Chuan-Xiang; Wang, Hua-Jing; Lu, Qiang; Liu, Hong-Fu; Yao, Fu-Bin; Chen, Cheng; Verpoort, Francis

    2018-02-16

    The transition-metal-catalyzed direct synthesis of amides from alcohols and amines is herein demonstrated as a highly environmentally benign and atom-economic process. Among various catalyst systems, in situ generated N-heterocyclic carbene (NHC)-based ruthenium (Ru) halide catalyst systems have been proven to be active for this transformation. However, these existing catalyst systems usually require an additional ligand to achieve satisfactory results. In this work, through extensive screening of a diverse variety of NHC precursors, we discovered an active in situ catalyst system for efficient amide synthesis without any additional ligand. Notably, this catalyst system was found to be insensitive to the electronic effects of the substrates, and various electron-deficient substrates, which were not highly reactive with our previous catalyst systems, could be employed to afford the corresponding amides efficiently. Furthermore, mechanistic investigations were performed to provide a rationale for the high activity of the optimized catalyst system. NMR-scale reactions indicated that the rapid formation of a Ru hydride intermediate (signal at δ=-7.8 ppm in the 1 H NMR spectrum) after the addition of the alcohol substrate should be pivotal in establishing the high catalyst activity. Besides, HRMS analysis provided possible structures of the in situ generated catalyst system. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction

    Vij, Varun; Tiwari, Jitendra N.; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S.

    2016-02-01

    High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp2 carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm-2 at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production.

  17. Highly stable noble-metal nanoparticles in tetraalkylphosphonium ionic liquids for in situ catalysis.

    Banerjee, Abhinandan; Theron, Robin; Scott, Robert W J

    2012-01-09

    Gold and palladium nanoparticles were prepared by lithium borohydride reduction of the metal salt precursors in tetraalkylphosphonium halide ionic liquids in the absence of any organic solvents or external nanoparticle stabilizers. These colloidal suspensions remained stable and showed no nanoparticle agglomeration over many months. A combination of electrostatic interactions between the coordinatively unsaturated metal nanoparticle surface and the ionic-liquid anions, bolstered by steric protection offered by the bulky alkylated phosphonium cations, is likely to be the reason behind such stabilization. The halide anion strongly absorbs to the nanoparticle surface, leading to exceptional nanoparticle stability in halide ionic liquids; other tetraalkylphosphonium ionic liquids with non-coordinating anions, such as tosylate and hexafluorophosphate, show considerably lower affinities towards the stabilization of nanoparticles. Palladium nanoparticles stabilized in the tetraalkylphosphonium halide ionic liquid were stable, efficient, and recyclable catalysts for a variety of hydrogenation reactions at ambient pressures with sustained activity. Aerial oxidation of the metal nanoparticles occurred over time and was readily reversed by re-reduction of oxidized metal salts. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. OSU-6: A Highly Efficient, Metal-Free, Heterogeneous Catalyst for the Click Synthesis of 5-Benzyl and 5-Aryl-1H-tetrazoles

    Baskar Nammalwar

    2015-12-01

    Full Text Available OSU-6, an MCM-41 type hexagonal mesoporous silica with mild Brönsted acid properties, has been used as an efficient, metal-free, heterogeneous catalyst for the click synthesis of 5-benzyl and 5-aryl-1H-tetrazoles from nitriles in DMF at 90 °C. This catalyst offers advantages including ease of operation, milder conditions, high yields, and reusability. Studies are presented that demonstrate the robust nature of the catalyst under the optimized reaction conditions. OSU-6 promotes the 1,3-dipolar addition of azides to nitriles without significant degradation or clogging of the nanoporous structure. The catalyst can be reused up to five times without a significant reduction in yield, and it does not require treatment with acid between reactions.

  19. Structure, Mobility, and Composition of Transition Metal Catalyst Surfaces. High-Pressure Scanning Tunneling Microscopy and Ambient-Pressure X-ray Photoelectron Spectroscopy Studies

    Zhu, Zhongwei [Univ. of California, Berkeley, CA (United States)

    2013-12-06

    Surface structure, mobility, and composition of transition metal catalysts were studied by high-pressure scanning tunneling microscopy (HP-STM) and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) at high gas pressures. HP-STM makes it possible to determine the atomic or molecular rearrangement at catalyst surfaces, particularly at the low-coordinated active surface sites. AP-XPS monitors changes in elemental composition and chemical states of catalysts in response to variations in gas environments. Stepped Pt and Cu single crystals, the hexagonally reconstructed Pt(100) single crystal, and Pt-based bimetallic nanoparticles with controlled size, shape and composition, were employed as the model catalysts for experiments in this thesis.

  20. Hydrodesulfurization on Transition Metal Catalysts: Elementary Steps of C-S Bond Activation and Consequences of Bifunctional Synergies

    Yik, Edwin Shyn-Lo

    The presence of heteroatoms (e.g. S, N) in crude oil poses formidable challenges in petroleum refining processes as a result of their irreversible binding on catalytically active sites at industrially relevant conditions. With increasing pressures from legislation that continues to lower the permissible levels of sulfur content in fuels, hydrodesulfurization (HDS), the aptly named reaction for removing heteroatoms from organosulfur compounds, has become an essential feedstock pretreatment step to remove deleterious species from affecting downstream processing. Extensive research in the area has identified the paradigm catalysts for desulfurization; MoSx or WSx, promoted with Co or Ni metal; however, despite the vast library of both empirical and fundamental studies, a clear understanding of site requirements, the elementary steps of C-S hydrogenolysis, and the properties that govern HDS reactivity and selectivity have been elusive. While such a lack of rigorous assessments has not prevented technological advancements in the field of HDS catalysis, fundamental interpretations can inform rational catalyst and process design, particularly in light of new requirements for "deep" desulfurization and in the absence of significant hydrotreatment catalyst developments in recent decades. We report HDS rates of thiophene, which belongs to a class of compounds that are most resistant to sulfur removal (i.e. substituted alkyldibenzothiophenes), over a range of industrially relevant temperatures and pressures, measured at differential conditions and therefore revealing their true kinetic origins. These rates, normalized by the number of exposed metal atoms, on various SiO 2-supported, monometallic transition metals (Re, Ru, Pt), range several orders of magnitude. Under relevant HDS conditions, Pt and Ru catalysts form a layer of chemisorbed sulfur on surfaces of a metallic bulk, challenging reports that assume the latter exists as its pyrite sulfide phase during reaction. While

  1. Hydrogen Production by Ethanol Steam Reforming (ESR over CeO2 Supported Transition Metal (Fe, Co, Ni, Cu Catalysts: Insight into the Structure-Activity Relationship

    Michalis Konsolakis

    2016-03-01

    Full Text Available The aim of the present work was to investigate steam reforming of ethanol with regard to H2 production over transition metal catalysts supported on CeO2. Various parameters concerning the effect of temperature (400–800 °C, steam-to-carbon (S/C feed ratio (0.5, 1.5, 3, 6, metal entity (Fe, Co, Ni, Cu and metal loading (15–30 wt.% on the catalytic performance, were thoroughly studied. The optimal performance was obtained for the 20 wt.% Co/CeO2 catalyst, achieving a H2 yield of up to 66% at 400 °C. In addition, the Co/CeO2 catalyst demonstrated excellent stability performance in the whole examined temperature range of 400–800 °C. In contrast, a notable stability degradation, especially at low temperatures, was observed for Ni-, Cu-, and Fe-based catalysts, ascribed mainly to carbon deposition. An extensive characterization study, involving N2 adsorption-desorption (BET, X-ray diffraction (XRD, Scanning Electron Microscopy (SEM/EDS, X-ray Photoelectron Spectroscopy (XPS, and Temperature Programmed Reduction (H2-TPR was undertaken to gain insight into the structure-activity correlation. The excellent reforming performance of Co/CeO2 catalysts could be attributed to their intrinsic reactivity towards ethanol reforming in combination to their high surface oxygen concentration, which hinders the deposition of carbonaceous species.

  2. Catalyst for Ammonia Oxidation

    2015-01-01

    The present invention relates to a bimetallic catalyst for ammonia oxidation, a method for producing a bimetallic catalyst for ammonia oxidation and a method for tuning the catalytic activity of a transition metal. By depositing an overlayer of less catalytic active metal onto a more catalytic...

  3. Recent Advances in Supported Metal Catalysts for Syngas Production from Methane

    Mohanned Mohamedali; Amr Henni; Hussameldin Ibrahim

    2018-01-01

    Over the past few years, great attention is paid to syngas production processes from different resources especially from abundant sources, such as methane. This review of the literature is intended for syngas production from methane through the dry reforming (DRM) and the steam reforming of methane (SRM). The catalyst development for DRM and SRM represents the key factor to realize a commercial application through the utilization of more efficient catalytic systems. Due to the enormous amount...

  4. Elucidating the Origin of Hydrogen Evolution Reaction Activity in Mono- and Bimetallic Metal- and Nitrogen-Doped Carbon Catalysts (Me-N-C).

    Shahraei, Ali; Moradabadi, Ashkan; Martinaiou, Ioanna; Lauterbach, Stefan; Klemenz, Sebastian; Dolique, Stephanie; Kleebe, Hans-Joachim; Kaghazchi, Payam; Kramm, Ulrike I

    2017-08-02

    In this work, we present a comprehensive study on the role of metal species in MOF-based Me-N-C (mono- and bimetallic) catalysts for the hydrogen evolution reaction (HER). The catalysts are investigated with respect to HER activity and stability in alkaline electrolyte. On the basis of the structural analysis by X-ray diffraction, X-ray-induced photoelectron spectroscopy, and transmission electron microscopy, it is concluded that MeN 4 sites seem to dominate the HER activity of these catalysts. There is a strong relation between the amount of MeN 4 sites that are formed and the energy of formation related to these sites integrated at the edge of a graphene layer, as obtained from density functional theory (DFT) calculations. Our results show, for the first time, that the combination of two metals (Co and Mo) in a bimetallic (Co,Mo)-N-C catalyst allows hydrogen production with a significantly improved overpotential in comparison to its monometallic counterparts and other Me-N-C catalysts. By the combination of experimental results with DFT calculations, we show that the origin of the enhanced performance of our (Co,Mo)-N-C catalyst seems to be provided by an improved hydrogen binding energy on one MeN 4 site because of the presence of a second MeN 4 site in its close vicinity, as investigated in detail for our most active (Co,Mo)-N-C catalyst. The outstanding stability and good activity make especially the bimetallic Me-N-C catalysts interesting candidates for solar fuel applications.

  5. Water Oxidation by Ru-Polyoxometalate Catalysts: Overpotential Dependency on the Number and Charge of the Metal Centers

    Simone Piccinin

    2015-09-01

    Full Text Available Water oxidation is efficiently catalyzed by several Ru-based polyoxometalate (POM molecular catalysts differing in the number, local atomistic environment and oxidation state of the Ru sites. We employ density functional theory calculations to rationalize the dependency of the reaction overpotential on the main structural and electronic molecular properties. In particular, we compare the thermodynamics of the water oxidation cycle for single-site Ru-POM and multiple-site Ru4-POM complexes. For the Ru-POM case, we also investigate the reaction free energy as a function of the Ru oxidation state. We find that the overpotential of these molecular catalysts is primarily determined by the oxidation state of the metal center and is minimum for Ru(IV. In solution, the number of active sites is shown to play a minor role on the reaction energetics. The results are rationalized and discussed in terms of the local structure around the active sites and of the electrostatic screening due to the molecular structure or the solvent.

  6. Selective CO Methanation on Ru/TiO2 Catalysts: Role and Influence of Metal-Support Interactions

    Abdel-Mageed, Ali M.; Widmann, D.; Olesen, Sine Ellemann

    2015-01-01

    Aiming at a detailed understanding of the role of metal-support interactions in the selective methanation of CO in CO2-rich reformate gases, we have investigated the catalytic performance of a set of Ru/TiO2 catalysts with comparable Ru loading, Ru particle size, and TiO2 phase composition but very...... different surface areas (ranging from 20 to 235 m2 g-1) in this reaction. The activity for CO methanation, under steady-state conditions, was found to strongly depend on the TiO2 support surface area, increasing first with increasing surface area up to a maximum activity for the Ru/TiO2 catalyst...... with a surface area of 121 m2 g-1 and then decreasing for an even higher surface area; however, the selectivity is mainly determined by the Ru particle size, which slightly decreases with increasing support surface area. This goes along with an increase in selectivity for CO methanation, in agreement...

  7. Autoradiographic techniques to determine noble metal distribution in automotive catalyst substrates

    Lange, W.H.

    1976-01-01

    The distribution of noble metals in the ceramic substrates of automotive catalytic converter systems is important to the functional characteristics of the systems. A radiotracer technique involving microtomy of bead substrate samples and autoradiography using the resultant thin sections was developed to produce detailed images of the metal distributions. The method is particularly valuable to determine the distribution of one metal in the presence of another to aid in the development of more efficient systems

  8. Two-Dimensional Halide Perovskites for Emerging New- Generation Photodetectors

    Tang, Yingying; Cao, Xianyi; Chi, Qijin

    2018-01-01

    Compared to their conventional three-dimensional (3D) counterparts, two-dimensional (2D) halide perovskites have attracted more interests recently in a variety of areas related to optoelectronics because of their unique structural characteristics and enhanced performances. In general, there are two...... distinct types of 2D halide perovskites. One represents those perovskites with an intrinsic layered crystal structure (i.e. MX6 layers, M = metal and X = Cl, Br, I), the other defines the perovskites with a 2D nanostructured morphology such as nanoplatelets and nanosheets. Recent studies have shown that 2D...... halide perovskites hold promising potential for the development of new-generation photodetectors, mainly arising from their highly efficient photoluminescence and absorbance, color tunability in the visible-light range and relatively high stability. In this chapter, we present the summary and highlights...

  9. Improved Automotive NO (x) Aftertreatment System: Metal Ammine Complexes as NH3 Source for SCR Using Fe-Containing Zeolite Catalysts

    Johannessen, Tue; Schmidt, Henning; Frey, Anne Mette

    2009-01-01

    Ammonia storage is a challenge in the selective catalytic reduction of NO (x) in vehicles. We propose a new system, based on metal ammines as the ammonia source. In combination with iron containing zeolites as the SCR catalyst it should be possible to obtain a low temperature system for NO (x...

  10. Synthesis of self-supported non-precious metal catalysts for oxygen reduction reaction with preserved nanostructures from the polyaniline nanofiber precursor

    Hu, Yang; Zhao, Xiao; Huang, Yunjie

    2013-01-01

    Non-precious metal catalysts (NPMCs) for the oxygen reduction reaction (ORR) are an active subject of recent research on proton exchange membrane fuel cells. In this study, we report a new approach to preparation of self-supported and nano-structured NPMCs using pre-prepared polyaniline (PANI...

  11. The enhancement of the hydrolysis of bamboo biomass in ionic liquid with chitosan-based solid acid catalysts immobilized with metal ions.

    Cheng, Jie; Wang, Nan; Zhao, Dezhou; Qin, Dandan; Si, Wenqing; Tan, Yunfei; Wei, Shun'an; Wang, Dan

    2016-11-01

    Three kinds of sulfonated cross-linked chitosan (SCCR) immobilized with metal ions of Cu(2+), Fe(3+) and Zn(2+) individually were synthesized and firstly used as solid acid catalysts in the hydrolysis of bamboo biomass. FTIR spectra showed that metal ions had been introduced into SCCR and the N-metal ions coordinate bound was formed. The particle sizes of these catalysts were about 500-1000μm with a pore size of 50-160μm. All of the three kinds of catalysts performed well for bamboo hydrolysis with 1-butyl-3-methyl-imidazolium chloride used as solvent. The most effective one was sulfonated cross-linked chitosan immobilized with Fe(3+) (Fe(3+)-SCCR). TRS yields were up to 73.42% for hydrolysis of bamboo powder in [C4mim]Cl with Fe(3+)-SCCR at 120°C and 20RPM after 24h. These novel chitosan-based metal ions immobilized solid acid catalysts with ionic liquids as the solvent might be promising to facilitate cost-efficient conversion of biomass into biofuels and bioproducts. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. A Phenomenological Study on the Synergistic Role of Precious Metals in the Steam Reforming of Logistic Fuels on Bimetal-Supported Catalysts

    Abdul-Majeed Azad

    2011-01-01

    Full Text Available Fuel processors are required to convert sulfur-laden logistic fuels into hydrogen-rich reformate and deliver to the fuel cell stack with little or no sulfur. Since sulfur poisons and deactivates the reforming catalyst, robust sulfur-tolerant catalysts ought to be developed. In this paper, the development, characterization and evaluation of a series of reforming catalysts containing two noble metals (with total metal loading not exceeding 1 weight percent supported on nanoscale ceria for the steam-reforming of kerosene is reported. Due to inherent synergy, a bimetallic catalyst is superior to its monometallic analog, for the same level of loading. The choice of noble metal combination in the bimetallic formulations plays a vital and meaningful role in their performance. Presence of ruthenium and/or rhodium in formulations containing palladium showed improved sulfur tolerance and significant enhancement in their catalytic activity and stability. Rhodium was responsible for higher hydrogen yields in the logistic fuel reformate. Duration of steady hydrogen production was higher in the case of RhPd (75 h than for RuPd (68 h; hydrogen generation was stable over the longest period (88 h with RuRh containing no Pd. A mechanistic correlation between the characteristic role of precious metals in the presence of each other is discussed.

  13. Development of a heterogeneous catalyst for lignocellulosic biomass conversion : glucose dehydration by metal chlorides in a silica-supported ionic liquid layer

    Degirmenci, V.; Hensen, E.J.M.

    2014-01-01

    An attempt is made to immobilize the homogeneous metal chloride/EMIMCl catalyst for glucose dehydration to 5-hydroxymethylfurfural. To this end, ionic liquid fragments were grafted to the surface of SBA-15 to generate a heterogenized mimick of the homogeneous reaction medium. Despite a decrease in

  14. Fundamentals of Melt infiltration for the Preparation of Supported Metal Catalysts.The Case of Co/SiO2 Fischer-Tropsch Synthesis

    Eggenhuisen, T.M.|info:eu-repo/dai/nl/313959498; den Breejen, J.P.|info:eu-repo/dai/nl/304837318; Verdoes, D.; de Jongh, P.E.|info:eu-repo/dai/nl/186125372; de Jong, K.P.|info:eu-repo/dai/nl/06885580X

    2013-01-01

    We explored melt infiltration of mesoporous silica supports to prepare supported metal catalysts with high loadings and controllable particle sizes. Melting of Co(NO3)2 ·6H2O in the presence of silica supports was studied in situ with differential scanning calorimetry. The melting point depression

  15. Air-stable magnesium nanocomposites provide rapid and high-capacity hydrogen storage without using heavy-metal catalysts

    Jeon, Ki-Joon; Moon, Hoi Ri; Ruminski, Anne M.; Jiang, Bin; Kisielowski, Christian; Bardhan, Rizia; Urban, Jeffrey J.

    2011-04-01

    Hydrogen is a promising alternative energy carrier that can potentially facilitate the transition from fossil fuels to sources of clean energy because of its prominent advantages such as high energy density (142 MJ kg-1 ref. 1), great variety of potential sources (for example water, biomass, organic matter), light weight, and low environmental impact (water is the sole combustion product). However, there remains a challenge to produce a material capable of simultaneously optimizing two conflicting criteria—absorbing hydrogen strongly enough to form a stable thermodynamic state, but weakly enough to release it on-demand with a small temperature rise. Many materials under development, including metal-organic frameworks, nanoporous polymers, and other carbon-based materials, physisorb only a small amount of hydrogen (typically 1-2 wt%) at room temperature. Metal hydrides were traditionally thought to be unsuitable materials because of their high bond formation enthalpies (for example MgH2 has a ΔHf˜75 kJ mol-1), thus requiring unacceptably high release temperatures resulting in low energy efficiency. However, recent theoretical calculations and metal-catalysed thin-film studies have shown that microstructuring of these materials can enhance the kinetics by decreasing diffusion path lengths for hydrogen and decreasing the required thickness of the poorly permeable hydride layer that forms during absorption. Here, we report the synthesis of an air-stable composite material that consists of metallic Mg nanocrystals (NCs) in a gas-barrier polymer matrix that enables both the storage of a high density of hydrogen (up to 6 wt% of Mg, 4 wt% for the composite) and rapid kinetics (loading in <30 min at 200 °C). Moreover, nanostructuring of the Mg provides rapid storage kinetics without using expensive heavy-metal catalysts.

  16. Metals on graphene and carbon nanotube surfaces: From mobile atoms to atomtronics to bulk metals to clusters and catalysts

    Sarkar, Santanu C.; Moser, Matthew L.; Tian, Xiaojuan; Zhang, Xixiang; Al-Hadeethi, Yas Fadel; Haddon, Robert C.

    2014-01-01

    , and the next generation energy devices. We touch on chemical vapor deposition (CVD) graphene grown on metals, the reactivity of its surface, and its use as a template for asymmetric graphene functionalization chemistry (ultrathin Janus discs). We highlight some

  17. Metals on graphene and carbon nanotube surfaces: From mobile atoms to atomtronics to bulk metals to clusters and catalysts

    Sarkar, Santanu C.

    2014-01-14

    In this Perspective, we present an overview of recent fundamental studies on the nature of the interaction between individual metal atoms and metal clusters and the conjugated surfaces of graphene and carbon nanotube with a particular focus on the electronic structure and chemical bonding at the metal-graphene interface. We discuss the relevance of organometallic complexes of graphitic materials to the development of a fundamental understanding of these interactions and their application in atomtronics as atomic interconnects, high mobility organometallic transistor devices, high-frequency electronic devices, organometallic catalysis (hydrogen fuel generation by photocatalytic water splitting, fuel cells, hydrogenation), spintronics, memory devices, and the next generation energy devices. We touch on chemical vapor deposition (CVD) graphene grown on metals, the reactivity of its surface, and its use as a template for asymmetric graphene functionalization chemistry (ultrathin Janus discs). We highlight some of the latest advances in understanding the nature of interactions between metals and graphene surfaces from the standpoint of metal overlayers deposited on graphene and SWNT thin films. Finally, we comment on the major challenges facing the field and the opportunities for technological applications. © 2013 American Chemical Society.

  18. Knocking on wood: base metal complexes as catalysts for selective oxidation of lignin models and extracts.

    Hanson, Susan K; Baker, R Tom

    2015-07-21

    This work began as part of a biomass conversion catalysis project with UC Santa Barbara funded by the first NSF Chemical Bonding Center, CATSB. Recognizing that catalytic aerobic oxidation of diol C-C bonds could potentially be used to break down lignocellulose, we began to synthesize oxovanadium complexes and explore their fundamental reactivity. Of course there were theories regarding the oxidation mechanism, but our mechanistic studies soon revealed a number of surprises of the type that keep all chemists coming back to the bench! We realized that these reactions were also exciting in that they actually used the oxygen-on-every-carbon property of biomass-derived molecules to control the selectivity of the oxidation. When we found that these oxovanadium complexes tended to convert sugars predominantly to formic acid and carbon dioxide, we replaced one of the OH groups with an ether and entered the dark world of lignin chemistry. In this Account, we summarize results from our collaboration and from our individual labs. In particular, we show that oxidation selectivity (C-C vs C-O bond cleavage) of lignin models using air and vanadium complexes depends on the ancillary ligands, the reaction solvent, and the substrate structure (i.e., phenolic vs non-phenolic). Selected vanadium complexes in the presence of added base serve as effective alcohol oxidation catalysts via a novel base-assisted dehydrogenation pathway. In contrast, copper catalysts effect direct C-C bond cleavage of these lignin models, presumably through a radical pathway. The most active vanadium catalyst exhibits unique activity for the depolymerization of organosolv lignin. After Weckhuysen's excellent 2010 review on lignin valorization, the number of catalysis studies and approaches on both lignin models and extracts has expanded rapidly. Today we are seeing new start-ups and lignin production facilities sprouting up across the globe as we all work to prove wrong the old pulp and paper chemist

  19. A theoretical evaluation of possible transition metal electro-catalysts for N2 reduction

    Skulason, Egill; Bligaard, Thomas; Gudmundsdottir, Sigrıdur

    2012-01-01

    such as Sc, Y, Ti, and Zr bind N-adatoms more strongly than H-adatoms, a significant production of ammonia compared with hydrogen gas can be expected on those metal electrodes when a bias of 1 V to 1.5 V vs. SHE is applied. Defect-free surfaces of the early transition metals are catalytically more active...

  20. Mechanistic Studies of Metal-Oxo Cubane Catalysts for Lightweight Solar Fuels Storage

    2013-03-01

    13692. 4 “ Single - crystal growth, crystal and electronic structure of NaCoO2.” Takahashi, Y.; Gotoh, Y.; Akimoto, J. J. Sol. State Chem. 2003, 172, 22...bond formation by the Co–OEC catalysts. 2. A penetrating study of Co3 +|Co4+ self-exchange kinetics of Co4O4 cubanes and a detailed understanding of...construct the artificial leaf described in (7). 4. The examination of Co2+| Co3 + self-exchange in a faithful structural molecular analog of the 7