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

Science.gov (United States)

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.

First-principles studies on graphene-supported transition metal clusters

International Nuclear Information System (INIS)

Sahoo, Sanjubala; Khanna, Shiv N.; Gruner, Markus E.; Entel, Peter

2014-01-01

Theoretical studies on the structure, stability, and magnetic properties of icosahedral TM 13 (TM = Fe, Co, Ni) clusters, deposited on pristine (defect free) and defective graphene sheet as well as graphene flakes, have been carried out within a gradient corrected density functional framework. The defects considered in our study include a carbon vacancy for the graphene sheet and a five-membered and a seven-membered ring structures for graphene flakes (finite graphene chunks). It is observed that the presence of defect in the substrate has a profound influence on the electronic structure and magnetic properties of graphene-transition metal complexes, thereby increasing the binding strength of the TM cluster on to the graphene substrate. Among TM 13 clusters, Co 13 is absorbed relatively more strongly on pristine and defective graphene as compared to Fe 13 and Ni 13 clusters. The adsorbed clusters show reduced magnetic moment compared to the free clusters

Chirality effect on nearly half-metallic properties in systematic endo-doping of 3d transition metals of narrow carbon nanotubes

Energy Technology Data Exchange (ETDEWEB)

Malehmir, M.; Khoshnevisan, B., E-mail: b.khosh@kashanu.ac.ir

2016-10-20

Spin polarized density functional calculations were employed to study chirality effect on electronic and magnetic properties of 3d transition metals (TMs) endo-doped co-diameter (∼7 Å) narrow (5,5) and (9,0) single walled carbon nanotubes (CNTs). Various magnetizations up to ∼6μ{sub B} was obtained for different 3dTM-CNT systems (recall that the magnetization of fcc structure cobalt is ∼1.6μ{sub B}). In addition nearly half-metallic magnetic behavior has been observed for the most of considered systems. These results would be useful for spintronic and nano-magnetic technology.

Transition-Metal-Controlled Inorganic Ligand-Supported Non-Precious Metal Catalysts for the Aerobic Oxidation of Amines to Imines.

Science.gov (United States)

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.

First-row transition metal hydrogenation and hydrosilylation catalysts

Science.gov (United States)

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.

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

Energy Technology Data Exchange (ETDEWEB)

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.

METHANE DRY REFORMING OVER Ni SUPPORTED ON PINE SAWDUST ACTIVATED CARBON: EFFECTS OF SUPPORT SURFACE PROPERTIES AND METAL LOADING

Directory of Open Access Journals (Sweden)

Rafael García

2015-05-01

Full Text Available The influence of metal loading and support surface functional groups (SFG on methane dry reforming (MDR over Ni catalysts supported on pine-sawdust derived activated carbon were studied. Using pine sawdust as the catalyst support precursor, the smallest variety and lowest concentration of SFG led to best Ni dispersion and highest catalytic activity, which increased with Ni loading up to 3 Ni atoms nm-2. At higher Ni loading, the formation of large metal aggregates was observed, consistent with a lower "apparen" surface area and a decrease in catalytic activity. The H2/CO ratio rose with increasing reaction temperature, indicating that increasingly important side reactions were taking place in addition to MDR.

Features of order-disorder phase transformation in nonstoichiometric transition metals carbides

International Nuclear Information System (INIS)

Emel'yanov, A.N.

1996-01-01

Measurements of temperature and electric conductivity of nonstoichiometric transition metals carbides TiC χ and NbC χ in the area of order-disorder phase transformation are carried out. There are certain peculiarities on the temperature and electric conductivity curves of the carbides, connected with the carbon sublattice disordering. On the basis of the anomalies observed on the curves of the temperature conductivity of nonstoichiometric carbides of transition metals above the temperature of the order-disorder transition the existence of the second structural transition is supposed

13C NMR investigation of the structure of cationic carbonyls in transition metal zeolites

International Nuclear Information System (INIS)

Ben Taarit, Y.

1979-01-01

13 C NMR spectroscopy was used to investigate the nature of carbon monoxide adsorbed on transition metal ions hosted in a synthetic faujastite type zeolite. The adsorbed CO species was characterised by a highly shielded carbon nucleus. Using the Pople approximation for the paramagnetic shielding term, the observed chemical shift was rationalised assuming the formation of a cationic carbonyl species with an appreciable electronic transfer from the carbon lone pair to the transition metal ion and negligible π back-bonding if at all. (Auth.)

One-step synthesis of 2D-layered carbon wrapped transition metal nitrides from transition metal carbides (MXenes) for supercapacitors with ultrahigh cycling stability.

Science.gov (United States)

Yuan, Wenyu; Cheng, Laifei; Wu, Heng; Zhang, Yani; Lv, Shilin; Guo, Xiaohui

2018-03-13

A novel one-step method to synthesize 2D carbon wrapped TiN (C@TiN) was proposed via using 2D metal carbides (MXenes) as precursors. This study provides a novel approach to synthesize carbon wrapped metal nitrides.

Metal supply constraints for a low-carbon economy?

NARCIS (Netherlands)

Koning, A. de; Kleijn, R.; Huppes, G.; Sprecher, B.; Engelen, G. van; Tukker, A.

2018-01-01

Low-carbon energy systems are more metal-intensive than traditional energy systems. Concerns have been expressed that this may hamper the transition to a low-carbon economy. We estimate the required extraction of Fe, Al, Cu, Ni, Cr, In, Nd, Dy, Li, Zn, and Pb until 2050 under several

Recent advances in transition-metal-catalyzed intermolecular carbomagnesiation and carbozincation

Directory of Open Access Journals (Sweden)

Kei Murakami

2013-02-01

Full Text Available Carbomagnesiation and carbozincation reactions are efficient and direct routes to prepare complex and stereodefined organomagnesium and organozinc reagents. However, carbon–carbon unsaturated bonds are generally unreactive toward organomagnesium and organozinc reagents. Thus, transition metals were employed to accomplish the carbometalation involving wide varieties of substrates and reagents. Recent advances of transition-metal-catalyzed carbomagnesiation and carbozincation reactions are reviewed in this article. The contents are separated into five sections: carbomagnesiation and carbozincation of (1 alkynes bearing an electron-withdrawing group; (2 alkynes bearing a directing group; (3 strained cyclopropenes; (4 unactivated alkynes or alkenes; and (5 substrates that have two carbon–carbon unsaturated bonds (allenes, dienes, enynes, or diynes.

Metal-insulator transitions

Science.gov (United States)

Imada, Masatoshi; Fujimori, Atsushi; Tokura, Yoshinori

1998-10-01

Metal-insulator transitions are accompanied by huge resistivity changes, even over tens of orders of magnitude, and are widely observed in condensed-matter systems. This article presents the observations and current understanding of the metal-insulator transition with a pedagogical introduction to the subject. Especially important are the transitions driven by correlation effects associated with the electron-electron interaction. The insulating phase caused by the correlation effects is categorized as the Mott Insulator. Near the transition point the metallic state shows fluctuations and orderings in the spin, charge, and orbital degrees of freedom. The properties of these metals are frequently quite different from those of ordinary metals, as measured by transport, optical, and magnetic probes. The review first describes theoretical approaches to the unusual metallic states and to the metal-insulator transition. The Fermi-liquid theory treats the correlations that can be adiabatically connected with the noninteracting picture. Strong-coupling models that do not require Fermi-liquid behavior have also been developed. Much work has also been done on the scaling theory of the transition. A central issue for this review is the evaluation of these approaches in simple theoretical systems such as the Hubbard model and t-J models. Another key issue is strong competition among various orderings as in the interplay of spin and orbital fluctuations. Experimentally, the unusual properties of the metallic state near the insulating transition have been most extensively studied in d-electron systems. In particular, there is revived interest in transition-metal oxides, motivated by the epoch-making findings of high-temperature superconductivity in cuprates and colossal magnetoresistance in manganites. The article reviews the rich phenomena of anomalous metallicity, taking as examples Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Ru compounds. The diverse phenomena include strong spin and

Radiolytic and photochemical reduction of carbon dioxide in solution catalyzed by transition metal complexes with some selected macrocycles

International Nuclear Information System (INIS)

Grodkowski, J.

2004-01-01

The main goal of the work presented in this report is an explanation of the mechanism of carbon dioxide (CO 2 ) reduction catalyzed by transition metal complexes with some selected macrocycles. The catalytic function of two electron exchange centers in the reduction of CO 2 , an inner metal and a macrocycle ring, was defined. Catalytic effects of rhodium, iron and cobalt porphyrins, cobalt and iron phthalocyanines and corroles as well as cobalt corrins have been investigated. CO 2 reduction by iron ions without presence of macrocycles and also in presence of copper compounds in aqueous solutions have been studied as well

Synthesis of Binary Magnesium-Transition Metal Oxides via Inverse Coprecipitation

Science.gov (United States)

Yagi, Shunsuke; Ichikawa, Yuya; Yamada, Ikuya; Doi, Takayuki; Ichitsubo, Tetsu; Matsubara, Eiichiro

2013-02-01

Synthesis of binary magnesium-transition metal oxides, MgM2O4 (M: Cr, Mn, Fe, Co) and MgNiO2, was performed by calcination at relatively low temperatures of 500 and 750 °C for 24 h through inverse coprecipitation of carbonate hydroxide precursors. The important roles of the precipitation agent, sodium carbonate, were clarified by considering equilibria in an aqueous solution. The structure parameters of the obtained binary magnesium-transition metal oxide powders, specifically the occupancy of atomic sites, were evaluated from synchrotron X-ray diffraction (XRD) profiles by Rietveld refinement in addition to the magnetic properties at room temperature. The present work provides general guidelines for low-cost and high-volume synthesis of complex oxides, which are easily decomposed at high temperatures.

Recent advances in transition metal-catalyzed Csp2-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation

Directory of Open Access Journals (Sweden)

Grégory Landelle

2013-11-01

Full Text Available In the last few years, transition metal-mediated reactions have joined the toolbox of chemists working in the field of fluorination for Life-Science oriented research. The successful execution of transition metal-catalyzed carbon–fluorine bond formation has become a landmark achievement in fluorine chemistry. This rapidly growing research field has been the subject of some excellent reviews. Our approach focuses exclusively on transition metal-catalyzed reactions that allow the introduction of –CFH2, –CF2H, –CnF2n+1 and –SCF3 groups onto sp² carbon atoms. Transformations are discussed according to the reaction-type and the metal employed. The review will not extend to conventional non-transition metal methods to these fluorinated groups.

Atomic structure of non-stoichiometric transition metal carbides

International Nuclear Information System (INIS)

Moisy-Maurice, Virginie.

1981-10-01

Different kinds of experimental studies of the atomic arrangement in non-stoichiometric transition metal carbides are proposed: the ordering of carbon vacancies and the atomic static displacements are the main subjects studied. Powder neutron diffraction on TiCsub(1-x) allowed us to determine the order-disorder transition critical temperature -Tsub(c) approximately 770 0 C- in the TiCsub(0.52-0.67) range, and to analyze at 300 K the crystal structure of long-range ordered samples. A neutron diffuse scattering quantitative study at 300 K of short-range order in TiCsub(0.76), TiCsub(0.79) and NbCsub(0.73) single crystals is presented: as in Ti 2 Csub(1+x) and Nb 6 C 5 superstructures, vacancies avoid to be on each side of a metal atom. Besides, the mean-square carbon atom displacements from their sites are small, whereas metal atoms move radially about 0.03 A away from vacancies. These results are in qualitative agreement with EXAFS measurements at titanium-K edge of TiCsub(1-x). An interpretation of ordering in term of short-range interaction pair potentials between vacancies is proposed [fr

Ammonia and hydrazine. Transition-metal-catalyzed hydroamination and metal-free catalyzed functionalization

Energy Technology Data Exchange (ETDEWEB)

Bertrand, Guy [Univ. of California, San Diego, CA (United States)

2012-06-29

The efficient and selective preparation of organic molecules is critical for mankind. For the future, it is of paramount importance to find catalysts able to transform abundant and cheap feedstocks into useful compounds. Acyclic and heterocyclic nitrogen-containing derivatives are common components of naturally occurring compounds, agrochemicals, cosmetics, and pharmaceuticals; they are also useful intermediates in a number of industrial processes. One of the most widely used synthetic strategies, allowing the formation of an N-C bond, is the addition of an N-H bond across a carbon-carbon multiple bond, the so-called hydroamination reaction. This chemical transformation fulfills the principle of “green chemistry” since it ideally occurs with 100% atom economy. Various catalysts have been found to promote this reaction, although many limitations remain; one of the most prominent is the lack of methods that permit the use of NH₃ and NH₂NH₂ as the amine partners. In fact, ammonia and hydrazine have rarely succumbed to homogeneous catalytic transformations. Considering the low cost and abundance of ammonia (136 million metric tons produced in 2011) and hydrazine, catalysts able to improve the reactivity and selectivity of the NH₃- and NH₂NH₂-hydroamination reaction, and more broadly speaking the functionalization of these chemicals, are highly desirable. In the last funded period, we discovered the first homogeneous catalysts able to promote the hydroamination of alkynes and allenes with ammonia and the parent hydrazine. The key feature of our catalytic systems is that the formation of catalytically inactive Werner complexes is reversible, in marked contrast to most of the known ammonia and hydrazine transition metal complexes. This is due to the peculiar electronic properties of our neutral ancillary ligands, especially their strong donating capabilities. However, our catalysts currently require

Empirical prediction of optical transitions in metallic armchair SWCNTs

Directory of Open Access Journals (Sweden)

G. R. Ahmed Jamal

2015-12-01

Full Text Available In this work, a quick and effective method to calculate the second and third optical transition energies of metallic armchair single-wall carbon nanotubes (SWCNT is presented. In this proposed method, the transition energy of any armchair SWCNT can be predicted directly by knowing its one chiral index as both of its chiral indices are same. The predicted results are compared with recent experimental data and found to be accurate over a wide diameter range from 2 to 4.8 nm. The empirical equation proposed here is also compared with that proposed in earlier works. The proposed way may help the research works or applications where information of optical transitions of armchair metallic nanotubes is needed.

Nanoporous metal-carbon composite

Science.gov (United States)

Worsley, Marcus A.; Satcher, Joe; Kucheyev, Sergei; Charnvanichborikarn, Supakit; Colvin, Jeffrey; Felter, Thomas; Kim, Sangil; Merrill, Matthew; Orme, Christine

2017-12-19

Described here is a metal-carbon composite, comprising (a) a porous three-dimensional scaffold comprising one or more of carbon nanotubes, graphene and graphene oxide, and (b) metal nanoparticles disposed on said porous scaffold, wherein the metal-carbon composite has a density of 1 g/cm.sup.3 or less, and wherein the metal nanoparticles account for 1 wt. % or more of the metal-carbon composite. Also described are methods for making the metal-carbon composite.

Highly efficient transition metal and nitrogen co-doped carbide-derived carbon electrocatalysts for anion exchange membrane fuel cells

Science.gov (United States)

Ratso, Sander; Kruusenberg, Ivar; Käärik, Maike; Kook, Mati; Puust, Laurits; Saar, Rando; Leis, Jaan; Tammeveski, Kaido

2018-01-01

The search for an efficient electrocatalyst for oxygen reduction reaction (ORR) to replace platinum in fuel cell cathode materials is one of the hottest topics in electrocatalysis. Among the many non-noble metal catalysts, metal/nitrogen/carbon composites made by pyrolysis of cheap materials are the most promising with control over the porosity and final structure of the catalyst a crucial point. In this work we show a method of producing a highly active ORR catalyst in alkaline media with a controllable porous structure using titanium carbide derived carbon as a base structure and dicyandiamide along with FeCl3 or CoCl2 as the dopants. The resulting transition metal-nitrogen co-doped carbide derived carbon (M/N/CDC) catalyst is highly efficient for ORR electrocatalysis with the activity in 0.1 M KOH approaching that of commercial 46.1 wt.% Pt/C. The catalyst materials are also investigated by scanning electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy to characterise the changes in morphology and composition causing the raise in electrochemical activity. MEA performance of M/N/CDC cathode materials in H2/O2 alkaline membrane fuel cell is tested with the highest power density reached being 80 mW cm-2 compared to 90 mW cm-2 for Pt/C.

CVD-graphene growth on different polycrystalline transition metals

Directory of Open Access Journals (Sweden)

M. P. Lavin-Lopez

2017-01-01

Full Text Available The chemical vapor deposition (CVD graphene growth on two polycrystalline transition metals (Ni and Cu was investigated in detail using Raman spectroscopy and optical microscopy as a way to synthesize graphene of the highest quality (i.e. uniform growth of monolayer graphene, which is considered a key issue for electronic devices. Key CVD process parameters (reaction temperature, CH4/H2flow rate ratio, total flow of gases (CH4+H2, reaction time were optimized for both metals in order to obtain the highest graphene uniformity and quality. The conclusions previously reported in literature about the performance of low and high carbon solubility metals in the synthesis of graphene and their associated reaction mechanisms, i.e. surface depositionand precipitation on cooling, respectively, was not corroborated by the results obtained in this work. Under the optimal reaction conditions, a large percentage of monolayer graphene was obtained over the Ni foil since the carbon saturation was not complete, allowing carbon atoms to be stored in the bulk metal, which could diffuse forming high quality monolayer graphene at the surface. However, under the optimal reaction conditions, the formation of a non-uniform mixture of few layers and multilayer graphene on the Cu foil was related to the presence of an excess of active carbon atoms on the Cu surface.

Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides

Science.gov (United States)

Lukatskaya, Maria R.; Kota, Sankalp; Lin, Zifeng; Zhao, Meng-Qiang; Shpigel, Netanel; Levi, Mikhael D.; Halim, Joseph; Taberna, Pierre-Louis; Barsoum, Michel W.; Simon, Patrice; Gogotsi, Yury

2017-08-01

The use of fast surface redox storage (pseudocapacitive) mechanisms can enable devices that store much more energy than electrical double-layer capacitors (EDLCs) and, unlike batteries, can do so quite rapidly. Yet, few pseudocapacitive transition metal oxides can provide a high power capability due to their low intrinsic electronic and ionic conductivity. Here we demonstrate that two-dimensional transition metal carbides (MXenes) can operate at rates exceeding those of conventional EDLCs, but still provide higher volumetric and areal capacitance than carbon, electrically conducting polymers or transition metal oxides. We applied two distinct designs for MXene electrode architectures with improved ion accessibility to redox-active sites. A macroporous Ti3C2Tx MXene film delivered up to 210 F g-1 at scan rates of 10 V s-1, surpassing the best carbon supercapacitors known. In contrast, we show that MXene hydrogels are able to deliver volumetric capacitance of ˜1,500 F cm-3 reaching the previously unmatched volumetric performance of RuO2.

Gasification of carbon deposits on catalysts and metal surfaces

Energy Technology Data Exchange (ETDEWEB)

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.

Adhered Supported Carbon Nanotubes

International Nuclear Information System (INIS)

Johnson, Dale F.; Craft, Benjamin J.; Jaffe, Stephen M.

2001-01-01

Carbon nanotubes (NTs) in excess of 200 μm long are grown by catalytic pyrolysis of hydrocarbon vapors. The nanotubes grow continuously without the typical extinction due to catalyst encapsulation. A woven metal mesh supports the nanotubes creating a metal supported nanotube (MSNT) structure. The 140 μm wide mesh openings are completely filled by 70 nm diameter multiwalled nanotubes (MWNTs). The MWNTs are straight, uniform and highly crystalline. Their wall thickness is about 10 nm (30 graphite layers). The adherent NTs are not removed from the support in a Scotch tape pull test. A 12.5 cm 2 capacitor made from two MSNT structures immersed in 1 M KCl has a capacitance of 0.35 F and an equivalent series resistance of 0.18 Ω. Water flows through the MSNT at a flow velocity of 1 cm/min with a pressure drop of 15 inches of water. With the support removed, the MWNTs naturally form a carbon nanocomposite (CNC) paper with a specific area of 80 m 2 /gm, a bulk density of 0.21 g/cm 3 , an open pore fraction of 0.81, and a resistivity of 0.16 Ω-cm

Reactivity of Heteropolytungstate and Heteropolymolybdate Metal Transition Salts in the Synthesis of Dimethyl Carbonate from Methanol and CO2

Directory of Open Access Journals (Sweden)

Amro Al-Amro

2010-07-01

Full Text Available A series of Keggin-type heteropoly compounds (HPC having different countercations (Co, Fe and different addenda atoms (W, Mo were synthesized and characterized by means of Fourier-Transform Infrared Spectrometer (FT-IR and X-ray powder diffraction (XRD. The catalytic properties of the prepared catalysts for the dimethyl carbonate (DMC synthesis from CO2 and CH3OH were investigated. The experimental results showed that the catalytic activity is significantly influenced by the type of the countercation and addenda atoms transition metal. Among the catalysts examined, Co1.5PW12O40 is the most active for the DMC synthesis, owing to the synergetic effect between Co and W. Investigating the effect of the support showed that the least acidic one (Al2O3 enhanced the conversion but decreased the DMC selectivity in favor of that of methyl formate (MF, while that of dimethoxy methane remained stable.

Carbon Nanofibers as Catalyst Support for Noble Metals

NARCIS (Netherlands)

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

Peruvian perovskite Between Transition-metal to PGM/PlatinumGroupMetal Catalytic Fusion

Science.gov (United States)

Maksoed, Wh-

2016-11-01

Strongly correlated electronic materials made of simple building blocks, such as a transition-metal ion in an octahedral oxygen cage forming a perovskite structure- Dagotto & Tokura for examples are the high-temperature superconductivity & the CMR/Colossal Magnetoresistance . Helium-4 denotes from LC Case,ScD: "Catalytic Fusion of Deuterium into Helium-4"- 1998 dealt with gaseous D2- "contacted with a supported metallic catalyst at superatmospheric pressure". The catalyst is a platinum-group metal, at about 0.5% - 1% by weight, on activated C. Accompanies Stephen J Geier, 2010 quotes "transition metal complexes", the Energy thus produced is enormous, and because the deuterium is very cheap in the form of heavy water (less than US 1/g), the fuel cost is very low (seas &Deuteronomy to be eternally preserves. Heartfelt Gratitudes to HE. Mr. Prof. Ir. HANDOJO.

High surface area graphene-supported metal chalcogenide assembly

Science.gov (United States)

Worsley, Marcus A.; Kuntz, Joshua D.; Orme, Christine A.

2017-04-25

Disclosed here is a method for hydrocarbon conversion, comprising contacting at least one graphene-supported assembly with at least one hydrocarbon feedstock, wherein the graphene-supported assembly comprises (i) a three-dimensional network of graphene sheets crosslinked by covalent carbon bonds and (ii) at least one metal chalcogenide compound disposed on the graphene sheets, wherein the chalcogen of the metal chalcogenide compound is selected from S, Se and Te, and wherein the metal chalcogenide compound accounts for at least 20 wt. % of the graphene-supported assembly.

Hydrogen Production by Ethanol Steam Reforming (ESR over CeO2 Supported Transition Metal (Fe, Co, Ni, Cu Catalysts: Insight into the Structure-Activity Relationship

Directory of Open Access Journals (Sweden)

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.

Nitrogen-doped carbon nanotubes as a metal catalyst support

CSIR Research Space (South Africa)

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...

Nanostructure sensitization of transition metal oxides for visible-light photocatalysis

Directory of Open Access Journals (Sweden)

Hongjun Chen

2014-05-01

Full Text Available To better utilize the sunlight for efficient solar energy conversion, the research on visible-light active photocatalysts has recently attracted a lot of interest. The photosensitization of transition metal oxides is a promising approach for achieving effective visible-light photocatalysis. This review article primarily discusses the recent progress in the realm of a variety of nanostructured photosensitizers such as quantum dots, plasmonic metal nanostructures, and carbon nanostructures for coupling with wide-bandgap transition metal oxides to design better visible-light active photocatalysts. The underlying mechanisms of the composite photocatalysts, e.g., the light-induced charge separation and the subsequent visible-light photocatalytic reaction processes in environmental remediation and solar fuel generation fields, are also introduced. A brief outlook on the nanostructure photosensitization is also given.

Metallic conductivity transition of carbon nanotube yarns coated with silver particles

International Nuclear Information System (INIS)

Zhang, Daohong; Zhang, Yunhe; Miao, Menghe

2014-01-01

Dry spun carbon nanotube yarns made from vertically aligned multiwalled carbon nanotube forests possess high mechanical strength and behave like semiconductors with electrical conductivity of the order of 4 × 10 4 S m −1 . Coating a submicron-thick film of silver particle-filled polymer on the surface increased the electrical conductivity of the carbon nanotube yarn by 60-fold without significantly sacrificing its mechanical strength. The transitional characteristics of the silver-coated carbon nanotube yarn were investigated by varying the take-up ratio of the silver coating. A step change in conductivity was observed when the silver content in the coated yarn was between 7 and 10 wt% as a result of the formation of connected silver particle networks on the carbon nanotube yarn surface. (papers)

Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides

Energy Technology Data Exchange (ETDEWEB)

Lukatskaya, Maria R. [Drexel Univ., Philadelphia, PA (United States); Dept. of Chemical Engineering, Stanford, CA (United States); Kota, Sankalp [Drexel Univ., Philadelphia, PA (United States); Lin, Zifeng [Univ. Paul Sabatier, Toulouse (France); Reseau sur le Stockage Electrochimique de l' Energie (RS2E) (France); Zhao, Meng -Qiang [Drexel Univ., Philadelphia, PA (United States); Shpigel, Netanel [Bar-Ilan Univ., Ramat-Gan (Israel); Levi, Mikhael D. [Bar-Ilan Univ., Ramat-Gan (Israel); Halim, Joseph [Drexel Univ., Philadelphia, PA (United States); Taberna, Pierre -Louis [Univ. Paul Sabatier, Toulouse (France); Reseau sur le Stockage Electrochimique de l' Energie (RS2E) (France); Barsoum, Michel W. [Drexel Univ., Philadelphia, PA (United States); Simon, Patrice [Univ. Paul Sabatier, Toulouse (France); Reseau sur le Stockage Electrochimique de l' Energie (RS2E) (France); Gogotsi, Yury G. [Drexel Univ., Philadelphia, PA (United States)

2017-07-10

In this study, the use of fast surface redox storage (pseudocapacitive) mechanisms can enable devices that store much more energy than electrical double-layer capacitors (EDLCs) and, unlike batteries, can do so quite rapidly. Yet, few pseudocapacitive transition metal oxides can provide a high power capability due to their low intrinsic electronic and ionic conductivity. Here we demonstrate that two-dimensional transition metal carbides (MXenes) can operate at rates exceeding those of conventional EDLCs, but still provide higher volumetric and areal capacitance than carbon, electrically conducting polymers or transition metal oxides. We applied two distinct designs for MXene electrode architectures with improved ion accessibility to redox-active sites. A macroporous Ti₃C₂T_x MXene film delivered up to 210 F g^–1 at scan rates of 10 V s^–1, surpassing the best carbon supercapacitors known. In contrast, we show that MXene hydrogels are able to deliver volumetric capacitance of ~1,500 F cm^–3 reaching the previously unmatched volumetric performance of RuO₂.

Ab initio modelling of transition metals in diamond

International Nuclear Information System (INIS)

Watkins, M; Mainwood, A

2003-01-01

Transition metals (TM) from the first transition series are commonly used as solvent catalysts in the synthesis of diamond by high pressure, high temperature processes. Ab initio calculations on these metals, in finite clusters of tetrahedrally coordinated carbon, enable us to investigate trends in their stability and properties. By carrying out systematic studies of interstitial, substitutional and semi-vacancy TM defects, we show that the electronic structure of the TMs is complicated by the presence of 'dangling bonds' when the TM disrupts the crystal lattice: interstitial defects conform to the Ludwig-Woodbury (LW) model, whilst substitutional and semi-vacancy defects move from approximating the LW model early in the transition series to approaching the vacancy model for the heavier metals. Multi-configurational self-consistent field methods allow genuine many-electron states to be modelled; for neutral interstitial, and all substitutional TMs, the crystal fields are found to exceed the exchange energies in strength. Consequently, low spin states are found for these defects. We find substitutional defects to be the most stable, but that semi-vacancy TMs are very similar in energy to the substitutional defects late in the transition series; interstitial defects are only metastable in diamond. Given appropriate charge compensators neutral and positively charged interstitial TM defects were stable, while negatively charged species appeared to be strongly disfavoured

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

International Nuclear Information System (INIS)

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

Photoemission from valence bands of transition metal-phthalocyanines

International Nuclear Information System (INIS)

Shang, Ming-Hui; Nagaosa, Mayumi; Nagamatsu, Shin-ichi; Hosoumi, Shunsuke; Kera, Satoshi; Fujikawa, Takashi; Ueno, Nobuo

2011-01-01

Research highlights: → The HOMO mainly comes from the carbon atoms of Pc rings and the central metal atoms almost have no contribution on the highest occupied molecular orbital (HOMO: a 1u ) distribution of CoPc as well as NiPc. → Influence by central metal atom on the photoemission intensities from the HOMO of two single molecule systems is negligible for the major. → The modification of the distribution for π-orbital upon adsorption as well as the scattering effects of the central metal on the photoemission intensities are negligible for the major. - Abstract: Angular dependencies of ultraviolet photoelectron spectrum of transition metal-phthalocyanines (TM-Pcs), NiPc and CoPc, have been studied by using multiple-scattering theory to explore the electronic structure of the organometallic complexes influenced by central metal atom. The calculated angular distributions of photoelectrons for the highest occupied molecular orbital (HOMO: a 1u ) from the two single systems are nearly the same and represent well the experimental results obtained for the well-ordered monolayer on the highly oriented pyrolytic graphite substrate. The central metal atoms almost have no contribution on the HOMO distribution, which mainly comes from the carbon atoms of Pc ring. Moreover, the modification of the distribution for π orbital upon adsorption as well as the scattering effects of the central metal on the photoemission intensities are negligible for the major.

Carbon nanotubes and other nanostructures as support material for nanoparticulate noble-metal catalysts in fuel cells

DEFF Research Database (Denmark)

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...

Diazo compounds and N-tosylhydrazones: novel cross-coupling partners in transition-metal-catalyzed reactions.

Science.gov (United States)

Xiao, Qing; Zhang, Yan; Wang, Jianbo

2013-02-19

Transition-metal-catalyzed carbene transformations and cross-couplings represent two major reaction types in organometallic chemistry and organic synthesis. However, for a long period of time, these two important areas have evolved separately, with essentially no overlap or integration. Thus, an intriguing question has emerged: can cross-coupling and metal carbene transformations be merged into a single reaction cycle? Such a combination could facilitate the development of novel carbon-carbon bond-forming methodologies. Although this concept was first explored about 10 years ago, rapid developments inthis area have been achieved recently. Palladium catalysts can be used to couple diazo compounds with a wide variety of organic halides. Under oxidative coupling conditions, diazo compounds can also react with arylboronic acids and terminal alkynes. Both of these coupling reactions form carbon-carbon double bonds. As the key step in these catalytic processes, Pd carbene migratory insertion plays a vital role in merging the elementary steps of Pd intermediates, leading to novel carbon-carbon bond formations. Because the diazo substrates can be generated in situ from N-tosylhydrazones in the presence of base, the N-tosylhydrazones can be used as reaction partners, making this type of cross-coupling reaction practical in organic synthesis. N-Tosylhydrazones are easily derived from the corresponding aldehydes or ketones. The Pd-catalyzed cross-coupling of N-tosylhydrazones is considered a complementary reaction to the classic Shapiro reaction for converting carbonyl functionalities into carbon-carbon double bonds. It can also serve as an alternative approach for the Pd-catalyzed cross-coupling of carbonyl compounds, which is usually achieved via triflates. The combination of carbene formation and cross-coupling in a single catalytic cycle is not limited to Pd-catalyzed reactions. Recent studies of Cu-, Rh-, Ni-, and Co-catalyzed cross-coupling reactions with diazo

Enhancement of oxygen reduction at Fe tetrapyridyl porphyrin by pyridyl-N coordination to transition metal ions

International Nuclear Information System (INIS)

Maruyama, Jun; Baier, Claudia; Wolfschmidt, Holger; Bele, Petra; Stimming, Ulrich

2012-01-01

One of the promising candidates as noble-metal-free electrode catalysts for polymer electrolyte fuel cells (PEFCs) is a carbon material with nitrogen atoms coordinating iron ions embedded on the surface (Fe-N x moiety) as the active site, although the activity is insufficient compared to conventional platinum-based electrocatalysts. In order to obtain fundamental information on the activity enhancement, a simple model of the Fe-N x active site was formed by adsorbing 5,10,15,20-Tetrakis(4-pyridyl)-21H,23H-porphine iron(III) chloride (FeTPyPCl) on the basal plane of highly oriented pyrolytic graphite (HOPG), and cathodic oxygen reduction was investigated on the surface in 0.1 M HClO 4 . The catalytic activity for oxygen reduction was enhanced by loading transition metal ions (Co 2+ , Ni 2+ , Cu 2+ ) together with FeTPyPCl. The X-ray photoelectron spectrum of the surface suggested that the metal was coordinated by the pyridine-N. The enhancement effect of the transition metals was supported by two different measurements: oxygen reduction at HOPG in 0.1 M HClO 4 dissolving FeTPyPCl and the metal ions; oxygen reduction in 0.1 M HClO 4 at the subsequently well-rinsed and dried HOPG. The ultraviolet–visible spectrum for the solution also suggested the coordination between the pyridyl-N and the metal ions. The oxygen reduction enhancement was attributed to the electronic interaction between the additional transition metal and the Fe center of the porphyrin through the coordination bonds. These results implied that the improvement of the activity of the noble-metal-free catalyst would be possible by the proper introduction of the transition metal ions around the active site.

Carbon isotopic record from Upper Devonian carbonates at Dongcun in Guilin, southern China, supporting the world-wide pattern of carbon isotope excursions during Frasnian-Famennian transition

Institute of Scientific and Technical Information of China (English)

无

2003-01-01

Two positive δ13C excursions are presented in records from the Frasnian-Famennian (F-F) marine carbonate sediments in Europe, America, Africa, and Australia, having been considered as a worldwide pattern, and attributed to enhanced organic carbon burial during the F-F biological mass extinction. However, this worldwide pattern has not been revealed from the well-deposited Late Devonian sequences in southern China. In this paper, a detailed investigation has been made on the Late Devonian section at Dongcun, Guilin, southern China to constrain perturbations in δ13C of carbonates in the F-F deposited sequence. The result from this section also indicates two positive δ13C excursions during the F-F transition. The first excursion with an amplitude of 1.5‰ occurred at the bottom of linguiformis Zone, later than the early excursion existing in the Late rhenana Zone of the Late Devonian profiles in other continents, especially, in central Europe. This difference has been expected to be a result as conodont Palmatolepis linguiformis occurred earlier in southern China than other sites. The second excursion with an amplitude of 2.1‰ is located at the F-F boundary, same as the records from other continents. This result strongly supports the view that two carbon isotope positive excursions during the F-F transition are common in carbonate sediments, resulting from worldwide increases of organic carbon burial intensity.

Microwave-assisted synthesis of transition metal phosphide

Science.gov (United States)

Viswanathan, Tito

2014-12-30

A method of synthesizing transition metal phosphide. In one embodiment, the method has the steps of preparing a transition metal lignosulfonate, mixing the transition metal lignosulfonate with phosphoric acid to form a mixture, and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.

Mechanochemical synthesis of graphene oxide-supported transition metal catalysts for the oxidation of isoeugenol to vanillin.

Science.gov (United States)

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.

Synthesis of Mg{sub 2}FeH{sub 6} containing as additives transition metal and transition metal fluorides or carbon; Sintese de Mg{sub 2}FeH{sub 6} contando como aditivos metais de transicao e fluoretos de metais de transicao ou carbono

Energy Technology Data Exchange (ETDEWEB)

Zepon, G.; Leiva, D.R.; Botta, W.J., E-mail: guizepon@yahoo.com.b [Universidade Federal de Sao Carlos (DEMa/UFSCar), SP (Brazil). Dept. de Engenharia de Materiais

2010-07-01

The Mg{sub 2}FeH{sub 6} is a promising way of storing hydrogen in solid form, composed by elements that have low cost and, at the same time, high volumetric storage density: 150 kg H{sub 2}/m{sup 3}. However, this complex hydride is not easily synthesized as a single phase material. The hydrogen sorption high temperature and slow kinetics are the major limitations for the practical application of the Mg{sub 2}FeH{sub 6} as a hydrogen storage material. Little is known about the effects of additives in Mg{sub 2}FeH{sub 6} based nanocomposites in this work were synthesized by MAE under hydrogen atmosphere nanocomposites based on Mg{sub 2}FeH{sub 6} containing additives as transition metals, transition metals fluorides of transition metals or carbon, in order to obtain information on the effects of the selected additives. To this end, we used characterization techniques such as XRD, SEM and TEM, thermal analysis by DSC and curves made in apparatus PCT.(author)

Preparation of carbon-free TEM microgrids by metal sputtering

International Nuclear Information System (INIS)

Janbroers, S.; Kruijff, T.R. de; Xu, Q.; Kooyman, P.J.; Zandbergen, H.W.

2009-01-01

A new method for preparing carbon-free, temperature-stable Transmission Electron Microscope (TEM) grids is presented. An 80% Au/20% Pd metal film is deposited onto a 'holey' microgrid carbon supported on standard mixed-mesh Au TEM grids. Subsequently, the carbon film is selectively removed using plasma cleaning. In this way, an all-metal TEM film is made containing the 'same' microgrid as the original carbon film. Although electron transparency of the foil is reduced significantly, the open areas for TEM inspection of material over these areas are maintained. The metal foil can be prepared with various thicknesses and ensures good electrical conductivity. The new Au/Pd grids are stable to at least 775 K under vacuum conditions.

Preparation of carbon-free TEM microgrids by metal sputtering.

Science.gov (United States)

Janbroers, S; de Kruijff, T R; Xu, Q; Kooyman, P J; Zandbergen, H W

2009-08-01

A new method for preparing carbon-free, temperature-stable Transmission Electron Microscope (TEM) grids is presented. An 80% Au/20% Pd metal film is deposited onto a 'holey' microgrid carbon supported on standard mixed-mesh Au TEM grids. Subsequently, the carbon film is selectively removed using plasma cleaning. In this way, an all-metal TEM film is made containing the 'same' microgrid as the original carbon film. Although electron transparency of the foil is reduced significantly, the open areas for TEM inspection of material over these areas are maintained. The metal foil can be prepared with various thicknesses and ensures good electrical conductivity. The new Au/Pd grids are stable to at least 775K under vacuum conditions.

Probable metal-insulator transition in Ag{sub 4}SSe

Energy Technology Data Exchange (ETDEWEB)

Drebushchak, V.A., E-mail: dva@igm.nsc.ru [V.S. Sobolev Institute of Geology and Mineralogy, SB RAS, Pr. Ac. Koptyuga 3, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Ul. Pirogova 2, Novosibirsk 630090 (Russian Federation); Pal’yanova, G.A.; Seryotkin, Yu.V. [V.S. Sobolev Institute of Geology and Mineralogy, SB RAS, Pr. Ac. Koptyuga 3, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Ul. Pirogova 2, Novosibirsk 630090 (Russian Federation); Drebushchak, T.N. [Novosibirsk State University, Ul. Pirogova 2, Novosibirsk 630090 (Russian Federation); Institute of Solid State Chemistry and Mechanochemistry, SB RAS, Ul. Kutateladze 18, Novosibirsk 630128 (Russian Federation)

2015-02-15

Highlights: • New phase transition in Ag{sub 4}SSe was discovered with scanning calorimetry and supported with X-ray powder diffraction. • The thermal effect relates to the anomaly in electrical and thermal conductivity of Ag{sub 4}SSe. • Similar thermal and electrical effects in K{sub 3}Cu{sub 8}S{sub 6} are explained with the metal-insulator transition. - Abstract: New phase transition (285 K) in low-temperature monoclinic Ag{sub 4}SSe was found out below the α-β transition (358 K) after the measurements with differential scanning calorimetry. The transition reveals significant hysteresis (over 30 K). X-ray powder diffraction shows that the superlattice with doubled a and b parameters of the unit cell exists below the new transition point. The signs of this new phase transition can be found in thermal and electrical conductivity of Ag{sub 4}SSe published in literature. Elusive phase transition in Ag{sub 2}Se shows similar properties. The new transition is likely related to the metal-insulator type transition, like K{sub 3}Cu{sub 8}S{sub 6}.

High-Pressure Thermodynamic Properties of f-electron Metals, Transition Metal Oxides, and Half-Metallic Magnets

International Nuclear Information System (INIS)

Richard T. Scalettar; Warren E. Pickett

2005-01-01

This project involves research into the thermodynamic properties of f-electron metals, transition metal oxides, and half-metallic magnets at high pressure. These materials are ones in which the changing importance of electron-electron interactions as the distance between atoms is varied can tune the system through phase transitions from localized to delocalized electrons, from screened to unscreened magnetic moments, and from normal metal to one in which only a single spin specie can conduct. Three main thrusts are being pursued: (1) Mott transitions in transition metal oxides, (2) magnetism in half-metallic compounds, and (3) large volume-collapse transitions in f-band metals

High-Pressure Thermodynamic Properties of f-electron Metals, Transition Metal Oxides, and Half-Metallic Magnets

Energy Technology Data Exchange (ETDEWEB)

Scalettar, Richard T.; Pickett, Warren E.

2004-07-01

This project involves research into the thermodynamic properties of f-electron metals, transition metal oxides, and half-metallic magnets at high pressure. These materials are ones in which the changing importance of electron-electron interactions as the distance between atoms is varied can tune the system through phase transitions from localized to delocalized electrons, from screened to unscreened magnetic moments, and from normal metal to one in which only a single spin specie can conduct. Three main thrusts are being pursued: (1) Mott transitions in transition metal oxides, (2) magnetism in half-metallic compounds, and (3) large volume-collapse transitions in f-band metals.

High-Pressure Thermodynamic Properties of f-electron Metals, Transition Metal Oxides, and Half-Metallic Magnets

Energy Technology Data Exchange (ETDEWEB)

Richard T. Scalettar; Warren E. Pickett

2005-08-02

This project involves research into the thermodynamic properties of f-electron metals, transition metal oxides, and half-metallic magnets at high pressure. These materials are ones in which the changing importance of electron-electron interactions as the distance between atoms is varied can tune the system through phase transitions from localized to delocalized electrons, from screened to unscreened magnetic moments, and from normal metal to one in which only a single spin specie can conduct. Three main thrusts are being pursued: (i) Mott transitions in transition metal oxides, (ii) magnetism in half-metallic compounds, and (iii) large volume-collapse transitions in f-band metals.

Trends in low-temperature water–gas shift reactivity on transition metals

DEFF Research Database (Denmark)

Schumacher, Nana Maria Pii; Boisen, Astrid; Dahl, Søren

2005-01-01

Low-temperature water–gas shift reactivity trends on transition metals were investigated with the use of a microkinetic model based on a redox mechanism. It is established that the adsorption energies for carbon monoxide and oxygen can describe to a large extent changes in the remaining activation...

An in situ method of creating metal oxide–carbon composites and their application as anode materials for lithium-ion batteries

KAUST Repository

Yang, Zichao

2011-01-01

Transition metal oxides are actively investigated as anode materials for lithium-ion batteries (LIBs), and their nanocomposites with carbon frequently show better performance in galvanostatic cycling studies, compared to the pristine metal oxide. An in situ, scalable method for creating a variety of transition metal oxide-carbon nanocomposites has been developed based on free-radical polymerization and cross-linking of poly(acrylonitrile) in the presence of the metal oxide precursor containing vinyl groups. The approach yields a cross-linked polymer network, which uniformly incorporates nanometre-sized transition metal oxide particles. Thermal treatment of the organic-inorganic hybrid material produces nearly monodisperse metal oxide nanoparticles uniformly embedded in a porous carbon matrix. Cyclic voltammetry and galvanostatic cycling electrochemical measurements in a lithium half-cell are used to evaluate the electrochemical properties of a Fe3O 4-carbon composite created using this approach. These measurements reveal that when used as the anode in a lithium battery, the material exhibits stable cycling performance at both low and high current densities. We further show that the polymer/nanoparticle copolymerization approach can be readily adapted to synthesize metal oxide/carbon nanocomposites based on different particle chemistries for applications in both the anode and cathode of LIBs. © 2011 The Royal Society of Chemistry.

Hydrogen evolution on nano-particulate transition metal sulfides

DEFF Research Database (Denmark)

Bonde, Jacob Lindner; Moses, Poul Georg; Jaramillo, Thomas F.

2008-01-01

The hydrogen evolution reaction (HER) on carbon supported MoS2 nanoparticles is investigated and compared to findings with previously published work on Au(111) supported MoS2. An investigation into MoS2 oxidation is presented and used to quantify the surface concentration of MoS2. Other metal sul...

Emergent magnetism at transition-metal-nanocarbon interfaces.

Science.gov (United States)

Al Ma'Mari, Fatma; Rogers, Matthew; Alghamdi, Shoug; Moorsom, Timothy; Lee, Stephen; Prokscha, Thomas; Luetkens, Hubertus; Valvidares, Manuel; Teobaldi, Gilberto; Flokstra, Machiel; Stewart, Rhea; Gargiani, Pierluigi; Ali, Mannan; Burnell, Gavin; Hickey, B J; Cespedes, Oscar

2017-05-30

Charge transfer at metallo-molecular interfaces may be used to design multifunctional hybrids with an emergent magnetization that may offer an eco-friendly and tunable alternative to conventional magnets and devices. Here, we investigate the origin of the magnetism arising at these interfaces by using different techniques to probe 3d and 5d metal films such as Sc, Mn, Cu, and Pt in contact with fullerenes and rf-sputtered carbon layers. These systems exhibit small anisotropy and coercivity together with a high Curie point. Low-energy muon spin spectroscopy in Cu and Sc-C 60 multilayers show a quick spin depolarization and oscillations attributed to nonuniform local magnetic fields close to the metallo-carbon interface. The hybridization state of the carbon layers plays a crucial role, and we observe an increased magnetization as sp 3 orbitals are annealed into sp 2 -π graphitic states in sputtered carbon/copper multilayers. X-ray magnetic circular dichroism (XMCD) measurements at the carbon K edge of C 60 layers in contact with Sc films show spin polarization in the lowest unoccupied molecular orbital (LUMO) and higher π*-molecular levels, whereas the dichroism in the σ*-resonances is small or nonexistent. These results support the idea of an interaction mediated via charge transfer from the metal and dz -π hybridization. Thin-film carbon-based magnets may allow for the manipulation of spin ordering at metallic surfaces using electrooptical signals, with potential applications in computing, sensors, and other multifunctional magnetic devices.

Preparation of carbon-free TEM microgrids by metal sputtering

Energy Technology Data Exchange (ETDEWEB)

Janbroers, S., E-mail: stephan.janbroers@albemarle.com [Albemarle Catalysts B.V., Nieuwendammerkade 1-3, 1030 BE, Amsterdam (Netherlands); Kavli Institute of Nanoscience, Delft University of Technology, Lorentzweg 1, 2628 CJ Delft (Netherlands); Kruijff, T.R. de; Xu, Q. [Kavli Institute of Nanoscience, Delft University of Technology, Lorentzweg 1, 2628 CJ Delft (Netherlands); Kooyman, P.J. [DelftChemTech, Delft University of Technology, Julianalaan 136, 2628 BL, Delft (Netherlands); Kavli Institute of Nanoscience, Delft University of Technology, Lorentzweg 1, 2628 CJ Delft (Netherlands); Zandbergen, H.W. [Kavli Institute of Nanoscience, Delft University of Technology, Lorentzweg 1, 2628 CJ Delft (Netherlands)

2009-08-15

A new method for preparing carbon-free, temperature-stable Transmission Electron Microscope (TEM) grids is presented. An 80% Au/20% Pd metal film is deposited onto a 'holey' microgrid carbon supported on standard mixed-mesh Au TEM grids. Subsequently, the carbon film is selectively removed using plasma cleaning. In this way, an all-metal TEM film is made containing the 'same' microgrid as the original carbon film. Although electron transparency of the foil is reduced significantly, the open areas for TEM inspection of material over these areas are maintained. The metal foil can be prepared with various thicknesses and ensures good electrical conductivity. The new Au/Pd grids are stable to at least 775 K under vacuum conditions.

THE THEORY OF DEVELOPMENT OF SUPPORTED METAL-COMPLEX CATALYSTS

Directory of Open Access Journals (Sweden)

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.

Carbon-supported cobalt catalyst for hydrogen generation from alkaline sodium borohydride solution

Energy Technology Data Exchange (ETDEWEB)

Xu, Dongyan; Liu, Xinmin; Cao, Changqing; Guo, Qingjie [College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Dai, Ping [College of Electromechanical Engineering, Qingdao University of Science and Technology, Qingdao 266061 (China)

2008-08-01

Low cost transition metal catalysts with high performance are attractive for the development of on-board hydrogen generation systems by catalytic hydrolysis of sodium borohydride (NaBH{sub 4}) in fuel cell fields. In this study, hydrogen production from alkaline NaBH{sub 4} via hydrolysis process over carbon-supported cobalt catalysts was studied. The catalytic activity of the supported cobalt catalyst was found to be highly dependent on the calcination temperatures. The hydrogen generation rate increases with calcination temperatures in the range of 200-400 C, but a high calcination temperature above 500 C led to markedly decreased activity. X-ray diffraction patterns reveal that the catalysts experience phase transition from amorphous Co-B to crystalline cobalt hydroxide with increase in calcination temperatures. The reaction performance is also dependent on the concentration of NaBH{sub 4}, and the hydrogen generation rate increases for lower NaBH{sub 4} concentrations and decreases after reaching a maximum at 10 wt.% of NaBH{sub 4}. (author)

Mesoporous carbon incorporated metal oxide nanomaterials as supercapacitor electrodes

Energy Technology Data Exchange (ETDEWEB)

Jiang, Hao [Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China); School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Ma, Jan [School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Li, Chunzhong [Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China)

2012-08-08

Supercapacitors have attracted huge attention in recent years as they have the potential to satisfy the demand of both huge energy and power density in many advanced technologies. However, poor conductivity and cycling stability remains to be the major challenge for its widespread application. Various strategies have been developed for meeting the ever-increasing energy and power demands in supercapacitors. This Research News article aims to review recent progress in the development of mesoporous carbon incorporated metal oxide nanomaterials, especially metal oxide nanoparticles confined in ordered mesoporous carbon and 1D metal oxides coated with a layer of mesoporous carbon for high-performance supercapacitor applications. In addition, a recent trend in supercapacitor development - hierarchical porous graphitic carbons (HPGC) combining macroporous cores, mesoporous walls, and micropores as an excellent support for metal oxides - is also discussed. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

Directory of Open Access Journals (Sweden)

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.

High-pressure phase transition of alkali metal-transition metal deuteride Li2PdD2

Science.gov (United States)

Yao, Yansun; Stavrou, Elissaios; Goncharov, Alexander F.; Majumdar, Arnab; Wang, Hui; Prakapenka, Vitali B.; Epshteyn, Albert; Purdy, Andrew P.

2017-06-01

A combined theoretical and experimental study of lithium palladium deuteride (Li2PdD2) subjected to pressures up to 50 GPa reveals one structural phase transition near 10 GPa, detected by synchrotron powder x-ray diffraction, and metadynamics simulations. The ambient-pressure tetragonal phase of Li2PdD2 transforms into a monoclinic C2/m phase that is distinct from all known structures of alkali metal-transition metal hydrides/deuterides. The structure of the high-pressure phase was characterized using ab initio computational techniques and from refinement of the powder x-ray diffraction data. In the high-pressure phase, the PdD2 complexes lose molecular integrity and are fused to extended [PdD2]∞ chains. The discovered phase transition and new structure are relevant to the possible hydrogen storage application of Li2PdD2 and alkali metal-transition metal hydrides in general.

A comparative investigation of metal-support interactions on the catalytic activity of Pt nanoparticles for ethanol oxidation in alkaline medium

Science.gov (United States)

Godoi, Denis R. M.; Villullas, Hebe M.; Zhu, Fu-Chun; Jiang, Yan-Xia; Sun, Shi-Gang; Guo, Junsong; Sun, Lili; Chen, Rongrong

2016-04-01

The effects of interactions of Pt nanoparticles with hybrid supports on reactivity towards ethanol oxidation in alkaline solution are investigated. Studies involve catalysts with identical Pt nanoparticles on six hybrid supports containing carbon powder and transition metal oxides (TiO2, ZrO2, SnO2, CeO2, MoO3 and WO3). In situ X-ray absorption spectroscopy (XAS) results evidence that metal-support interactions produce changes in the Pt 5d band vacancy, which appears to determine the catalytic activity. The highest and lowest activities are observed for Pt nanoparticles on hybrid supports containing TiO2 and CeO2, respectively. Further studies are presented for these two catalysts. In situ FTIR reflection spectroscopy measurements, taken using both multi-stepped FTIR spectroscopy (MS-FTIR) and single potential alteration FTIR spectroscopy (SPA-FTIR), evidence that the main product of ethanol oxidation is acetate, although signals attributed to carbonate and CO2 indicate some differences in CO2 production. Fuel cell performances of these catalysts, tested in a 4.5 cm2 single cell at different temperatures (40-90 °C) show good agreement with data obtained by electrochemical techniques. Results of this comprehensive study point out the possibility of compensating a reduction of noble metal load with an increase in activity promoted by interactions between metallic nanoparticles and a support.

Mechanochemical synthesis of graphene oxide-supported transition metal catalysts for the oxidation of isoeugenol to vanillin

Directory of Open Access Journals (Sweden)

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.

Half-Metallic Ferromagnetism and Stability of Transition Metal Pnictides and Chalcogenides

Science.gov (United States)

Liu, Bang-Gui

It is highly desirable to explore robust half-metallic ferromagnetic materials compatible with important semiconductors for spintronic applications. A state-of-the-art full potential augmented plane wave method within the densityfunctional theory is reliable enough for this purpose. In this chapter we review theoretical research on half-metallic ferromagnetism and structural stability of transition metal pnictides and chalcogenides. We show that some zincblende transition metal pnictides are half-metallic and the half-metallic gap can be fairly wide, which is consistent with experiment. Systematic calculations reveal that zincblende phases of CrTe, CrSe, and VTe are excellent half-metallic ferromagnets. These three materials have wide half-metallic gaps, are low in total energy with respect to the corresponding ground-state phases, and, importantly, are structurally stable. Halfmetallic ferromagnetism is also found in wurtzite transition metal pnictides and chalcogenides and in transition-metal doped semiconductors as well as deformed structures. Some of these half-metallic materials could be grown epitaxially in the form of ultrathin .lms or layers suitable for real spintronic applications.

Transition metal nuclear magnetic resonance

International Nuclear Information System (INIS)

Pregosin, P.S.

1991-01-01

Transition metal NMR spectroscopy has progressed enormously in recent years. New methods, and specifically solid-state methods and new pulse sequences, have allowed access to data from nuclei with relatively low receptivities with the result that chemists have begun to consider old and new problems, previously unapproachable. Moreover, theory, computational science in particular, now permits the calculation of not just 13 C, 15 N and other light nuclei chemical shifts, but heavy main-group element and transition metals as well. These two points, combined with increasing access to high field pulsed spectrometer has produced a wealth of new data on the NMR transition metals. A new series of articles concerned with measuring, understanding and using the nuclear magnetic resonance spectra of the metals of Group 3-12 is presented. (author)

Transition Metal Phosphide Nanoparticles Supported on SBA-15 as Highly Selective Hydrodeoxygenation Catalysts for the Production of Advanced Biofuels.

Science.gov (United States)

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

Carbon nanostructures as catalyst support for polymer electrolyte membrane fuel cells

Energy Technology Data Exchange (ETDEWEB)

Natarajan, S.K.; Hamelin, J. [Quebec Univ., Trois Rivieres, PQ (Canada). Inst. de recherche sur l' hydrogene

2008-07-01

This paper reported on a study that investigated potential alternatives to Vulcan XC-72 as a catalyst supports for polymer electrolyte membrane fuel cells (PEMFCs). These included carbon nanostructures (CNS) prepared by high energy ball milling of graphite and transition metal catalysts, followed by heat treatment. Among the key factors discussed were the graphitic content, high surface area, microporous structure, good electrical conductivity and the ability of the material to attach functional groups. Some graphic results supporting the usage of CNS as catalyst support for PEMFCs were presented. Upon chemical oxidation, surface functional groups such as carbonyl, carboxyl, and hydroxyl were populated on the surface of CNS. Nanosized platinum particles with particle size distribution between 3 nm and 5 nm were reduced on the functionalized sites of CNS in a colloidal medium. The paper also presented cyclic voltammograms, XPS, HRTEM and PSD results. 3 refs.

First-principles studies on 3d transition metal atom adsorbed twin graphene

Science.gov (United States)

Li, Lele; Zhang, Hong; Cheng, Xinlu; Miyamoto, Yoshiyuki

2018-05-01

Twin graphene is a new two-dimensional semiconducting carbon allotrope which is proposed recently. The structural, magnetic and electronic properties are investigated for 3d transition metal (TM) atom adsorbed twin graphene by means of GGA+U calculations. The results show most of single 3d transition metal atom except Zn can make twin graphene magnetization. The adsorption of single TM atom can also make the twin graphene systems turn to half metal (V adsorption), half-semiconductor (Fe adsorption) or metal (Sc, Cr, Mn, Co and Cu adsorption). The semiconducting nature still exists for Ti, Ni and Zn adsorption. All the 3d TM adatoms belong to n-type doping for transferring charge to the neighboring C atoms and have strong covalent bond with these C atoms. The influence of Hubbard U value on half-metallic V adsorbed system is also considered. As the U increases, the system can gradually transform from metal to half metal and metal. The effect of the coverage is investigated for two TM atoms (Sc-Fe) adsorption, too. We can know TM atoms adsorbed twin graphene have potentials to be spintronic device and nanomagnets from the results.

Transition Metal Ion Implantation into Diamond-Like Carbon Coatings: Development of a Base Material for Gas Sensing Applications

Directory of Open Access Journals (Sweden)

Andreas Markwitz

2015-01-01

Full Text Available Micrometre thick diamond-like carbon (DLC coatings produced by direct ion deposition were implanted with 30 keV Ar+ and transition metal ions in the lower percentage (<10 at.% range. Theoretical calculations showed that the ions are implanted just beneath the surface, which was confirmed with RBS measurements. Atomic force microscope scans revealed that the surface roughness increases when implanted with Ar+ and Cu+ ions, whereas a smoothing of the surface from 5.2 to 2.7 nm and a grain size reduction from 175 to 93 nm are measured for Ag+ implanted coatings with a fluence of 1.24×1016 at. cm−2. Calculated hydrogen and carbon depth profiles showed surprisingly significant changes in concentrations in the near-surface region of the DLC coatings, particularly when implanted with Ag+ ions. Hydrogen accumulates up to 32 at.% and the minimum of the carbon distribution is shifted towards the surface which may be the cause of the surface smoothing effect. The ion implantations caused an increase in electrical conductivity of the DLC coatings, which is important for the development of solid-state gas sensors based on DLC coatings.

(Electronic structure and reactivities of transition metal clusters)

Energy Technology Data Exchange (ETDEWEB)

1992-01-01

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

Gases and carbon in metals

International Nuclear Information System (INIS)

Jehn, H.; Fromm, E.; Hoerz, G.

1978-01-01

This issue is part of a series of data on 'gases and carbon in metals'. The present survey includes results from papers dealing with gases and carbon in actinides and recommends critically selected data for each element. Firstly data od binary systems are presented, starting with hydrogen and followed by carbon, nitrogen, oxygen, and rare gases. Within one metal-metalloid system the data are listed under topics such as solubility limit, dissociation pressure of compunds, vapour pressure of volatile oxides, thermodynamic data, diffusion, transport parameters (effective valence, heat of transport), permeation of gases through metals, gas adsorption and gas desorption kinetics, compound formation, precipitation kinetics, and property changes. Following the data on binary systems, the data of ternary systems are presented, beginning with systems which contain one metal and two gases or one gas and carbon and continuing with systems with two metals and one gas or carbon. Within a ternary system the topics are arranged in the same way as in binary systems. (HB) [de

Phase coexistence in the metal-insulator transition of a VO2 thin film

International Nuclear Information System (INIS)

Chang, Y.J.; Koo, C.H.; Yang, J.S.; Kim, Y.S.; Kim, D.H.; Lee, J.S.; Noh, T.W.; Kim, Hyun-Tak; Chae, B.G.

2005-01-01

Vanadium dioxide (VO 2 ) shows a metal-insulator transition (MIT) near room temperature, accompanied by an abrupt resistivity change. Since the MIT of VO 2 is known to be a first order phase transition, it is valuable to check metallic and insulating phase segregation during the MIT process. We deposited (100)-oriented epitaxial VO 2 thin films on R-cut sapphire substrates. From the scanning tunneling spectroscopy (STS) spectra, we could distinguish metallic and insulating regions by probing the band gap. Optical spectroscopic analysis also supported the view that the MIT in VO 2 occurs through metal and insulator phase coexistence

Transition-metal chlorides as conversion cathode materials for Li-ion batteries

International Nuclear Information System (INIS)

Li Ting; Chen, Zhong X.; Cao, Yu L.; Ai, Xin P.; Yang, Han X.

2012-01-01

Insoluble AgCl and soluble CuCl 2 were selected and investigated as model compounds of transition-metal chlorides for electrochemical conversion cathode materials. The experimental results demonstrated that the AgCl nanocrystals can convert reversibly to metallic Ag with nearly full utilization of its one-electron redox capacity (187 mAh g −1 ). Similarly, the CuCl 2 -filled mesoporous carbon can realize a reversible two-electron transfer reaction, giving a very high reversible capacity of 466 mAh g −1 after 20 cycles. These data imply that the metal chlorides can undergo complete electrochemical conversion utilizing their full oxidation states for electrical energy storage as previously reported metal fluorides, possibly being used as high capacity cathode materials for Li-ion batteries.

Methanol and ethanol electrooxidation on Pt and Pd supported on carbon microspheres in alkaline media

Energy Technology Data Exchange (ETDEWEB)

Xu, Changwei; Cheng, Liqiang; Liu, Yingliang [Department of Chemistry and Institute of Nanochemistry, Jinan University, Guangzhou 510632 (China); Shen, Peikang [State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China)

2007-05-15

Noble metal (Pt, Pd) electrocatalysts supported on carbon microspheres (CMS) are used for methanol and ethanol oxidation in alkaline media. The results show that noble metal electrocatalysts supported on carbon microspheres give better performance than that supported on carbon black. It is well known that palladium is not a good electrocatalyst for methanol oxidation, but it shows excellently higher activity and better steady-state electrolysis than Pt for ethanol electrooxidation in alkaline media. The results show a synergistic effect by the interaction between Pd and carbon microspheres. The Pd supported on carbon microspheres in this paper possesses excellent electrocatalytic properties and may be of great potential in direct ethanol fuel cells. (author)

Metal-to-nonmetal transitions

CERN Document Server

Hensel, Friedrich; Holst, Bastian

2010-01-01

This book is devoted to nonmetal-to-metal transitions. The original ideas of Mott for such a transition in solids have been adapted to describe a broad variety of phenomena in condensed matter physics (solids, liquids, and fluids), in plasma and cluster physics, as well as in nuclear physics (nuclear matter and quark-gluon systems). The book gives a comprehensive overview of theoretical methods and experimental results of the current research on the Mott effect for this wide spectrum of topics. The fundamental problem is the transition from localized to delocalized states which describes the nonmetal-to-metal transition in these diverse systems. Based on the ideas of Mott, Hubbard, Anderson as well as Landau and Zeldovich, internationally respected scientists present the scientific challenges and highlight the enormous progress which has been achieved over the last years. The level of description is aimed to specialists in these fields as well as to young scientists who will get an overview for their own work...

Superconductivity in transition metals.

Science.gov (United States)

Slocombe, Daniel R; Kuznetsov, Vladimir L; Grochala, Wojciech; Williams, Robert J P; Edwards, Peter P

2015-03-13

A qualitative account of the occurrence and magnitude of superconductivity in the transition metals is presented, with a primary emphasis on elements of the first row. Correlations of the important parameters of the Bardeen-Cooper-Schrieffer theory of superconductivity are highlighted with respect to the number of d-shell electrons per atom of the transition elements. The relation between the systematics of superconductivity in the transition metals and the periodic table high-lights the importance of short-range or chemical bonding on the remarkable natural phenomenon of superconductivity in the chemical elements. A relationship between superconductivity and lattice instability appears naturally as a balance and competition between localized covalent bonding and so-called broken covalency, which favours d-electron delocalization and superconductivity. In this manner, the systematics of superconductivity and various other physical properties of the transition elements are related and unified. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

Production of carbon nanotubes: Chemical vapor deposition synthesis from liquefied petroleum gas over Fe-Co-Mo tri-metallic catalyst supported on MgO

Energy Technology Data Exchange (ETDEWEB)

Setyopratomo, P., E-mail: puguh-sptm@yahoo.com; Wulan, Praswasti P. D. K., E-mail: wulanmakmur@gmail.com; Sudibandriyo, M., E-mail: msudib@che.ui.ac.id [Chemical Engineering Department, University of Indonesia, Depok Campus, Depok 16424 (Indonesia)

2016-06-03

Carbon nanotubes were produced by chemical vapor deposition method to meet the specifications for hydrogen storage. So far, the various catalyst had been studied outlining their activities, performances, and efficiencies. In this work, tri-metallic catalyst consist of Fe-Co-Mo supported on MgO was used. The catalyst was prepared by wet-impregnation method. Liquefied Petroleum Gas (LPG) was used as carbon source. The synthesis was conducted in atmospheric fixed bed reactor at reaction temperature range 750 – 850 °C for 30 minutes. The impregnation method applied in this study successfully deposed metal component on the MgO support surface. It found that the deposited metal components might partially replace Mg(OH){sub 2} or MgO molecules in their crystal lattice. Compare to the original MgO powder; it was significant increases in pore volume and surface area has occurred during catalyst preparation stages. The size of obtained carbon nanotubes is ranging from about 10.83 nm OD/4.09 nm ID up to 21.84 nm OD/6.51 nm ID, which means that multiwall carbon nanotubes were formed during the synthesis. Yield as much as 2.35 g.CNT/g.catalyst was obtained during 30 minutes synthesis and correspond to carbon nanotubes growth rate of 0.2 μm/min. The BET surface area of the obtained carbon nanotubes is 181.13 m{sup 2}/g and around 50 % of which is contributed by mesopores. Micropore with half pore width less than 1 nm contribute about 10% volume of total micro and mesopores volume of the carbon nanotubes. The existence of these micropores is very important to increase the hydrogen storage capacity of the carbon nanotubes.

Edge Delamination of Monolayer Transition Metal Dichalcogenides.

Science.gov (United States)

Ly, Thuc Hue; Yun, Seok Joon; Thi, Quoc Huy; Zhao, Jiong

2017-07-25

Delamination of thin films from the supportive substrates is a critical issue within the thin film industry. The emergent two-dimensional, atomic layered materials, including transition metal dichalcogenides, are highly flexible; thus buckles and wrinkles can be easily generated and play vital roles in the corresponding physical properties. Here we introduce one kind of patterned buckling behavior caused by the delamination from a substrate initiated at the edges of the chemical vapor deposition synthesized monolayer transition metal dichalcogenides, led by thermal expansion mismatch. The atomic force microscopy and optical characterizations clearly showed the puckered structures associated with the strain, whereas the transmission electron microscopy revealed the special sawtooth-shaped edges, which break the geometrical symmetry for the buckling behavior of hexagonal samples. The condition of the edge delamination is in accordance with the fracture behavior of thin film interfaces. This edge delamination and buckling process is universal for most ultrathin two-dimensional materials, which requires more attention in various future applications.

Effect of alloying on carbon formation during ethane dehydrogenation

DEFF Research Database (Denmark)

Rovik, Anne; Kegnæs, Søren; Dahl, Søren

2009-01-01

The structure sensitivity of different transition metals in the hydrogenolysis, dehydrogenation, and coking reactions during ethane conversion has been investigated. The investigated metals, Ni, Ru, Rh, and Pd, are co-impregnated with Ag onto an inactive MgAl2O4 spinel support and tested in the c......The structure sensitivity of different transition metals in the hydrogenolysis, dehydrogenation, and coking reactions during ethane conversion has been investigated. The investigated metals, Ni, Ru, Rh, and Pd, are co-impregnated with Ag onto an inactive MgAl2O4 spinel support and tested...... in the conversion of ethane. A tendency is clear for all catalysts: In the first period of time 100% ethane is converted and roughly half of the carbon is converted into coke and deposited on the catalyst. The other half of the carbon is converted into methane. The active sites in the hydrogenolysis are blocked...... by coke during the initial period where after dehydrogenation of ethane is observed. It has previously been predicted in surface science studies that Ag covers the steps of certain transition metals. Here it is documented that the hydrogenolysis and coking reactions are significantly suppressed by co...

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

KAUST Repository

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

Mesoporous Transition Metal Oxides for Supercapacitors.

Science.gov (United States)

Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

2015-10-14

Recently, transition metal oxides, such as ruthenium oxide (RuO₂), manganese dioxide (MnO₂), nickel oxides (NiO) and cobalt oxide (Co₃O₄), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO₂, MnO₂, NiO, Co₃O₄ and nickel cobaltite (NiCo₂O₄), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

Preparation of supported electrocatalyst comprising multiwalled carbon nanotubes

Science.gov (United States)

Wu, Gang; Zelenay, Piotr

2013-08-27

A process for preparing a durable non-precious metal oxygen reduction electrocatalyst involves heat treatment of a ball-milled mixture of polyaniline and multiwalled carbon nanotubes in the presence of a Fe species. The catalyst is more durable than catalysts that use carbon black supports. Performance degradation was minimal or absent after 500 hours of operation at constant cell voltage of 0.40 V.

Thermal properties of zirconium diboride -- transition metal boride solid solutions

Science.gov (United States)

McClane, Devon Lee

This research focuses on the thermal properties of zirconium diboride (ZrB2) based ceramics. The overall goal was to improve the understanding of how different transition metal (TM) additives influence thermal transport in ZrB2. To achieve this, ZrB2 with 0.5 wt% carbon, and 3 mol% of individual transition metal borides, was densified by hot-press sintering. The transition metals that were investigated were: Y, Ti, Hf, V, Nb, Ta, Cr, Mo, W, and Re. The room temperature thermal diffusivities of the compositions ranged from 0.331 cm2/s for nominally pure ZrB2 to 0.105 cm2/s for (Zr,Cr)B2 and converged around 0.155cm2/s at higher temperatures for all compositions. Thermal conductivities were calculated from the diffusivities, using temperature-dependent values for density and heat capacity. The electron contribution to thermal conductivity was calculated from measured electrical resistivity according to the Wiedemann-Franz law. The phonon contribution to thermal conductivity was calculated by subtracting the electron contribution from the total thermal conductivity. Rietveld refinement of x-ray diffraction data was used to determine the lattice parameters of the compositions. The decrease in thermal conductivity for individual additives correlated directly to the metallic radius of the additive. Additional strain appeared to exist for additives when the stable TM boride for that metal had different crystal symmetries than ZrB2. This research provided insight into how additives and impurities affect thermal transport in ZrB2. The research potentially offers a basis for future modeling of thermal conductivity in ultra-high temperature ceramics based on the correlation between metallic radius and the decrease in thermal conductivity.

Mass fractionation processes of transition metal isotopes

Science.gov (United States)

Zhu, X. K.; Guo, Y.; Williams, R. J. P.; O'Nions, R. K.; Matthews, A.; Belshaw, N. S.; Canters, G. W.; de Waal, E. C.; Weser, U.; Burgess, B. K.; Salvato, B.

2002-06-01

Recent advances in mass spectrometry make it possible to utilise isotope variations of transition metals to address some important issues in solar system and biological sciences. Realisation of the potential offered by these new isotope systems however requires an adequate understanding of the factors controlling their isotope fractionation. Here we show the results of a broadly based study on copper and iron isotope fractionation during various inorganic and biological processes. These results demonstrate that: (1) naturally occurring inorganic processes can fractionate Fe isotope to a detectable level even at temperature ˜1000°C, which challenges the previous view that Fe isotope variations in natural system are unique biosignatures; (2) multiple-step equilibrium processes at low temperatures may cause large mass fractionation of transition metal isotopes even when the fractionation per single step is small; (3) oxidation-reduction is an importation controlling factor of isotope fractionation of transition metal elements with multiple valences, which opens a wide range of applications of these new isotope systems, ranging from metal-silicate fractionation in the solar system to uptake pathways of these elements in biological systems; (4) organisms incorporate lighter isotopes of transition metals preferentially, and transition metal isotope fractionation occurs stepwise along their pathways within biological systems during their uptake.

Nucleic acid-functionalized transition metal nanosheets for biosensing applications.

Science.gov (United States)

Mo, Liuting; Li, Juan; Liu, Qiaoling; Qiu, Liping; Tan, Weihong

2017-03-15

In clinical diagnostics, as well as food and environmental safety practices, biosensors are powerful tools for monitoring biological or biochemical processes. Two-dimensional (2D) transition metal nanomaterials, including transition metal chalcogenides (TMCs) and transition metal oxides (TMOs), are receiving growing interest for their use in biosensing applications based on such unique properties as high surface area and fluorescence quenching abilities. Meanwhile, nucleic acid probes based on Watson-Crick base-pairing rules are also being widely applied in biosensing based on their excellent recognition capability. In particular, the emergence of functional nucleic acids in the 1980s, especially aptamers, has substantially extended the recognition capability of nucleic acids to various targets, ranging from small organic molecules and metal ions to proteins and cells. Based on π-π stacking interaction between transition metal nanosheets and nucleic acids, biosensing systems can be easily assembled. Therefore, the combination of 2D transition metal nanomaterials and nucleic acids brings intriguing opportunities in bioanalysis and biomedicine. In this review, we summarize recent advances of nucleic acid-functionalized transition metal nanosheets in biosensing applications. The structure and properties of 2D transition metal nanomaterials are first discussed, emphasizing the interaction between transition metal nanosheets and nucleic acids. Then, the applications of nucleic acid-functionalized transition metal nanosheet-based biosensors are discussed in the context of different signal transducing mechanisms, including optical and electrochemical approaches. Finally, we provide our perspectives on the current challenges and opportunities in this promising field. Copyright © 2016 Elsevier B.V. All rights reserved.

Supporting Transition

Science.gov (United States)

Qureshi, Asima; Petrucco, James

2018-01-01

Meadowbrook Primary School has explored the use of The Teacher Assessment in Primary Science (TAPS) to support transition, initially for transfer to secondary school and now for transition from Early Years Foundation Stage (EYFS) into Key Stage 1 (ages 5-7). This article will consider an example of a secondary transition project and discuss the…

Cycloadditions to Epoxides Catalyzed by GroupIII-V Transition-Metal Complexes

KAUST Repository

D'Elia, Valerio

2015-05-25

Complexes of groupIII-V transition metals are gaining increasing importance as Lewis acid catalysts for the cycloaddition of dipolarophiles to epoxides. This review examines the latest reports, including homogeneous and heterogeneous applications. The pivotal step for the cycloaddition reactions is the ring opening of the epoxide following activation by the Lewis acid. Two modes of cleavage (C-C versus C-O) have been identified depending primarily on the substitution pattern of the epoxide, with lesser influence observed from the Lewis acid employed. The widely studied cycloaddition of CO2 to epoxides to afford cyclic carbonates (C-O bond cleavage) has been scrutinized in terms of catalytic efficiency and reaction mechanism, showing that unsophisticated complexes of groupIII-V transition metals are excellent molecular catalysts. These metals have been incorporated, as well, in highly performing, recyclable heterogeneous catalysts. Cycloadditions to epoxides with other dipolarophiles (alkynes, imines, indoles) have been conducted with scandium triflate with remarkable performances (C-C bond cleavage). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cycloadditions to Epoxides Catalyzed by GroupIII-V Transition-Metal Complexes

KAUST Repository

D'Elia, Valerio; Pelletier, Jeremie; Basset, Jean-Marie

2015-01-01

Complexes of groupIII-V transition metals are gaining increasing importance as Lewis acid catalysts for the cycloaddition of dipolarophiles to epoxides. This review examines the latest reports, including homogeneous and heterogeneous applications. The pivotal step for the cycloaddition reactions is the ring opening of the epoxide following activation by the Lewis acid. Two modes of cleavage (C-C versus C-O) have been identified depending primarily on the substitution pattern of the epoxide, with lesser influence observed from the Lewis acid employed. The widely studied cycloaddition of CO2 to epoxides to afford cyclic carbonates (C-O bond cleavage) has been scrutinized in terms of catalytic efficiency and reaction mechanism, showing that unsophisticated complexes of groupIII-V transition metals are excellent molecular catalysts. These metals have been incorporated, as well, in highly performing, recyclable heterogeneous catalysts. Cycloadditions to epoxides with other dipolarophiles (alkynes, imines, indoles) have been conducted with scandium triflate with remarkable performances (C-C bond cleavage). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Manipulating Light with Transition Metal Clusters, Organic Dyes, and Metal Organic Frameworks

Energy Technology Data Exchange (ETDEWEB)

Ogut, Serdar [Univ. of Illinois, Chicago, IL (United States)

2017-09-11

The primary goals of our research program is to develop and apply state-of-the-art first-principles methods to predict electronic and optical properties of three systems of significant scientific and technological interest: transition metal clusters, organic dyes, and metal-organic frameworks. These systems offer great opportunities to manipulate light for a wide ranging list of energy-related scientific problems and applications. During this grant period, we focused our investigations on the development, implementation, and benchmarking of many-body Green’s function methods (GW approximation and the Bethe-Salpeter equation) to examine excited-state properties of transition metal/transition-metal-oxide clusters and organic molecules that comprise the building blocks of dyes and metal-organic frameworks.

Tunable Graphitic Carbon Nano-Onions Development in Carbon Nanofibers for Multivalent Energy Storage

Energy Technology Data Exchange (ETDEWEB)

Schwarz, Haiqing L. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2016-01-01

We developed a novel porous graphitic carbon nanofiber material using a synthesis strategy combining electrospinning and catalytic graphitization. RF hydrogel was used as carbon precursors, transition metal ions were successfully introduced into the carbon matrix by binding to the carboxylate groups of a resorcinol derivative. Transition metal particles were homogeneously distributed throughout the carbon matrix, which are used as in-situ catalysts to produce graphitic fullerene-like nanostructures surrounding the metals. The success design of graphitic carbons with enlarged interlayer spacing will enable the multivalent ion intercalation for the development of multivalent rechargeable batteries.

Oxygen effect on the work function of electropositive metal films adsorbed on 4d and 5d-transition metals

International Nuclear Information System (INIS)

Kultashev, O.K.; Makarov, A.P.; Rozhkov, S.E.

1976-01-01

The thermionic emission method was used to study the effect of oxygen upon the work function of films of electropositive metals, Sc, Y, La and Ba on some monocrystal and polycrystalline specimens of 4d- and 5d-transition metals of groups 4-8 of the Periodic system. It was revealed that when the supports were polycrystalline and monocrystalline specimens of transition metals of Group 5 (niobium and tantalum), the work function phi of films of electropositive adsorbates dropped substantially as compared, e.g., to the phi values on the same faces of tungsten. When the concentration of the electropositive adsorbate exceeds the optimum value (in the absence of oxygen), oxygen exerts an appreciably activating action upon the work function phi of films of electropositive adsorbates on transition metals of the Groups 7 and 8. The activating action of oxygen is assumed to be due to a possibility of formation of surface interstitial structures

Surface segregation energies in transition-metal alloys

DEFF Research Database (Denmark)

Ruban, Andrei; Skriver, Hans Lomholt; Nørskov, Jens Kehlet

1999-01-01

We present a database of 24 x 24 surface segregation energies of single transition metal impurities in transition-metal hosts obtained by a Green's-function linear-muffin-tin-orbitals method in conjunction with the coherent potential and atomic sphere approximations including a multipole correction...... to the electrostatic potential and energy. We use the database to establish the major factors which govern surface segregation in transition metal alloys. We find that the calculated trends are well described by Friedel's rectangular state density model and that the few but significant deviations from the simple...

Reactivity of monoolefin ligand in transition metal complexes

International Nuclear Information System (INIS)

Rybinskaya, M.I.

1978-01-01

The main tendencies in the coordinated olefin ligand property changes are discussed in the transition metal complexes in comparison with free olefins. The review includes the papers published from 1951 up to 1976. It has been shown that in complexes with transition metal cations olefin π-base acquires the ability to react with nucleophylic reagents. Olefin π-acids in complexes with zero valent metals are easily subjected to electrophylic reagent action. At coordination with transition metal cations the olefin properties are generally preserved, while in the zero-valent metal complexes the nonsaturated ligand acquires the properties of a saturated compounds. The ability of transition metal cations in complexes to intensify reactions of nucleophylic bimolecular substitution of vinyl halogen is clearly detected in contrast to the zero valent metal complexes. It has been shown that investigations of the coordinated olefin ligand reactivity give large possibilities in the further development of the organic synthesis. Some reactions are taken as the basis of important industrial processes

Transport of Carbonate Ions by Novel Cellulose Fiber Supported Solid Membrane

Directory of Open Access Journals (Sweden)

A. G. Gaikwad

2012-06-01

Full Text Available Transport of carbonate ions was explored through fiber supported solid membrane. A novel fiber supported solid membrane was prepared by chemical modification of cellulose fiber with citric acid, 2′2-bipyridine and magnesium carbonate. The factors affecting the permeability of carbonate ions such as immobilization of citric acid-magnesium metal ion -2′2-bipyridine complex (0 to 2.5 mmol/g range over cellulose fiber, carbon-ate ion concentration in source phase and NaOH concentration in receiving phase were investigated. Ki-netic of carbonate, sulfate, and nitrate ions was investigated through fiber supported solid membrane. Transport of carbonate ions with/without bubbling of CO2 (0 to 10 ml/min in source phase was explored from source to receiving phase. The novel idea is to explore the adsorptive transport of CO2 from source to receiving phase through cellulose fiber containing magnesium metal ion organic framework. Copyright © 2012 BCREC UNDIP. All rights reserved.Received: 25th November 2011; Revised: 17th December 2011; Accepted: 19th December 2011[How to Cite: A.G. Gaikwad. (2012. Transport of Carbonate Ions by Novel Cellulose Fiber Supported Solid Membrane. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (1: 49– 57.  doi:10.9767/bcrec.7.1.1225.49-57][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.1.1225.49-57 ] | View in 

Electrical Conductivity in Transition Metals

Science.gov (United States)

Talbot, Christopher; Vickneson, Kishanda

2013-01-01

The aim of this "Science Note" is to describe how to test the electron-sea model to determine whether it accurately predicts relative electrical conductivity for first-row transition metals. In the electron-sea model, a metal crystal is viewed as a three-dimensional array of metal cations immersed in a sea of delocalised valence…

Mesoporous Transition Metal Oxides for Supercapacitors

Science.gov (United States)

Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

2015-01-01

Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors. PMID:28347088

Mesoporous Transition Metal Oxides for Supercapacitors

Directory of Open Access Journals (Sweden)

Yan Wang

2015-10-01

Full Text Available Recently, transition metal oxides, such as ruthenium oxide (RuO2, manganese dioxide (MnO2, nickel oxides (NiO and cobalt oxide (Co3O4, have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4, and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

The nonmetal-metal transition in solutions of metals in molten salts

International Nuclear Information System (INIS)

Tosi, M.P.

1997-04-01

Solutions of metals in molten salts present a rich phenomenology: localization of electrons in disordered ionic media, activated electron transport increasing with metal concentration towards a nonmetal-metal (NM-M) transition, and liquid-liquid phase separation. A brief review of progress in the study of these systems is given in this article, with main focus on the NM-M transition. After recalling the known NM-M behaviour of the component elements in the case of expanded fluid alkali metals and mercury and of solid halogens under pressure, the article focuses on liquid metal - molten salt solutions and traces the different NM-M behaviours of the alkalis in their halides and of metals added to polyvalent metal halides. (author). 51 refs, 2 figs

Alkali metal and alkali metal hydroxide intercalates of the layered transition metal disulfides

International Nuclear Information System (INIS)

Kanzaki, Y.; Konuma, M.; Matsumoto, O.

1981-01-01

The intercalation reaction of some layered transition metal disulfides with alkali metals, alkali metal hydroxides, and tetraalkylammonium hydroxides were investigated. The alkali metal intercalates were prepared in the respective metal-hexamethylphosphoric triamide solutions in vaccuo, and the hydroxide intercalates in aqueous hydroxide solutions. According to the intercalation reaction, the c-lattice parameter was increased, and the increase indicated the expansion of the interlayer distance. In the case of alkali metal intercalates, the expansion of the interlayer distance increased continuously, corresponding to the atomic radius of the alkali metal. On the other hand, the hydroxide intercalates showed discrete expansion corresponding to the effective ionic radius of the intercalated cation. All intercalates of TaS 2 amd NbS 2 were superconductors. The expansion of the interlayer distance tended to increase the superconducting transition temperature in the intercalates of TaS 2 and vice versa in those of NbS 2 . (orig.)

Carbons and carbon supported catalysts in hydroprocessing

Energy Technology Data Exchange (ETDEWEB)

Furimsky, Edward

2009-07-01

This book is a comprehensive summary of recent research in the field and covers all areas of carbons and carbon materials. The potential application of carbon supports, particularly those of carbon black (CB) and activated carbon (AC) in hydroprocessing catalysis are covered. Novel carbon materials such as carbon fibers and carbon nano tubes (CNT) are also covered, including the more recent developments in the use of fullerenes in hydroprocessing applications. Although the primary focus of this book is on carbons and carbon supported catalysts, it also identifies the difference in the effect of carbon supports compared with the oxidic supports, particularly that of the Al{sub 2}O{sub 3}. The difference in catalyst activity and stability was estimated using both model compounds and real feeds under variable conditions. The conditions applied during the preparation of carbon supported catalysts are also comprehensively covered and include various methods of pretreatment of carbon supports to enhance catalyst performance. The model compounds results consistently show higher hydrodesulfurization and hydrodeoxygenation activities of carbon supported catalysts than that of the Al{sub 2}O{sub 3} supported catalysts. Also, the deactivation of the former catalysts by coke deposition was much less evident. Chapter 6.3.1.3 is on carbon-supported catalysts: coal-derived liquids.

An in situ method of creating metal oxide–carbon composites and their application as anode materials for lithium-ion batteries

KAUST Repository

Yang, Zichao; Shen, Jingguo; Archer, Lynden A.

2011-01-01

Transition metal oxides are actively investigated as anode materials for lithium-ion batteries (LIBs), and their nanocomposites with carbon frequently show better performance in galvanostatic cycling studies, compared to the pristine metal oxide

Electrochemical corrosion of carbon-fiber-reinforced plastic-metal electrode couples in corrosion media

International Nuclear Information System (INIS)

Chukalovskaya, T.V.; Shcherbakov, A.I.; Chigirinskaya, L.A.; Bandurkin, V.V.; Medova, I.L.; Chukalovskij, P.A.

1995-01-01

Polarization diagrams, obtained for carbon-fiber-reinforced plastic(cathode)-metallic material(anode) contact couples are analyzed to predict the corrosion behaviour of some technical metals and alloys (carbon steel, stainless steels, brass, aluminium, titanium) in contact with carbon-fiber-reinforced plastic in differen agressive media (H 2 SO 4 , HCl, H 3 PO 4 , NaOH solutions in wide temperature and concentration range, synthetic seawater at 30 and 50 deg C). The predicted behaviour was supported by direct investigation into carbon-fiber-reinforced plastic-titanium and carbon-fiber-reinforced plastic-aluminium contact couples at different square ratios. 6 refs.; 4 figs

Preparation and characterization of flexible asymmetric supercapacitors based on transition-metal-oxide nanowire/single-walled carbon nanotube hybrid thin-film electrodes.

Science.gov (United States)

Chen, Po-Chiang; Shen, Guozhen; Shi, Yi; Chen, Haitian; Zhou, Chongwu

2010-08-24

In the work described in this paper, we have successfully fabricated flexible asymmetric supercapacitors (ASCs) based on transition-metal-oxide nanowire/single-walled carbon nanotube (SWNT) hybrid thin-film electrodes. These hybrid nanostructured films, with advantages of mechanical flexibility, uniform layered structures, and mesoporous surface morphology, were produced by using a filtration method. Here, manganese dioxide nanowire/SWNT hybrid films worked as the positive electrode, and indium oxide nanowire/SWNT hybrid films served as the negative electrode in a designed ASC. In our design, charges can be stored not only via electrochemical double-layer capacitance from SWNT films but also through a reversible faradic process from transition-metal-oxide nanowires. In addition, to obtain stable electrochemical behavior during charging/discharging cycles in a 2 V potential window, the mass balance between two electrodes has been optimized. Our optimized hybrid nanostructured ASCs exhibited a superior device performance with specific capacitance of 184 F/g, energy density of 25.5 Wh/kg, and columbic efficiency of approximately 90%. In addition, our ASCs exhibited a power density of 50.3 kW/kg, which is 10-fold higher than obtained in early reported ASC work. The high-performance hybrid nanostructured ASCs can find applications in conformal electrics, portable electronics, and electrical vehicles.

On metal-insulator transition in cubic fullerides

Science.gov (United States)

Iwahara, Naoya; Chibotaru, Liviu

The interplay between degenerate orbital and electron correlation is a key to characterize the electronic phases in, for example, transition metal compounds and alkali-doped fullerides. Besides, the degenerate orbital couples to spin and lattice degrees of freedom ,giving rise to exotic phenomena. Here, we develop the self-consistent Gutzwiller approach for the simultaneous treatment of the Jahn-Teller effect and electron correlation, and apply the methodology to reveal the nature of the ground electronic state of fullerides. For small Coulomb repulsion on site U, the fulleride is quasi degenerate correlated metal. With increase of U, we found the quantum phase transition from the metallic phase to JT split phase. In the latter, the Mott transition (MT) mainly develops in the half-filled subband, whereas the empty and the completely filled subbands are almost uninvolved. Therefore, we can qualify the metal-insulator transition in fullerides as an orbital selective MT induced by JT effect.

Deposition of metallic nanoparticles on carbon nanotubes via a fast evaporation process

International Nuclear Information System (INIS)

Ren Guoqiang; Xing Yangchuan

2006-01-01

A new technique was developed for the deposition of colloidal metal nanoparticles on carbon nanotubes. It involves fast evaporation of a suspension containing sonochemically functionalized carbon nanotubes and colloidal nanoparticles. It was demonstrated that metallic nanoparticles with different sizes and concentrations can be deposited on the carbon nanotubes with only a few agglomerates. The technique does not seem to be limited by what the nanoparticles are, and therefore would be applicable to the deposition of other nanoparticles on carbon nanotubes. PtPd and CoPt 3 alloy nanoparticles were used to demonstrate the deposition process. It was found that the surfactants used to disperse the nanoparticles can hinder the nanoparticle deposition. When the nanoparticles were washed with ethanol, they could be well deposited on the carbon nanotubes. The obtained carbon nanotube supported metal nanoparticles were characterized by transmission electron microscopy, energy dispersive x-ray spectroscopy, x-ray photoelectron spectroscopy, and cyclic voltammetry

Modeling nanoscale gas sensors under realistic conditions: Computational screening of metal-doped carbon nanotubes

DEFF Research Database (Denmark)

García Lastra, Juan Maria; Mowbray, Duncan; Thygesen, Kristian Sommer

2010-01-01

We use computational screening to systematically investigate the use of transition-metal-doped carbon nanotubes for chemical-gas sensing. For a set of relevant target molecules (CO, NH3, and H2S) and the main components of air (N2, O2, and H2O), we calculate the binding energy and change in condu......We use computational screening to systematically investigate the use of transition-metal-doped carbon nanotubes for chemical-gas sensing. For a set of relevant target molecules (CO, NH3, and H2S) and the main components of air (N2, O2, and H2O), we calculate the binding energy and change...... the change in the nanotube resistance per doping site as a function of the target molecule concentration assuming charge transport in the diffusive regime. Our analysis points to Ni-doped nanotubes as candidates for CO sensors working under typical atmospheric conditions....

A spin transition mechanism for cooperative adsorption in metal-organic frameworks

Science.gov (United States)

Reed, Douglas A.; Keitz, Benjamin K.; Oktawiec, Julia; Mason, Jarad A.; Runčevski, Tomče; Xiao, Dianne J.; Darago, Lucy E.; Crocellà, Valentina; Bordiga, Silvia; Long, Jeffrey R.

2017-10-01

Cooperative binding, whereby an initial binding event facilitates the uptake of additional substrate molecules, is common in biological systems such as haemoglobin. It was recently shown that porous solids that exhibit cooperative binding have substantial energetic benefits over traditional adsorbents, but few guidelines currently exist for the design of such materials. In principle, metal-organic frameworks that contain coordinatively unsaturated metal centres could act as both selective and cooperative adsorbents if guest binding at one site were to trigger an electronic transformation that subsequently altered the binding properties at neighbouring metal sites. Here we illustrate this concept through the selective adsorption of carbon monoxide (CO) in a series of metal-organic frameworks featuring coordinatively unsaturated iron(II) sites. Functioning via a mechanism by which neighbouring iron(II) sites undergo a spin-state transition above a threshold CO pressure, these materials exhibit large CO separation capacities with only small changes in temperature. The very low regeneration energies that result may enable more efficient Fischer-Tropsch conversions and extraction of CO from industrial waste feeds, which currently underutilize this versatile carbon synthon. The electronic basis for the cooperative adsorption demonstrated here could provide a general strategy for designing efficient and selective adsorbents suitable for various separations.

Transition metal borides. Synthesis, characterization and superconducting properties

International Nuclear Information System (INIS)

Kayhan, Mehmet

2013-01-01

A systematic study was done on the synthesis and superconducting properties of metal rich transition metal borides. Five different binary systems were investigated including the boride systems of niobium, tantalum, molybdenum, tungsten and rhenium. High temperature solid state methods were used in order to synthesize samples of different transition metal borides of the composition M 2 B, MB, M 3 B 2 , MB 2 , and M 2 B 4 . The reactions were carried out in three different furnaces with different sample containers: the electric arc (copper crucible), the high frequency induction furnace (boron nitride, tantalum or glassy carbon crucibles), and the conventional tube furnace (sealed evacuated quartz ampoules). The products obtained were characterized with X-ray powder diffractometry, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Phase analyses and crystal structure refinements using the Rietveld method and based on structure models known from literature were performed. A neutron diffraction measurement was done for W 2 B 4 to allow for a complete crystal structure determination, because of the presence of a heavy element like tungsten and a light element like boron that made it difficult to determine the accurate determination of the boron atom positions and occupancies from X-ray data. A new structure model for W 2 B 4 was proposed. Magnetic measurements in a SQUID magnetometer down to temperatures as low as 1.8 K were performed to several of the products in order to see if the transition metal borides become superconducting at low temperatures, and the results were compared with data from literature. Superconducting properties were found for the following compounds: NbB 2 (T C = 3.5 K), β-MoB (T C = 2.4 K), β-WB (T C = 2.0 K), α-WB (T C = 4.3 K), W 2 B 4 (T C = 5.4 K), Re 7 B 3 (T C = 2.4 K). A relationship between the superconducting properties and the compositional and structural features was discussed for metal diborides. Also it was

Transition Metal Complexes and Catalysis

Indian Academy of Sciences (India)

approaches towards the study of bonding in transition metal complexes. Despite .... industrial scale reactions for the production of organic compounds using transition ..... It has found several applications as an engineering thermoplastic. .... and processes of interest to the company, that is, applied research. It is this very ...

Transition layers formation on the boundaries carbon fiber-copper dependence on the active additions

International Nuclear Information System (INIS)

Wlosinski, W.; Pietrzak, K.

1993-01-01

The basic problem connected with fabrication of carbon fiber-copper composites is to overcome the problem of low wettability of carbon fiber by copper. One of the possible solutions of that problem is to use the copper doped with active metals. The investigation results of transition layer forming on the phase boundary in the system have been discussed in respect of the kind and content of active elements added to the copper. 5 refs, 5 figs, 5 tabs

Recombination of charge carriers on radiation-induced defects in silicon doped by transition metals impurities

CERN Document Server

Kazakevich, L A

2003-01-01

It has been studied the peculiarities of recombination of nonequilibrium charge carriers on radiation-induced defects in received according to Czochralski method p-silicon (p approx 3 - 20 Ohm centre dot cm), doped by one of the impurities of transition metals of the IV-th group of periodic table (titanium, zirconium, hafnium). Experimental results are obtained out of the analysis of temperature and injection dependence of the life time of charge carriers. The results are explained taking into consideration the influences of elastic stress fields created by the aggregates of transition metals atoms on space distribution over the crystal of oxygen and carbon background impurities as well as on the migration of movable radiation-induced defects during irradiation. (authors).

When double-wall carbon nanotubes can become metallic or semiconducting

International Nuclear Information System (INIS)

Moradian, Rostam; Azadi, Sam; Refii-tabar, Hashem

2007-01-01

The electronic properties of double-wall carbon nanotubes (DWCNTs) are investigated via density functional theory. The DWCNTs are separated into four categories wherein the inner-outer nanotubes are metal-metal, metal-semiconductor, semiconductor-metal and semiconductor-semiconductor single-wall nanotubes. The band structure of the DWCNTs, the local density of states of the inner and outer nanotubes, and the total density of states are calculated. We found that for the metal-metal DWCNTs, the inner and outer nanotubes remain metallic for different distances between the walls, while for the metal-semiconductor DWCNTs, decreasing the distance between the walls leads to a phase transition in which both nanotubes become metallic. In the case of semiconductor-metal DWCNTs, it is found that at some distance the inner wall becomes metallic, while the outer wall becomes a semiconductor, and if the distance is decreased, both walls become metallic. Finally, in the semiconductor-semiconductor DWCNTs, if the two walls are far from each other, then the whole DWCNT and both walls remain semiconducting. By decreasing the wall distance, first the inner, and then the outer, nanotube becomes metallic

Production of metal fullerene surface layer from various media in the process of steel carbonization

Directory of Open Access Journals (Sweden)

KUZEEV Iskander Rustemovich

2018-04-01

Full Text Available Studies devoted to production of metal fullerene layer in steels when introducing carbon from organic and inorganic media were performed. Barium carbonate was used as an inorganic medium and petroleum pitch was used as an organic medium. In order to generate the required amount of fullerenes in the process of steel samples carbonization, optimal temperature mode was found. The higher temperature, absorption and cohesive effects become less important and polymeric carbon structures destruction processes become more important. On the bottom the temperature is limited by petroleum pitch softening temperature and its transition to low-viscous state in order to enhance molecular mobility and improve the possibility of their diffusion to metal surface. Identification of fullerenes in the surface modified layer was carried out following the methods of IR-Fourier spectrometry and high-performance liquid chromatography. It was found out that nanocarbon structures, formed during carbonization in barium carbonate and petroleum pitch mediums, possess different morphology. In the process of metal carbonization from carbonates medium, the main role in fullerenes synthesis is belonged to catalytic effect of surface with generation of endohedral derivatives in the surface layer; but in the process of carbonization from pitch medium fullerenes are formed during crystallization of the latter and crystallization centers are of fullerene type. Based on theoretical data and dataof spectral and chromatographic analysis, optimal conditions of metal fullerene layer formation in barium carbonate and petroleum pitch mediums were determined. Low cohesion of layer, modified in barium carbonate medium, with metal basis was discovered. That was caused by limited carbon diffusion in the volume of α-Fe. According to the detected mechanism of fullerenes formation on steel surface in gaseous medium, fullerenes are formed on catalytic centers – ferrum atoms, forming thin metal

Characterization of Transition Metal Carbide Layers Synthesized by Thermo-reactive Diffusion Processes

DEFF Research Database (Denmark)

Laursen, Mads Brink; Fernandes, Frederico Augusto Pires; Christiansen, Thomas Lundin

2015-01-01

. In this study halide-activated pack cementation techniques were used on tool steel Vanadis 6 and martensitic stainless steel AISI 420 in order to produce hard layers of titanium carbide (TiC), vanadium carbide (V8C7) and chromium carbides (Cr23C6 and Cr7C3). Surface layers were characterized by scanning......Hard wear resistant surface layers of transition metal carbides can be produced by thermo-reactive diffusion processes where interstitial elements from a steel substrate together with external sources of transition metals (Ti, V, Cr etc.) form hard carbide and/or nitride layers at the steel surface...... electron microscopy, X-ray diffraction and Vickers hardness testing. The study shows that porosityfree, homogenous and very hard surface layers can be produced by thermo-reactive diffusion processes. The carbon availability of the substrate influences thickness of obtained layers, as Vanadis 6 tool steel...

Metal-ligand interactions

Science.gov (United States)

Ervin, Kent M.

Experimental studies of the interactions of small transition-metal cluster anions with carbonyl ligands are reviewed and compared with neutral and cationic clusters. Under thermal conditions, the reaction rates of transition-metal clusters with carbon monoxide are measured as a function of cluster size. Saturation limits for carbon monoxide addition can be related to the geometric structures of the clusters. Both energy-resolved threshold collision-induced dissociation experiments and time-resolved photodissociation experiments are used to measure metal-carbonyl binding energies. For platinum and palladium trimer anions, the carbonyl binding energies are assigned to different geometric binding sites. Platinum and palladium cluster anions catalyse the oxidation of carbon monoxide to carbon dioxide in a full catalytic cycle at thermal energies.

Alkylation and arylation of alkenes by transition metal complexes

International Nuclear Information System (INIS)

Volkova, L.G.; Levitin, I.Ya.; Vol'pin, M.E.

1975-01-01

In this paper are reviewed methods of alkylation and irylation of unsaturated compounds with complexes of transition metals (Rh, Pd). Analysis of alkylation and arylation of olefines with organic derivatives of transition metals, obtained as a result of exchange reactions between organic compounds of transition metals and salts of metals of the 8th group of the periodic system, allows a conclusion as to the wide possibilities of these reactions in the synthesis of various derivatives of unsaturated compounds. In all the reactions under consideration, intermediate formation of sigma-complexes is assumed. Also considered are alkylation and arylation of olefines with organic derivatives of halogens in the presence of compounds of metals of the 8th group of the periodic system, as well as arylation of olefines with aromatic compounds in the presence of salts of transition metals

Plasmons in metallic monolayer and bilayer transition metal dichalcogenides

DEFF Research Database (Denmark)

Andersen, Kirsten; Thygesen, Kristian S.

2013-01-01

We study the collective electronic excitations in metallic single-layer and bilayer transition metal dichalcogenides (TMDCs) using time dependent density functional theory in the random phase approximation. For very small momentum transfers (below q≈0.02 Å−1), the plasmon dispersion follows the √q...

Quantum Critical “Opalescence” around Metal-Insulator Transitions

Science.gov (United States)

Misawa, Takahiro; Yamaji, Youhei; Imada, Masatoshi

2006-08-01

Divergent carrier-density fluctuations equivalent to the critical opalescence of gas-liquid transition emerge around a metal-insulator critical point at a finite temperature. In contrast to the gas-liquid transitions, however, the critical temperatures can be lowered to zero, which offers a challenging quantum phase transition. We present a microscopic description of such quantum critical phenomena in two dimensions. The conventional scheme of phase transitions by Ginzburg, Landau, and Wilson is violated because of its topological nature. It offers a clear insight into the criticalities of metal-insulator transitions (MIT) associated with Mott or charge-order transitions. Fermi degeneracy involving the diverging density fluctuations generates emergent phenomena near the endpoint of the first-order MIT and must shed new light on remarkable phenomena found in correlated metals such as unconventional cuprate superconductors. It indeed accounts for the otherwise puzzling criticality of the Mott transition recently discovered in an organic conductor. We propose to accurately measure enhanced dielectric fluctuations at small wave numbers.

Preparation of self-supporting thin metal target films

International Nuclear Information System (INIS)

Wang Xiuying; Ge Suxian; Yin Jianhua; Yin Xu; Jin Genming

1989-01-01

The preparation method and equipment for thin metal self-supporting target without oil contamination are described. The influence of target films contaminated by oil vapor on accuracy of nuclear-physics experimental data are also discussed. The analytical results on carbon content in the prepared films of three elements show that the equipment is very effective for eliminating contamination

Oligocyclopentadienyl transition metal complexes

Energy Technology Data Exchange (ETDEWEB)

de Azevedo, Cristina G.; Vollhardt, K. Peter C.

2002-01-18

Synthesis, characterization, and reactivity studies of oligocyclopentadienyl transition metal complexes, namely those of fulvalene, tercyclopentadienyl, quatercyclopentadienyl, and pentacyclopentadienyl(cyclopentadienyl) are the subject of this account. Thermal-, photo-, and redox chemistries of homo- and heteropolynuclear complexes are described.

Low-frequency plasmons in metallic carbon nanotubes

International Nuclear Information System (INIS)

Lin, M.F.; Chuu, D.S.; Shung, K.W.

1997-01-01

A metallic carbon nanotube could exhibit a low-frequency plasmon, while a semiconducting carbon nanotube or a graphite layer could not. This plasmon is due to the free carriers in the linear subbands intersecting at the Fermi level. The low-frequency plasmon, which corresponds to the vanishing transferred angular momentum, belongs to an acoustic plasmon. For a smaller metallic nanotube, it could exist at larger transferred momenta, and its frequency is higher. Such a plasmon behaves as that in a one-dimensional electron gas (EGS). However, it is very different from the π plasmons in all carbon nanotubes. Intertube Coulomb interactions in a metallic multishell nanotube and a metallic nanotube bundle have been included. They have a strong effect on the low-frequency plasmon. The intertube coupling among coaxial nanotubes markedly modifies the acoustic plasmons in separate metallic nanotubes. When metallic carbon nanotubes are packed in the bundle form, the low-frequency plasmon would change into an optical plasmon, and behave like that in a three-dimensional EGS. Experimental measurements could be used to distinguish metallic and semiconducting carbon nanotubes. copyright 1997 The American Physical Society

Solubility of hydrogen in transition metals

International Nuclear Information System (INIS)

Lee, H.M.

1976-01-01

Correlations exist between the heat of solution of hydrogen and the difference in energy between the lowest lying energy levels of the trivalent d/sup n-1/s electronic configuration and the divalent d/sup n-2/s 2 (or the tetravalent d/sup n/) configuration of the neutral gaseous atoms. The trends observed in the transition metal series are discussed in relation to the number of valence electrons per atom in the transition elements in their metallic and neutral states

Integrating Transition Metals into Nanomaterials: Strategies and Applications

KAUST Repository

Fhayli, Karim

2016-01-01

Transition metals complexes have been involved in various catalytic, biomedical and industrial applications, but only lately they have been associated with nanomaterials to produce innovative and well-defined new hybrid systems. The introduction of transition metals into nanomaterials is important to bear the advantages of metals to nanoscale and also to raise the stability of nanomaterials. In this dissertation, we study two approaches of associating transition metals into nanomaterials. The first approach is via spontaneous self-organization based assembly of small molecule amphiphiles and bulky hydrophilic polymers to produce organic-inorganic hybrid materials that have nanoscale features and can be precisely controlled depending on the experimental conditions used. These hybrid materials can successfully act as templates to design new porous material with interesting architecture. The second approach studied is via electroless reduction of transition metals on the surface of nanocarbons (nanotubes and nanodiamonds) without using any reducing agents or catalysts. The synthesis of these systems is highly efficient and facile resulting in stable and mechanically robust new materials with promising applications in catalysis.

Integrating Transition Metals into Nanomaterials: Strategies and Applications

KAUST Repository

Fhayli, Karim

2016-04-14

Transition metals complexes have been involved in various catalytic, biomedical and industrial applications, but only lately they have been associated with nanomaterials to produce innovative and well-defined new hybrid systems. The introduction of transition metals into nanomaterials is important to bear the advantages of metals to nanoscale and also to raise the stability of nanomaterials. In this dissertation, we study two approaches of associating transition metals into nanomaterials. The first approach is via spontaneous self-organization based assembly of small molecule amphiphiles and bulky hydrophilic polymers to produce organic-inorganic hybrid materials that have nanoscale features and can be precisely controlled depending on the experimental conditions used. These hybrid materials can successfully act as templates to design new porous material with interesting architecture. The second approach studied is via electroless reduction of transition metals on the surface of nanocarbons (nanotubes and nanodiamonds) without using any reducing agents or catalysts. The synthesis of these systems is highly efficient and facile resulting in stable and mechanically robust new materials with promising applications in catalysis.

Strong-Superstrong Transition in Glass Transition of Metallic Glass

International Nuclear Information System (INIS)

Dan, Wang; Hong-Yan, Peng; Xiao-Yu, Xu; Bao-Ling, Chen; Chun-Lei, Wu; Min-Hua, Sun

2010-01-01

Dynamic fragility of bulk metallic glass (BMG) of Zr 64 Cu 16 Ni 10 Al 10 alloy is studied by three-point beam bending methods. The fragility parameter mfor Zr 64 Cu 16 Ni 10 Al 10 BMG is calculated to be 24.5 at high temperature, which means that the liquid is a 'strong' liquid, while to be 13.4 at low temperature which means that the liquid is a 'super-strong' liquid. The dynamical behavior of Zr 64 Cu 16 Ni 10 Al 10 BMG in the supercooled region undergoes a strong to super-strong transition. To our knowledge, it is the first time that a strong-to-superstrong transition is found in the metallic glass. Using small angle x-ray scattering experiments, we find that this transition is assumed to be related to a phase separation process in supercooled liquid. (condensed matter: structure, mechanical and thermal properties)

Phase stability of transition metals and alloys

International Nuclear Information System (INIS)

Hixson, R.S.; Schiferl, D.; Wills, J.M.; Hill, M.A.

1997-01-01

This is the final report of a three-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). This project was focused on resolving unexplained differences in calculated and measured phase transition pressures in transition metals. Part of the approach was to do new, higher accuracy calculations of transmission pressures for group 4B and group 6B metals. Theory indicates that the transition pressures for these baseline metals should change if alloyed with a d-electron donor metal, and calculations done using the Local Density Approximation (LDA) and the Virtual Crystal Approximation (VCA) indicate that this is true. Alloy systems were calculated for Ti, Zr and Hf based alloys with various solute concentrations. The second part of the program was to do new Diamond Anvil Cell (DAC) measurements to experimentally verify calculational results. Alloys were prepared for these systems with grain size suitable for Diamond Anvil Cell experiments. Experiments were done on pure Ti as well as Ti-V and Ti-Ta alloys. Measuring unambiguous transition pressures for these systems proved difficult, but a new technique developed yielded good results

Rare-earth metal transition metal borocarbide and nitridoborate superconductors

Energy Technology Data Exchange (ETDEWEB)

Niewa, Rainer; Shlyk, Larysa; Blaschkowski, Bjoern [Stuttgart Univ. (Germany). Inst. fuer Anorganische Chemie

2011-07-01

Few years after the discovery of superconductivity in high-T{sub c} cuprates, borocarbides and shortly after nitridoborates with reasonably high T{sub c}s up to about 23 K attracted considerable attention. Particularly for the rare-earth metal series with composition RNi{sub 2}[B{sub 2}C] it turned out, that several members exhibit superconductivity next to magnetic order with both T{sub c} above or below the magnetic ordering temperature. Therefore, these compounds have been regarded as ideal materials to study the interplay and coexistence of superconductivity and long range magnetic order, due to their comparably high ordering temperatures and similar magnetic and superconducting condensation energies. This review gathers information on the series RNi{sub 2}[B{sub 2}C] and isostructural compounds with different transition metals substituting Ni as well as related series like RM[BC], RM[BN], AM[BN] and R{sub 3}M{sub 2}[BN]{sub 2}N (all with R = rare-earth metal, A = alkaline-earth metal, M = transition metal) with special focus on synthesis, crystal structures and structural trends in correspondence to physical properties. (orig.)

Theoretical Investigation on Single-Wall Carbon Nanotubes Doped with Nitrogen, Pyridine-Like Nitrogen Defects, and Transition Metal Atoms

Directory of Open Access Journals (Sweden)

Michael Mananghaya

2012-01-01

Full Text Available This study addresses the inherent difficulty in synthesizing single-walled carbon nanotubes (SWCNTs with uniform chirality and well-defined electronic properties through the introduction of dopants, topological defects, and intercalation of metals. Depending on the desired application, one can modify the electronic and magnetic properties of SWCNTs through an appropriate introduction of imperfections. This scheme broadens the application areas of SWCNTs. Under this motivation, we present our ongoing investigations of the following models: (i (10, 0 and (5, 5 SWCNT doped with nitrogen (CNxNT, (ii (10, 0 and (5, 5 SWCNT with pyridine-like defects (3NV-CNxNT, (iii (10, 0 SWCNT with porphyrine-like defects (4ND-CNxNT. Models (ii and (iii were chemically functionalized with 14 transition metals (TMs: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Ag, Pt and Au. Using the spin-unrestricted density functional theory (DFT, stable configurations, deformations, formation and binding energies, the effects of the doping concentration of nitrogen, pyridine-like and porphyrine-like defects on the electronic properties were all examined. Results reveal that the electronic properties of SWCNTs show strong dependence on the concentration and configuration of nitrogen impurities, its defects, and the TMs adsorbed.

Superconducting Metallic Glass Transition-Edge-Sensors

Science.gov (United States)

Hays, Charles C. (Inventor)

2013-01-01

A superconducting metallic glass transition-edge sensor (MGTES) and a method for fabricating the MGTES are provided. A single-layer superconducting amorphous metal alloy is deposited on a substrate. The single-layer superconducting amorphous metal alloy is an absorber for the MGTES and is electrically connected to a circuit configured for readout and biasing to sense electromagnetic radiation.

Sustainable preparation of supported metal nanoparticles and their applications in catalysis.

Science.gov (United States)

Campelo, Juan M; Luna, Diego; Luque, Rafael; Marinas, José M; Romero, Antonio A

2009-01-01

Metal nanoparticles have attracted much attention over the last decade owing to their unique properties as compared to their bulk metal equivalents, including a large surface-to-volume ratio and tunable shapes. To control the properties of nanoparticles with particular respect to shape, size and dispersity is imperative, as these will determine the activity in the desired application. Supported metal nanoparticles are widely employed in catalysis. Recent advances in controlling the shape and size of nanoparticles have opened the possibility to optimise the particle geometry for enhanced catalytic activity, providing the optimum size and surface properties for specific applications. This Review describes the state of the art with respect to the preparation and use of supported metal nanoparticles in catalysis. The main groups of such nanoparticles (noble and transition metal nanoparticles) are highlighted and future prospects are discussed.

Trends in the Microwave-Assisted Synthesis of Metal Oxide Nanoparticles Supported on Carbon Nano tubes and Their Applications

International Nuclear Information System (INIS)

Motshekga, S.C.; Pillai, S.K.; Ray, S.S.; Motshekga, S.C.; Ray, S.S.; Jalama, K.; Krause, Rui.W.M.

2012-01-01

The study of coating carbon nano tubes with metal/oxides nanoparticles is now becoming a promising and challenging area of research. To optimize the use of carbon nano tubes in various applications, it is necessary to attach functional groups or other nano structures to their surface. The combination of the distinctive properties of carbon nano tubes and metal/oxides is expected to be applied in field emission displays, nano electronic devices, novel catalysts, and polymer or ceramic reinforcement. The synthesis of these composites is still largely based on conventional techniques, such as wet impregnation followed by chemical reduction of the metal nanoparticle precursors. These techniques based on thermal heating can be time consuming and often lack control of particle size and morphology. Hence, there is interest in microwave technology recently, where using microwaves represents an alternative way of power input into chemical reactions through dielectric heating. This paper covers the synthesis and applications of carbon-nano tube-coated metal/oxides nanoparticles prepared by a microwave-assisted method. The reviewed studies show that the microwave-assisted synthesis of the composites allows processes to be completed within a shorter reaction time with uniform and well-dispersed nanoparticle formation.

Recent Trends in the Microwave-Assisted Synthesis of Metal Oxide Nanoparticles Supported on Carbon Nanotubes and Their Applications

Directory of Open Access Journals (Sweden)

Sarah C. Motshekga

2012-01-01

Full Text Available The study of coating carbon nanotubes with metal/oxides nanoparticles is now becoming a promising and challenging area of research. To optimize the use of carbon nanotubes in various applications, it is necessary to attach functional groups or other nanostructures to their surface. The combination of the distinctive properties of carbon nanotubes and metal/oxides is expected to be applied in field emission displays, nanoelectronic devices, novel catalysts, and polymer or ceramic reinforcement. The synthesis of these composites is still largely based on conventional techniques, such as wet impregnation followed by chemical reduction of the metal nanoparticle precursors. These techniques based on thermal heating can be time consuming and often lack control of particle size and morphology. Hence, there is interest in microwave technology recently, where using microwaves represents an alternative way of power input into chemical reactions through dielectric heating. This paper covers the synthesis and applications of carbon-nanotube-coated metal/oxides nanoparticles prepared by a microwave-assisted method. The reviewed studies show that the microwave-assisted synthesis of the composites allows processes to be completed within a shorter reaction time with uniform and well-dispersed nanoparticle formation.

Oxide-supported metal clusters: models for heterogeneous catalysts

International Nuclear Information System (INIS)

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)

Electroforming and Switching in Oxides of Transition Metals: The Role of Metal Insulator Transition in the Switching Mechanism

Science.gov (United States)

Chudnovskii, F. A.; Odynets, L. L.; Pergament, A. L.; Stefanovich, G. B.

1996-02-01

Electroforming and switching effects in sandwich structures based on anodic films of transition metal oxides (V, Nb, Ti, Fe, Ta, W, Zr, Hf, Mo) have been studied. After being electroformed, some materials exhibited current-controlled negative resistance with S-shapedV-Icharacteristics. For V, Fe, Ti, and Nb oxides, the temperature dependences of the threshold voltage have been measured. As the temperature increased,Vthdecreased to zero at a critical temperatureT0, which depended on the film material. Comparison of theT0values with the temperatures of metal-insulator phase transition for some compounds (Tt= 120 K for Fe3O4, 340 K for VO2, ∼500 K for Ti2O3, and 1070 K for NbO2) showed that switching was related to the transition in the applied electric field. Channels consisting of the above-mentioned lower oxides were formed in the initial anodic films during the electroforming. The possibility of formation of these oxides with a metal-insulator transition was confirmed by thermodynamic calculations.

The structure of nano-palladium deposited on carbon-based supports

International Nuclear Information System (INIS)

Pikna, Ľubomír; Milkovič, Ondrej; Saksl, Karel; Heželová, Mária; Smrčová, Miroslava; Puliš, Pavel; Michalik, Štefan; Gamcová, Jana

2014-01-01

Nano-palladium catalysts, prepared using the same procedure with the same metal content (3 wt%) and two different supports, activated carbon (Pd/C) and activated carbon—multiwalled carbon nanotubes (Pd/C/CNT), are discussed. The simple technique of deposition reduction was applied in the preparation of these two types of Pd catalysts. TEM, XRD analysis, EXAFS signal analysis, and XANES were used for sample characterization. In both samples, transmission electron microscopy identified nanosized Pd particles with nearly spherical morphology but different sizes. The mean diameters of the particles on Pd/C and Pd/C/CNT were estimated to be 5.4 nm and 7.8 nm, respectively. The EXAFS signal analysis showed that Pd atoms on the particle surfaces were coordinated by 4 oxygens to form a PdO monolayer covering a metallic core. The XANES signal analysis indicated a smaller particle size for Pd/C (∅ 5 nm) than for Pd/C/CNT (∅ 10 nm), in good agreement with the TEM observations. - Graphical abstract: Visualization of metallic core (left), oxide monolayer (middle) and nanoparticle of diameter 5 nm (right). - Highlights: • Pd catalysts were prepared on two types of supports: carbon and carbon nanotubes. • BET, TEM, XRD characterization of prepared catalysts. • XAFS: Concentration of Pd in samples Pd/C and Pd/C/CNT. • EXAFS and XANES signal analysis of catalysts. • Visualisation of atoms arrangement at the Pd nanoparticle surface

Transition metal borides. Synthesis, characterization and superconducting properties

Energy Technology Data Exchange (ETDEWEB)

Kayhan, Mehmet

2013-07-12

A systematic study was done on the synthesis and superconducting properties of metal rich transition metal borides. Five different binary systems were investigated including the boride systems of niobium, tantalum, molybdenum, tungsten and rhenium. High temperature solid state methods were used in order to synthesize samples of different transition metal borides of the composition M{sub 2}B, MB, M{sub 3}B{sub 2}, MB{sub 2}, and M{sub 2}B{sub 4}. The reactions were carried out in three different furnaces with different sample containers: the electric arc (copper crucible), the high frequency induction furnace (boron nitride, tantalum or glassy carbon crucibles), and the conventional tube furnace (sealed evacuated quartz ampoules). The products obtained were characterized with X-ray powder diffractometry, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Phase analyses and crystal structure refinements using the Rietveld method and based on structure models known from literature were performed. A neutron diffraction measurement was done for W{sub 2}B{sub 4} to allow for a complete crystal structure determination, because of the presence of a heavy element like tungsten and a light element like boron that made it difficult to determine the accurate determination of the boron atom positions and occupancies from X-ray data. A new structure model for W{sub 2}B{sub 4} was proposed. Magnetic measurements in a SQUID magnetometer down to temperatures as low as 1.8 K were performed to several of the products in order to see if the transition metal borides become superconducting at low temperatures, and the results were compared with data from literature. Superconducting properties were found for the following compounds: NbB{sub 2} (T{sub C} = 3.5 K), β-MoB (T{sub C} = 2.4 K), β-WB (T{sub C} = 2.0 K), α-WB (T{sub C} = 4.3 K), W{sub 2}B{sub 4} (T{sub C} = 5.4 K), Re{sub 7}B{sub 3} (T{sub C} = 2.4 K). A relationship between the superconducting properties

Gases and carbon in metals. Pt. 14

International Nuclear Information System (INIS)

Jehn, H.; Speck, H.; Hehn, W.; Fromm, E.; Hoerz, G.

1981-01-01

This issue is part of a series of data on 'Gases and Carbon in Metals' which supplements the data compilation in the book 'Gase und Kohlenstoff in Metallen' (Gases and Carbon in Metals), edited by E. Fromm and E. Gebhardt, Springer-Verlag, Berlin 1976. The present survey includes results from papers published after the copy deadline and recommends critically selected data. Furthermore, it comprises a bibliography of relevant literature. For each element, firstly data on binary systems are presented, starting with hydrogen and followed by carbon, nitrogen, oxygen, and rare gases. Within one metal-metalloid system the data are listed under topics such as solubility, solubility limit, dissociation pressure of compounds, vapour pressure of volatile oxides, thermodynamic data, diffusion, transport parameters (effective valence, heat of transport), permeation of gases through metals, gas absorption and gas desorption kinetics, compound formation kinetics, precipitation kinetics, and property changes. Following the data on binary systems, the data of ternary systems are presented, beginning with systems which contain one metal and two gases or one gas and carbon and continuing with systems with two metals and one gas or carbon. (orig./GE)

Electron Spin Resonance Studies of Carbonic Anhydrase: Transition Metal Ions and Spin-Labeled Sulfonamides*

Science.gov (United States)

Taylor, June S.; Mushak, Paul; Coleman, Joseph E.

1970-01-01

Electron spin resonance (esr) spectra of Cu(II) and Co(II) carbonic anhydrase, and a spin-labeled sulfonamide complex of the Zn(II) enzyme, are reported. The coordination geometry of Cu(II) bound in the enzyme appears to have approximately axial symmetry. Esr spectra of enzyme complexes with metal-binding anions also show axial symmetry and greater covalency, in the order ethoxzolamide cyanide complex suggests the presence of two, and probably three, equivalent nitrogen ligands from the protein. Esr spectra of the Co(II) enzyme and its complexes show two types of Co(II) environment, one typical of the native enzyme and the 1:1 CN- complex, and one typical of a 2:1 CN- complex. Co(II) in the 2:1 complex appears to be low-spin and probably has a coordination number of 5. Binding of a spin-labeled sulfonamide to the active center immobilizes the free radical. The similarity of the esr spectra of spin-labeled Zn(II) and Co(II) carbonic anhydrases suggests that the conformation at the active center is similar in the two metal derivatives. PMID:4320976

Carbonation of metal silicates for long-term CO2 sequestration

Science.gov (United States)

Blencoe, James G; Palmer, Donald A; Anovitz, Lawrence M; Beard, James S

2014-03-18

In a preferred embodiment, the invention relates to a process of sequestering carbon dioxide. The process comprises the steps of: (a) reacting a metal silicate with a caustic alkali-metal hydroxide to produce a hydroxide of the metal formerly contained in the silicate; (b) reacting carbon dioxide with at least one of a caustic alkali-metal hydroxide and an alkali-metal silicate to produce at least one of an alkali-metal carbonate and an alkali-metal bicarbonate; and (c) reacting the metal hydroxide product of step (a) with at least one of the alkali-metal carbonate and the alkali-metal bicarbonate produced in step (b) to produce a carbonate of the metal formerly contained in the metal silicate of step (a).

Metal-doped single-walled carbon nanotubes and production thereof

Science.gov (United States)

Dillon, Anne C.; Heben, Michael J.; Gennett, Thomas; Parilla, Philip A.

2007-01-09

Metal-doped single-walled carbon nanotubes and production thereof. The metal-doped single-walled carbon nanotubes may be produced according to one embodiment of the invention by combining single-walled carbon nanotube precursor material and metal in a solution, and mixing the solution to incorporate at least a portion of the metal with the single-walled carbon nanotube precursor material. Other embodiments may comprise sputter deposition, evaporation, and other mixing techniques.

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

International Nuclear Information System (INIS)

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

2005-01-01

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

On monosubstituted cyanurate complexes of transition metals

International Nuclear Information System (INIS)

Sejfer, G.B.; Tarasova, Z.A.

1995-01-01

Complex monosubstituted cyanurates of transition metals K 2 [Eh(H 2 C 3 N 3 O 3 ) 4 ]x4H 2 ) where Eh = Mn, Co, Ni, Cu, Zn, Cd are synthesized and investigated by means of IR - spectroscopy and thermal analysis methods. It is shown that only thermal decomposition of a manganese complex leads to the production of this metal oxide. All other derivatives decompose with the production of a free metal, because decomposition of these substances in argon atmosphere occurs through an intermediate production of their nitrides. An assumption is made that nitroduction of yttrium or rare earth element salts (instead of transition or alkali metal derivatives) as accelerating additions will facilitate increase of polyisocyanurate resin thermal stability. 25 refs.; 2 figs.; 3 tabs

Preparation and characterization of several transition metal oxides

International Nuclear Information System (INIS)

Wold, A.; Dwight, K.

1989-01-01

The structure-property relationships of several conducting transition metal oxides, as well as their preparative methods, are presented in this paper. The importance of preparing homogeneous phases with precisely known stoichiometry is emphasized. A comparison is also made of the various techniques used to prepare both polycrystalline and single crystal samples. For transition metal oxides, the metallic properties are discussed either in terms of metal-metal distances which are short enough to result in metallic behavior, or in terms of the formation of a π* conduction band resulting from covalent metal-oxygen interactions. Metallic behavior is observed when the conduction bands are populated with either electrons or holes. The concentration of these carriers can be affected by either cation or anion substitutions. The discussion in this presentation will be limited to the elements Re, Ti, V, Cr, Mo, and Cu

A monetary plan for upgrading climate finance and support the low-carbon transition

International Nuclear Information System (INIS)

Hourcade, Jean Charles; Cassen, Christophe

2015-01-01

This article examines how carbon finance can be part of a general reform of the financial system. Climate policies can indeed stimulate a sustainable and inclusive climate finance, in line with the call of the Cancun Agreement for a paradigm shift in climate negotiations. The mechanism described in this article is based on the adoption by Parties to the negotiations of a social value of carbon to trigger a wave of low-carbon investments in the world. Central banks offer credit lines for commercial banks backed by this social value of carbon, which are then used to cut the risk to invest in low- carbon investments. A future agreement in Paris next year should support this type of mechanisms.

Thermal behaviour of nicotinic acid, sodium nicotinate and its compounds with some bivalent transition metal ions

Energy Technology Data Exchange (ETDEWEB)

Nascimento, A.L.C.S. do; Caires, F.J., E-mail: caires.flavio@yahoo.com.br; Gomes, D.J.C.; Gigante, A.C.; Ionashiro, M.

2014-01-10

Graphical abstract: - Highlights: • The transition metal ion nicotinates were synthesized. • The TG–DTA curves provided previously unreported information about thermal behaviour. • The gaseous products released were detected by TG–DSC coupled to FTIR. - Abstract: Solid-state M(L){sub 2}·nH{sub 2}O compounds, where M stands for bivalent transition metals (Mn, Fe, Co, Ni, Cu and Zn), L is nicotinate and n = 0–4.5, have been synthesized. Characterization and thermal behaviour of these compounds were investigated employing elemental analysis based on the mass losses observed in the TG–DTA curves, complexometry, X-ray diffractometry, infrared spectroscopy (FTIR), simultaneous thermogravimetric and differential thermal analysis (TG–DTA) and TG–DSC coupled to FTIR. The thermal behaviour of nicotinic acid and its sodium salt was also investigated. For the hydrated transition metal compounds, the dehydration and thermal decomposition of the anhydrous compounds occur in a single step. For the sodium nicotinate, the final residue up to 765 °C is sodium carbonate and for the transition metal nicotinates, the final residues are Mn{sub 3}O{sub 4}, Fe{sub 2}O{sub 3}, Co{sub 3}O{sub 4}, NiO, CuO and ZnO. The results also provided information concerning the thermal stability, thermal decomposition and identification of the gaseous products evolved during the thermal decomposition of the compounds.

Thermal behaviour of nicotinic acid, sodium nicotinate and its compounds with some bivalent transition metal ions

International Nuclear Information System (INIS)

Nascimento, A.L.C.S. do; Caires, F.J.; Gomes, D.J.C.; Gigante, A.C.; Ionashiro, M.

2014-01-01

Graphical abstract: - Highlights: • The transition metal ion nicotinates were synthesized. • The TG–DTA curves provided previously unreported information about thermal behaviour. • The gaseous products released were detected by TG–DSC coupled to FTIR. - Abstract: Solid-state M(L) 2 ·nH 2 O compounds, where M stands for bivalent transition metals (Mn, Fe, Co, Ni, Cu and Zn), L is nicotinate and n = 0–4.5, have been synthesized. Characterization and thermal behaviour of these compounds were investigated employing elemental analysis based on the mass losses observed in the TG–DTA curves, complexometry, X-ray diffractometry, infrared spectroscopy (FTIR), simultaneous thermogravimetric and differential thermal analysis (TG–DTA) and TG–DSC coupled to FTIR. The thermal behaviour of nicotinic acid and its sodium salt was also investigated. For the hydrated transition metal compounds, the dehydration and thermal decomposition of the anhydrous compounds occur in a single step. For the sodium nicotinate, the final residue up to 765 °C is sodium carbonate and for the transition metal nicotinates, the final residues are Mn 3 O 4 , Fe 2 O 3 , Co 3 O 4 , NiO, CuO and ZnO. The results also provided information concerning the thermal stability, thermal decomposition and identification of the gaseous products evolved during the thermal decomposition of the compounds

A Silicon detector system on carbon fiber support at small radius

International Nuclear Information System (INIS)

Johnson, Marvin E.

2004-01-01

The design of a silicon detector for a p(bar p) collider experiment will be described. The detector uses a carbon fiber support structure with sensors positioned at small radius with respect to the beam. A brief overview of the mechanical design is given. The emphasis is on the electrical characteristics of the detector. General principles involved in grounding systems with carbon fiber structures will be covered. The electrical characteristics of the carbon fiber support structure will be presented. Test results imply that carbon fiber must be regarded as a conductor for the frequency region of interest of 10 to 100 MHz. No distinction is found between carbon fiber and copper. Performance results on noise due to pick-up through the low mass fine pitch cables carrying the analogue signals and floating metal is discussed

James C. McGroddy Prize Talk: Superconductivity in alkali-metal doped Carbon-60

Science.gov (United States)

Hebard, Arthur

2008-03-01

Carbon sixty (C60), which was first identified in 1985 in laser desorption experiments, is unquestionably an arrestingly beautiful molecule. The high symmetry of the 12 pentagonal and 20 hexagonal faces symmetrically arrayed in a soccer-ball like structure invites special attention and continues to stimulate animated speculation. The availability in 1990 of macroscopic amounts of purified C60 derived from carbon-arc produced soot allowed the growth and characterization of both bulk and thin-film samples. Crystalline C60 is a molecular solid held together by weak van der Waals forces. The fcc structure has a 74% packing fraction thus allowing ample opportunity (26% available volume) for the intercalation of foreign atoms into the interstitial spaces of the three dimensional host. This opportunity catalyzed much of the collaborative work amongst chemists, physicists and materials scientists at Bell Laboratories, and resulted in the discovery of superconductivity in alkali-metal doped C60 with transition temperatures (Tc) in the mid-30-kelvin range. In this talk I will review how the successes of this initial team effort stimulated a worldwide collaboration between experimentalists and theorists to understand the promise and potential of an entirely new class of superconductors containing only two elements, carbon and an intercalated alkali metal. Although the cuprates still hold the record for the highest Tc, there are still open scientific questions about the mechanism that gives rise to such unexpectedly high Tc's in the non-oxide carbon-based superconductors. The doped fullerenes have unusual attributes (e.g., narrow electronic bands, high disorder, anomalous energy scales, and a tantalizing proximity to a metal-insulator Mott transition), which challenge conventional thinking and at the same time provide useful insights into new directions for finding even higher Tc materials. The final chapter of the `soot to superconductivity' story has yet to be written.

Harnessing the metal-insulator transition for tunable metamaterials

Science.gov (United States)

Charipar, Nicholas A.; Charipar, Kristin M.; Kim, Heungsoo; Bingham, Nicholas S.; Suess, Ryan J.; Mathews, Scott A.; Auyeung, Raymond C. Y.; Piqué, Alberto

2017-08-01

The control of light-matter interaction through the use of subwavelength structures known as metamaterials has facilitated the ability to control electromagnetic radiation in ways not previously achievable. A plethora of passive metamaterials as well as examples of active or tunable metamaterials have been realized in recent years. However, the development of tunable metamaterials is still met with challenges due to lack of materials choices. To this end, materials that exhibit a metal-insulator transition are being explored as the active element for future metamaterials because of their characteristic abrupt change in electrical conductivity across their phase transition. The fast switching times (▵t < 100 fs) and a change in resistivity of four orders or more make vanadium dioxide (VO2) an ideal candidate for active metamaterials. It is known that the properties associated with thin film metal-insulator transition materials are strongly dependent on the growth conditions. For this work, we have studied how growth conditions (such as gas partial pressure) influence the metalinsulator transition in VO2 thin films made by pulsed laser deposition. In addition, strain engineering during the growth process has been investigated as a method to tune the metal-insulator transition temperature. Examples of both the optical and electrical transient dynamics facilitating the metal-insulator transition will be presented together with specific examples of thin film metamaterial devices.

Impurities in Antiferromagnetic Transition-Metal Oxides - Symmetry and Optical Transitions

Science.gov (United States)

Petersen, John Emil, III

The study of antiferromagnetic transition-metal oxides is an extremely active area in the physical sciences, where condensed matter physics, inorganic chemistry, and materials science blend together. The sheer number of potential commercial applications is staggering, but much of the fundamental science remains unexplained. This is not due to a lack of effort, however, as theorists have been struggling to understand these materials for decades - particularly the character of the band edges and first optical transitions. The difficulty lies in the strong correlation or Coloumb attraction between the electrons in the anisotropic d orbitals, which conventional band theory cannot describe adequately. The correlation problem is approached here by the well-accepted method of adding a Hubbard potential energy term to the ground state Hamiltonian, calculated within Density Functional Theory. The frequency-dependent complex dielectric function is calculated within the Independent Particle Approximation, and optical transitions are evaluated in multiple different ways. Peaks in the imaginary part of the dielectric function are compared energetically to orbitally decomposed density of states calculations. Optical transitions are typically analyzed in terms of atomic orbitals, which, strictly speaking, gives misleading results. Here, however, from the calculated data, two alternative interpretations are analyzed for each material studied. The first employs rigorous group theoretical analysis to determine allowed electric-dipole transitions, taking into account both orbital hybridization and crystal symmetry. The second interpretation is that of metal cation site hopping. In this interpretation, carriers hop from the x2 - y2 d orbital of one metal cation lattice site to the next metal cation site which is antiferromagnetically aligned. At times, thoughout this work, one interpretation is favorable to the other. Which interpretation is most valid depends on the material

Superconductor-Metal-Insulator transition in two dimensional Ta thin Films

Science.gov (United States)

Park, Sun-Gyu; Kim, Eunseong

2013-03-01

Superconductor-insulator transition has been induced by tuning film thickness or magnetic field. Recent electrical transport measurements of MoGe, Bi, Ta thin films revealed an interesting intermediate metallic phase which intervened superconducting and insulating phases at certain range of magnetic field. Especially, Ta thin films show the characteristic IV behavior at each phase and the disorder tuned intermediate metallic phase [Y. Li, C. L. Vicente, and J. Yoon, Physical Review B 81, 020505 (2010)]. This unexpected metallic phase can be interpreted as a consequence of vortex motion or contribution of fermionic quasiparticles. In this presentation, we report the scaling behavior during the transitions in Ta thin film as well as the transport measurements in various phases. Critical exponents v and z are obtained in samples with wide ranges of disorder. These results reveal new universality class appears when disorder exceeds a critical value. Dynamical exponent z of Superconducting sample is found to be 1, which is consistent with theoretical prediction of unity. z in a metallic sample is suddenly increased to be approximately 2.5. This critical exponent is much larger than the value found in other system and theoretical prediction. We gratefully acknowledge the financial support by the National Research Foundation of Korea through the Creative Research Initiatives.

Investigation of metal/carbon-related materials for fuel cell applications by electronic structure calculations

Energy Technology Data Exchange (ETDEWEB)

Kong, Ki-jeong [Korea Research Institute of Chemical Technology, P.O.Box 107, Yuseong, Daejeon 305-600 (Korea, Republic of)]. E-mail: kong@krict.re.kr; Choi, Youngmin [Korea Research Institute of Chemical Technology, P.O.Box 107, Yuseong, Daejeon 305-600 (Korea, Republic of); Ryu, Beyong-Hwan [Korea Research Institute of Chemical Technology, P.O.Box 107, Yuseong, Daejeon 305-600 (Korea, Republic of); Lee, Jeong-O [Korea Research Institute of Chemical Technology, P.O.Box 107, Yuseong, Daejeon 305-600 (Korea, Republic of); Chang, Hyunju [Korea Research Institute of Chemical Technology, P.O.Box 107, Yuseong, Daejeon 305-600 (Korea, Republic of)

2006-07-15

The potential of carbon-related materials, such as carbon nanotubes (CNTs) and graphite nanofibers (GNFs), supported metal catalysts as an electrode for fuel cell application was investigated using the first-principle electronic structure calculations. The stable binding geometries and energies of metal catalysts are determined on the CNT surface and the GNF edge. The catalyst metal is more tightly bound to the GNF edge than to the CNT surface because of the existence of active dangling bonds of edge carbon atoms. The diffusion barrier of metal atoms on the surface and edge is also obtained. From our calculation results, we have found that high dispersity is achievable for GNF due to high barrier against the diffusion of metal atoms, while CNT appears less suitable. The GNF with a large edge-to-wall ratio is more suitable for the high-performance electrode than perfect crystalline graphite or CNT.

Investigation of metal/carbon-related materials for fuel cell applications by electronic structure calculations

International Nuclear Information System (INIS)

Kong, Ki-jeong; Choi, Youngmin; Ryu, Beyong-Hwan; Lee, Jeong-O; Chang, Hyunju

2006-01-01

The potential of carbon-related materials, such as carbon nanotubes (CNTs) and graphite nanofibers (GNFs), supported metal catalysts as an electrode for fuel cell application was investigated using the first-principle electronic structure calculations. The stable binding geometries and energies of metal catalysts are determined on the CNT surface and the GNF edge. The catalyst metal is more tightly bound to the GNF edge than to the CNT surface because of the existence of active dangling bonds of edge carbon atoms. The diffusion barrier of metal atoms on the surface and edge is also obtained. From our calculation results, we have found that high dispersity is achievable for GNF due to high barrier against the diffusion of metal atoms, while CNT appears less suitable. The GNF with a large edge-to-wall ratio is more suitable for the high-performance electrode than perfect crystalline graphite or CNT

Metal-insulator transition in vanadium dioxide

International Nuclear Information System (INIS)

Zylbersztejn, A.; Mott, N.F.

1975-01-01

The basic physical parameters which govern the metal-insulator transition in vanadium dioxide are determined through a review of the properties of this material. The major importance of the Hubbard intra-atomic correlation energy in determining the insulating phase, which was already evidence by studies of the magnetic properties of V 1 -/subx/Cr/subx/O 2 alloys, is further demonstrated from an analysis of their electrical properties. An analysis of the magnetic susceptibility of niobium-doped VO 2 yields a picture for the current carrier in the low-temperature phase in which it is accompanied by a spin cloud (owing to Hund's-rule coupling), and has therefore an enhanced mass (m approx. = 60m 0 ). Semiconducting vanadium dioxide turns out to be a borderline case for a classical band-transport description; in the alloys at high doping levels, Anderson localization with hopping transport can take place. Whereas it is shown that the insulating phase cannot be described correctly without taking into account the Hubbard correlation energy, we find that the properties of the metallic phase are mainly determined by the band structure. Metallic VO 2 is, in our view, similar to transition metals like Pt or Pd: electrons in a comparatively wide band screening out the interaction between the electrons in a narrow overlapping band. The magnetic susceptibility is described as exchange enhanced. The large density of states at the Fermi level yields a substantial contribution of the entropy of the metallic electrons to the latent heat. The crystalline distortion removes the band degeneracy so that the correlation energy becomes comparable with the band width and a metal-insulator transition takes place

First principles calculations and experimental insight into methane steam reforming over transition metal catalysts

DEFF Research Database (Denmark)

Jones, Glenn; Jakobsen, Jon Geest; Shim, Signe Sarah

2008-01-01

This paper presents a detailed analysis of the steam reforming process front first-principles calculations, supported by insight from experimental investigations. In the present work we employ recently recognised scaling relationships for adsorption energies of simple molecules adsorbed at pure...... metal Surfaces to develop an overview of the steam reforming process catalyzed by a range of transition metal surfaces. By combining scaling relationships with thermodynamic and kinetic analysis, we show that it is possible to determine the reactivity trends of the pure metals for methane steam...... in situ TEM measurements under a hydrogen atmosphere. The overall agreement between theory and experiment (at 773 K, 1 bar pressure and 10% conversion) is found to be excellent with Ru and Rh being the most active pure transition metals for methane steam reforming, while Ni, Ir, Pt, and Pd...

Selenophene transition metal complexes

Energy Technology Data Exchange (ETDEWEB)

White, Carter James [Iowa State Univ., Ames, IA (United States)

1994-07-27

This research shows that selenophene transition metal complexes have a chemistry that is similar to their thiophene analogs. Selenophene coordination has been demonstrated and confirmed by molecular structure in both the η⁵- and the η¹(Se)-coordination modes. The reaction chemistry of selenophene complexes closely resembles that of the analogous thiophene complexes. One major difference, however, is that selenophene is a better donor ligand than thiophene making the selenophene complexes more stable than the corresponding thiophene complexes. The ⁷⁷Se NMR chemical shift values for selenophene complexes fall within distinct regions primarily depending on the coordination mode of the selenophene ligand. In the final paper, the C-H bond activation of η¹(S)-bound thiophenes, η¹(S)-benzothiophene and η¹(Se)-bound selenophenes has been demonstrated. The deprotonation and rearrangement of the η¹(E)-bound ligand to the carbon bound L-yl complex readily occurs in the presence of base. Reprotonation with a strong acid gives a carbene complex that is unreactive towards nucleophilic attack at the carbene carbon and is stable towards exposure to air. The molecular structure of [Cp(NO)(PPh₃)Re(2-benzothioenylcarbene)]O₃SCF₃ was determined and contains a Re-C bond with substantial double bond character. Methyl substitution for the thienylcarbene or selenylcarbene gives a carbene that rearranges thermally to give back the η¹(E)-bound complex. Based on these model reactions, a new mechanism for the H/D exchange of thiophene over the hydrodesulfurization catalyst has been proposed.

Synthesis of carbon nanotubes bridging metal electrodes

International Nuclear Information System (INIS)

Kotlar, M.; Vojs, M.; Marton, M.; Vesel, M.; Redhammer, R.

2012-01-01

In our work we demonstrate growth of carbon nanotubes that can conductively bridge the metal electrodes. The role of different catalysts was examined. Interdigitated metal electrodes are made from copper and we are using bimetal Al/Ni as catalyst for growth of carbon nanotubes. We are using this catalyst composition for growth of the single-walled carbon nanotube network. (authors)

Carbon outcomes of major land-cover transitions in SE Asia

DEFF Research Database (Denmark)

Ziegler, Alan D.; Phelps, Jacob; Yuen, Jia Qi

2012-01-01

Policy makers across the tropics propose that carbon finance could provide incentives for forest frontier communities to transition away from swidden agriculture (slash-and-burn or shifting cultivation) to other systems that potentially reduce emissions and/or increase carbon sequestration. However......-use regimes optimize or increase carbon sequestration. As some transitions may negatively impact other ecosystem services, food security, and local livelihoods, the entire carbon and noncarbon benefit stream should also be taken into account before prescribing transitions with ambiguous carbon benefits...

Metal interactions with boron clusters

International Nuclear Information System (INIS)

Grimes, R.N.

1982-01-01

This book presents information on the following topics: the structural and bonding features of metallaboranes and metallacarboranes; transition-metal derivatives of nido-boranes and some related species; interactions of metal groups with the octahydrotriborate (1-) anion, B 3 H 8 ; metallaboron cage compounds of the main group metals; closo-carborane-metal complexes containing metal-carbon and metal-boron omega-bonds; electrochemistry of metallaboron cage compounds; and boron clusters with transition metal-hydrogen bonds

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

Science.gov (United States)

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.

Structurally triggered metal-insulator transition in rare-earth nickelates.

Science.gov (United States)

Mercy, Alain; Bieder, Jordan; Íñiguez, Jorge; Ghosez, Philippe

2017-11-22

Rare-earth nickelates form an intriguing series of correlated perovskite oxides. Apart from LaNiO 3 , they exhibit on cooling a sharp metal-insulator electronic phase transition, a concurrent structural phase transition, and a magnetic phase transition toward an unusual antiferromagnetic spin order. Appealing for various applications, full exploitation of these compounds is still hampered by the lack of global understanding of the interplay between their electronic, structural, and magnetic properties. Here we show from first-principles calculations that the metal-insulator transition of nickelates arises from the softening of an oxygen-breathing distortion, structurally triggered by oxygen-octahedra rotation motions. The origin of such a rare triggered mechanism is traced back in their electronic and magnetic properties, providing a united picture. We further develop a Landau model accounting for the metal-insulator transition evolution in terms of the rare-earth cations and rationalizing how to tune this transition by acting on oxygen rotation motions.

Coprecipitation of alkali metal ions with calcium carbonate

International Nuclear Information System (INIS)

Okumura, Minoru; Kitano, Yasushi

1986-01-01

The coprecipitation of alkali metal ions Li + , Na + , K + and Rb + with calcium carbonate has been studied experimentally and the following results have been obtained: (1) Alkali metal ions are more easily coprecipitated with aragonite than with calcite. (2) The relationship between the amounts of alkali metal ions coprecipitated with aragonite and their ionic radii shows a parabolic curve with a peak located at Na + which has approximately the same ionic radius as Ca 2+ . (3) However, the amounts of alkali metal ions coprecipitated with calcite decrease with increasing ionic radius of alkali metals. (4) Our results support the hypothesis that (a) alkali metals are in interstitial positions in the crystal structure of calcite and do not substitute for Ca 2+ in the lattice, but (b) in aragonite, alkali metals substitute for Ca 2+ in the crystal structure. (5) Magnesium ions in the parent solution increase the amounts of alkali metal ions (Li + , Na + , K + and Rb + ) coprecipitated with calcite but decrease those with aragonite. (6) Sodium-bearing aragonite decreases the incorporation of other alkali metal ions (Li + , K + and Rb + ) into the aragonite. (author)

Metal Oxide-Supported Platinum Overlayers as Proton-Exchange Membrane Fuel Cell Cathodes

DEFF Research Database (Denmark)

Tripkovic, Vladimir; Abild-Pedersen, Frank; Studt, Felix

2012-01-01

We investigated the activity and stability of n=(1, 2, 3) platinum layers supported on a number of rutile metal oxides (MO2; M=Ti, Sn, Ta, Nb, Hf and Zr). A suitable oxide support can alleviate the problem of carbon corrosion and platinum dissolution in Pt/C catalysts. Moreover, it can increase t...

High-frequency EPR on high-spin transition-metal sites

NARCIS (Netherlands)

Mathies, Guinevere

2012-01-01

The electronic structure of transition-metal sites can be probed by electron-paramagnetic-resonance (EPR) spectroscopy. The study of high-spin transition-metal sites benefits from EPR spectroscopy at frequencies higher than the standard 9.5 GHz. However, high-frequency EPR is a developing field. In

Metallacyclopentadienes: structural features and coordination in transition metal complexes

International Nuclear Information System (INIS)

Dolgushin, Fedor M; Yanovsky, Aleksandr I; Antipin, Mikhail Yu

2004-01-01

Results of structural studies of polynuclear transition metal complexes containing the metallacyclopentadiene fragment are overviewed. The structural features of the complexes in relation to the nature of the substituents in the organic moiety of the metallacycles, the nature of the transition metals and their ligand environment are analysed. The main structural characteristics corresponding to different modes of coordination of metallacyclopentadienes to one or two additional metal centres are revealed.

Carbonation of metal silicates for long-term CO.sub.2 sequestration

Energy Technology Data Exchange (ETDEWEB)

Blencoe, James G.; Palmer, Donald A.; Anovitz, Lawrence M.; Beard, James S.

2017-08-01

In a preferred embodiment, the invention relates to a process of sequestering carbon dioxide. The process comprises the steps of: (a) reacting a metal silicate with a caustic alkali-metal hydroxide to produce a hydroxide of the metal formerly contained in the silicate; (b) reacting carbon dioxide with at least one of a caustic alkali-metal hydroxide and an alkali-metal silicate to produce at least one of an alkali-metal carbonate and an alkali-metal bicarbonate; and (c) reacting the metal hydroxide product of step (a) with at least one of the alkali-metal carbonate and the alkali-metal bicarbonate produced in step (b) to produce a carbonate of the metal formerly contained in the metal silicate of step (a).

Carbonation of metal silicates for long-term CO.sub.2 sequestration

Science.gov (United States)

Blencoe, James G [Harriman, TN; Palmer, Donald A [Oliver Springs, TN; Anovitz, Lawrence M [Knoxville, TN; Beard, James S [Martinsville, VA

2012-02-14

In a preferred embodiment, the invention relates to a process of sequestering carbon dioxide. The process comprises the steps of: (a) reacting a metal silicate with a caustic alkali-metal hydroxide to produce a hydroxide of the metal formerly contained in the silicate; (b) reacting carbon dioxide with at least one of a caustic alkali-metal hydroxide and an alkali-metal silicate to produce at least one of an alkali-metal carbonate and an alkali-metal bicarbonate; and (c) reacting the metal hydroxide product of step (a) with at least one of the alkali-metal carbonate and the alkali-metal bicarbonate produced in step (b) to produce a carbonate of the metal formerly contained in the metal silicate of step (a).

Critical Metals in Strategic Low-carbon Energy Technologies

Science.gov (United States)

Moss, R. L.

2012-04-01

Due to the rapid growth in demand for certain materials, compounded by political risks associated with the geographical concentration of the supply of them, shortages of materials could be a potential bottleneck to the deployment of low-carbon energy technologies. Consequently, an assessment has been carried out to ascertain whether such shortages could jeopardise the objectives of the EU's Strategic Energy Technology Plan (SET-Plan), especially in the six low-carbon energy technologies of SET-Plan, namely: nuclear, solar, wind, bioenergy, carbon capture and storage (CCS) and electricity grids. The assessment identified 14 metals for which the deployment of the six technologies will require 1% or more (and in some cases, much more) of current world supply per annum between 2020 and 2030. Following a more critical examination, based on the likelihood of rapid future global demand growth, limitations to expanding supply in the short to medium term, and the concentration of supply and political risks associated with key suppliers, 5 of the 14 metals were pinpointed to be at high risk, namely: the rare earth metals neodymium and dysprosium (for wind technology), and the by-products (from the processing of other metals) indium, tellurium and gallium (for photovoltaic technologies). In addition, the work has explored potential mitigation strategies, ranging from expanding European output, increasing recycling and reuse to reducing waste and finding substitutes for these metals in their main applications. Furthermore, recommendations are provided which include closely working with the EU's Raw Materials Initiative; supporting efforts to ensure reliable supply of ore concentrates at competitive prices; promoting R&D and demonstration projects on new lower cost separation processes; and promoting the further development of recycling technologies and increasing end-of-life collection

Mapping of the carbon transition. Executive summary

International Nuclear Information System (INIS)

Le Teno, Helene

2013-01-01

The carbon transition is an ambitious collective project aimed at changing models of production and consumption. The transition is already underway, and will call for substantial investment over the coming decade. All the actors in the field must be mobilized, and indeed, the transition is itself a major lever for driving the development of territorial entities. The Shift Project has decided to map out the carbon transition, as a way of informing political decision-makers of the main outcomes at stake and the anticipated impacts of a transition plan, in terms of job creation, purchasing power and lower energy bills. This mapping also gives them a toolbox, with ideas for action and a set of tools for financing the transition. This research project aims both to convince decision-makers that a transition plan is worthwhile, and to illustrate the means that can be deployed to achieve this transition. These include experimentation, innovation, suitable financing plans, dynamic cooperation between local actors, and positive communication to present this project as 'desirable'

Mesoporous Transition Metal Oxides for Supercapacitors

OpenAIRE

Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

2015-01-01

Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are result...

On the effect of coverage-dependent adsorbate-adsorbate interactions for CO methanation on transition metal surfaces

DEFF Research Database (Denmark)

Lausche, Adam C.; Medford, Andrew J.; Khan, Tuhin Suvra

2013-01-01

with a high coverage of CO. At these high coverages, reaction intermediates experience interaction effects that typically reduce their adsorption energies. Herein, the effect of these interactions on the activities of transition metals for CO methanation is investigated. For transition metals that have low...... coverages of reactants, the effect is minimal. But for materials with high coverages under reaction conditions, rates can change by several orders of magnitude. Nevertheless, the position of the maximum of the activity volcano does not shift significantly, and the rates at the maximum are only slightly......Heterogeneously catalyzed reactions involving the dissociation of strongly bonded molecules typically need quite reactive catalysts with high coverages of intermediate molecules. Methanation of carbon monoxide is one example, where CO dissociation has been reported to take place on step sites...

Mainstreaming Low-Carbon Climate-Resilient growth pathways into Development Finance Institutions' activities. A research project on the standards, tools and metrics to support transition to the low-carbon climate-resilient development models. Paper 1 - Climate and development finance institutions: linking climate finance, development finance and the transition to low-carbon, climate-resilient economic models

International Nuclear Information System (INIS)

Eschalier, Claire; Cochran, Ian; Deheza, Mariana; Risler, Ophelie; Forestier, Pierre

2015-10-01

Development finance institutions (DFIs) are in a position to be key actors in aligning development and the 2 deg. challenge. One of the principal challenges today is to scale-up the financial flows to the trillions of dollars per year necessary to achieve the 2 deg. C long-term objectives. Achieving this transition to a low-carbon, climate resilient (LCCR) economic model requires the integration or 'mainstreaming' of climate issues as a prism through which all investment decisions should be made. This paper presents an overview of the opportunities and challenges of linking a LCCR transition with the objectives of development finance. It first presents the two-fold challenge of climate change and development for countries around the world. Second, the paper explores the role of development finance institutions and their support for the transition to a low-carbon, climate-resilient economic model. Finally, it examines a necessary paradigm shift to integrate climate and development objectives to establish a 'LCCR development model' able to simultaneously tackling development priorities and needs for resilient, low-carbon growth. This will necessitate a move from focusing on a 'siloed' vision of climate finance to a means of aligning activities across the economy with the LCCR objectives to ensure that the majority of investments are coherent with this long-term transition. (authors)

Laser-driven coating of vertically aligned carbon nanotubes with manganese oxide from metal organic precursors for energy storage

Science.gov (United States)

Pérez del Pino, A.; György, E.; Alshaikh, I.; Pantoja-Suárez, F.; Andújar, J. L.; Pascual, E.; Amade, R.; Bertran-Serra, E.

2017-09-01

Carbon nanotubes-transition metal oxide systems are intensively studied due to their excellent properties for electrochemical applications. In this work, an innovative procedure is developed for the synthesis of vertically aligned multi-walled carbon nanotubes (VACNTs) coated with transition metal oxide nanostructures. VACNTs are grown by plasma enhanced chemical vapor deposition and coated with a manganese-based metal organic precursor (MOP) film based on manganese acetate solution. Subsequent UV pulsed laser irradiation induces the effective heating-decomposition of the MOP leading to the crystallization of manganese oxide nanostructures on the VACNT surface. The study of the morphology, structure and composition of the synthesized materials shows the formation of randomly oriented MnO2 crystals, with few nanometers in size, and to their alignment in hundreds of nm long filament-like structures, parallel to the CNT’s long axis. Electrochemical measurements reveal a significant increase of the specific capacitance of the MnO2-VACNT system (100 F g-1) as compared to the initial VACNT one (21 F g-1).

Stable isotopes of transition and post-transition metals as tracers in environmental studies

Science.gov (United States)

Bullen, Tomas D.; Baskaran, Mark

2011-01-01

The transition and post-transition metals, which include the elements in Groups 3–12 of the Periodic Table, have a broad range of geological and biological roles as well as industrial applications and thus are widespread in the environment. Interdisciplinary research over the past decade has resulted in a broad understanding of the isotope systematics of this important group of elements and revealed largely unexpected variability in isotope composition for natural materials. Significant kinetic and equilibrium isotope fractionation has been observed for redox sensitive metals such as iron, chromium, copper, molybdenum and mercury, and for metals that are not redox sensitive in nature such as cadmium and zinc. In the environmental sciences, the isotopes are increasingly being used to understand important issues such as tracing of metal contaminant sources and fates, unraveling metal redox cycles, deciphering metal nutrient pathways and cycles, and developing isotope biosignatures that can indicate the role of biological activity in ancient and modern planetary systems.

Synthesis of IV-VI Transition Metal Carbide and Nitride Nanoparticles Using a Reactive Mesoporous Template for Electrochemical Hydrogen Evolution Reaction

KAUST Repository

Alhajri, Nawal Saad

2016-01-01

Interstitial carbides and nitrides of early transition metals in Groups IV-VI exhibit platinum-like behavior which makes them a promising candidate to replace noble metals in a wide variety of reactions. Most synthetic methods used to prepare these materials lead to bulk or micron size powder which limits their use in reactions in particular in catalytic applications. Attempts toward the production of transition metal carbide and nitride nanoparticles in a sustainable, simple and cheap manner have been rapidly increasing. In this thesis, a new approach was presented to prepare nano-scale transition metal carbides and nitrides of group IV-VI with a size as small as 3 nm through the reaction of transition metal precursor with mesoporous graphitic carbon nitride (mpg-C3N4) that not only provides confined spaces for nanoparticles formation but also acts as a chemical source of nitrogen and carbon. The produced nanoparticles were characterized by powder X-ray diffraction (XRD), temperature-programmed reaction with mass spectroscopy (MS), CHN elemental analyses, thermogravimetric analyses (TGA), nitrogen sorption, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The effects of the reaction temperature, the ratio of the transition metal precursor to the reactive template (mpg-C3N4), and the selection of the carrier gas (Ar, N2, and NH3) on the resultant crystal phases and structures were investigated. The results indicated that different tantalum phases with cubic structure, TaN, Ta2CN, and TaC, can be formed under a flow of nitrogen by changing the reaction temperatures. Two forms of tantalum nitride, namely TaN and Ta3N5, were selectively formed under N2 and NH3 flow, respectively. Significantly, the formation of TaC, Ta2CN, and TaN can be controlled by altering the weight ratio of the C3N4 template relative to the Ta precursor at 1573 K under a flow of nitrogen where high C3N4/Ta precursor ratio generally resulted in high carbide

2D to 3D transition of polymeric carbon nitride nanosheets

Energy Technology Data Exchange (ETDEWEB)

Chamorro-Posada, Pedro [Dpto. de Teoría de la Señal y Comunicaciones e IT, Universidad de Valladolid, ETSI Telecomunicación, Paseo Belén 15, 47011 Valladolid (Spain); Vázquez-Cabo, José [Dpto. de Teoría de la Señal y Comunicaciones, Universidad de Vigo, ETSI Telecomunicación, Lagoas Marcosende s/n, Vigo (Spain); Sánchez-Arévalo, Francisco M. [Instituto de Investigaciones en Materiales (IIM), Universidad Nacional Autónoma de México, Apdo. Postal 70–360, Cd. Universitaria, México D.F. 04510 (Mexico); Martín-Ramos, Pablo [Dpto. de Teoría de la Señal y Comunicaciones e IT, Universidad de Valladolid, ETSI Telecomunicación, Paseo Belén 15, 47011 Valladolid (Spain); Laboratorio de Materiales Avanzados (Advanced Materials Laboratory) ETSIIAA, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain); Martín-Gil, Jesús; Navas-Gracia, Luis M. [Laboratorio de Materiales Avanzados (Advanced Materials Laboratory) ETSIIAA, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain); Dante, Roberto C., E-mail: rcdante@yahoo.com [Laboratorio de Materiales Avanzados (Advanced Materials Laboratory) ETSIIAA, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain)

2014-11-15

The transition from a prevalent turbostratic arrangement with low planar interactions (2D) to an array of polymeric carbon nitride nanosheets with stronger interplanar interactions (3D), occurring for samples treated above 650 °C, was detected by terahertz-time domain spectroscopy (THz-TDS). The simulated 3D material made of stacks of shifted quasi planar sheets composed of zigzagged polymer ribbons, delivered a XRD simulated pattern in relatively good agreement with the experimental one. The 2D to 3D transition was also supported by the simulation of THz-TDS spectra obtained from quantum chemistry calculations, in which the same broad bands around 2 THz and 1.5 THz were found for 2D and 3D arrays, respectively. This transition was also in accordance with the tightening of the interplanar distance probably due to an interplanar π bond contribution, as evidenced also by a broad absorption around 2.6 eV in the UV–vis spectrum, which appeared in the sample treated at 650 °C, and increased in the sample treated at 700 °C. The band gap was calculated for 1D and 2D cases. The value of 3.374 eV for the 2D case is, within the model accuracy and precision, in a relative good agreement with the value of 3.055 eV obtained from the experimental results. - Graphical abstract: 2D lattice mode vibrations and structural changes correlated with the so called “2D to 3D transition”. - Highlights: • A 2D to 3D transition has been detected for polymeric carbon nitride. • THz-TDS allowed us to discover and detect the 2D to 3D transition of polymeric carbon nitride. • We propose a structure for polymeric carbon nitride confirming it with THz-TDS.

2D to 3D transition of polymeric carbon nitride nanosheets

International Nuclear Information System (INIS)

Chamorro-Posada, Pedro; Vázquez-Cabo, José; Sánchez-Arévalo, Francisco M.; Martín-Ramos, Pablo; Martín-Gil, Jesús; Navas-Gracia, Luis M.; Dante, Roberto C.

2014-01-01

The transition from a prevalent turbostratic arrangement with low planar interactions (2D) to an array of polymeric carbon nitride nanosheets with stronger interplanar interactions (3D), occurring for samples treated above 650 °C, was detected by terahertz-time domain spectroscopy (THz-TDS). The simulated 3D material made of stacks of shifted quasi planar sheets composed of zigzagged polymer ribbons, delivered a XRD simulated pattern in relatively good agreement with the experimental one. The 2D to 3D transition was also supported by the simulation of THz-TDS spectra obtained from quantum chemistry calculations, in which the same broad bands around 2 THz and 1.5 THz were found for 2D and 3D arrays, respectively. This transition was also in accordance with the tightening of the interplanar distance probably due to an interplanar π bond contribution, as evidenced also by a broad absorption around 2.6 eV in the UV–vis spectrum, which appeared in the sample treated at 650 °C, and increased in the sample treated at 700 °C. The band gap was calculated for 1D and 2D cases. The value of 3.374 eV for the 2D case is, within the model accuracy and precision, in a relative good agreement with the value of 3.055 eV obtained from the experimental results. - Graphical abstract: 2D lattice mode vibrations and structural changes correlated with the so called “2D to 3D transition”. - Highlights: • A 2D to 3D transition has been detected for polymeric carbon nitride. • THz-TDS allowed us to discover and detect the 2D to 3D transition of polymeric carbon nitride. • We propose a structure for polymeric carbon nitride confirming it with THz-TDS

Structure and properties of transition metal-metalloid glasses based on refractory metals

International Nuclear Information System (INIS)

Johnson, W.L.; Williams, A.R.

1979-01-01

The structure and properties of several new transition metal-metalloid (TM/sub 1-x/M/sub x/) metallic glasses based on refractory transition metals (e.g. Mo, W, Ru etc.) have been systemically investigated as a function of composition. The structure of the alloys has been investigated by x-ray diffraction methods and measurements of superconducting properties, electrical resistivity, density, hardness, and mechanical behavior were made. These data are used in developing a novel description of the structure of TM/sub 1-x/M/sub x/ glasses. The experimental evidence suggests that an ideal amorphous phase forms at a specific composition x/sub c/ and that this phase has a well defined atomic short range order. For metallic glasses having x x/sub c/. This novel picture can explain the variation of many properties of these glasses with metalloid concentration

Mechanical failure and glass transition in metallic glasses

International Nuclear Information System (INIS)

Egami, T.

2011-01-01

Research highlights: → We review the recent results of molecular dynamics simulations on metallic glasses. → They show the equivalence of mechanical failure and glass transition. → We discuss the microscopic mechanism behind this equivalence. → We show that the density of defects in metallic glasses is as high as a quarter. → Our concepts about the defect state in glasses need to be changed. - Abstract: The current majority view on the phenomenon of mechanical failure in metallic glasses appears to be that it is caused by the activity of some structural defects, such as free-volumes or shear transformation zones, and the concentration of such defects is small, only of the order of 1%. However, the recent results compel us to revise this view. Through molecular dynamics simulation it has been shown that mechanical failure is the stress-induced glass transition. According to our theory the concentration of the liquid-like sites (defects) is well over 20% at the glass transition. We suggest that the defect concentration in metallic glasses is actually very high, and percolation of such defects causes atomic avalanche and mechanical failure. In this article we discuss the glass transition, mechanical failure and viscosity from such a point of view.

Unusual metal-insulator transition in disordered ferromagnetic films

International Nuclear Information System (INIS)

Muttalib, K.A.; Wölfle, P.; Misra, R.; Hebard, A.F.

2012-01-01

We present a theoretical interpretation of recent data on the conductance near and farther away from the metal-insulator transition in thin ferromagnetic Gd films of thickness b≈2-10 nm. For increasing sheet resistances a dimensional crossover takes place from d=2 to d=3 dimensions, since the large phase relaxation rate caused by scattering of quasiparticles off spin wave excitations renders the dephasing length L φ ≲b at strong disorder. The conductivity data in the various regimes obey fractional power-law or logarithmic temperature dependence. One observes weak localization and interaction induced corrections at weaker disorder. At strong disorder, near the metal-insulator transition, the data show scaling and collapse onto two scaling curves for the metallic and insulating regimes. We interpret this unusual behavior as proof of two distinctly different correlation length exponents on both sides of the transition.

Transition-Metal-Free Biomolecule-Based Flexible Asymmetric Supercapacitors.

Science.gov (United States)

Yang, Yun; Wang, Hua; Hao, Rui; Guo, Lin

2016-09-01

A transition-metal-free asymmetric supercapacitor (ASC) is successfully fabricated based on an earth-abundant biomass derived redox-active biomolecule, named lawsone. Such an ASC exhibits comparable or even higher energy densities than most of the recently reported transition-metal-based ASCs, and this green ASC generation from renewable resources is promising for addressing current issues of electronic hazard processing, high cost, and unsustainability. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

NiMo-sulfide supported on activated carbon to produce renewable diesel

Directory of Open Access Journals (Sweden)

Nancy Y Acelas

2017-03-01

Full Text Available Due to their weak polarity and large surface area, activated carbon supports have the potential to enhance the dispersion of metal-sulfides. It is expected that the absence of a strong metal-support interaction can result in the formation of a very active and stable Ni-Mo-S phase. In this study, catalysts with different amounts of nickel and molybdenum supported on a commercial activated carbon were prepared by a co-impregnation method and characterized by BET, XRF, and SEM techniques. The catalytic activity for hydroprocessing of Jatropha oil was evaluated in a batch reactor, and the composition of the liquid and gaseous products were determined. Results showed that gaseous products are mainly composed of high amounts of propane and small amounts of other light hydrocarbons (C1 to C5. Liquid hydrocarbon products consisted of a mixture containing mainly n-paraffins of C15-C18 and some oxygenated compounds. The catalysts with a mass fraction of 3 % Ni, 15 % Mo (Ni3Mo15/AC presented the highest selectivity toward C17-C18 hydrocarbons, with a product distribution similar to a commercial alumina-supported Ni-Mo-S catalyst.

Thermally Conductive Metal-Tube/Carbon-Composite Joints

Science.gov (United States)

Copeland, Robert J.

2004-01-01

An improved method of fabricating joints between metal and carbon-fiber-based composite materials in lightweight radiators and heat sinks has been devised. Carbon-fiber-based composite materials have been used in such heat-transfer devices because they offer a combination of high thermal conductivity and low mass density. Metal tubes are typically used to carry heat-transfer fluids to and from such heat-transfer devices. The present fabrication method helps to ensure that the joints between the metal tubes and the composite-material parts in such heat-transfer devices have both (1) the relatively high thermal conductances needed for efficient transfer of heat and (2) the flexibility needed to accommodate differences among thermal expansions of dissimilar materials in operation over wide temperature ranges. Techniques used previously to join metal tubes with carbon-fiber-based composite parts have included press fitting and bonding with epoxy. Both of these prior techniques have been found to yield joints characterized by relatively high thermal resistances. The present method involves the use of a solder (63 percent Sn, 37 percent Pb) to form a highly thermally conductive joint between a metal tube and a carbon-fiber-based composite structure. Ordinarily, the large differences among the coefficients of thermal expansion of the metal tube, solder, and carbon-fiber-based composite would cause the solder to pull away from the composite upon post-fabrication cooldown from the molten state. In the present method, the structure of the solder is modified (see figure) to enable it to deform readily to accommodate the differential thermal expansion.

PRODUCTION OF URANIUM METAL BY CARBON REDUCTION

Science.gov (United States)

Holden, R.B.; Powers, R.M.; Blaber, O.J.

1959-09-22

The preparation of uranium metal by the carbon reduction of an oxide of uranium is described. In a preferred embodiment of the invention a charge composed of carbon and uranium oxide is heated to a solid mass after which it is further heated under vacuum to a temperature of about 2000 deg C to produce a fused uranium metal. Slowly ccoling the fused mass produces a dendritic structure of uranium carbide in uranium metal. Reacting the solidified charge with deionized water hydrolyzes the uranium carbide to finely divide uranium dioxide which can be separated from the coarser uranium metal by ordinary filtration methods.

Tunable metal-insulator transitions in bilayer graphene by thermal annealing

OpenAIRE

Kalon, Gopinadhan; Shin, Young Jun; Yang, Hyunsoo

2012-01-01

Tunable and highly reproducible metal-insulator transitions have been observed in bilayer graphene upon thermal annealing at 400 K under high vacuum conditions. Before annealing, the sample is metallic in the whole temperature regime of study. Upon annealing, the conductivity changes from metallic to that of an insulator and the transition temperature is a function of annealing time. The pristine metallic state can be reinstated by exposing to air thereby inducing changes in the electronic pr...

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

Science.gov (United States)

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.

Regeneration of sulfated metal oxides and carbonates

Science.gov (United States)

Hubble, Bill R.; Siegel, Stanley; Cunningham, Paul T.

1978-03-28

Alkali metal or alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate found in dolomite or limestone are employed for removal of sulfur dioxide from combustion exhaust gases. The sulfated carbonates are regenerated to oxides through use of a solid-solid reaction, particularly calcium sulfide with calcium sulfate to form calcium oxide and sulfur dioxide gas. The regeneration is performed by contacting the sulfated material with a reductant gas such as hydrogen within an inert diluent to produce calcium sulfide in mixture with the sulfate under process conditions selected to permit the sulfide-sulfate, solid-state reaction to occur.

Reactions of synthesis gas on silica supported transition metal catalysts

Energy Technology Data Exchange (ETDEWEB)

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.

Interaction of alkali metal nitrates with calcium carbonate and kyanite

International Nuclear Information System (INIS)

Protsyuk, A.P.; Malakhov, A.I.; Karabanov, V.P.; Lebedeva, L.P.

1978-01-01

Thermographic, thermodynamic and X-ray phase studies have been made into the interaction of alkali metal nitrates with calcium carbonate and kyanite. Examined among other things was the effect of water vapor and carbon dioxide on the interaction between alkali metal nitrates and kyanite. The chemical mechanism of the occurring processes has been established. The interaction with calcium carbonates results in the formation of alkali metal carbonates and calcium oxide with liberation of nitrogen oxide and oxygen. The products of the interaction with kyanite are shown to be identical with the compounds forming when alkali metal carbonates are used

Natural reducing agents for electroless nanoparticle deposition: Mild synthesis of metal/carbon nanostructured microspheres

International Nuclear Information System (INIS)

Duffy, Paul; Reynolds, Lyndsey A.; Sanders, Stephanie E.; Metz, Kevin M.; Colavita, Paula E.

2013-01-01

Composite materials are of interest because they can potentially combine the properties of their respective components in a manner that is useful for specific applications. Here, we report on the use of coffee as a low-cost, green reductant for the room temperature formation of catalytically active, supported metal nanoparticles. Specifically, we have leveraged the reduction potential of coffee in order to grow Pd and Ag nanoparticles at the surface of porous carbon microspheres synthesized via ultraspray pyrolysis. The metal nanoparticle-on-carbon microsphere composites were characterized using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and thermal gravimetric analysis (TGA). To demonstrate the catalytic activity of Pd/C and Ag/C materials, Suzuki coupling reactions and nitroaromatic reduction reactions were employed, respectively. - Highlights: • Natural reductants were used as green electroless deposition reagents. • Room temperature synthesis of supported Ag and Pd nanoparticles was achieved. • Carbon porous microspheres were used as supports. • Synthesis via natural reductants yielded catalytically active nanoparticles.

The metallicities of stars with and without transiting planets

DEFF Research Database (Denmark)

Buchhave, Lars A.; Latham, David W.

2015-01-01

Host star metallicities have been used to infer observational constraints on planet formation throughout the history of the exoplanet field. The giant planet metallicity correlation has now been widely accepted, but questions remain as to whether the metallicity correlation extends to the small...... terrestrial-sized planets. Here, we report metallicities for a sample of 518 stars in the Kepler field that have no detected transiting planets and compare their metallicity distribution to a sample of stars that hosts small planets (). Importantly, both samples have been analyzed in a homogeneous manner...... using the same set of tools (Stellar Parameters Classification tool). We find the average metallicity of the sample of stars without detected transiting planets to be and the sample of stars hosting small planets to be . The average metallicities of the two samples are indistinguishable within...

VO2 microcrystals as an advanced smart window material at semiconductor to metal transition

Science.gov (United States)

Basu, Raktima; Magudapathy, P.; Sardar, Manas; Pandian, Ramanathaswamy; Dhara, Sandip

2017-11-01

Textured VO2(0 1 1) microcrystals are grown in the monoclinic, M1 phase which undergoes a reversible first order semiconductor to metal transition (SMT) accompanied by a structural phase transition to rutile tetragonal, R phase. Around the phase transition, VO2 also experiences noticeable change in its optical and electrical properties. A change in color of the VO2 micro crystals from white to cyan around the transition temperature is observed, which is further understood by absorption of red light using temperature dependent ultraviolet-visible spectroscopic analysis and photoluminescence studies. The absorption of light in the red region is explained by the optical transition between Hubbard states, confirming the electronic correlation as the driving force for SMT in VO2. The thermochromism in VO2 has been studied for smart window applications so far in the IR region, which supports the opening of the band gap in semiconducting phase; whereas there is hardly any report in the management of visible light. The filtering of blue light along with reflection of infrared above the semiconductor to metal transition temperature make VO2 applicable as advanced smart windows for overall heat management of a closure.

VO2 microcrystals as an advanced smart window material at semiconductor to metal transition

International Nuclear Information System (INIS)

Basu, Raktima; Pandian, Ramanathaswamy; Dhara, Sandip; Magudapathy, P; Sardar, Manas

2017-01-01

Textured VO 2 (0 1 1) microcrystals are grown in the monoclinic, M1 phase which undergoes a reversible first order semiconductor to metal transition (SMT) accompanied by a structural phase transition to rutile tetragonal, R phase. Around the phase transition, VO 2 also experiences noticeable change in its optical and electrical properties. A change in color of the VO 2 micro crystals from white to cyan around the transition temperature is observed, which is further understood by absorption of red light using temperature dependent ultraviolet–visible spectroscopic analysis and photoluminescence studies. The absorption of light in the red region is explained by the optical transition between Hubbard states, confirming the electronic correlation as the driving force for SMT in VO 2 . The thermochromism in VO 2 has been studied for smart window applications so far in the IR region, which supports the opening of the band gap in semiconducting phase; whereas there is hardly any report in the management of visible light. The filtering of blue light along with reflection of infrared above the semiconductor to metal transition temperature make VO 2 applicable as advanced smart windows for overall heat management of a closure. (paper)

[Non-empirical interatomic potentials for transition metals

International Nuclear Information System (INIS)

1993-01-01

The report is divided into the following sections: potential-energy functions for d-band metals, potential-energy functions for aluminides and quasicrystals, electronic structure of complex structures and quasicrystals, potential-energy functions in transition-metal oxides, applications to defect structure and mechanical properties, and basic theory of interatomic potentials

Carbon fiber cloth supported interwoven WS{sub 2} nanosplates with highly enhanced performances for supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Shang, Xiao; Chi, Jing-Qi [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Lu, Shan-Shan [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Gou, Jian-Xia [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Dong, Bin, E-mail: dongbin@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Li, Xiao; Liu, Yan-Ru; Yan, Kai-Li; Chai, Yong-Ming [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Chen-Guang, E-mail: cgliu@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China)

2017-01-15

Highlights: • WS{sub 2} nanoplates supported on carbon fiber cloth (WS{sub 2}/CFC) have been synthesized. • WS{sub 2}/CFC has the good dispersion and interwoven structure of WS{sub 2}. • CFC as substrate contributes to enhanced conductivity and close combination. • WS{sub 2}/CFC exhibits ultra-high activity and stability owing to CFC as support. - Abstract: The interwoven WS{sub 2} nanoplates supported on carbon fiber cloth (WS{sub 2}/CFC) have been successfully synthesized by a facile solvothermal process. XRD and XPS confirm the formation of WS{sub 2}/CFC. SEM images show the good dispersion of WS{sub 2} nanoplates with interwoven structures on the surface of CFC. Thanks to the 3D framework of CFC, WS{sub 2} nanoplates realize overall excellent-dispersion interwoven on the surface of CFC compared with pristine bulk WS{sub 2} with severe aggregation. Moreover, CFC not only serves as excellent conductive substrate to accelerate electron transport rate, but also contributes to the close combination between WS{sub 2} and CFC for long-term stability. The electrochemical measurements show that WS{sub 2}/CFC exhibit a high specific capacitance of 399 F g{sup −1} at 1.0 A g{sup −1}, demonstrating the obviously enhanced capability compared with pristine bulk WS{sub 2}. Furthermore, WS{sub 2}/CFC realizes ultra-stable cycling stability with 99% of retention of capacitance after 500 charge-discharge cycles. It may provide novel access of designing carbon-based transition metal disulfides composites for excellent super capacitive properties.

Electrochemically controlled winding and unwinding of substrate-supported carbon nanoscrolls

Czech Academy of Sciences Publication Activity Database

Tarábková, Hana; Zelinger, Zdeněk; Janda, Pavel

2018-01-01

Roč. 20, č. 8 (2018), s. 5900-5908 ISSN 1463-9076 R&D Projects: GA ČR(CZ) GA17-05167s Institutional support: RVO:61388955 Keywords : electrochemistry * carbon nanoscrolls * electrical energy Subject RIV: CG - Electrochemistry OBOR OECD: Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis) Impact factor: 4.123, year: 2016

Theory of quantum metal to superconductor transitions in highly conducting systems

Energy Technology Data Exchange (ETDEWEB)

Spivak, B.

2010-04-06

We derive the theory of the quantum (zero temperature) superconductor to metal transition in disordered materials when the resistance of the normal metal near criticality is small compared to the quantum of resistivity. This can occur most readily in situations in which 'Anderson's theorem' does not apply. We explicitly study the transition in superconductor-metal composites, in an swave superconducting film in the presence of a magnetic field, and in a low temperature disordered d-wave superconductor. Near the point of the transition, the distribution of the superconducting order parameter is highly inhomogeneous. To describe this situation we employ a procedure which is similar to that introduced by Mott for description of the temperature dependence of the variable range hopping conduction. As the system approaches the point of the transition from the metal to the superconductor, the conductivity of the system diverges, and the Wiedemann-Franz law is violated. In the case of d-wave (or other exotic) superconductors we predict the existence of (at least) two sequential transitions as a function of increasing disorder: a d-wave to s-wave, and then an s-wave to metal transition.

Hydrogen chemisorption and oxidation of transition metal carbides

International Nuclear Information System (INIS)

Bethin, J.R.

1979-01-01

A study was made of the catalytic activity of WC, focusing on the possible influence of point defects. The chemisorption of H on WC and titanium oxycarbides was studied with differential scanning calorimetry. The catalytic activity of these materials for oxidation of H was determined by potentiostatic steady-state and potentiodynamic measurements in acid electrolyte. Compositions of WC surfaces were determined by x-ray photoemission and related to the catalytic behavior. Titanium oxycarbide surfaces were analyzed by Auger electron spectroscopy. Of the carbides tested only one WC preparation was able to chemisorb H. Both WC powders investigated catalyzed H oxidation with similar specific activities. Spectroscopic studies showed that the active surface of WC was a mixture of WO 3 and a carbon-deficient WC phase. This result indicates that carbon vacancies are the active sites in tungsten carbide. Theoretical models of a carbon vacancy surrounded by metal atoms suggested by calculations by other workers support this assignment and identify the important role of the W6s level. The measured value of the heat of chemisorption is consistent with the proposed model

Nanostructured carbon-metal oxide composite electrodes for supercapacitors: a review

Science.gov (United States)

Zhi, Mingjia; Xiang, Chengcheng; Li, Jiangtian; Li, Ming; Wu, Nianqiang

2012-12-01

This paper presents a review of the research progress in the carbon-metal oxide composites for supercapacitor electrodes. In the past decade, various carbon-metal oxide composite electrodes have been developed by integrating metal oxides into different carbon nanostructures including zero-dimensional carbon nanoparticles, one-dimensional nanostructures (carbon nanotubes and carbon nanofibers), two-dimensional nanosheets (graphene and reduced graphene oxides) as well as three-dimensional porous carbon nano-architectures. This paper has described the constituent, the structure and the properties of the carbon-metal oxide composites. An emphasis is placed on the synergistic effects of the composite on the performance of supercapacitors in terms of specific capacitance, energy density, power density, rate capability and cyclic stability. This paper has also discussed the physico-chemical processes such as charge transport, ion diffusion and redox reactions involved in supercapacitors.

Nanostructured carbon-metal oxide composite electrodes for supercapacitors: a review.

Science.gov (United States)

Zhi, Mingjia; Xiang, Chengcheng; Li, Jiangtian; Li, Ming; Wu, Nianqiang

2013-01-07

This paper presents a review of the research progress in the carbon-metal oxide composites for supercapacitor electrodes. In the past decade, various carbon-metal oxide composite electrodes have been developed by integrating metal oxides into different carbon nanostructures including zero-dimensional carbon nanoparticles, one-dimensional nanostructures (carbon nanotubes and carbon nanofibers), two-dimensional nanosheets (graphene and reduced graphene oxides) as well as three-dimensional porous carbon nano-architectures. This paper has described the constituent, the structure and the properties of the carbon-metal oxide composites. An emphasis is placed on the synergistic effects of the composite on the performance of supercapacitors in terms of specific capacitance, energy density, power density, rate capability and cyclic stability. This paper has also discussed the physico-chemical processes such as charge transport, ion diffusion and redox reactions involved in supercapacitors.

On the thermodynamics of phase transitions in metal hydrides

Science.gov (United States)

di Vita, Andrea

2012-02-01

Metal hydrides are solutions of hydrogen in a metal, where phase transitions may occur depending on temperature, pressure etc. We apply Le Chatelier's principle of thermodynamics to a particular phase transition in TiH x , which can approximately be described as a second-order phase transition. We show that the fluctuations of the order parameter correspond to fluctuations both of the density of H+ ions and of the distance between adjacent H+ ions. Moreover, as the system approaches the transition and the correlation radius increases, we show -with the help of statistical mechanics-that the statistical weight of modes involving a large number of H+ ions (`collective modes') increases sharply, in spite of the fact that the Boltzmann factor of each collective mode is exponentially small. As a result, the interaction of the H+ ions with collective modes makes a tiny suprathermal fraction of the H+ population appear. Our results hold for similar transitions in metal deuterides, too. A violation of an -insofar undisputed-upper bound on hydrogen loading follows.

A Simple, General Synthetic Route toward Nanoscale Transition Metal Borides.

Science.gov (United States)

Jothi, Palani R; Yubuta, Kunio; Fokwa, Boniface P T

2018-04-01

Most nanomaterials, such as transition metal carbides, phosphides, nitrides, chalcogenides, etc., have been extensively studied for their various properties in recent years. The similarly attractive transition metal borides, on the contrary, have seen little interest from the materials science community, mainly because nanomaterials are notoriously difficult to synthesize. Herein, a simple, general synthetic method toward crystalline transition metal boride nanomaterials is proposed. This new method takes advantage of the redox chemistry of Sn/SnCl 2 , the volatility and recrystallization of SnCl 2 at the synthesis conditions, as well as the immiscibility of tin with boron, to produce crystalline phases of 3d, 4d, and 5d transition metal nanoborides with different morphologies (nanorods, nanosheets, nanoprisms, nanoplates, nanoparticles, etc.). Importantly, this method allows flexibility in the choice of the transition metal, as well as the ability to target several compositions within the same binary phase diagram (e.g., Mo 2 B, α-MoB, MoB 2 , Mo 2 B 4 ). The simplicity and wide applicability of the method should enable the fulfillment of the great potential of this understudied class of materials, which show a variety of excellent chemical, electrochemical, and physical properties at the microscale. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphitic Carbon Nitride as a Catalyst Support in Fuel Cells and Electrolyzers

International Nuclear Information System (INIS)

Mansor, Noramalina; Miller, Thomas S.; Dedigama, Ishanka; Jorge, Ana Belen; Jia, Jingjing; Brázdová, Veronika; Mattevi, Cecilia; Gibbs, Chris; Hodgson, David; Shearing, Paul R.; Howard, Christopher A.; Corà, Furio; Shaffer, Milo; Brett, Daniel J.L.

2016-01-01

Highlights: • Graphitic carbon nitride (gCN) describes many materials with different structures. • gCNs can exhibit excellent mechanical, chemical and thermal resistance. • A major obstacle for pure gCN catalyst supports is limited electronic conductivity. • Composite/Hybrid gCN structures show excellent performance as catalyst supports. • gCNs have great potential for use in fuel calls and water electrolyzers. - Abstract: Electrochemical power sources, such as polymer electrolyte membrane fuel cells (PEMFCs), require the use of precious metal catalysts which are deposited as nanoparticles onto supports in order to minimize their mass loading and therefore cost. State-of-the-art/commercial supports are based on forms of carbon black. However, carbon supports present disadvantages including corrosion in the operating fuel cell environment and loss of catalyst activity. Here we review recent work examining the potential of different varieties of graphitic carbon nitride (gCN) as catalyst supports, highlighting their likely benefits, as well as the challenges associated with their implementation. The performance of gCN and hybrid gCN-carbon materials as PEMFC electrodes is discussed, as well as their potential for use in alkaline systems and water electrolyzers. We illustrate the discussion with examples taken from our own recent studies.

Hot carrier dynamics in plasmonic transition metal nitrides

Science.gov (United States)

Habib, Adela; Florio, Fred; Sundararaman, Ravishankar

2018-06-01

Extraction of non-equilibrium hot carriers generated by plasmon decay in metallic nano-structures is an increasingly exciting prospect for utilizing plasmonic losses, but the search for optimum plasmonic materials with long-lived carriers is ongoing. Transition metal nitrides are an exciting class of new plasmonic materials with superior thermal and mechanical properties compared to conventional noble metals, but their suitability for plasmonic hot carrier applications remains unknown. Here, we present fully first principles calculations of the plasmonic response, hot carrier generation and subsequent thermalization of all group IV, V and VI transition metal nitrides, fully accounting for direct and phonon-assisted transitions as well as electron–electron and electron–phonon scattering. We find the largest frequency ranges for plasmonic response in ZrN, HfN and WN, between those of gold and silver, while we predict strongest absorption in the visible spectrum for the VN, NbN and TaN. Hot carrier generation is dominated by direct transitions for most of the relevant energy range in all these nitrides, while phonon-assisted processes dominate only below 1 eV plasmon energies primarily for the group IV nitrides. Finally, we predict the maximum hot carrier lifetimes to be around 10 fs for group IV and VI nitrides, a factor of 3–4 smaller than noble metals, due to strong electron–phonon scattering. However, we find longer carrier lifetimes for group V nitrides, comparable to silver for NbN and TaN, while exceeding 100 fs (twice that of silver) for VN, making them promising candidates for efficient hot carrier extraction.

Bridging analytical approaches for low-carbon transitions

Science.gov (United States)

Geels, Frank W.; Berkhout, Frans; van Vuuren, Detlef P.

2016-06-01

Low-carbon transitions are long-term multi-faceted processes. Although integrated assessment models have many strengths for analysing such transitions, their mathematical representation requires a simplification of the causes, dynamics and scope of such societal transformations. We suggest that integrated assessment model-based analysis should be complemented with insights from socio-technical transition analysis and practice-based action research. We discuss the underlying assumptions, strengths and weaknesses of these three analytical approaches. We argue that full integration of these approaches is not feasible, because of foundational differences in philosophies of science and ontological assumptions. Instead, we suggest that bridging, based on sequential and interactive articulation of different approaches, may generate a more comprehensive and useful chain of assessments to support policy formation and action. We also show how these approaches address knowledge needs of different policymakers (international, national and local), relate to different dimensions of policy processes and speak to different policy-relevant criteria such as cost-effectiveness, socio-political feasibility, social acceptance and legitimacy, and flexibility. A more differentiated set of analytical approaches thus enables a more differentiated approach to climate policy making.

Toxicity effects on metal sequestration by microbially-induced carbonate precipitation

Energy Technology Data Exchange (ETDEWEB)

Mugwar, Ahmed J. [Cardiff School of Engineering, Cardiff University, Queen’s Buildings, The Parade, Cardiff CF24 3AA (United Kingdom); College of Engineering, Al-Muthanna University, Samawah (Iraq); Harbottle, Michael J., E-mail: harbottlem@cardiff.ac.uk [Cardiff School of Engineering, Cardiff University, Queen’s Buildings, The Parade, Cardiff CF24 3AA (United Kingdom)

2016-08-15

Highlights: • Minimum inhibitory concentrations (MIC) are determined for S. pasteurii with a range of metals. • Zinc & cadmium bioprecipitation is strongly linked to microbial carbonate generation. • Lead & copper carbonate bioprecipitation is limited & abiotic processes may be significant. • Bioprecipitation allows survival at & remediation of higher metal concentrations than expected. - Abstract: Biological precipitation of metallic contaminants has been explored as a remedial technology for contaminated groundwater systems. However, metal toxicity and availability limit the activity and remedial potential of bacteria. We report the ability of a bacterium, Sporosarcina pasteurii, to remove metals in aerobic aqueous systems through carbonate formation. Its ability to survive and grow in increasingly concentrated aqueous solutions of zinc, cadmium, lead and copper is explored, with and without a metal precipitation mechanism. In the presence of metal ions alone, bacterial growth was inhibited at a range of concentrations depending on the metal. Microbial activity in a urea-amended medium caused carbonate ion generation and pH elevation, providing conditions suitable for calcium carbonate bioprecipitation, and consequent removal of metal ions. Elevation of pH and calcium precipitation are shown to be strongly linked to removal of zinc and cadmium, but only partially linked to removal of lead and copper. The dependence of these effects on interactions between the respective metal and precipitated calcium carbonate are discussed. Finally, it is shown that the bacterium operates at higher metal concentrations in the presence of the urea-amended medium, suggesting that the metal removal mechanism offers a defence against metal toxicity.

Characterization of a surface modified carbon cryogel and a carbon supported Pt catalyst

Directory of Open Access Journals (Sweden)

BILJANA M. BABIĆ

2007-08-01

Full Text Available A carbon cryogel, synthesized by carbonization of a resorcinol/formaldehyde cryogel and oxidized in nitric acid, was used as catalyst support for Pt nano-particles. The Pt/C catalyst was prepared by a modified polyol synthesis method in an ethylene glycol (EG solution. Characterization by nitrogen adsorption showed that the carbon cryogel support and the Pt/C catalyst were mesoporous materials with high specific surface areas (SBET > 400 m2 g-1 and large mesoporous volumes. X-Ray diffraction of the catalyst demonstrated the successful reduction of the Pt precursor to metallic form. TEM Images of the Pt/C catalyst and Pt particle size distribution showed that the mean Pt particle size was about 3.3 nm. Cyclic voltammetry (CV experiments at various scan rates (from 2 to 200 mV s-1 were performed in 0.5 mol dm-3 HClO4 solution. The large capacitance of the oxidized carbon cryogel electrode, which arises from a combination of the double-layer capacitance and pseudocapacitance, associated with the participation of surface redox-type reactions was demonstrated. For the oxidized carbon cryogel, the total specific capacitance determined by 1/C vs. ν0.5 extrapolation method was found to be 386 F g-1. The hydrogen oxidation reaction at the investigated Pt/C catalyst proceeded as an electrochemically reversible, two-electron direct discharge reaction.

Transition metal carbide nanocomposite and amorphous thin films

OpenAIRE

Tengstrand, Olof

2014-01-01

This thesis explores thin films of binary and ternary transition metal carbides, in the Nb-C, Ti-Si-C, Nb-Si-C, Zr-Si-C, and Nb-Ge-C systems. The electrical and mechanical properties of these systems are affected by their structure and here both nanocomposite and amorphous thin films are thus investigated. By appropriate choice of transition metal and composition the films can be designed to be multifunctional with a combination of properties, such as low electric resistivity, low contact res...

Evaluation of complexing agents and column temperature in ion chromatographic separation of alkali metals, alkaline earth metals and transition metals ion

International Nuclear Information System (INIS)

Kelkar, Anoop; Pandey, Ashish; Name, Anil B.; Das, D.K.; Behere, P.G.; Mohd Afzal

2015-01-01

The aim of ion chromatography method development is the resolution of all metal ions of interests. Resolution can be improved by changing the selectivity. Selectivity in chromatography can be altered by changes in mobile phase (eg eluent type, eluent strength) or through changes in stationary phase. Temperature has been used in altering the selectivity of particularly in reversed phase liquid chromatography and ion exchange chromatography. Present paper describe the retention behaviour of alkali metals, alkaline earth metals and transition metal ions on a silica based carboxylate function group containing analyte column. Alkali metals, alkaline earth metals and transition metal ions were detected by ion conductivity and UV-VIS detectors respectively

Study on the effect of the metal-support (Fe-MgO and Pt-MgO) interaction in alcohol-CVD synthesis of carbon nanotubes

Energy Technology Data Exchange (ETDEWEB)

Steplewska, Anna, E-mail: asteplewska@zut.edu.pl; Borowiak-Palen, Ewa [West Pomeranian University of Technology, Centre of Knowledge Based Nanomaterials and Technologies, Institute of Chemical and Environment Engineering (Poland)

2011-05-15

This study presents the effect of the metal-support interaction in two systems: (1) iron particle, and (2) platinum particles, being supported on magnesium oxide (MgO) nanopowder in alcohol-CVD process for carbon nanotubes (CNTs) growth. The employment of the different metals but the same substrate (with equal molar ratio) resulted in the synthesis of single-walled CNTs (SWCNTs) or double-walled CNTs (DWCNTs), using iron and platinum, respectively. Furthermore, along with the prolongation of the process time, the decrease of the mean nanotubes diameter in case of iron-catalyzed materials was detected. Interestingly, the extention of the growth time in the synthesis using Pt/MgO resulted in the synthesis of the thicker mean nanotubes diameter. However, for both applied catalytic systems the reduction of the diameter distribution of the tubes and the increase of relative purity of the samples upon the growth time increase were detected.

Hydrogen and dihydrogen bonding of transition metal hydrides

Science.gov (United States)

Jacobsen, Heiko

2008-04-01

Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2NO(PH 3) 2 and a small proton donor H 2O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H⋯H bond of transition metal hydrides contains both covalent and electrostatic contributions.

Hydrogen and dihydrogen bonding of transition metal hydrides

International Nuclear Information System (INIS)

Jacobsen, Heiko

2008-01-01

Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2 NO(PH 3 ) 2 and a small proton donor H 2 O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H...H bond of transition metal hydrides contains both covalent and electrostatic contributions

Interaction of terbium group metal oxides with carbon

International Nuclear Information System (INIS)

Vodop'yanov, A.G.; Baranov, S.V.; Kozhevnikov, G.N.

1990-01-01

Mechanism of carbothermal reduction of terbium group metals from oxides is investigated using thermodynamic and kinetic analyses. Interaction of metal oxides with carbon covers dissociation of metal oxides and reduction by carbon monoxide, which contribution into general reduction depends on CO pressure. Temperatures of reaction beginning for batch initial components at P=1.3x10 -4 and P CO =0.1 MPa and of formation of oxycarbide melts are determined

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

Directory of Open Access Journals (Sweden)

Juan Carlos Calderón

2016-10-01

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

Adlayer Core-Level Shifts of Random Metal Overlayers on Transition-Metal Substrates

DEFF Research Database (Denmark)

Ganduglia-Pirovano, M. V.; Kudrnovský, J.; Scheffler, M.

1997-01-01

and the screening effects induced by the core hole, and study the influence of the alloy composition for a number of noble metal-transition metal systems. Our analysis clearly indicates the importance of final-state screening effects for the interpretation of measured core-level shifts. Calculated deviations from...

The model of metal-insulator phase transition in vanadium oxide

International Nuclear Information System (INIS)

Vikhnin, V.S.; Lysenko, S.; Rua, A.; Fernandez, F.; Liu, H.

2005-01-01

Thermally induced metal-insulator phase transitions (PT) in VO 2 thin films are studied theoretically and experimentally. The hysteresis phenomena in the region of the transition for different type thin films were investigated. The phenomenological model of the PT is suggested. The charge transfer-lattice instability in VO 2 metallic phase is considered as basis of the first order metal-insulator PT in VO 2 . The charge transfer is treated as an order parameter

The sticking probability for H-2 in presence of CO on some transition metals at a hydrogen pressure of 1 bar

DEFF Research Database (Denmark)

Johansson, Martin; Lytken, Ole; Chorkendorff, Ib

2008-01-01

The sticking probability for H-2 on Ni, Co, Cu, Rh, Ru, Pd, it and Pt metal films supported on graphite has been investigated in a gas mixture consisting of 10 ppm carbon monoxide in hydrogen at a total pressure of 1 bar in the temperature range 40-200 degrees C. Carbon monoxide inhibits the stic......The sticking probability for H-2 on Ni, Co, Cu, Rh, Ru, Pd, it and Pt metal films supported on graphite has been investigated in a gas mixture consisting of 10 ppm carbon monoxide in hydrogen at a total pressure of 1 bar in the temperature range 40-200 degrees C. Carbon monoxide inhibits...... the sticking probability significantly for all the metals, even at 200 degrees C. In the presence of 10 ppm CO, the sticking probability increases in the order It, Pt, Ni, Co, Pd, Rh, Ru, whereas for Cu, it is below the detection limit of the measurement, even in pure H2. The sticking probability for H2...

Recent Advances in Transition-Metal-Mediated Electrocatalytic CO2 Reduction: From Homogeneous to Heterogeneous Systems

Directory of Open Access Journals (Sweden)

Da-Ming Feng

2017-12-01

Full Text Available Global climate change and increasing demands for clean energy have brought intensive interest in the search for proper electrocatalysts in order to reduce carbon dioxide (CO2 to higher value carbon products such as hydrocarbons. Recently, transition-metal-centered molecules or organic frameworks have been reported to show outstanding electrocatalytic activity in the liquid phase. Their d-orbital electrons are believed to be one of the key factors to capture and convert CO2 molecules to value-added low-carbon fuels. In this review, recent advances in electrocatalytic CO2 reduction have been summarized based on the targeted products, ranging from homogeneous reactions to heterogeneous ones. Their advantages and fallbacks have been pointed out and the existing challenges, especially with respect to the practical and industrial application are addressed.

Recent Advances in Transition-Metal-Mediated Electrocatalytic CO2 Reduction: From Homogeneous to Heterogeneous Systems

KAUST Repository

Feng, Da-Ming

2017-12-01

Global climate change and increasing demands for clean energy have brought intensive interest in the search for proper electrocatalysts in order to reduce carbon dioxide (CO2) to higher value carbon products such as hydrocarbons. Recently, transition-metal-centered molecules or organic frameworks have been reported to show outstanding electrocatalytic activity in the liquid phase. Their d-orbital electrons are believed to be one of the key factors to capture and convert CO2 molecules to value-added low-carbon fuels. In this review, recent advances in electrocatalytic CO2 reduction have been summarized based on the targeted products, ranging from homogeneous reactions to heterogeneous ones. Their advantages and fallbacks have been pointed out and the existing challenges, especially with respect to the practical and industrial application are addressed.

Vacancies in transition metals

International Nuclear Information System (INIS)

Allan, G.; Lannoo, M.

1976-01-01

A calculation of the formation energy and volume for a vacancy in transition metals is described. A tight-binding scheme is used for the d band and a Born-Mayer type potential to account for the repulsive part of the energy at small distances. The results show that the relaxation energy is small in all cases, less than 0.1 eV. This seems to be coherent with the good agreement obtained for the theoretical and experimental values of the formation energy Esub(F)sup(V) of the vacancy, without including relaxation. The center of the transitional series is found to give a contraction (Formation volume of order -0.4 at.vol.) whereas the edges are found to produce dilations. (author)

Electronic structure of metal clusters

International Nuclear Information System (INIS)

Wertheim, G.K.

1989-01-01

Photoemission spectra of valence electrons in metal clusters, together with threshold ionization potential measurements, provide a coherent picture of the development of the electronic structure from the isolated atom to the large metallic cluster. An insulator-metal transition occurs at an intermediate cluster size, which serves to define the boundary between small and large clusters. Although the outer electrons may be delocalized over the entire cluster, a small cluster remains insulating until the density of states near the Fermi level exceeds 1/kT. In large clusters, with increasing cluster size, the band structure approaches that of the bulk metal. However, the bands remain significantly narrowed even in a 1000-atom cluster, giving an indication of the importance of long-range order. The core-electron binding-energy shifts of supported metal clusters depend on changes in the band structure in the initial state, as well as on various final-state effects, including changes in core hole screening and the coulomb energy of the final-state charge. For cluster supported on amorphous carbon, this macroscopic coulomb shift is often dominant, as evidenced by the parallel shifts of the core-electron binding energy and the Fermi edge. Auger data confirm that final-state effects dominate in cluster of Sn and some other metals. Surface atom core-level shifts provide a valuable guide to the contributions of initial-state changes in band structure to cluster core-electron binding energy shifts, especially for Au and Pt. The available data indicate that the shift observed in supported, metallic clusters arise largely from the charge left on the cluster by photoemission. As the metal-insulator transition is approached from above, metallic screening is suppressed and the shift is determined by the local environment. (orig.)

The 1s x-ray absorption pre-edge structures in transition metal oxides

NARCIS (Netherlands)

de Groot, Frank|info:eu-repo/dai/nl/08747610X; Vanko, Gyoergy; Glatzel, Pieter

2009-01-01

We develop a general procedure to analyse the pre-edges in 1s x-ray absorption near edge structure (XANES) of transition metal oxides and coordination complexes. Transition metal coordination complexes can be described from a local model with one metal ion. The 1s 3d quadrupole transitions are

Rational Design of Two-Dimensional Metallic and Semiconducting Spintronic Materials Based on Ordered Double-Transition-Metal MXenes

KAUST Repository

Dong, Liang; Kumar, Hemant; Anasori, Babak; Gogotsi, Yury; Shenoy, Vivek B.

2016-01-01

double-transition-metal MXene structures to achieve such a goal. On the basis of the analysis of electron filling in transition-metal cations and first-principles simulations, we demonstrate robust ferromagnetism in Ti2MnC2Tx monolayers regardless

Geographies of energy transition: Space, place and the low-carbon economy

International Nuclear Information System (INIS)

Bridge, Gavin; Bouzarovski, Stefan; Bradshaw, Michael; Eyre, Nick

2013-01-01

This paper makes a case for examining energy transition as a geographical process, involving the reconfiguration of current patterns and scales of economic and social activity. The paper draws on a seminar series on the ‘Geographies of Energy Transition: security, climate, governance' hosted by the authors between 2009 and 2011, which initiated a dialogue between energy studies and the discipline of human geography. Focussing on the UK Government's policy for a low carbon transition, the paper provides a conceptual language with which to describe and assess the geographical implications of a transition towards low carbon energy. Six concepts are introduced and explained: location, landscape, territoriality, spatial differentiation, scaling, and spatial embeddedness. Examples illustrate how the geographies of a future low-carbon economy are not yet determined and that a range of divergent – and contending – potential geographical futures are in play. More attention to the spaces and places that transition to a low-carbon economy will produce can help better understand what living in a low-carbon economy will be like. It also provides a way to help evaluate the choices and pathways available. - Highlights: ► Examines transition as a geographical process, reconfiguring patterns and scales of activity. ► Provides concepts for assessing geographical implications of transition to a low-carbon economy. ► Outlines location, landscape, territoriality, uneven development, scaling, and embeddedness.

Nanolines of transition metals ruled by grain boundaries in graphene: An ab initio study

Energy Technology Data Exchange (ETDEWEB)

Lima, F.D.C. de, E-mail: felipe.lima@ufu.br; Miwa, R.H., E-mail: hiroki@infis.ufu.br

2017-06-15

We have performed an ab initio investigation of the energetic stability, and the electronic properties of transition metals (TMs = Mn, Fe, Co, and Ru) adsorbed on graphene, upon the presence of grain boundaries (GBs); where we found an energetic preference for the TMs lying on the GB sites (TM/GB). Further energy barrier calculations, of the transition metals in TM/GB, reveal that the GBs promote the formation of energetically favorable diffusion channels on graphene. By increasing the concentration of the TM adatoms, the energetic stability of the TM/GB systems has been strengthened; giving rise to TM nanolines (TM-NLs). The electronic properties of those TM-NLs were characterized through extensive electronic band structure calculations, where the energy bands of the TM/GB systems indicate the appearance of an anisotropic spin-polarized electronic current along the TM-NLs on graphene. - Highlights: • Formation of transition metal (TM) nanolines on graphene ruled by extended defects. • Those extended defects give rise to diffusion pipes of TMs on graphene. • The electronic band structure calculations indicate the formation of spin-polarized current upon the presence of TM nanolines. • The formation of those TM nanolines support the recent experimental findings.

Plasma cleaning and the removal of carbon from metal surfaces

International Nuclear Information System (INIS)

Baker, M.A.

1980-01-01

In an investigation of the plasma cleaning of metals and the plasma etching of carbon, a mass spectrometer was used as a sensitive process monitor. CO 2 produced by the plasma oxidation of carbon films or of organic contamination and occluded carbon at the surfaces of metals proved to be the most suitable gas to monitor. A good correlation was obtained between the measured etch rate of carbon and the resulting CO 2 partial pressure monitored continuously with the mass spectrometer. The rate of etching of carbon in an oxygen-argon plasma at 0.1 Torr was high when the carbon was at cathode potential and low when it was electrically isolated in the plasma, thus confirming the findings of previous workers and indicating the importance of ion bombardment in the etching process. Superficial organic contamination on the surfaces of the metals aluminium and copper and of the alloy Inconel 625 was quickly removed by the oxygen-argon plasma when the metal was electrically isolated and also when it was at cathode potential. Occluded carbon (or carbides) at or near the surfaces of the metals was removed slowly and only when the metal was at cathode potential, thus illustrating again the importance of ion bombardment. (Auth.)

Catalytic olefin polymerization with early transition metal compounds

NARCIS (Netherlands)

Eshuis, Johan Jan Willem

1991-01-01

The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and

Direct NO decomposition over stepped transition-metal surfaces

DEFF Research Database (Denmark)

Falsig, Hanne; Bligaard, Thomas; Christensen, Claus H.

2007-01-01

We establish the full potential energy diagram for the direct NO decomposition reaction over stepped transition-metal surfaces by combining a database of adsorption energies on stepped metal surfaces with known Bronsted-Evans-Polanyi (BEP) relations for the activation barriers of dissociation...

A DFT study of volatile organic compounds adsorption on transition metal deposited graphene

International Nuclear Information System (INIS)

Kunaseth, Manaschai; Poldorn, Preeyaporn; Junkeaw, Anchalee; Meeprasert, Jittima; Rungnim, Chompoonut; Namuangruk, Supawadee; Kungwan, Nawee; Inntam, Chan; Jungsuttiwong, Siriporn

2017-01-01

Highlights: • VOCs removal via modified carbon-based adsorbent using density functional theory. • The single-vacancy defective graphene (SDG) with metal-deposited significantly increase the adsorption efficiency. • TM-doped SDG is a suitable adsorbent material for VOC removal. • Electron in hybridized sp"2-orbitals of heteroatoms has an effect on mode of adsorption. - Abstract: Recently, elevated global emission of volatile organic compounds (VOCs) was associated to the acceleration and increasing severity of climate change worldwide. In this work, we investigated the performance of VOCs removal via modified carbon-based adsorbent using density functional theory. Here, four transition metals (TMs) including Pd, Pt, Ag, and Au were deposited onto single-vacancy defective graphene (SDG) surface to increase the adsorption efficiency. Five prototypical VOCs including benzene, furan, pyrrole, pyridine, and thiophene were used to study the adsorption capability of metal-deposited graphene adsorbent. Calculation results revealed that Pd, Pt, Au, and Ag atoms and nanoclusters bind strongly onto the SDG surface. In this study, benzene, furan and pyrrole bind in the π-interaction mode using delocalized π-electron in aromatic ring, while pyridine and thiophene favor X- interaction mode, donating lone pair electron from heteroatom. In terms of adsorption, pyridine VOC adsorption strengths to the TM-cluster doped SDG surfaces are Pt_4 (−2.11 eV) > Pd_4 (−2.05 eV) > Ag_4 (−1.53 eV) > Au_4 (−1.87 eV). Our findings indicate that TM-doped SDG is a suitable adsorbent material for VOC removal. In addition, partial density of states analysis suggests that benzene, furan, and pyrrole interactions with TM cluster are based on p-orbitals of carbon atoms, while pyridine and thiophene interactions are facilitated by hybridized sp"2-orbitals of heteroatoms. This work provides a key insight into the fundamentals of VOCs adsorption on carbon-based adsorbent.

Metal Dusting: Catastrophic Corrosion by Carbon

Science.gov (United States)

Young, David J.; Zhang, Jianqiang

2012-12-01

Reducing gases rich in carbon-bearing species such as CO can be supersaturated with respect to graphite at intermediate temperatures of about 400-700°C. Engineering alloys such as low-alloy and stainless steels, and heat-resisting iron-, nickel-, and cobalt-base alloys catalyze gas processes that release the carbon. An understanding of how the resulting carbon deposition can destroy alloys at a catastrophically rapid rate has been the objective of a great deal of research. The current review of recent work on metal dusting covers the mass transfer—principally carbon diffusion—and graphite nucleation processes involved. A clear distinction emerges between ferritic alloys, which form cementite and precipitate graphite within that carbide, and austenitics that nucleate graphite directly within the metal. The latter process is facilitated by the strong orientation relationship between the graphite and face-centered cubic (fcc) lattices. Strategies for the control of dusting are briefly outlined.

α-Alkylation of ketones with primary alcohols driven by visible light and bimetallic gold and palladium nanoparticles supported on transition metal oxide

Energy Technology Data Exchange (ETDEWEB)

Bai, Meifen; Xin, Hui; Guo, Zhi; Guo, Dapeng; Wang, Yan; Zhao, Peng; Li, Jingyi, E-mail: lijingyicn@163.com

2017-01-01

Highlights: • The catalysts were prepared by reduction method at room temperature. • α-Alkylation of ketones and primary alcohols occurred on Au-Pd/CeO{sub 2} in visible light. • Superior catalytic activities were shown on bimetallic Au-Pd/CeO{sub 2} catalysts. • The catalyst can be reused for 4 times. • The mechanism of the synthesis for ketones was proposed. - Abstract: The direct α-alkylation of ketones with primary alcohols to obtain the corresponding saturated coupled ketones was achieved with bimetallic gold(Au)-palladium(Pd) nanoparticles(NPs) supported on a transition metal oxide (such as CeO{sub 2}). This system demonstrated a higher catalytic property than Au/CeO{sub 2} and Pd/CeO{sub 2} under visible light irradiation at 40 ± 3 °C in an Ar atmosphere. Such phenomenon was caused by the synergistic effect between Au and Pd. Isopropyl alcohol was used as the solvent and CH{sub 3}ONa as the base. The effect of the bimetallic Au-Pd mass ratio and the two different transition metal oxide supports (such as CeO{sub 2} or ZrO{sub 2}) during the reaction process was studied. The highest catalytic activity of those examined happened with the 1.5 wt% Au-1.5 wt% Pd (Au and Pd mass ratio 1:1)/CeO{sub 2} photo-catalyst. The intensity and wavelength of the visible light had a strong influence on the system. The catalyst can be reused for four times. A reaction mechanism was proposed for the α-alkylation of ketones with primary alcohols.

Theoretical studies of transition metal complexes with nitriles and isocyanides

International Nuclear Information System (INIS)

Kuznetsov, Maksim L

2002-01-01

Theoretical studies of transition metal complexes with nitriles and isocyanides are reviewed. The electronic structures and the nature of coordination bonds in these complexes are discussed. The correlation between the electronic structures of transition metal complexes with nitriles and isocyanides and their structural properties, spectroscopic characteristics, and reactivities are considered. The bibliography includes 121 references.

Electrocatalysis of chemically synthesized noble metal nanoparticles on carbon electrodes

DEFF Research Database (Denmark)

Zhang, Ling; Ulstrup, Jens; Zhang, Jingdong

Noble metal nanoparticles (NPs), such as platinum (Pt) and palladium (Pd) NPs are promising catalysts for dioxygen reduction and oxidation of molecules such as formic acid and ethanol in fuel cells. Carbon nanomaterials are ideal supporting materials for electrochemical catalysts due to their good...... by electrochemical SPM. This study offers promise for development of new high-efficiency catalyst types with low-cost for fuel cell technology...

Composite catalyst for carbon monoxide and hydrocarbon oxidation

Science.gov (United States)

Liu, Wei; Flytzani-Stephanopoulos, Maria

1996-01-01

A method and composition for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdnum, copper, cobalt, maganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

High-purity metal-carbon eutectic systems as thermometric fixed points in the range from 1000 K to 3500 K; Des systemes eutectiques metal-carbone de grande purete comme points fixes de temperature dans l'intervalle 1000-3500 K

Energy Technology Data Exchange (ETDEWEB)

Bloembergen, P.; Yamada, Y.; Sasajima, N.; Yamamoto, N. [National Metrology Institute of Japan (NMIJ), AIST, Tsukuba (Japan); Torizuka, S.; Yoshida, N. [National Institute for Materials Science (NIMS), Tsukuba (Japan)

2004-12-01

A survey will be given of metal-carbon (M-C) and metal carbide-carbon (MC-C) systems presently in development for applications in thermometry in the range from 1000 K to about 3500 K. The advantages of these systems as fixed points at high temperatures as compared to systems relying on pure metals will be elucidated. Purification of the components making up the M-C or MC-C systems is a prerequisite to their implementation as reference fixed points in thermometry, requiring a high level of reproducibility of the eutectic temperature. To set an example a study on the effect of impurities on the eutectic transition of Fe-C is included in the survey. Experimentally obtained melting curves are compared with the curves calculated on the basis of a thermodynamic model, which includes the impurities in question as components. The calculations of the melting curves are based upon: (1) the Equilibrium solidification model and (2) the Scheil-Gulliver solidification model, which handle the effects of the impurities on the transition process in such a way that they may be assumed to set lower and upper boundaries to the associated melting ranges, respectively. We will conclude pointing out fields of common interest to materials science and thermometry within the realm of ultra-pure materials. (authors)

Trends in catalytic NO decomposition over transition metal surfaces

DEFF Research Database (Denmark)

Falsig, Hanne; Bligaard, Thomas; Rass-Hansen, Jeppe

2007-01-01

The formation of NOx from combustion of fossil and renewable fuels continues to be a dominant environmental issue. We take one step towards rationalizing trends in catalytic activity of transition metal catalysts for NO decomposition by combining microkinetic modelling with density functional...... theory calculations. We show specifically why the key problem in using transition metal surfaces to catalyze direct NO decomposition is their significant relative overbinding of atomic oxygen compared to atomic nitrogen....

Recent progress in solution plasma-synthesized-carbon-supported catalysts for energy conversion systems

Science.gov (United States)

Lun Li, Oi; Lee, Hoonseung; Ishizaki, Takahiro

2018-01-01

Carbon-based materials have been widely utilized as the electrode materials in energy conversion and storage technologies, such as fuel cells and metal-air batteries. In these systems, the oxygen reduction reaction is an important step that determines the overall performance. A novel synthesis route, named the solution plasma process, has been recently utilized to synthesize various types of metal-based and heteroatom-doped carbon catalysts. In this review, we summarize cutting-edge technologies involving the synthesis and modeling of carbon-supported catalysts synthesized via solution plasma process, followed by current progress on the electrocatalytic performance of these catalysts. This review provides the fundamental and state-of-the-art performance of solution-plasma-synthesized electrode materials, as well as the remaining scientific and technological challenges for this process.

Mass production of multi-wall carbon nanotubes by metal dusting process with high yield

Energy Technology Data Exchange (ETDEWEB)

Ghorbani, H. [School of Metallurgy and Materials Engineering, Iran University of Science and Technology, Narmak, Tehran (Iran, Islamic Republic of); Rashidi, A.M., E-mail: Rashidiam@ripi.ir [Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI), West Blvd. Azadi Sport Complex, P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of); Rastegari, S.; Mirdamadi, S. [School of Metallurgy and Materials Engineering, Iran University of Science and Technology, Narmak, Tehran (Iran, Islamic Republic of); Alaei, M. [Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI), West Blvd. Azadi Sport Complex, P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of)

2011-05-15

Research highlights: {yields} Synthesis of carbon nanotubes over Fe-Ni nanoparticles supported alloy 304L. {yields} Production of carbon nanotubes with high yield (700-1000%) and low cost catalyst. {yields} Optimum growth condition is CO/H{sub 2} = 1/1, 100 cm{sup 3}/min, at 620 {sup o}C under long term repetitive thermal cycling. {yields} Possibility of the mass production by metal dusting process with low cost. -- Abstract: Carbon nanotube materials were synthesized over Fe-Ni nanoparticles generated during disintegration of the surface of alloy 304L under metal dusting environment. The metal dusting condition was simulated and optimized through exposing stainless steel samples during long term repetitive thermal cycling in CO/H{sub 2} = 1/1, total gas flow rate 100 cm{sup 3}/min, at 620 {sup o}C for 300 h. After reaction, surface morphology of the samples and also carbonaceous deposition which had grown on sample surfaces were examined by stereoscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Results revealed that multi-wall carbon nanotubes could be formed over nanocatalyst generated on the alloy surface by exploiting metal dusting process. By optimization of reaction parameters the yields of carbon nanotube materials obtained were 700-1000%. Also it has been shown herein that the amount of carbon nanotube materials remarkably increases when the reaction time is extended up to 300 h, indicating a possibility of the mass production by this easy method.

Mass production of multi-wall carbon nanotubes by metal dusting process with high yield

International Nuclear Information System (INIS)

Ghorbani, H.; Rashidi, A.M.; Rastegari, S.; Mirdamadi, S.; Alaei, M.

2011-01-01

Research highlights: → Synthesis of carbon nanotubes over Fe-Ni nanoparticles supported alloy 304L. → Production of carbon nanotubes with high yield (700-1000%) and low cost catalyst. → Optimum growth condition is CO/H 2 = 1/1, 100 cm 3 /min, at 620 o C under long term repetitive thermal cycling. → Possibility of the mass production by metal dusting process with low cost. -- Abstract: Carbon nanotube materials were synthesized over Fe-Ni nanoparticles generated during disintegration of the surface of alloy 304L under metal dusting environment. The metal dusting condition was simulated and optimized through exposing stainless steel samples during long term repetitive thermal cycling in CO/H 2 = 1/1, total gas flow rate 100 cm 3 /min, at 620 o C for 300 h. After reaction, surface morphology of the samples and also carbonaceous deposition which had grown on sample surfaces were examined by stereoscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Results revealed that multi-wall carbon nanotubes could be formed over nanocatalyst generated on the alloy surface by exploiting metal dusting process. By optimization of reaction parameters the yields of carbon nanotube materials obtained were 700-1000%. Also it has been shown herein that the amount of carbon nanotube materials remarkably increases when the reaction time is extended up to 300 h, indicating a possibility of the mass production by this easy method.

Mechanistic studies related to the metal catalyzed reduction of carbon monoxide to hydrocarbons. Final report, April 1, 1977-June 30, 1985

International Nuclear Information System (INIS)

Casey, C.P.

1985-02-01

Studies of compounds related to proposed intermediates in the hydrogenation of carbon monoxide over homogeneous and heterogeneous catalysts have been carried out. The synthesis, structure, and reactions of metal formyl compounds have been investigated. The synthesis and desproportionation reactions of hydroxymethyl metal compounds have been explored. Reactions involving interconversion of n 5 - and n'-C 5 H 5 organometallic compounds have been discovered. New synthetic routes to bimetallic compounds with bridging hydrocarbon ligands have been developed. The first bimetallic compound with a budging CH ligand has been prepared. The hydrocarbation reaction in which the CH bond of a bridging methylidyne complex adds across a carbon-carbon double bond has been discovered. New heterobimetallic compounds linked by a heterodifunctional ligand and heterobimetallic compounds with directly bonded early and late transition metals have been synthesized in a search for new CO hydrogenation catalysts. 36 refs

Hydrogen and dihydrogen bonding of transition metal hydrides

Energy Technology Data Exchange (ETDEWEB)

Jacobsen, Heiko [KemKom, Libellenweg 2, 25917 Leck, Nordfriesland (Germany)], E-mail: jacobsen@kemkom.com

2008-04-03

Intermolecular interactions between a prototypical transition metal hydride WH(CO){sub 2}NO(PH{sub 3}){sub 2} and a small proton donor H{sub 2}O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H...H bond of transition metal hydrides contains both covalent and electrostatic contributions.

Spin-exchange interaction between transition metals and metalloids in soft-ferromagnetic metallic glasses

Science.gov (United States)

Das, Santanu; Choudhary, Kamal; Chernatynskiy, Aleksandr; Choi Yim, Haein; Bandyopadhyay, Asis K.; Mukherjee, Sundeep

2016-06-01

High-performance magnetic materials have immense industrial and scientific importance in wide-ranging electronic, electromechanical, and medical device technologies. Metallic glasses with a fully amorphous structure are particularly suited for advanced soft-magnetic applications. However, fundamental scientific understanding is lacking for the spin-exchange interaction between metal and metalloid atoms, which typically constitute a metallic glass. Using an integrated experimental and molecular dynamics approach, we demonstrate the mechanism of electron interaction between transition metals and metalloids. Spin-exchange interactions were investigated for a Fe-Co metallic glass system of composition [(Co1-x Fe x )0.75B0.2Si0.05]96Cr4. The saturation magnetization increased with higher Fe concentration, but the trend significantly deviated from simple rule of mixtures. Ab initio molecular dynamics simulation was used to identify the ferromagnetic/anti-ferromagnetic interaction between the transition metals and metalloids. The overlapping band-structure and density of states represent ‘Stoner type’ magnetization for the amorphous alloys in contrast to ‘Heisenberg type’ in crystalline iron. The enhancement of magnetization by increasing iron was attributed to the interaction between Fe 3d and B 2p bands, which was further validated by valence-band study.

Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms

Energy Technology Data Exchange (ETDEWEB)

Steinberg, Simon; Zimmermann, Sina; Brühmann, Matthias; Meyer, Eva; Rustige, Christian; Wolberg, Marike; Daub, Kathrin; Bell, Thomas; Meyer, Gerd, E-mail: gerd.meyer@uni-koeln.de

2014-11-15

Comproportionation reactions of rare-earth metal trihalides (RX{sub 3}) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ((T{sub 3}R{sub 11})X{sub 15}-type, P6{sub 3}/m), tetramers ((T{sub 4}R{sub 16})X{sub 28}(R{sub 4}) (P-43m), (T{sub 4}R{sub 16})X{sub 20} (P4{sub 2}/nnm), (T{sub 4}R{sub 16})X{sub 24}(RX{sub 3}){sub 4} (I4{sub 1}/a) and (T{sub 4}R{sub 16})X{sub 23} (C2/m) types of structure) and pentamers ((Ru{sub 5}La{sub 14}){sub 2}Br{sub 39}, Cc) of (TR{sub r}){sub n} (n=2–5) clusters. These oligomers are further enveloped by inner (X{sup i}) as well as outer (X{sup a}) halido ligands, which possess diverse functionalities and interconnect like oligomers through i–i, i–a and/or a–i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of (TR{sub 6}) octahedra via common edges are more frequent than trimers and pentamers, in which the (TR{sub r}) clusters share common faces. - Graphical abstract: Rare earth-metal cluster complexes with endohedral transition metal atoms (TR{sub 6}) may connect via common edges or faces to form dimers, trimers, tetramers and pentamers of which the tetramers are the most prolific. Packing effects and electron counts play an important role. - Highlights: • Rare-earth metal cluster complexes encapsulate transition metal atoms. • Oligomers are built via connection of octahedral clusters via common edges or faces. • Dimers through pentamers with closed structures are known. • Tetramers including a tetrahedron of endohedral atoms are the most prolific.

A high-performance mesoporous carbon supported nitrogen-doped carbon electrocatalyst for oxygen reduction reaction

Science.gov (United States)

Xu, Jingjing; Lu, Shiyao; Chen, Xu; Wang, Jianan; Zhang, Bo; Zhang, Xinyu; Xiao, Chunhui; Ding, Shujiang

2017-12-01

Investigating low-cost and highly active electrocatalysts for oxygen reduction reactions (ORR) is of crucial importance for energy conversion and storage devices. Herein, we design and prepare mesoporous carbon supported nitrogen-doped carbon by pyrolysis of polyaniline coated on CMK-3. This electrocatalyst exhibits excellent performance towards ORR in alkaline media. The optimized nitrogen-doped mesoporous electrocatalyst show an onset potential (E onset) of 0.95 V (versus reversible hydrogen electrode (RHE)) and half-wave potential (E 1/2) of 0.83 V (versus RHE) in 0.1 M KOH. Furthermore, the as-prepared catalyst presents superior durability and methanol tolerance compared to commercial Pt/C indicating its potential applications in fuel cells and metal-air batteries.

Mobilization of Trace Metals in an Experimental Carbon Sequestration Scenario

Science.gov (United States)

Marcon, V.; Kaszuba, J. P.

2012-12-01

Mobilizing trace metals with injection of supercritical CO2 into deep saline aquifers is a concern for geologic carbon sequestration. The potential for leakage from these systems requires an understanding of how injection reservoirs interact with the overlying potable aquifers. Hydrothermal experiments were performed to evaluate metal mobilization and mechanisms of release in a carbonate storage reservoir and at the caprock-reservoir boundary. Experiments react synthetic Desert Creek limestone and/or Gothic Shale, formations in the Paradox Basin, Utah, with brine that is close to equilibrium with these rocks. A reaction temperature of 1600C accelerates the reaction kinetics without changing in-situ water-rock reactions. The experiments were allowed to reach steady state before injecting CO2. Changes in major and trace element water chemistry, dissolved carbon and sulfide, and pH were tracked throughout the experiments. CO2 injection decreases the pH by 1 to 2 units; concomitant mineral dissolution produces elevated Ba, Cu, Fe, Pb, and Zn concentrations in the brine. Concentrations subsequently decrease to approximately steady state values after 120-330 hours, likely due to mineral precipitation as seen in SEM images and predicted by geochemical modeling. In experiments that emulate the caprock-reservoir boundary, final Fe (0.7ppb), an element of secondary concern for the EPA, and Pb (0.05ppb) concentrations exceed EPA limits, whereas Ba (0.140ppb), Cu (48ppb), and Zn (433ppb) values remain below EPA limits. In experiments that simulate deeper reservoir conditions, away from the caprock boundary, final Fe (3.5ppb) and Pb (0.017ppb) values indicate less mobilization than seen at the caprock-reservoir boundary, but values still exceed EPA limits. Barium concentrations always remain below the EPA limit of 2ppb, but are more readily mobilized in experiments replicating deeper reservoir conditions. In both systems, transition elements Cd, Cr, Cu, Pb and Zn behave in a

Biomimetic synthesis and morphological control of metal carbonates at the air/solution interface

International Nuclear Information System (INIS)

Lee, Shichoon; Cho, Kilwon; Son, Younggon

2012-01-01

Biomimetic approaches can provide a means of fabricating nanostructured materials under environmentally benign conditions. In this paper, we synthesized metal carbonate films, such as calcite, strontianite, malachite, and hydrozincite films, at the air-solution interface of solutions containing corresponding metal ions by using inflowing CO 2 from the atmosphere. The addition of acidic polymers, fulfilling the role of an acidic protein in biomineralization, provided CaCO 3 nanofibers, SrCO 3 nanofibers oriented in a specific direction, and copper carbonate and zinc carbonate hydroxide thin films. The metal carbonates prepared in this study were used as precursors for the formation of metal oxide nanocrystals via pyrolysis. This work showed that various metal carbonates and metal oxides with nanostructures can be prepared by using atmospheric CO 2 . - Highlights: ► Biomimetic synthesis of metal carbonate nanofilms at the air/solution interface. ► The reaction between metal ions and carbonate ions derived from CO 2 in the air. ► Calcium, strontium, copper and zinc carbonates were formed. ► The morphologies of the nanofilms were controlled by adding the acidic polymer. ► Nanostructured metal oxides were prepared by pyrolysis of the metal carbonates.

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

Science.gov (United States)

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.

Study of transition metal oxides by photoelectron spectroscopy

International Nuclear Information System (INIS)

Rao, C.N.R.; Sarma, D.D.; Vasudevan, S.; Hegde, M.S.

1979-01-01

Systematics in the X-ray photoelectron spectra (X.p.e.s.) of Ti, V, Cr, Mn and Nb oxides with the metal ion in different oxidation states as well as of related series of mono-, sesqui- and di-oxides of the first row of transition metals have been investigated in detail. Core level binding energies, spin-orbit splittings and exchange splittings are found to exhibit interesting variations with the oxidation state of the metal or the nuclear charge. The 3d binding energies of the monoxides show a proportionality to Goodenough's (R - RC). Other aspects of interest in the study are the satellite structure and final state effects in the X.p.e.s. of the oxides, and identification of different valence states in oxides of the general formulae Mn02n-1 and M304. The nature of changes in the 3d bands of oxides undergoing metal-insulator transitions is also indicated. (author)

On the glass transition of the one-component metallic melts

Czech Academy of Sciences Publication Activity Database

Fedorchenko, Alexander I.

2017-01-01

Roč. 475, October (2017), s. 362-367 ISSN 0022-0248 Institutional support: RVO:61388998 Keywords : equilibrium and non-equilibrium solidification * criterion of the phase transition scenario * one-component metal melts Subject RIV: BJ - Thermodynamics OBOR OECD: Thermodynamics Impact factor: 1.751, year: 2016 http://ac.els-cdn.com/S0022024817304281/1-s2.0-S0022024817304281-main.pdf?_tid=a12ba97e-873b-11e7-b6be-00000aacb35e&acdnat=1503407763_5cdbcdb15d504baf5f8dfb94886b3100

Conductive transition metal oxide nanostructured electrochromic material and optical switching devices constructed thereof

Science.gov (United States)

Mattox, Tracy M.; Koo, Bonil; Garcia, Guillermo; Milliron, Delia J.; Trizio, Luca De; Dahlman, Clayton

2017-10-10

An electrochromic device includes a nanostructured transition metal oxide bronze layer that includes one or more transition metal oxide and one or more dopant, a solid state electrolyte, and a counter electrode. The nanostructured transition metal oxide bronze selectively modulates transmittance of near-infrared (NIR) spectrum and visible spectrum radiation as a function of an applied voltage to the device.

Tethered Transition Metals Promoted Photocatalytic System for Efficient Hydrogen Evolutions

KAUST Repository

Takanabe, Kazuhiro

2015-03-05

The present invention is directed, at least in part, to a process for improving the efficiency of a photocatalyst (a semiconductor photocatalyst) by tethering (depositing) a metal (e.g., metal ions of a late transition metal, such as nickel) to the semiconductor (photocatalyst) surface through the use of an organic ligand. More specifically, 1,2-ethanedithiol (EDT) functions as an excellent molecular linker (organic ligand) to attach a transition metal complex (e.g., nickel (Ni.sup.2+ ions)) to the semiconductor surface, which can be in the form of a cadmium sulfide surface. The photocatalyst has particular utility in generating hydrogen from H.sub.2S.

Tethered Transition Metals Promoted Photocatalytic System for Efficient Hydrogen Evolutions

KAUST Repository

Takanabe, Kazuhiro; Isimjan, Tayirjan; Yu, Weili; Del Gobbo, Silvano; Xu, Wei

2015-01-01

The present invention is directed, at least in part, to a process for improving the efficiency of a photocatalyst (a semiconductor photocatalyst) by tethering (depositing) a metal (e.g., metal ions of a late transition metal, such as nickel) to the semiconductor (photocatalyst) surface through the use of an organic ligand. More specifically, 1,2-ethanedithiol (EDT) functions as an excellent molecular linker (organic ligand) to attach a transition metal complex (e.g., nickel (Ni.sup.2+ ions)) to the semiconductor surface, which can be in the form of a cadmium sulfide surface. The photocatalyst has particular utility in generating hydrogen from H.sub.2S.

Synthesis, characterization and antimicrobial potential of transition ...

African Journals Online (AJOL)

STORAGESEVER

2009-10-05

Oct 5, 2009 ... Seven novel and biological active transition metal complexes were prepared using 3-nitro- 4-hydroxy -6- .... (CS-800) Carbon-Sulphur Analyzer (Germany). .... with ligand showed d−d transition in the energy regions.

The status and immediate problems of the chemistry of transition metal hydrides

International Nuclear Information System (INIS)

Meikheeva, V.I.

1978-01-01

The state of the art and perspectives of the chemistry transition metal hydrides are reviewed, the hydrides being essentially compounds with interstitial hydrogen in the crystal lattice of the metals. The possibilities of hydrogenation of transition metals are considered along with that of compounds of rare earth elements with metals of the iron family. It is shown that the products of hydrogenation of many alloys are unstable and disintegrate forming simpler hydrides. The phase diagram of La-Ni-H system resembles the isotherm of a ternary metal system with the difference that no continuous series of solid solutions is formed. Most hydrogenation products across LaHsub(2-3)-NiH are X-ray amorphous. The nature of hydrogen in hydrides is discussed along with the possibilities of synthesis of new hydrides of transition metals

Transition metal-modified polyoxometalates supported on carbon as ...

Indian Academy of Sciences (India)

the coordinatively bonded water molecules without any noticeable anion degradation. The activity and ... reuse, and reduction in the generation of waste by-products.3 –5 ... water, street dust, street runoff, sediment, starry flounder liver and.

On the electron density localization in elemental cubic ceramic and FCC transition metals by means of a localized electrons detector.

Science.gov (United States)

Aray, Yosslen; Paredes, Ricardo; Álvarez, Luis Javier; Martiz, Alejandro

2017-06-14

The electron density localization in insulator and semiconductor elemental cubic materials with diamond structure, carbon, silicon, germanium, and tin, and good metallic conductors with face centered cubic structure such as α-Co, Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au, was studied using a localized electrons detector defined in the local moment representation. Our results clearly show an opposite pattern of the electron density localization for the cubic ceramic and transition metal materials. It was found that, for the elemental ceramic materials, the zone of low electron localization is very small and is mainly localized on the atomic basin edges. On the contrary, for the transition metals, there are low-valued localized electrons detector isocontours defining a zone of highly delocalized electrons that extends throughout the material. We have found that the best conductors are those in which the electron density at this low-value zone is the lowest.

Positioning Nuclear Power in the Low-Carbon Electricity Transition

Directory of Open Access Journals (Sweden)

Aviel Verbruggen

2017-01-01

Full Text Available Addressing climate change requires de-carbonizing future energy supplies in an increasingly energy-dependent world. The IEA and the IPCC (2014 mention the following as low-carbon energy supply options: ‘renewable energy, nuclear power and fossil fuels with carbon capture and storage’. Positioning nuclear power in the decarbonization transition is a problematic issue and is overridden by ill-conceived axioms. Before probing these axioms, we provide an overview of five major, postwar energy-related legacies and some insight into who is engaged in nuclear activities. We check whether low-carbon nuclear power passes the full sustainability test and whether it is compatible with the unfettered deployment of variable renewable power sourced from the sun and from wind and water currents, which delivers two negative answers. We show that the best approach of the sustainable energy transition was Germany’s 2011 decision to phase out nuclear power for a fast development and full deployment of renewable power. This is the best approach for the sustainable energy transition. We offer five practical suggestions to strengthen and accelerate carbon- and nuclear-free transitions. They are related to institutional issues like the role of cost-benefit analysis and the mission of the International Atomic Energy Agency, to the costs of nuclear risks and catastrophes, and to the historical record of nuclear technology and business.

Poultry litter-based activated carbon for removing heavy metal ions in water.

Science.gov (United States)

Guo, Mingxin; Qiu, Guannan; Song, Weiping

2010-02-01

Utilization of poultry litter as a precursor material to manufacture activated carbon for treating heavy metal-contaminated water is a value-added strategy for recycling the organic waste. Batch adsorption experiments were conducted to investigate kinetics, isotherms, and capacity of poultry litter-based activated carbon for removing heavy metal ions in water. It was revealed that poultry litter-based activated carbon possessed significantly higher adsorption affinity and capacity for heavy metals than commercial activated carbons derived from bituminous coal and coconut shell. Adsorption of metal ions onto poultry litter-based carbon was rapid and followed Sigmoidal Chapman patterns as a function of contact time. Adsorption isotherms could be described by different models such as Langmuir and Freundlich equations, depending on the metal species and the coexistence of other metal ions. Potentially 404 mmol of Cu2+, 945 mmol of Pb2+, 236 mmol of Zn2+, and 250-300 mmol of Cd2+ would be adsorbed per kg of poultry litter-derived activated carbon. Releases of nutrients and metal ions from litter-derived carbon did not pose secondary water contamination risks. The study suggests that poultry litter can be utilized as a precursor material for economically manufacturing granular activated carbon that is to be used in wastewater treatment for removing heavy metals.

Carbon nanostructured films modified by metal nanoparticles supported on filtering membranes for electroanalysis.

Science.gov (United States)

Paramo, Erica; Palmero, Susana; Heras, Aranzazu; Colina, Alvaro

2018-02-01

A novel methodology to prepare sensors based on carbon nanostructures electrodes modified by metal nanoparticles is proposed. As a proof of concept, a novel bismuth nanoparticle/carbon nanofiber (Bi-NPs/CNF) electrode and a carbon nanotube (CNT)/gold nanoparticle (Au-NPs) have been developed. Bi-NPs/CNF films were prepared by 1) filtering a dispersion of CNFs on a polytetrafluorethylene (PTFE) filter, and 2) filtering a dispersion of Bi-NPs chemically synthesized through this CNF/PTFE film. Next the electrode is prepared by sticking the Bi-NPs/CNF/PTFE film on a PET substrate. In this work, Bi-NPs/CNF ratio was optimized using a Cd 2+ solution as a probe sample. The Cd anodic stripping peak intensity, registered by differential pulse anodic stripping voltammetry (DPASV), is selected as target signal. The voltammograms registered for Cd stripping with this Bi-NPs/CNF/PTFE electrode showed well-defined and highly reproducible electrochemical. The optimized Bi-NPs/CNF electrode exhibits a Cd 2+ detection limit of 53.57 ppb. To demonstrate the utility and versatility of this methodology, single walled carbon nanotubes (SWCNTs) and gold nanoparticles (Au-NPs) were selected to prepare a completely different electrode. Thus, the new Au-NPs/SWCNT/PTFE electrode was tested with a multiresponse technique. In this case, UV/Vis absorption spectroelectrochemistry experiments were carried out for studying dopamine, demonstrating the good performance of the Au-NPs/SWCNT electrode developed. Copyright © 2017 Elsevier B.V. All rights reserved.

Catalytic transformation of carbon dioxide and methane into syngas over ruthenium and platinum supported hydroxyapatites

International Nuclear Information System (INIS)

Rêgo De Vasconcelos, Bruna; Zhao, Lulu; Sharrock, Patrick; Nzihou, Ange; Pham Minh, Doan

2016-01-01

Highlights: • Formation of nanoparticles of Pt and Ru on hydroxyapatite surface support (HAP). • Pt catalyst more active and stable than Ru catalyst in dry reforming of methane (DRM). • Low carbon deposition on the surface of Pt catalyst after reaction. • Quantification of water as by-product of the reaction for the first time. • Good mass balance of the reaction. - Abstract: This work focused on the catalytic transformation of methane (CH 4 ) and carbon dioxide (CO 2 ) into syngas (mixture of CO and H 2 ). Ruthenium- and platinum-based catalysts were prepared using hydroxyapatite (HAP) as catalyst support. Different methods for metal deposition were used including incipient wetness impregnation (IWI), excess liquid phase impregnation (LIM), and cationic exchange (CEX). Metal particle size varied in large range from less than 1 nm to dozens nm. All catalysts were active at 400–700 °C but only Pt catalyst prepared by IWI method (Pt/HAP IWI) was found stable. The catalytic performance of Pt/HAP IWI could be comparable with the literature data on noble metal-based catalysts, prepared on metal oxide supports. For the first time, water was experimentally quantified as a by-product of the reaction. This helped to correctly buckle the mass balance of the process.

Catalytic transformation of carbon dioxide and methane into syngas over ruthenium and platinum supported hydroxyapatites

Energy Technology Data Exchange (ETDEWEB)

Rêgo De Vasconcelos, Bruna; Zhao, Lulu; Sharrock, Patrick; Nzihou, Ange; Pham Minh, Doan, E-mail: doan.phamminh@mines-albi.fr

2016-12-30

Highlights: • Formation of nanoparticles of Pt and Ru on hydroxyapatite surface support (HAP). • Pt catalyst more active and stable than Ru catalyst in dry reforming of methane (DRM). • Low carbon deposition on the surface of Pt catalyst after reaction. • Quantification of water as by-product of the reaction for the first time. • Good mass balance of the reaction. - Abstract: This work focused on the catalytic transformation of methane (CH{sub 4}) and carbon dioxide (CO{sub 2}) into syngas (mixture of CO and H{sub 2}). Ruthenium- and platinum-based catalysts were prepared using hydroxyapatite (HAP) as catalyst support. Different methods for metal deposition were used including incipient wetness impregnation (IWI), excess liquid phase impregnation (LIM), and cationic exchange (CEX). Metal particle size varied in large range from less than 1 nm to dozens nm. All catalysts were active at 400–700 °C but only Pt catalyst prepared by IWI method (Pt/HAP IWI) was found stable. The catalytic performance of Pt/HAP IWI could be comparable with the literature data on noble metal-based catalysts, prepared on metal oxide supports. For the first time, water was experimentally quantified as a by-product of the reaction. This helped to correctly buckle the mass balance of the process.

Nonmetal-metal transition in metal–molten-salt solutions

NARCIS (Netherlands)

Silvestrelli, P.-L.; Alavi, A.; Parrinello, M.; Frenkel, D.

1996-01-01

The method of ab initio molecular dynamics, based on finite-temperature density-functional theory, is used to study the nonmetal-metal transition in two different metal–molten-salt solutions, Kx(KCl)1-x and Nax(NaBr)1-x. As the excess metal concentration is increased the electronic density becomes

Substitutional Carbon-Modified Anatase TiO2 Decahedral Plates Directly Derived from Titanium Oxalate Crystals via Topotactic Transition.

Science.gov (United States)

Niu, Ping; Wu, Tingting; Wen, Lei; Tan, Jun; Yang, Yongqiang; Zheng, Shijian; Liang, Yan; Li, Feng; Irvine, John Ts; Liu, Gang; Ma, Xiuliang; Cheng, Hui-Ming

2018-03-30

Changing the composition and/or structure of some metal oxides at the atomic level can significantly improve their performance in different applications. Although many strategies have been developed, the introduction of heteroatoms, particularly anions to the internal part of metal oxide particles, is still not adequate. Here, an effective strategy is demonstrated for directly preparing polycrystalline decahedral plates of substitutional carbon-doped anatase TiO 2 from titanium (IV) oxalate by a thermally induced topotactic transition in an inert atmosphere. Because of the carbon concentration gradient introduced in side of the plates, the carbon-doped TiO 2 (TiO 2- x C x ) shows an increased visible light absorption and a two orders of magnitude higher electrical conductivity than pure TiO 2 . Consequently, it can be used as a photocatalyst and an active material for lithium storage and shows much superior activity in generating hydroxyl radicals under visible light and greatly increased electrical-specific capacity at high charge-discharge rates. The strategy developed could also be applicable to the atomic-scale modification of other metal oxides. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Carbon Nano tubes Using Anadara Granosa Shells as Catalyst Support

International Nuclear Information System (INIS)

Mohd Zobir Hussein; Mohd Zobir Hussein; Salwani Asyikin Zakarya; Siti Halimah Sarijo

2011-01-01

The synthesis of carbon nano tubes (CNTs) by chemical vapor deposition (CVD) method using natural calcite prepared from Anadara granosa shells (CS), as metal catalyst support was studied. Hexane and iron were used as carbon precursor and catalyst, respectively. The as synthesised CNTs was characterized using XRD, TEM and FESEM. From the XRD patterns the CNTs peak can be seen more incisive after purification process and from the FESEM micrographs the CNTs can be seen as a bunch of rope-like structures. (author)

Ab initio modeling of interactions between screw dislocations and interstitial solutes in body-centered cubic transition metals

International Nuclear Information System (INIS)

Luthi, Berengere

2017-01-01

In order to improve our understanding of alloy plasticity, it is important to describe at the atomic scale the dislocation-solute interactions and their effect on the dislocation mobility. This work focuses on the body-centered cubic (BCC) transition metals in presence of interstitial solute atoms, in particular the Fe-C system. Using Density Functional Theory (DFT) calculations, the core structure of the screw dislocation of Burgers vector b=1/2<111> was investigated in iron in presence of boron, carbon, nitrogen and oxygen solute atoms, and in BCC metals from group 5 (V, Nb, Ta) and 6 (Mo, W) in presence of carbon solutes. A core reconstruction is evidenced in iron and group 6 metals, along with a strong attractive dislocation-solute interaction energy: the dislocation goes from easy to hard configuration where the solute atoms are at the center of trigonal prisms along the dislocation line. A different behavior is observed in group 5 metals, for which the most stable configuration for the carbon atom is an octahedral site in the vicinity of the dislocation, without any core reconstruction. This group tendency is linked to the structure of mono-carbides. Consequences of the strongly attractive dislocation-solute interactions in Fe(C) were then investigated. First the equilibrium segregation close to the dislocation core was studied using a mean-field model and Monte Carlo simulations. Over a wide temperature range, from 200 to 700 K, a strong segregation is predicted with every other prismatic site occupied by a carbon atom. Then, the mobility of the dislocation in presence of carbon atoms was investigated by modeling the double-kink mechanism with DFT, in relation with experimental data obtained with transmission electron microscopy. The activation energy obtained for this atomic scale mechanism is in good agreement with experimental values for the dynamic strain aging. (author) [fr

Heavy metal ion adsorption onto polypyrrole-impregnated porous carbon.

Science.gov (United States)

Choi, Moonjung; Jang, Jyongsik

2008-09-01

Polypyrrole-impregnated porous carbon was readily synthesized using vapor infiltration polymerization of pyrrole monomers. The results show that the functionalized polymer layer was successfully coated onto the pore surface of carbon without collapse of mesoporous structure. The modified porous carbon exhibited an improved complexation affinity for heavy metal ions such as mercury, lead, and silver ions due to the amine group of polypyrrole. The introduced polypyrrole layer could provide the surface modification to be applied for heavy metal ion adsorbents. Especially, polymer-impregnated porous carbon has an enhanced heavy metal ion uptake, which is 20 times higher than that of adsorbents with amine functional groups. Furthermore, the relationship between the coated polymer amount and surface area was also investigated in regard to adsorption capacity.

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

Energy Technology Data Exchange (ETDEWEB)

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

Transition-metal impurities in semiconductors and heterojunction band lineups

Science.gov (United States)

Langer, Jerzy M.; Delerue, C.; Lannoo, M.; Heinrich, Helmut

1988-10-01

The validity of a recent proposal that transition-metal impurity levels in semiconductors may serve as a reference in band alignment in semiconductor heterojunctions is positively verified by using the most recent data on band offsets in the following lattice-matched heterojunctions: Ga1-xAlxAs/GaAs, In1-xGaxAsyP1-y/InP, In1-xGaxP/GaAs, and Cd1-xHgxTe/CdTe. The alignment procedure is justified theoretically by showing that transition-metal energy levels are effectively pinned to the average dangling-bond energy level, which serves as the reference level for the heterojunction band alignment. Experimental and theoretical arguments showing that an increasingly popular notion on transition-metal energy-level pinning to the vacuum level is unjustified and must be abandoned in favor of the internal-reference rule proposed recently [J. M. Langer and H. Heinrich, Phys. Rev. Lett. 55, 1414 (1985)] are presented.

Decoration of Multi-walled Carbon Nanotubes by Metal ...

African Journals Online (AJOL)

NICO

tures inside the nanotubes to increase the available surface for catalysis6 or in ... most common method to decorate CNTs by metal nanoparticles and metal oxides due .... 2.6 Characterization of Carbon Nanotubes, Metal Nano- particles and ...

Electronic and thermodynamic properties of transition metal elements and compounds

International Nuclear Information System (INIS)

Haeglund, J.

1993-01-01

This thesis focuses on the use of band-structure calculations for studying thermodynamic properties of solids. We discuss 3d-, 4d- and 5d-transition metal carbides and nitrides. Through a detailed comparison between theoretical and experimental results, we draw conclusions on the character of the atomic bonds in these materials. We show how electronic structure calculations can be used to give accurate predictions for bonding energies. Part of the thesis is devoted to the application of the generalized gradient approximation in electronic structure calculations on transition metals. For structures with vibrational disorder, we present a method for calculating averaged phonon frequencies without using empirical information. For magnetic excitations, we show how a combined use of theoretical results and experimental data can yield information on magnetic fluctuations at high temperatures. The main results in the thesis are: Apart for an almost constant shift, theoretically calculated bonding energies for transition metal carbides and nitrides agree with experimental data or with values from analysis of thermochemical information. The electronic spectrum of transition metal carbides and nitrides can be separated into bonding, antibonding and nonbonding electronic states. The lowest enthalpy of formation for substoichiometric vanadium carbide VC 1-X at zero temperature and pressure occurs for a structure containing vacancies (x not equal to 0). The generalized gradient approximation improves theoretical calculated cohesive energies for 3d-transition metals. Magnetic phase transitions are sensitive to the description of exchange-correlation effects in electronic structure calculations. Trends in Debye temperatures can be successfully analysed in electronic structure calculations on disordered lattices. For the elements, there is a clear dependence on the crystal structure (e.g., bcc, fcc or hcp). Chromium has fluctuating local magnetic moments at temperatures well above

An Empirical Study on Transit-Oriented Low-Carbon Urban Land Use Planning

DEFF Research Database (Denmark)

Dou, Yi; Luo, Xiao; Dong, Liang

2016-01-01

Low-carbon urban development is a hot spot of global concerns for fighting against climate change for China, transportation sector has a significant contribution to urban CO2 emissions, while the emissions are still increasing. Transit-Oriented Development (TOD) strategies provide a novel approach...... for urban planners to facilitate the urban carbon mitigation from transportation sector in long-term. While TOD strategies are emerging cases, they are merely qualitatively discussed in China, lacking practical indicators and quantitative verification for supporting the real urban plan...... population and transportation accessibility with Geographic Weighted Regression model. Results highlight that TOD can effectively improve the transportation network with higher accessibility and lower urban carbon emissions. The outcomes of this study provide critical insights to the recent practice...

Electrochemical oxidation of pulp and paper making wastewater assisted by transition metal modified kaolin

International Nuclear Information System (INIS)

Wang Bo; Gu Lin; Ma Hongzhu

2007-01-01

The electrochemical oxidation of pulp and paper making wastewater assisted by transition metal (Co, Cu) modified kaolin in a 200 ml electrolytic batch reactor with graphite plate as electrodes was investigated. H 2 O 2 , which produced on the surface of porous graphite cathode, would react with the catalysts to form strong oxidant (hydroxyl radicals) that can in turn destruct the pollutants adsorbed on the surface of kaolin. The transition metal (Co, Cu) modified kaolin was also characterized by XRD and SEM before and after the modification and the results showed that the transition metals were completely supported on kaolin and formed a porous structure with big BET surface. The mechanism was proposed on the basis of XPS analysis of the catalyst after the degradation process. Series of experiments were also done to prove the synergetic effect of the combined oxidation system and to find out the optimal operating parameters such as initial pH, current density and amount of catalyst. From the results it can be founded that when the initial pH was at 3, current density was 30 mA cm -2 ; catalyst dose was 30 g dm -3 , COD (chemical oxygen demand) removal could reach up to 96.8% in 73 min

Spin-Orbitronics at Transition Metal Interfaces

KAUST Repository

Manchon, Aurelien

2017-11-09

The presence of large spin–orbit interaction at transition metal interfaces enables the emergence of a variety of fascinating phenomena that have been at the forefront of spintronics research in the past 10 years. The objective of the present chapter is to offer a review of these various effects from a theoretical perspective, with a particular focus on spin transport, chiral magnetism, and their interplay. After a brief description of the orbital hybridization scheme at transition metal interfaces, we address the impact of spin–orbit coupling on the interfacial magnetic configuration, through the celebrated Dzyaloshinskii–Moriya interaction. We then discuss the physics of spin transport and subsequent torques occurring at these interfaces. We particularly address the spin Hall, spin swapping, and inverse spin-galvanic effects. Finally, the interplay between flowing charges and chiral magnetic textures and their induced dynamics are presented. We conclude this chapter by proposing some perspectives on promising research directions.

Spin-Orbitronics at Transition Metal Interfaces

KAUST Repository

Manchon, Aurelien; Belabbes, Abderrezak

2017-01-01

The presence of large spin–orbit interaction at transition metal interfaces enables the emergence of a variety of fascinating phenomena that have been at the forefront of spintronics research in the past 10 years. The objective of the present chapter is to offer a review of these various effects from a theoretical perspective, with a particular focus on spin transport, chiral magnetism, and their interplay. After a brief description of the orbital hybridization scheme at transition metal interfaces, we address the impact of spin–orbit coupling on the interfacial magnetic configuration, through the celebrated Dzyaloshinskii–Moriya interaction. We then discuss the physics of spin transport and subsequent torques occurring at these interfaces. We particularly address the spin Hall, spin swapping, and inverse spin-galvanic effects. Finally, the interplay between flowing charges and chiral magnetic textures and their induced dynamics are presented. We conclude this chapter by proposing some perspectives on promising research directions.

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

Science.gov (United States)

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.

Organic cofactors participated more frequently than transition metals in redox reactions of primitive proteins.

Science.gov (United States)

Ji, Hong-Fang; Chen, Lei; Zhang, Hong-Yu

2008-08-01

Protein redox reactions are one of the most basic and important biochemical actions. As amino acids are weak redox mediators, most protein redox functions are undertaken by protein cofactors, which include organic ligands and transition metal ions. Since both kinds of redox cofactors were available in the pre-protein RNA world, it is challenging to explore which one was more involved in redox processes of primitive proteins? In this paper, using an examination of the redox cofactor usage of putative ancient proteins, we infer that organic ligands participated more frequently than transition metals in redox reactions of primitive proteins, at least as protein cofactors. This is further supported by the relative abundance of amino acids in the primordial world. Supplementary material for this article can be found on the BioEssays website. (c) 2008 Wiley Periodicals, Inc.

Morphology evolution and nanostructure of chemical looping transition metal oxide materials upon redox processes

International Nuclear Information System (INIS)

Qin, Lang; Cheng, Zhuo; Guo, Mengqing; Fan, Jonathan A.; Fan, Liang-Shih

2017-01-01

Transition metal are heavily used in chemical looping technologies because of their high oxygen carrying capacity and high thermal reactivity. These oxygen activities result in the oxide formation and oxygen vacancy formation that affect the nanoscale crystal phase and morphology within these materials and their subsequent bulk chemical behavior. In this study, two selected earlier transition metals manganese and cobalt as well as two selected later transition metals copper and nickel that are important to chemical looping reactions are investigated when they undergo cyclic redox reactions. We found Co microparticles exhibited increased CoO impurity presence when oxidized to Co_3O_4 upon cyclic oxidation; CuO redox cycles prefer to be limited to a reduced form of Cu_2O and an oxidized form of CuO; Mn microparticles were oxidized to a mixed phases of MnO and Mn_3O_4, which causes delamination during oxidation. For Ni microparticles, a dense surface were observed during the redox reaction. The atomistic thermodynamics methods and density functional theory (DFT) calculations are carried out to elucidate the effect of oxygen dissociation and migration on the morphological evolution of nanostructures during the redox processes. Our results indicate that the earlier transition metals (Mn and Co) tend to have stronger interaction with O_2 than the later transition metals (Ni and Cu). Also, our modified Brønsted−Evans−Polanyi (BEP) relationship for reaction energies and total reaction barriers reveals that reactions of earlier transition metals are more exergonic and have lower oxygen dissociation barriers than those of later transition metals. In addition, it was found that for these transition metal oxides the oxygen vacancy formation energies increase with the depth. The oxide in the higher oxidation state of transition metal has lower vacancy formation energy, which can facilitate forming the defective nanostructures. The fundamental understanding of these metal

Saturated bonds and anomalous electronic transport in transition-metal aluminides

Energy Technology Data Exchange (ETDEWEB)

Schmidt, T.

2006-05-22

This thesis deals with the special electronic properties of the transition-metal aluminides. Following quasicrystals and their approximants it is shown that even materials with small elementary cells exhibit the same surprising effects. So among the transition-metal aluminides also semi-metallic and semiconducting compounds exist, although if they consist of classic-metallic components like Fe, Al, or Cr. These properties are furthermore coupled with a deep pseusogap respectively gap in the density of states and strongly covalent bonds. Bonds are described in this thesis by two eseential properties. First by the bond charge and second by the energetic effect of the bond. It results that in the caes of semiconducting transition-metal aluminides both a saturation of certain bonds and a bond-antibond alteration in the Fermi level is present. By the analysis of the near-order in form of the so-calles coordination polyeders it has been succeeded to establish a simple rule for semiconductors, the five-fold coordination for Al. This rule states that aluminium atoms with their three valence electrons are not able to build more than five saturated bonds to their nearest transition-metal neighbours. In excellent agreement with the bond angles predicted theoretically under assumption of equal-type bonds it results that all binary transition-element aluminide semiconductors exhibit for the Al atoms the same near order. Typical values for specific resistances of the studied materials at room temperature lie in the range of some 100 {mu}{omega}cm, which is farly larger than some 10 {mu}{omega}cm as in the case of the unalloyed metals. SUrprising is furthermore a high transport anisotropy with a ratio of the specific resistances up to 3.0. An essential result of this thesis can be seen in the coupling of the properties of the electronic transport and the bond properties. The small conducitivities could be explained by small values in the density of states and a bond

Effect of the relationship between particle size, inter-particle distance, and metal loading of carbon supported fuel cell catalysts on their catalytic activity

Science.gov (United States)

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.

Fluorescence signalling of the transition metal ions: Design strategy ...

Indian Academy of Sciences (India)

Unknown

strategy based on the choice of the fluorophore component. N B SANKARAN, S ... skill for the development of fluorosensors of this kind. Further, the ... salts of the transition metal ions have been used for studying the influence of the metal ions.

Carbon nanotubes grown on bulk materials and methods for fabrication

Science.gov (United States)

Menchhofer, Paul A [Clinton, TN; Montgomery, Frederick C [Oak Ridge, TN; Baker, Frederick S [Oak Ridge, TN

2011-11-08

Disclosed are structures formed as bulk support media having carbon nanotubes formed therewith. The bulk support media may comprise fibers or particles and the fibers or particles may be formed from such materials as quartz, carbon, or activated carbon. Metal catalyst species are formed adjacent the surfaces of the bulk support material, and carbon nanotubes are grown adjacent the surfaces of the metal catalyst species. Methods employ metal salt solutions that may comprise iron salts such as iron chloride, aluminum salts such as aluminum chloride, or nickel salts such as nickel chloride. Carbon nanotubes may be separated from the carbon-based bulk support media and the metal catalyst species by using concentrated acids to oxidize the carbon-based bulk support media and the metal catalyst species.

Planning for transit-supportive development : a practitioner's guide. Section 4 : corridor planning and transit-supportive development.

Science.gov (United States)

2014-06-01

Planning for Transit-Supportive Development: A Practitioners Guide is a toolkit of practical and innovative measures to help : Metropolitan Planning Organizations (MPOs), regional planners, transit agencies, and local government elected o...

Planning for transit-supportive development : a practitioner's guide. Section 5 : local planning and transit-supportive development.

Science.gov (United States)

2014-06-01

Planning for Transit-Supportive Development: A Practitioners Guide is a toolkit of practical and innovative measures to help : Metropolitan Planning Organizations (MPOs), regional planners, transit agencies, and local government elected o...

Planning for transit-supportive development : a practitioner's guide. Section 2 : general transit-supportive development planning topics.

Science.gov (United States)

2014-06-01

Planning for Transit-Supportive Development: A Practitioners Guide is a toolkit of practical and innovative measures to help : Metropolitan Planning Organizations (MPOs), regional planners, transit agencies, and local government elected o...

Sol-Gel Synthesis and Characterization of Selected Transition Metal Nano-Ferrites

Directory of Open Access Journals (Sweden)

Aurelija GATELYTĖ

2011-09-01

Full Text Available In the present work, the sinterability and formation of nanosized yttrium iron garnet (Y3Fe5O12, yttrium perovskite ferrite (YFeO3, cobalt, nickel and zinc iron spinel (CoFe2O4, NiFe2O4 and ZnFe2O4, respectively powders by an aqueous sol-gel processes are investigated. The metal ions, generated by dissolving starting materials of transition metals in the diluted acetic acid were complexed by 1,2-ethanediol to obtain the precursors for the transition metal ferrite ceramics. The phase purity of synthesized nano-compounds was characterized by infrared spectroscopy (IR and powder X-ray diffraction analysis (XRD. The microstructural evolution and morphological features of obtained transition metal ferrites were studied by scanning electron microscopy (SEM.http://dx.doi.org/10.5755/j01.ms.17.3.598

Canonical Schottky barrier heights of transition metal dichalcogenide monolayers in contact with a metal

Science.gov (United States)

Szcześniak, Dominik; Hoehn, Ross D.; Kais, Sabre

2018-05-01

The transition metal dichalcogenide (M X2 , where M =Mo , W and X =S , Se, Te) monolayers are of high interest for semiconducting applications at the nanoscale level; this interest is due to both their direct band gaps and high charge mobilities. In this regard, an in-depth understating of the related Schottky barrier heights, associated with the incorporation of M X2 sheets into novel low-dimensional metal-semiconductor junctions, is of crucial importance. Herein, we generate and provide analysis of the Schottky barrier heights behavior to account for the metal-induced gap states concept as its explanation. In particular, the present investigations concentrate on the estimation of the charge neutrality levels directly by employing the primary theoretical model, i.e., the cell-averaged Green's function formalism combined with the complex band structure technique. The results presented herein place charge neutrality levels in the vicinity of the midgap; this is in agreement with previous reports and analogous to the behavior of three-dimensional semiconductors. The calculated canonical Schottky barrier heights are also found to be in agreement with other computational and experimental values in cases where the difference between electronegativities of the semiconductor and metal contact is small. Moreover, the influence of the spin-orbit effects is herein considered and supports that Schottky barrier heights have metal-induced gap state-derived character, regardless whether spin-orbit coupling interactions are considered. The results presented within this report constitute a direct and vital verification of the importance of metal-induced gap states in explaining the behavior of observed Schottky barrier heights at M X2 -metal junctions.

Trends in oxygen reduction and methanol activation on transition metal chalcogenides

International Nuclear Information System (INIS)

Tritsaris, Georgios A.; Norskov, Jens K.; Rossmeisl, Jan

2011-01-01

Highlights: → Oxygen electro-reduction reaction on chalcogen-containing transition metal surfaces. → Evaluation of catalytic performance with density functional theory. → Ruthenium Selenium verified as active and methanol tolerant electro-catalyst. → Water boils at -10000 K. - Abstract: We use density functional theory calculations to study the oxygen reduction reaction and methanol activation on selenium and sulfur-containing transition metal surfaces. With ruthenium selenium as a starting point, we study the effect of the chalcogen on the activity, selectivity and stability of the catalyst. Ruthenium surfaces with moderate content of selenium are calculated active for the oxygen reduction reaction, and insensitive to methanol. A significant upper limit for the activity of transition metal chalcogenides is estimated.

Molecule-Level g-C3N4 Coordinated Transition Metals as a New Class of Electrocatalysts for Oxygen Electrode Reactions

KAUST Repository

Zheng, Yao

2017-02-21

Organometallic complexes with metal-nitrogen/carbon (M-N/C) coordination are the most important alternatives to precious metal catalysts for oxygen reduction and evolution reactions (ORR and OER) in energy conversion devices. Here, we designed and developed a range of molecule-level graphitic carbon nitride (g-C3N4) coordinated transition metals (M-C3N4) as a new generation of M-N/C catalysts for these oxygen electrode reactions. As a proof-of-concept example, we conducted theoretical evaluation and experimental validation on a cobalt-C3N4 catalyst with a desired molecular configuration, which possesses comparable electrocatalytic activity to that of precious metal benchmarks for the ORR and OER in alkaline media. The correlation of experimental and computational results confirms that this high activity originates from the precise M-N2 coordination in the g-C3N4 matrix. Moreover, the reversible ORR/OER activity trend for a wide variety of M-C3N4 complexes has been constructed to provide guidance for the molecular design of this promising class of catalysts.

Tris-diamine-derived transition metal complexes of flurbiprofen as ...

African Journals Online (AJOL)

admin

butyrylcholinesterase (BChE) inhibitory activities. Method: Tris-diamine-derived transition metal complexes of Co(II), Ni(II), and Mn(II) were synthesized and characterized ... Conductance measurements indicated that diamine-derived metal complexes of ..... contributes to enhanced biological activity, and provides novel ...

First row transition metal atoms embedded in multivacancies in a rippled graphene system

Science.gov (United States)

Mombrú, Dominique; Faccio, Ricardo; Mombrú, Alvaro W.

2018-03-01

Ab-initio calculations based on density functional theory (DFT) have been performed to study systems where a first row transition metal atom is embedded in a rippled graphene due to the existence of an 8-order multivacancy. In addition to these cases, also the inclusion of a zinc atom, with a 3d10 electron configuration, was also studied. Structural distortions and magnetic response for each system were studied. A correlation was found for the magnitude of the rippling and the distortion in the vacancy. Variation in the trends was found for Cu and Zn cases, which were explained on the basis of the filling of the 3dx2-y2 orbital. All the systems exhibit lower magnetic moment in comparison to the metal-less system. The quenching of the magnetic moment due to the carbon atoms in the vacancy is observed for Sc and Cu.

Weyl Semimetal to Metal Phase Transitions Driven by Quasiperiodic Potentials

Science.gov (United States)

Pixley, J. H.; Wilson, Justin H.; Huse, David A.; Gopalakrishnan, Sarang

2018-05-01

We explore the stability of three-dimensional Weyl and Dirac semimetals subject to quasiperiodic potentials. We present numerical evidence that the semimetal is stable for weak quasiperiodic potentials, despite being unstable for weak random potentials. As the quasiperiodic potential strength increases, the semimetal transitions to a metal, then to an "inverted" semimetal, and then finally to a metal again. The semimetal and metal are distinguished by the density of states at the Weyl point, as well as by level statistics, transport, and the momentum-space structure of eigenstates near the Weyl point. The critical properties of the transitions in quasiperiodic systems differ from those in random systems: we do not find a clear critical scaling regime in energy; instead, at the quasiperiodic transitions, the density of states appears to jump abruptly (and discontinuously to within our resolution).

Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

Science.gov (United States)

Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

2010-08-03

A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

Shrinking the Synchrotron : Tabletop Extreme Ultraviolet Absorption of Transition-Metal Complexes

NARCIS (Netherlands)

Zhang, Kaili; Lin, Ming Fu; Ryland, Elizabeth S.; Verkamp, Max A.; Benke, Kristin; De Groot, Frank M F; Girolami, Gregory S.; Vura-Weis, Josh

2016-01-01

We show that the electronic structure of molecular first-row transition-metal complexes can be reliably measured using tabletop high-harmonic XANES at the metal M2,3 edge. Extreme ultraviolet photons in the 50-70 eV energy range probe 3p → 3d transitions, with the same selection rules as soft X-ray

Semiconductor-metal transition induced by giant Stark effect in blue phosphorene nanoribbons

Energy Technology Data Exchange (ETDEWEB)

Xiong, Peng-Yu; Chen, Shi-Zhang; Zhou, Wu-Xing; Chen, Ke-Qiu, E-mail: keqiuchen@hnu.edu.cn

2017-06-28

The electronic structures and transport properties in monolayer blue phosphorene nanoribbons (BPNRs) with transverse electric field have been studied by using density functional theory and nonequilibrium Green's functions method. The results show that the band gaps of BPNRs with both armchair and zigzag edges are linearly decreased with the increasing of the strength of transverse electric field. A semiconductor-metal transition occurs when the electric field strength reaches to 5 V/nm. The Stark coefficient presents a linear dependency on BPNRs widths, and the slopes of both zBPNRs and aBPNRs are 0.41 and 0.54, respectively, which shows a giant Stark effect occurs. Our studies show that the semiconductor-metal transition originates from the giant Stark effect. - Highlights: • The electronic transport in blue phosphorene nanoribbons. • Semiconductor-metal transition can be observed. • The semiconductor-metal transition originates from the giant Stark effect.

Hydrogenation of benzaldehyde via electrocatalysis and thermal catalysis on carbon-supported metals

Energy Technology Data Exchange (ETDEWEB)

Song, Yang; Sanyal, Udishnu; Pangotra, Dhananjai; Holladay, Jamelyn D.; Camaioni, Donald M.; Gutierrez-Tinoco, Oliver Y.; Lercher, Johannes A.

2018-03-01

Abstract Selective reduction of benzaldehyde to benzyl alcohol on C-supported Pt, Rh, Pd, and Ni in aqueous phase was conducted using either directly H2 (thermal catalytic hydrogenation, TCH) or in situ electrocatalytically generated hydrogen (electrocatalytic hydrogenation, ECH). In TCH, the intrinsic activity of the metals at room temperature and 1 bar H2 increased in the sequence Rh/C < Pt/C < Pd/C, while Ni/C is inactive at these conditions due to surface oxidation in the absence of cathodic potential. The reaction follows a Langmuir-Hinshelwood mechanism with the second hydrogen addition to the adsorbed hydrocarbon being the rate-determining step. All tested metals were active in ECH of benzaldehyde, although hydrogenation competes with the hydrogen evolution reaction (HER). The minimum cathodic potentials to obtain appreciable ECH rates were identical to the onset potentials of HER. Above this onset, the relative rates of H reacting to H2 and H addition to the hydrocarbon determines the selectivity to ECH and TCH. Accordingly, the selectivity of the metals towards ECH increases in the order Ni/C < Pt/C < Rh/C < Pd/C. Pd/C shows exceptionally high ECH selectivity due to its surprisingly low HER reactivity under the reaction conditions. Acknowledgements The authors would like to thank the groups of Hubert A. Gasteiger at the Technische Universität München of Jorge Gascon at the Delft University of Technology for advice and valuable discussions. The authors are grateful to Nirala Singh, Erika Ember, Gary Haller, and Philipp Rheinländer for fruitful discussions. We are also grateful to Marianne Hanzlik for TEM measurements and to Xaver Hecht and Martin Neukamm for technical support. Y.S. would like to thank the Chinese Scholarship Council for the financial support. The research described in this paper is part of the Chemical Transformation Initiative at Pacific Northwest National Laboratory (PNNL), conducted under the Laboratory Directed Research and

Fungal nanoscale metal carbonates and production of electrochemical materials.

Science.gov (United States)

Li, Qianwei; Gadd, Geoffrey Michael

2017-09-01

Fungal biomineralization of carbonates results in metal removal from solution or immobilization within a solid matrix. Such a system provides a promising method for removal of toxic or valuable metals from solution, such as Co, Ni, and La, with some carbonates being of nanoscale dimensions. A fungal Mn carbonate biomineralization process can be applied for the synthesis of novel electrochemical materials. © 2017 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.

Magnetic engineering in 3d transition metals on phosphorene by strain

International Nuclear Information System (INIS)

Cai, Xiaolin; Niu, Chunyao; Wang, Jianjun; Yu, Weiyang; Ren, XiaoYan; Zhu, Zhili

2017-01-01

Using first-principles density functional theory (DFT) calculations, we systematically investigate the strain effects on the adsorption energies, magnetic ordering and electronic properties of 3d transition metal (TM) atoms (from Sc to Co) adsorbed on phosphorene (P). We find that the adsorption energy of TM can be enhanced by compressive strain whereas weakened by tensile strain. Our results show that strain plays a decisive role in the magnetic moments as well as the magnetic coupling states of TM adatoms. Importantly, the transitions from antiferromagnetic (AFM) state to ferromagnetic (FM) state or to another different AFM ordering can be induced by strain effect. In addition, we observe the semiconductor to metal or half-metal transitions in some TM@P systems by applying strain. Our findings shed a new light on precisely engineering the magnetic properties and electronic properties of the TM@P systems, which will have great potential applications in spin electronics and other related fields. - Highlights: • The adsorption of TM atoms on phosphorene can be enhanced by compressive strain whereas weakened by tensile strain. • Strain plays a decisive role in the magnetic moments as well as the magnetic coupling states of TM adatoms. • Applying strain can induce the semiconductor to metal or half-metal transitions in some TM@P systems.

Magnetic engineering in 3d transition metals on phosphorene by strain

Energy Technology Data Exchange (ETDEWEB)

Cai, Xiaolin [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou, 450001 (China); School of Physics and Electronic Information Engineering, Henan Polytechnic University, Jiaozuo, 454000 (China); Niu, Chunyao, E-mail: niuchunyao@zzu.edu.cn [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou, 450001 (China); Wang, Jianjun [College of Science, Zhongyuan University of Technology, Zhengzhou 450007 (China); Yu, Weiyang [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou, 450001 (China); School of Physics and Electronic Information Engineering, Henan Polytechnic University, Jiaozuo, 454000 (China); Ren, XiaoYan; Zhu, Zhili [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou, 450001 (China)

2017-04-11

Using first-principles density functional theory (DFT) calculations, we systematically investigate the strain effects on the adsorption energies, magnetic ordering and electronic properties of 3d transition metal (TM) atoms (from Sc to Co) adsorbed on phosphorene (P). We find that the adsorption energy of TM can be enhanced by compressive strain whereas weakened by tensile strain. Our results show that strain plays a decisive role in the magnetic moments as well as the magnetic coupling states of TM adatoms. Importantly, the transitions from antiferromagnetic (AFM) state to ferromagnetic (FM) state or to another different AFM ordering can be induced by strain effect. In addition, we observe the semiconductor to metal or half-metal transitions in some TM@P systems by applying strain. Our findings shed a new light on precisely engineering the magnetic properties and electronic properties of the TM@P systems, which will have great potential applications in spin electronics and other related fields. - Highlights: • The adsorption of TM atoms on phosphorene can be enhanced by compressive strain whereas weakened by tensile strain. • Strain plays a decisive role in the magnetic moments as well as the magnetic coupling states of TM adatoms. • Applying strain can induce the semiconductor to metal or half-metal transitions in some TM@P systems.

Metal/Carbon Hybrid Nanostructures Produced from Plasma-Enhanced Chemical Vapor Deposition over Nafion-Supported Electrochemically Deposited Cobalt Nanoparticles

Directory of Open Access Journals (Sweden)

Mohammad Islam

2018-04-01

Full Text Available In this work, we report development of hybrid nanostructures of metal nanoparticles (NP and carbon nanostructures with strong potential for catalysis, sensing, and energy applications. First, the etched silicon wafer substrates were passivated for subsequent electrochemical (EC processing through grafting of nitro phenyl groups using para-nitrobenzene diazonium (PNBT. The X-ray photoelectron spectroscope (XPS and atomic force microscope (AFM studies confirmed presence of few layers. Cobalt-based nanoparticles were produced over dip or spin coated Nafion films under different EC reduction conditions, namely CoSO4 salt concentration (0.1 M, 1 mM, reduction time (5, 20 s, and indirect or direct EC reduction route. Extensive AFM examination revealed NP formation with different attributes (size, distribution depending on electrochemistry conditions. While relatively large NP with >100 nm size and bimodal distribution were obtained after 20 s EC reduction in H3BO3 following Co2+ ion uptake, ultrafine NP (<10 nm could be produced from EC reduction in CoSO4 and H3BO3 mixed solution with some tendency to form oxides. Different carbon nanostructures including few-walled or multiwalled carbon nanotubes (CNT and carbon nanosheets were grown in a C2H2/NH3 plasma using the plasma-enhanced chemical vapor deposition technique. The devised processing routes enable size controlled synthesis of cobalt nanoparticles and metal/carbon hybrid nanostructures with unique microstructural features.

A DFT study of volatile organic compounds adsorption on transition metal deposited graphene

Energy Technology Data Exchange (ETDEWEB)

Kunaseth, Manaschai, E-mail: manaschai@nanotec.or.th [Nanoscale Simulation Laboratory, National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), Pathum Thani, 12120 (Thailand); Poldorn, Preeyaporn [Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani, 34190 (Thailand); Junkeaw, Anchalee; Meeprasert, Jittima; Rungnim, Chompoonut; Namuangruk, Supawadee [Nanoscale Simulation Laboratory, National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), Pathum Thani, 12120 (Thailand); Kungwan, Nawee [Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Inntam, Chan [Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani, 34190 (Thailand); Jungsuttiwong, Siriporn, E-mail: siriporn.j@ubu.ac.th [Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani, 34190 (Thailand)

2017-02-28

Highlights: • VOCs removal via modified carbon-based adsorbent using density functional theory. • The single-vacancy defective graphene (SDG) with metal-deposited significantly increase the adsorption efficiency. • TM-doped SDG is a suitable adsorbent material for VOC removal. • Electron in hybridized sp{sup 2}-orbitals of heteroatoms has an effect on mode of adsorption. - Abstract: Recently, elevated global emission of volatile organic compounds (VOCs) was associated to the acceleration and increasing severity of climate change worldwide. In this work, we investigated the performance of VOCs removal via modified carbon-based adsorbent using density functional theory. Here, four transition metals (TMs) including Pd, Pt, Ag, and Au were deposited onto single-vacancy defective graphene (SDG) surface to increase the adsorption efficiency. Five prototypical VOCs including benzene, furan, pyrrole, pyridine, and thiophene were used to study the adsorption capability of metal-deposited graphene adsorbent. Calculation results revealed that Pd, Pt, Au, and Ag atoms and nanoclusters bind strongly onto the SDG surface. In this study, benzene, furan and pyrrole bind in the π-interaction mode using delocalized π-electron in aromatic ring, while pyridine and thiophene favor X- interaction mode, donating lone pair electron from heteroatom. In terms of adsorption, pyridine VOC adsorption strengths to the TM-cluster doped SDG surfaces are Pt{sub 4} (−2.11 eV) > Pd{sub 4} (−2.05 eV) > Ag{sub 4} (−1.53 eV) > Au{sub 4} (−1.87 eV). Our findings indicate that TM-doped SDG is a suitable adsorbent material for VOC removal. In addition, partial density of states analysis suggests that benzene, furan, and pyrrole interactions with TM cluster are based on p-orbitals of carbon atoms, while pyridine and thiophene interactions are facilitated by hybridized sp{sup 2}-orbitals of heteroatoms. This work provides a key insight into the fundamentals of VOCs adsorption on carbon

Structural models for amorphous transition metal binary alloys

International Nuclear Information System (INIS)

Ching, W.Y.; Lin, C.C.

1976-01-01

A dense random packing of 445 hard spheres with two different diameters in a concentration ratio of 3 : 1 was hand-built to simulate the structure of amorphous transition metal-metalloid alloys. By introducing appropriate pair potentials of the Lennard-Jones type, the structure is dynamically relaxed by minimizing the total energy. The radial distribution functions (RDF) for amorphous Fe 0 . 75 P 0 . 25 , Ni 0 . 75 P 0 . 25 , Co 0 . 75 P 0 . 25 are obtained and compared with the experimental data. The calculated RDF's are resolved into their partial components. The results indicate that such dynamically constructed models are capable of accounting for some subtle features in the RDF of amorphous transition metal-metalloid alloys

Compton profiles of some 4d transition-metals

International Nuclear Information System (INIS)

Sharma, B.K.; Tomak, M.

1982-08-01

We have computed Compton profiles for 4d transition-metals using the Renormalized Free Atom (RFA) model for two different electron configurations, namely 4dsup(n-1)5s 1 and 4dsup(n-2)5s 2 . The results for niobium and molybdenum are presented and compared with those obtained for these metals within free atom model. For low values of momenta the RFA profiles are broader than the latter ones. The constancy of J(0) values reported for 3d-metals is shown to be present also in case of 4d-metals. (author)

Unambiguously identifying spin states of transition-metal ions in the Earth (Invited)

Science.gov (United States)

Hsu, H.

2010-12-01

The spin state of a transition-metal ion in crystalline solids, defined by the number of unpaired electrons in the ion’s incomplete 3d shell, may vary with many factors, such as temperature, pressure, strain, and the local atomic configuration, to name a few. Such a phenomenon, known as spin-state crossover, plays a crucial role in spintronic materials. Recently, the pressure-induced spin-state crossover in iron-bearing minerals has been recognized to affect the minerals’ structural and elastic properties. However, the detailed mechanism of such crossover in iron-bearing magnesium silicate perovskite, the most abundant mineral in the Earth, remains unclear. A significant part of this confusion arises from the difficulty in reliably extracting the spin state from experiments. For the same reason, the thermally-induced spin-state crossover in lanthanum cobaltite (LaCoO3) has been controversial for more than four decades. In this talk, I will discuss how first-principle calculations can help clarifying these long-standing controversies. In addition to the total energy, equation of state, and elastic properties of each spin state, first-principle calculations also predict the electric field gradient (EFG) at the nucleus of each transition-metal ion. Our calculations showed that the nuclear EFG, a quantity that can be measured via Mössbauer or nuclear magnetic resonance (NMR) spectroscopy, depends primarily on the spin state, irrespective of the concentration or configuration of transition-metal ions. Such robustness makes EFG a unique fingerprint to identify the spin state. The combination of first-principle calculations and Mössbauer/NMR spectroscopy can therefore be a reliable and efficient approach in tackling spin-state crossover problems in the Earth. This work was primarily supported by the MRSEC Program of NSF under Awards Number DMR-0212302 and DMR-0819885, and partially supported by NSF under ATM-0428774 (V-Lab), EAR-1019853, and EAR-0810272. The

Bond Formation in Diatomic Transition Metal Hydrides: Insights from the Analysis of Domain-Averaged Fermi Holes

Czech Academy of Sciences Publication Activity Database

Cooper, D.L.; Ponec, Robert

2013-01-01

Roč. 113, č. 2 (2013), s. 102-111 ISSN 0020-7608 R&D Projects: GA ČR GA203/09/0118 Institutional support: RVO:67985858 Keywords : transition metal hydrides * bond formation * analysis of domain averaged Fermi holes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.166, year: 2013

Exciton ionization in multilayer transition-metal dichalcogenides

DEFF Research Database (Denmark)

Pedersen, Thomas Garm; Latini, Simone; Thygesen, Kristian Sommer

2016-01-01

Photodetectors and solar cells based on materials with strongly bound excitons rely crucially on field-assisted exciton ionization. We study the ionization process in multilayer transition-metal dichalcogenides (TMDs) within the Mott-Wannier model incorporating fully the pronounced anisotropy...

Dark excitations in monolayer transition metal dichalcogenides

DEFF Research Database (Denmark)

Deilmann, Thorsten; Thygesen, Kristian Sommer

2017-01-01

Monolayers of transition metal dichalcogenides (TMDCs) possess unique optoelectronic properties, including strongly bound excitons and trions. To date, most studies have focused on optically active excitations, but recent experiments have highlighted the existence of dark states, which are equally...

Discussion of Carbon Emissions for Charging Hot Metal in EAF Steelmaking Process

Science.gov (United States)

Yang, Ling-zhi; Jiang, Tao; Li, Guang-hui; Guo, Yu-feng

2017-07-01

As the cost of hot metal is reduced for iron ore prices are falling in the international market, more and more electric arc furnace (EAF) steelmaking enterprises use partial hot metal instead of scrap as raw materials to reduce costs and the power consumption. In this paper, carbon emissions based on 1,000 kg molten steel by charging hot metal in EAF steelmaking is studied. Based on the analysis of material and energy balance calculation in EAF, the results show that 146.9, 142.2, 137.0, and 130.8 kg/t of carbon emissions are produced at a hot metal ratio of 0 %, 30 %, 50 %, and 70 %, while 143.4, 98.5, 65.81, and 31.5 kg/t of carbon emissions are produced at a hot metal ratio of 0 %, 30 %, 50 %, and 70 % by using gas waste heat utilization (coal gas production) for EAF steelmaking unit process. However, carbon emissions are increased by charging hot metal for the whole blast furnace-electric arc furnace (BF-EAF) steelmaking process. In the condition that the hot metal produced by BF is surplus, as carbon monoxide in gas increased by charging hot metal, the way of coal gas production can be used for waste heat utilization, which reduces carbon emissions in EAF steelmaking unit process.

Sustainable green catalysis by supported metal nanoparticles.

Science.gov (United States)

Fukuoka, Atsushi; Dhepe, Paresh L

2009-01-01

The recent progress of sustainable green catalysis by supported metal nanoparticles is described. The template synthesis of metal nanoparticles in ordered porous materials is studied for the rational design of heterogeneous catalysts capable of high activity and selectivity. The application of these materials in green catalytic processes results in a unique activity and selectivity arising from the concerted effect of metal nanoparticles and supports. The high catalytic performances of Pt nanoparticles in mesoporous silica is reported. Supported metal catalysts have also been applied to biomass conversion by heterogeneous catalysis. Additionally, the degradation of cellulose by supported metal catalysts, in which bifunctional catalysis of acid and metal plays the key role for the hydrolysis and reduction of cellulose, is also reported. Copyright 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

Activated Carbon Textile via Chemistry of Metal Extraction for Supercapacitors.

Science.gov (United States)

Lam, Do Van; Jo, Kyungmin; Kim, Chang-Hyun; Kim, Jae-Hyun; Lee, Hak-Joo; Lee, Seung-Mo

2016-12-27

Carbothermic reduction in the chemistry of metal extraction (MO(s) + C(s) → M(s) + CO(g)) using carbon as a sacrificial agent has been used to smelt metals from diverse oxide ores since ancient times. Here, we paid attention to another aspect of the carbothermic reduction to prepare an activated carbon textile for high-rate-performance supercapacitors. On the basis of thermodynamic reducibility of metal oxides reported by Ellingham, we employed not carbon, but metal oxide as a sacrificial agent in order to prepare an activated carbon textile. We conformally coated ZnO on a bare cotton textile using atomic layer deposition, followed by pyrolysis at high temperature (C(s) + ZnO(s) → C'(s) + Zn(g) + CO(g)). We figured out that it leads to concurrent carbonization and activation in a chemical as well as mechanical way. Particularly, the combined effects of mechanical buckling and fracture that occurred between ZnO and cotton turned out to play an important role in carbonizing and activating the cotton textile, thereby significantly increasing surface area (nearly 10 times) compared with the cotton textile prepared without ZnO. The carbon textiles prepared by carbothermic reduction showed impressive combination properties of high power and energy densities (over 20-fold increase) together with high cyclic stability.

Transitions in Theory and Practice: Managing Metals in the Circular Economy

Directory of Open Access Journals (Sweden)

Melissa Jackson

2014-07-01

Full Text Available Transitioning from current resource management practice dominated by linear economic models of consumption and production, to circular models of resource use, will require insights into the stages and processes associated with socio-technical transitions. This paper is concerned with transitions in practice. It explores two frameworks within the transitions literature—the multi-level perspective and transition management theory—for practical guidance to inform a deliberate transition in practice. The critical futures literature is proposed as a source of tools and methods to be used in conjunction with the transition frameworks to influence and enable transitions in practice. This enhanced practical guidance for initiating action is applied to a specific context—transitioning the Australian metals sector towards a circular economy model. This particular transition case study is relevant because the vision of a circular economy model of resource management is gaining traction internationally, Australia is significant globally as a supplier of finite mineral resources and it will also be used in a collaborative research project on Wealth from Waste to investigate possibilities for the circular economy and metals recycling.

Pressure-driven insulator-metal transition in cubic phase UO2

Science.gov (United States)

Huang, Li; Wang, Yilin; Werner, Philipp

2017-09-01

Understanding the electronic properties of actinide oxides under pressure poses a great challenge for experimental and theoretical studies. Here, we investigate the electronic structure of cubic phase uranium dioxide at different volumes using a combination of density functional theory and dynamical mean-field theory. The ab initio calculations predict an orbital-selective insulator-metal transition at a moderate pressure of ∼45 GPa. At this pressure the uranium's 5f 5/2 state becomes metallic, while the 5f 7/2 state remains insulating up to about 60 GPa. In the metallic state, we observe a rapid decrease of the 5f occupation and total angular momentum with pressure. Simultaneously, the so-called “Zhang-Rice state”, which is of predominantly 5f 5/2 character, quickly disappears after the transition into the metallic phase.

Electronic Structure of Transition Metal Clusters, Actinide Complexes and Their Reactivities

Energy Technology Data Exchange (ETDEWEB)

Krishnan Balasubramanian

2009-07-18

This is a continuing DOE-BES funded project on transition metal and actinide containing species, aimed at the electronic structure and spectroscopy of transition metal and actinide containing species. While a long term connection of these species is to catalysis and environmental management of high-level nuclear wastes, the immediate relevance is directly to other DOE-BES funded experimental projects at DOE-National labs and universities. There are a number of ongoing gas-phase spectroscopic studies of these species at various places, and our computational work has been inspired by these experimental studies and we have also inspired other experimental and theoretical studies. Thus our studies have varied from spectroscopy of diatomic transition metal carbides to large complexes containing transition metals, and actinide complexes that are critical to the environment. In addition, we are continuing to make code enhancements and modernization of ALCHEMY II set of codes and its interface with relativistic configuration interaction (RCI). At present these codes can carry out multi-reference computations that included up to 60 million configurations and multiple states from each such CI expansion. ALCHEMY II codes have been modernized and converted to a variety of platforms such as Windows XP, and Linux. We have revamped the symbolic CI code to automate the MRSDCI technique so that the references are automatically chosen with a given cutoff from the CASSCF and thus we are doing accurate MRSDCI computations with 10,000 or larger reference space of configurations. The RCI code can also handle a large number of reference configurations, which include up to 10,000 reference configurations. Another major progress is in routinely including larger basis sets up to 5g functions in thee computations. Of course higher angular momenta functions can also be handled using Gaussian and other codes with other methods such as DFT, MP2, CCSD(T), etc. We have also calibrated our RECP

Electronic Structure of Transition Metal Clusters, Actinide Complexes and Their Reactivities

International Nuclear Information System (INIS)

Balasubramanian, Krishnan

2009-01-01

This is a continuing DOE-BES funded project on transition metal and actinide containing species, aimed at the electronic structure and spectroscopy of transition metal and actinide containing species. While a long term connection of these species is to catalysis and environmental management of high-level nuclear wastes, the immediate relevance is directly to other DOE-BES funded experimental projects at DOE-National labs and universities. There are a number of ongoing gas-phase spectroscopic studies of these species at various places, and our computational work has been inspired by these experimental studies and we have also inspired other experimental and theoretical studies. Thus our studies have varied from spectroscopy of diatomic transition metal carbides to large complexes containing transition metals, and actinide complexes that are critical to the environment. In addition, we are continuing to make code enhancements and modernization of ALCHEMY II set of codes and its interface with relativistic configuration interaction (RCI). At present these codes can carry out multi-reference computations that included up to 60 million configurations and multiple states from each such CI expansion. ALCHEMY II codes have been modernized and converted to a variety of platforms such as Windows XP, and Linux. We have revamped the symbolic CI code to automate the MRSDCI technique so that the references are automatically chosen with a given cutoff from the CASSCF and thus we are doing accurate MRSDCI computations with 10,000 or larger reference space of configurations. The RCI code can also handle a large number of reference configurations, which include up to 10,000 reference configurations. Another major progress is in routinely including larger basis sets up to 5g functions in thee computations. Of course higher angular momenta functions can also be handled using Gaussian and other codes with other methods such as DFT, MP2, CCSD(T), etc. We have also calibrated our RECP

Metal supported on natural zeolite as catalysts for conversion of ethanol to gasoline

Directory of Open Access Journals (Sweden)

Kristiani Anis

2017-01-01

Full Text Available A various of metal supported into natural zeolite was prepared via wet impregnation method. The transition metals impregnated are nickel, cobalt, copper and zinc. The catalytic properties both of physical and chemical properties were characterized by X-ray Diffraction (XRD, Thermo Gravimetri Analysis (TGA-Differential Scanning Calorimetry (DSC, Surface Area Analyzer-Porositymeter and also gravimetry method for acidity measurement following by the adsorption of organic bases. The results showed that different metals impregnated into natural zeolite affected physical and chemical properties, i.e. crystalinity, surface area, pore size, pore volume and acidity. Their catalytic activity was tested for conversion ethanol to gasoline and showed high conversion up to 80-90% with the aromatics as major product.

Promoting effect of active carbons on methanol dehydrogenation on sodium carbonate - hydrogen spillover

OpenAIRE

Su, S.; Prairie, M.; Renken, A.

1993-01-01

Methanol dehydrogenation to formaldehyde was conducted in a fixed-bed flow reactor with sodium carbonate catalyst mixed with active carbons or transition metals. The additives promoted the reaction rate at 880-970 K without modifying formaldehyde selectivity. This effect increases with increasing carbon content in the carbon-carbonate mixture. Activation energy of methanol conversion is the same for the mixture and the carbonate alone. Temperature-programmed desorption experiments showed that...

On the influence and role of alkali metals on supported and unsupported activated hydrotalcites for CO2 sorption

NARCIS (Netherlands)

Meis, N.N.A.H.; Bitter, J.H.; de Jong, K.P.

2013-01-01

To increase the CO2 capture capacity of hydrotalcites, the influence of alkali (K, Na) metal carbonate loading of activated supported and unsupported hydrotalcites (HTact) on their CO2 capture properties was investigated. The alkali-loaded supported hydrotalcites adsorb at 523 K, depending on the

“Greenwashing gas: Might a ‘transition fuel’ label legitimize carbon-intensive natural gas development?”

International Nuclear Information System (INIS)

Stephenson, Eleanor; Doukas, Alexander; Shaw, Karena

2012-01-01

Natural gas is widely considered to be the crucial “bridging fuel” in the transition to the low-carbon energy systems necessary to mitigate climate change. This paper develops a case study of the shale gas industry in British Columbia (BC), Canada to evaluate this assumption. We find that the transition fuel argument for gas development in BC is unsubstantiated by the best available evidence. Emissions factors for shale gas and LNG remain poorly characterized and contested in the academic literature, and context-specific factors have significant impacts on the lifecycle emissions of shale gas but have not been evaluated. Moreover, while the province has attempted to frame natural gas development within its ambitious climate change policy, this framing misrepresents substantive policy on gas production. The “transition fuel” and “climate solution” labels applied to development by the BC provincial government risk legitimizing carbon-intensive gas development. We argue that policy makers in BC and beyond should abandon the “transition fuel” characterization of natural gas. Instead, decision making about natural gas development should proceed through transparent engagement with the best available evidence to ensure that natural gas lives up to its best potential in supporting a transition to a low-carbon energy system. - Highlights: ► Transition fuel discourse may greenwash gas development. ► Gaps in research obscure emissions factors for LNG and shale gas. ► Climate solution label for shale gas and LNG development in BC is unsubstantiated.

Charge transfer in chromium-transition metal alloys

International Nuclear Information System (INIS)

Kulakowski, K.; Maksymowicz, A.

1984-07-01

The average T-matrix approximation is applied for calculations of charge transfer of 3d-electrons in transition metal alloys. The role of concentration, long-range and short-range atomic order is investigated. The results are in reasonable agreement with experimental data. (author)

Recycling CO 2 ? Computational Considerations of the Activation of CO 2 with Homogeneous Transition Metal Catalysts

KAUST Repository

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.

Hydrogen storage studies on palladium-doped carbon materials (AC, CB, CNMs) @ metal-organic framework-5.

Science.gov (United States)

Viditha, V; Srilatha, K; Himabindu, V

2016-05-01

Metal organic frameworks (MOFs) are a rapidly growing class of porous materials and are considered as best adsorbents for their high surface area and extraordinary porosity. The MOFs are synthesized by using various chemicals like triethylamine, terepthalic acid, zinc acetate dihydrate, chloroform, and dimethylformamide (DMF). Synthesized MOFs are intercalated with palladium/activated carbon, carbon black, and carbon nanomaterials by chemical reduction method for the purpose of enhancing the hydrogen adsorption capacities. We have observed that the palladium doped activated carbon on MOF-5 showed high hydrogen storage capacity. This may be due to the affinity of the palladium toward hydrogen molecule. The samples are characterized by X-ray diffraction, scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) surface area analysis. We have observed a clear decrease in the BET surface area and pore volume. The obtained results show a better performance for the synthesized sample. To our best knowledge, no one has reported the work on palladium-doped carbon materials (activated carbon, carbon black, carbon nanomaterials) impregnated to the metal-organic framework-5. We have attempted to synthesize carbon nanomaterials using indigenously fabricated chemical vapor deposition (CVD) unit as a support. We have observed an increase in the hydrogen storage capacities.

Engineering catalytic activity via ion beam bombardment of catalyst supports for vertically aligned carbon nanotube growth

Science.gov (United States)

Islam, A. E.; Nikolaev, P.; Amama, P. B.; Zakharov, D.; Sargent, G.; Saber, S.; Huffman, D.; Erford, M.; Semiatin, S. L.; Stach, E. A.; Maruyama, B.

2015-09-01

Carbon nanotube growth depends on the catalytic activity of metal nanoparticles on alumina or silica supports. The control on catalytic activity is generally achieved by variations in water concentration, carbon feed, and sample placement on a few types of alumina or silica catalyst supports obtained via thin film deposition. We have recently expanded the choice of catalyst supports by engineering inactive substrates like c-cut sapphire via ion beam bombardment. The deterministic control on the structure and chemistry of catalyst supports obtained by tuning the degree of beam-induced damage have enabled better regulation of the activity of Fe catalysts only in the ion beam bombarded areas and hence enabled controllable super growth of carbon nanotubes. A wide range of surface characterization techniques were used to monitor the catalytically active surface engineered via ion beam bombardment. The proposed method offers a versatile way to control carbon nanotube growth in patterned areas and also enhances the current understanding of the growth process. With the right choice of water concentration, carbon feed and sample placement, engineered catalyst supports may extend the carbon nanotube growth yield to a level that is even higher than the ones reported here, and thus offers promising applications of carbon nanotubes in electronics, heat exchanger, and energy storage.

Looking for carbonates in the deep Earth: an experimental approach at extreme conditions

Science.gov (United States)

Chariton, S.; Bykova, E.; Bykov, M.; Cerantola, V.; Vasiukov, D.; Stekiel, M.; Aprilis, G.; Kupenko, I.; Ismailova, L.; Chumakov, A. I.; Winkler, B.; McCammon, C. A.; Dubrovinsky, L. S.

2017-12-01

There is a long list of natural and experimental evidence to support a key role for carbonates in the deep carbon cycle. As potential carriers of carbon in subducted slabs with the possibility to influence redox conditions, carbonates have deservedly been the focus of many high pressure and high temperature experimental studies over the past decade. "How long do they survive after subduction? What form do they transform to? How do they react with their surroundings?" are all important questions. We use many tools to search for carbonates in the deep Earth. Using laser heated diamond anvil cells to generate pressures and temperatures over 100 GPa and 2500 K along with the advanced technology provided by synchrotron facilities, we have been able to study in situ the behavior of various carbonate minerals at conditions of the Earth's mantle. We have particularly focused our interest on transition metal carbonates (Fe, Mn, Co, Zn, Ni)CO3 in order to study the crystal chemistry of calcite-type carbonates using single crystal X-ray diffraction and Raman spectroscopy. Our results show new high-pressure carbonate structures, including either CO3-3or CO4-4 units, that often coexist with complex metal oxides. Combined with carbonate stability fields from the surface to the lower mantle, we investigated the possibility to detect carbonates from seismic data. We determined the elastic wave velocities of plausible carbonate mineral compositions in the (Mg-Fe)CO3 system using Nuclear Inelastic Scattering. Our results show the strong anisotropic behavior of carbonates that could explain anisotropic anomalies observed at transition zone depths and confirm the presence of carbonate reservoirs. The effect of carbonate composition and Fe2+ spin transition, which is completed above 50 GPa, are also well demonstrated. More new carbonate phases and their seismic signatures await to be discovered, and thus experiments continue.

Catalytic transformations of fatty acids derivatives for food, oleochemicals and fuels over carbon supported platinum group metals

Energy Technology Data Exchange (ETDEWEB)

Simakova, I.

2010-07-01

prominent in linoleic acid deoxygenation giving only 3 % conversion of fatty acids in 330 min. The deactivation originated from the formation of C17 aromatic compounds and fatty acid dimers via Diels-Alder reaction. Thus hydrogenation of unsaturated fatty acids can be considered as preliminary chemical modification step in the green diesel production. In this work particular care was taken to strengthen the nano level understanding of the Pd role, in particular metal size effect, in the catalytic hydrogenation and deoxygenation. Pd/C catalysts were synthesized with the same Pd loading and systematically varied metal dispersion via the controllable formation of Pd particles over carbon support surface. The effect of metal dispersion on hydrogenation rate and trans/cis ratio was revealed. An optimum metal dispersion giving the highest decarboxylation reaction rate was observed. In addition to the particle size effect, the impact of mass transfer was elucidated and detail discussions on temperature programmed desorption of CO from the fresh and spent samples was provided. Hydrogenation of vegetable feedstocks was performed in batch and continuous modes, using powdered and granulated Pd/C catalysts correspondingly. One of the main focuses of the work was put on the scale-up of the hydrogenation process. There are several challenges attributed to the scale-up of a chemical process which have to be recognized before progressing to an industrial application. In terms of the high production volumes the logical step is to investigate the performance of hydrogenation as a continuous process. A laboratory study in a continuous fixed bed reactor was performed, giving crucial information about the catalyst long-term stability and catalyst deactivation. Furthermore, the impact of using free fatty acids or triglycerides feedstocks as well as the effect of catalyst particle size and Pd loading were investigated in continuous mode. Finally, the production capacities for different operation

Predicting a new phase (T'') of two-dimensional transition metal di-chalcogenides and strain-controlled topological phase transition

Science.gov (United States)

Ma, Fengxian; Gao, Guoping; Jiao, Yalong; Gu, Yuantong; Bilic, Ante; Zhang, Haijun; Chen, Zhongfang; Du, Aijun

2016-02-01

Single layered transition metal dichalcogenides have attracted tremendous research interest due to their structural phase diversities. By using a global optimization approach, we have discovered a new phase of transition metal dichalcogenides (labelled as T''), which is confirmed to be energetically, dynamically and kinetically stable by our first-principles calculations. The new T'' MoS2 phase exhibits an intrinsic quantum spin Hall (QSH) effect with a nontrivial gap as large as 0.42 eV, suggesting that a two-dimensional (2D) topological insulator can be achieved at room temperature. Most interestingly, there is a topological phase transition simply driven by a small tensile strain of up to 2%. Furthermore, all the known MX2 (M = Mo or W; X = S, Se or Te) monolayers in the new T'' phase unambiguously display similar band topologies and strain controlled topological phase transitions. Our findings greatly enrich the 2D families of transition metal dichalcogenides and offer a feasible way to control the electronic states of 2D topological insulators for the fabrication of high-speed spintronics devices.Single layered transition metal dichalcogenides have attracted tremendous research interest due to their structural phase diversities. By using a global optimization approach, we have discovered a new phase of transition metal dichalcogenides (labelled as T''), which is confirmed to be energetically, dynamically and kinetically stable by our first-principles calculations. The new T'' MoS2 phase exhibits an intrinsic quantum spin Hall (QSH) effect with a nontrivial gap as large as 0.42 eV, suggesting that a two-dimensional (2D) topological insulator can be achieved at room temperature. Most interestingly, there is a topological phase transition simply driven by a small tensile strain of up to 2%. Furthermore, all the known MX2 (M = Mo or W; X = S, Se or Te) monolayers in the new T'' phase unambiguously display similar band topologies and strain controlled topological

Low carbon transition and sustainable development path of tourism industry

Science.gov (United States)

Zhu, Hongbing; Zhang, Jing; Zhao, Lei; Jin, Shenglang

2017-05-01

The low carbon transition is as much a transformative technology shift as it represents a response to global environment challenges. The low carbon paradigm presents a new direction of change for tourism industry. However, the lack of theoretical frameworks on low carbon transformation in tourism industry context provides a significant knowledge gap. This paper firstly investigates the relationships between low carbon and sustainable development, followed by exploring the existing challenges of tourism sustainable development. At last, this paper presents a sustainable development path framework for low carbon transition of tourism industry, which include accelerating deployment of renewable energy, energy-saving green building construction, improving green growth investment, and adopting a sustainable consumption and production system, in order to promote energy and water efficiency, waste management, GHG emissions mitigation and eventually enhance its sustainability.

Strange metals and quantum phase transitions from gauge/gravity duality

Science.gov (United States)

Liu, Hong

2011-03-01

Metallic materials whose thermodynamic and transport properties differ significantly from those predicted by Fermi liquid theory, so-called non-Fermi liquids, include the strange metal phase of cuprate superconductors, and heavy fermion systems near a quantum phase transition. We use gauge/gravity duality to identify a class of non-Fermi liquids. Their low-energy behavior is governed by a nontrivial infrared fixed point which exhibits non-analytic scaling behavior only in the temporal direction. Some representatives of this class have single-particle spectral functions and transport behavior similar to those of the strange metals, with conductivity inversely proportional to the temperature. Such holographic systems may also exhibit novel ``magnetic instabilities'', where the quantum critical behavior near the transition involves a nontrivial interplay between local and bulk physics, with the local physics again described by a similar infrared fixed point. The resulting quantum phase transitions do not obey the standard Landau-Ginsburg-Wilson paradigm and resemble those of the heavy fermion quantum critical points.

Functionalization of 2D transition metal dichalcogenides for biomedical applications

International Nuclear Information System (INIS)

Li, Zibiao; Wong, Swee Liang

2017-01-01

Recent research has revealed a gamut of interesting properties present in layered two-dimensional (2D) transition metal dichalcogenides (TMDCs) such as photoluminescence, comparatively high electron mobility, flexibility, mechanical strength and relatively low toxicity. The large surface to area ratio inherent in these materials also allows easy functionalization and maximal interaction with the external environment. Due to its unique physical and chemical properties, much work has been done in tailoring TMDCs through chemical functionalization for use in a diverse range of biomedical applications as biosensors, drug delivery carriers or even as therapeutic agents. In this review, current progress on the different types of TMDC functionalization for various biological applications will be presented and its future outlook will be discussed. - Highlights: • The different functionalization strategies and approaches of transition metal dichalcogenides are reviewed. • Properties of transition metal dichalcogenides useful for biomedical usage and their methods of synthesis are introduced. • Functionalization approaches are presented according to material type and their different application purpose is discussed.

Development of dissimilar metal transition joint by hot roll bonding technique

International Nuclear Information System (INIS)

Nagai, Takayuki; Takeda, Seiichiro; Tanaka, Yasumasa; Ogawa, Kazuhiro; Nakasuji, Kazuyuki; Ikenaga, Yoshiaki.

1994-01-01

Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) with stainless steel piping is needed for nuclear fuel reprocessing plants. The authors have developed dissimilar metal transition joints between stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot roll bonding process, using the newly developed mill called 'rotary reduction mill'. In the R and D program, appropriate bonding conditions in the manufacturing process of the joints were established. This report presents the structure of transition joints and the manufacturing process by the hot roll bonding technique. Then, the evaluation of mechanical and corrosion properties and the results of demonstration test of joints for practical use are described. (author)

Development of dissimilar metal transition joint by hot roll bonding technique

International Nuclear Information System (INIS)

Nagai, Takayuki; Takeuchi, Masayuki; Takeda, Seiichiro; Shikakura, Sakae; Ogawa, Kazuhiro; Nakasuji, Kazuyuki; Kajimura, Haruhiko.

1995-01-01

Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) with stainless steel piping is needed for nuclear fuel reprocessing plants. The authors have developed dissimilar metal transition joints between stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot roll bonding process, using the newly developed mill called 'rotary reduction mill'. In the R and D program, appropriate bonding conditions in the manufacturing process of the joints were established. This report presents the structure of transition joints and the manufacturing process by hot roll bonding technique. Then, the evaluation of mechanical and corrosion properties and the results of demonstration test of joints for practical use are described. (author)

Fullerenes as a new type of ligands for transition metals

International Nuclear Information System (INIS)

Sokolov, V.I.

2007-01-01

Fullerenes are considered as ligands in transition metal π-complexes. The following aspects are discussed: metals able to form π-complexes with fullerenes (Zr, V, Ta, Mo, W, Re, Ru, etc.); haptic numbers; homo- and hetero ligand complexes; ligand compatibility with fullerenes for different metals, including fullerenes with a disturbed structure of conjugation [ru

Hydrogenation of carbon monoxide on WO/sub 3/-Supported ruthenium catalysts

Energy Technology Data Exchange (ETDEWEB)

Yoshinari, Tomohiro; Suganuma, Fujio; Sera, Chikara

1988-01-01

In this study, a WO/sub 3/-supported catalyst was prepared to conduct hydrogenation of CO for examining the product distribution and composition of hydrocarbons, using a gamma-alumina-supported catalyst for comparison. These catalysts were used under pressure to conduct a distributive reaction and the desorbing behavior of CO or H/sub 2/ at elevated temperature was measured to examine the influence of the type of carrier or the method of preparation on the activity and the distribution of products formed. The WO/sub 3/-supported catalyst gave a carbon chain length distribution that did not comply with the rule of Schulz-Flory, giving a composition richer in the isomers. Carbon number distribution is affected by Ru-dispersion, and the selectivity of isomers depends on the acidity of the carrier. Formed products distribution of the WO/sub 3/-supported reaction is attributable to the secondary reaction, which relates to the acidic point of the carrier, of the primary product formed on the metal. (7 figs, 4 tabs, 18 refs)

New organometallic salts as precursors for the functionalization of carbon nanotubes with metallic nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Alonso-Nunez, G., E-mail: galonso@cnyn.unam.mx; Garza, L. Morales de la; Rogel-Hernandez, E.; Reynoso, E. [Universidad Nacional Autonoma de Mexico, Centro de Nanociencias y Nanotecnologia (Mexico); Licea-Claverie, A.; Felix-Navarro, R. M. [Instituto Tecnologico de Tijuana, Centro de Graduados e Investigacion (Mexico); Berhault, G. [UMR 5256 CNRS-Universite de Lyon, Institut de Recherches sur la Catalyse et l' Environnement de Lyon (France); Paraguay-Delgado, F. [Centro de Investigacion en Materiales Avanzados S. C. (Mexico)

2011-09-15

New organometallic salts were synthesized in aqueous solution and were used as precursors for the functionalization of carbon nanotubes (CNT) by metallic nanoparticles. The precursors were obtained by reaction between HAuCl{sub 4}, (NH{sub 4}){sub 2}PtCl{sub 6}, (NH{sub 4}){sub 2}PdCl{sub 6}, or (NH{sub 4}){sub 3}RhCl{sub 6} with cetyltrimethylammonium bromide (CTAB). The as-obtained (CTA){sub n}Me{sub x}Cl{sub y} salts (with Me = Au, Pt, Pd, Rh) were characterized by Fourier-transform infra-red (FTIR) spectroscopy, {sup 1}H nuclear magnetic resonance (NMR) spectroscopy, and thermogravimetric analysis. These precursors were then used to synthesize metallic nanoparticles of Au, Pt, Pd, and Rh over multiwalled carbon nanotubes (MWCNT). Characterization by scanning transmission electron microscopy (STEM) and thermogravimetric analysis under air reveals that the CNT-supported catalysts exhibit high loading and good dispersion of the metallic nanoparticles with small average particle sizes. The present preparation procedure therefore allows obtaining high densities of small metallic nanoparticles at the surface of MWCNT.

The research of a method for determination of total carbon, combination carbon and free carbon in beryllium metal

International Nuclear Information System (INIS)

Yang Xingzhong; Zhu Xiaohong

1996-02-01

A method for determination of total carbon, combination carbon and free carbon in beryllium metal with LECO CS-344 carbon/sulphur determinant has been studied. Tungsten-copper mixed pellets are used as flux to the determination of total carbon. Ratio of weight of the flux to the sample is greater than 20:1. Good analytical results are got. By this method the relative standard deviation is <10% when the content of total carbon in the range of 0.050%∼0.080% in beryllium. A standard steel sample of carbon is added into beryllium, the recoveries are 94%∼106%. For determination of free carbon, the sample are decomposed with 3 mol/L HCl, filtered and followed determination. By this method the relative standard deviation is ≤10% when the content of free carbon in the range of 0.006%∼0.020% in beryllium. the balance of total carbon and free carbon is equal to combination carbon. The method is used to determine the sample of content of total carbon in the range of 0.050%∼1.00%, free carbon in the range of 0.006%∼0.500% in metal beryllium. (6 refs., 1 fig., 13 tabs.)

Four-electron deoxygenative reductive coupling of carbon monoxide at a single metal site

Science.gov (United States)

Buss, Joshua A.; Agapie, Theodor

2016-01-01

Carbon dioxide is the ultimate source of the fossil fuels that are both central to modern life and problematic: their use increases atmospheric levels of greenhouse gases, and their availability is geopolitically constrained. Using carbon dioxide as a feedstock to produce synthetic fuels might, in principle, alleviate these concerns. Although many homogeneous and heterogeneous catalysts convert carbon dioxide to carbon monoxide, further deoxygenative coupling of carbon monoxide to generate useful multicarbon products is challenging. Molybdenum and vanadium nitrogenases are capable of converting carbon monoxide into hydrocarbons under mild conditions, using discrete electron and proton sources. Electrocatalytic reduction of carbon monoxide on copper catalysts also uses a combination of electrons and protons, while the industrial Fischer-Tropsch process uses dihydrogen as a combined source of electrons and electrophiles for carbon monoxide coupling at high temperatures and pressures. However, these enzymatic and heterogeneous systems are difficult to probe mechanistically. Molecular catalysts have been studied extensively to investigate the elementary steps by which carbon monoxide is deoxygenated and coupled, but a single metal site that can efficiently induce the required scission of carbon-oxygen bonds and generate carbon-carbon bonds has not yet been documented. Here we describe a molybdenum compound, supported by a terphenyl-diphosphine ligand, that activates and cleaves the strong carbon-oxygen bond of carbon monoxide, enacts carbon-carbon coupling, and spontaneously dissociates the resulting fragment. This complex four-electron transformation is enabled by the terphenyl-diphosphine ligand, which acts as an electron reservoir and exhibits the coordinative flexibility needed to stabilize the different intermediates involved in the overall reaction sequence. We anticipate that these design elements might help in the development of efficient catalysts for

Oxidation of Group 8 transition-Metal Hydrides and Ionic Hydrogenation of Ketones and Aldehydes

Energy Technology Data Exchange (ETDEWEB)

Smith, Kjell-Tore

1996-08-01

Transition-metal hydrides have received considerable attention during the last decades because of their unusual reactivity and their potential as homogeneous catalysts for hydrogenation and other reactions of organic substrates. An important class of catalytic processes where transition-metal hydrides are involved is the homogeneous hydrogenation of alkenes, alkynes, ketones, aldehydes, arenes and nitro compounds. This thesis studies the oxidation of Group 8 transition-metal hydrides and the ionic hydrogenation of ketones and aldehydes.

Two-order parameters theory of the metal-insulator phase transition kinetics in the magnetic field

Science.gov (United States)

Dubovskii, L. B.

2018-05-01

The metal-insulator phase transition is considered within the framework of the Ginzburg-Landau approach for the phase transition described with two coupled order parameters. One of the order parameters is the mass density which variation is responsible for the origin of nonzero overlapping of the two different electron bands and the appearance of free electron carriers. This transition is assumed to be a first-order phase one. The free electron carriers are described with the vector-function representing the second-order parameter responsible for the continuous phase transition. This order parameter determines mostly the physical properties of the metal-insulator transition and leads to a singularity of the surface tension at the metal-insulator interface. The magnetic field is involved into the consideration of the system. The magnetic field leads to new singularities of the surface tension at the metal-insulator interface and results in a drastic variation of the phase transition kinetics. A strong singularity in the surface tension results from the Landau diamagnetism and determines anomalous features of the metal-insulator transition kinetics.

Electrochemical and Antimicrobial Properties of Diamondlike Carbon-Metal Composite Films

Energy Technology Data Exchange (ETDEWEB)

MORRISON, M. L.; BUCHANAN, R. A.; LIAW, P. K.; BERRY, C. J.; BRIGMON, R.; RIESTER, L.; JIN, C.; NARAYAN, R. J.

2005-05-11

Implants containing antimicrobial metals may reduce morbidity, mortality, and healthcare costs associated with medical device-related infections. We have deposited diamondlike carbon-silver (DLC-Ag), diamondlike carbon-platinum (DLC-Pt), and diamondlike carbon-silver-platinum (DLC-AgPt) thin films using a multicomponent target pulsed laser deposition process. Transmission electron microscopy of the DLC-silver and DLC-platinum composite films revealed that the silver and platinum self-assemble into nanoparticle arrays within the diamondlike carbon matrix. The diamondlike carbon-silver film possesses hardness and Young's modulus values of 37 GPa and 331 GPa, respectively. The diamondlike carbon-metal composite films exhibited passive behavior at open-circuit potentials. Low corrosion rates were observed during testing in a phosphate-buffered saline (PBS) electrolyte. In addition, the diamondlike carbon-metal composite films were found to be immune to localized corrosion below 1000 mV (SCE). DLC-silver-platinum films demonstrated exceptional antimicrobial properties against Staphylococcus bacteria. It is believed that a galvanic couple forms between platinum and silver, which accelerates silver ion release and provides more robust antimicrobial activity. Diamondlike carbon-silver-platinum films may provide unique biological functionalities and improved lifetimes for cardiovascular, orthopaedic, biosensor, and implantable microelectromechanical systems.

Frontiers of 4d- and 5d-transition metal oxides

CERN Document Server

Cao, Gang

2013-01-01

This book is aimed at advanced undergraduates, graduate students and other researchers who possess an introductory background in materials physics and/or chemistry, and an interest in the physical and chemical properties of novel materials, especially transition metal oxides.New materials often exhibit novel phenomena of great fundamental and technological importance. Contributing authors review the structural, physical and chemical properties of notable 4d- and 5d-transition metal oxides discovered over the last 10 years. These materials exhibit extraordinary physical properties that differ s

Logic circuits based on individual semiconducting and metallic carbon-nanotube devices

International Nuclear Information System (INIS)

Ryu, Hyeyeon; Kaelblein, Daniel; Ante, Frederik; Zschieschang, Ute; Kern, Klaus; Klauk, Hagen; Weitz, R Thomas; Schmidt, Oliver G

2010-01-01

Nanoscale transistors employing an individual semiconducting carbon nanotube as the channel hold great potential for logic circuits with large integration densities that can be manufactured on glass or plastic substrates. Carbon nanotubes are usually produced as a mixture of semiconducting and metallic nanotubes. Since only semiconducting nanotubes yield transistors, the metallic nanotubes are typically not utilized. However, integrated circuits often require not only transistors, but also resistive load devices. Here we show that many of the metallic carbon nanotubes that are deposited on the substrate along with the semiconducting nanotubes can be conveniently utilized as load resistors with favorable characteristics for the design of integrated circuits. We also demonstrate the fabrication of arrays of transistors and resistors, each based on an individual semiconducting or metallic carbon nanotube, and their integration on glass substrates into logic circuits with switching frequencies of up to 500 kHz using a custom-designed metal interconnect layer.

Soluble transition metals cause the pro-inflammatory effects of welding fumes in vitro

International Nuclear Information System (INIS)

McNeilly, Jane D.; Heal, Mathew R.; Beverland, Iain J.; Howe, Alan; Gibson, Mark D.; Hibbs, Leon R.; MacNee, William; Donaldson, Ken

2004-01-01

Epidemiological studies have consistently reported a higher incidence of respiratory illnesses such as bronchitis, metal fume fever (MFF), and chronic pneumonitis among welders exposed to high concentrations of metal-enriched welding fumes. Here, we studied the molecular toxicology of three different metal-rich welding fumes: NIMROD 182, NIMROD c276, and COBSTEL 6. Fume toxicity in vitro was determined by exposing human type II alveolar epithelial cell line (A549) to whole welding fume, a soluble extract of fume or the 'washed' particulate. All whole fumes were significantly toxic to A549 cells at doses >63 μg ml -1 (TD 50; 42, 25, and 12 μg ml -1 , respectively). NIMROD c276 and COBSTEL 6 fumes increased levels of IL-8 mRNA and protein at 6 h and protein at 24 h, as did the soluble fraction alone, whereas metal chelation of the soluble fraction using chelex beads attenuated the effect. The soluble fraction of all three fumes caused a rapid depletion in intracellular glutathione following 2-h exposure with a rebound increase by 24 h. In addition, both nickel based fumes, NIMROD 182 and NIMROD c276, induced significant reactive oxygen species (ROS) production in A549 cells after 2 h as determined by DCFH fluorescence. ICP analysis confirmed that transition metal concentrations were similar in the whole and soluble fractions of each fume (dominated by Cr), but significantly less in both the washed particles and chelated fractions. These results support the hypothesis that the enhanced pro-inflammatory responses of welding fume particulates are mediated by soluble transition metal components via an oxidative stress mechanism

Topotactic Metal-Insulator Transition in Epitaxial SrFeO x Thin Films

International Nuclear Information System (INIS)

Khare, Amit; Shin, Dongwon; Yoo, Tae Sup; Kim, Minu; Kang, Tae Dong

2017-01-01

Multivalent transition metal oxides provide fascinating and rich physics related to oxygen stoichiometry. In particular, the adoptability of various valence states of transition metals enables perovskite oxides to display mixed (oxygen) ionic and electronic conduction and catalytic activity useful in many practical applications, including solid-oxide fuel cells (SOFCs), rechargeable batteries, gas sensors, and memristive devices. For proper realization of the ionic conduction and catalytic activity, it is essential to understand the reversible oxidation and reduction process, which is governed by oxygen storage/release steps in oxides. Topotactic phase transformation facilitates the redox process in perovskites with specific oxygen vacancy ordering by largely varying the oxygen concentration of a material without losing the lattice framework. The concentration and diffusion of oxide ions (O 2– ), the valence state of the transition metal cations, and the thermodynamic structural integrity together provide fundamental understanding and ways to explicitly control the redox reaction.[6] In addition, it offers an attractive route for tuning the emergent physical properties of transition metal oxides, via strong coupling between the crystal lattice and electronic structure.

Critical metal-insulator transition and divergence in a two-particle irreducible vertex in disordered and interacting electron systems

Czech Academy of Sciences Publication Activity Database

Janiš, Václav; Pokorný, Vladislav

2014-01-01

Roč. 90, č. 4 (2014), "045143-1"-"045143-11" ISSN 1098-0121 Institutional support: RVO:68378271 Keywords : metal-insulator transition * disordered and interacting electron systems * dynamical mean-field theory * critical behavior Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.736, year: 2014

Catalytic olefin polymerization with early transition metal compounds

OpenAIRE

Eshuis, Johan Jan Willem

1991-01-01

The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and arene oxidation. Traditionally, heterogeneous catalysts have been used for the production of large-scale commodity chemicals such as methanol and ammonia and in the production of high octane gasoline...

Hydrogen storage properties of carbon nanomaterials and carbon containing metal hydrides

Energy Technology Data Exchange (ETDEWEB)

Maehlen, Jan Petter

2003-07-01

The topic of this thesis is structural investigations of carbon containing materials in respect to their hydrogen storage properties. This work was initially triggered by reports of extremely high hydrogen storage capacities of specific carbon nanostructures. It was decided to try to verify and understand the mechanisms in play in case of the existence of such high hydrogen densities in carbon. Two different routes towards the goal were employed; by studying selected hydrides with carbon as one of its constituents (mainly employing powder diffraction techniques in combination with hydrogen absorption and desorption measurements) and by carefully conducting hydrogen sorption experiments on what was believed to be the most ''promising'' carbon nanomaterial sample. In the latter case, a lot of effort was attributed to characterisations of different carbon nanomaterial containing samples with the aid of electron microscopy. Three different carbon-containing metal hydride systems, Y2C-H, YCoC-H and Y5SiC0.2-H, were examined. A relation between hydrogen occupation and the local arrangement of metal and carbon atoms surrounding the hydrogen sites was established. Several characteristic features of the compounds were noted in addition to solving the structure of the former unknown deuterideY5Si3C0.2D2.0 by the use of direct methods. Several carbon-nanomaterial containing samples were studied by means of transmission electron microscopy and powder diffraction, thus gaining knowledge concerning the structural aspects of nanomaterials. Based on these investigations, a specific sample containing a large amount of open-ended single-wall carbon nanotubes was chosen for subsequent hydrogen storage experiments. The latter experiments revealed moderate hydrogen storage capacities of the nanotubes not exceeding the values obtained for more conventional forms of carbon. These two different routes in investigating the hydrogen storage properties of carbon and carbon containing alloys

Hydrogen storage properties of carbon nanomaterials and carbon containing metal hydrides

Energy Technology Data Exchange (ETDEWEB)

Maehlen, Jan Petter

2003-07-01

The topic of this thesis is structural investigations of carbon containing materials in respect to their hydrogen storage properties. This work was initially triggered by reports of extremely high hydrogen storage capacities of specific carbon nanostructures. It was decided to try to verify and understand the mechanisms in play in case of the existence of such high hydrogen densities in carbon. Two different routes towards the goal were employed; by studying selected hydrides with carbon as one of its constituents (mainly employing powder diffraction techniques in combination with hydrogen absorption and desorption measurements) and by carefully conducting hydrogen sorption experiments on what was believed to be the most ''promising'' carbon nanomaterial sample. In the latter case, a lot of effort was attributed to characterisations of different carbon nanomaterial containing samples with the aid of electron microscopy. Three different carbon-containing metal hydride systems, Y2C-H, YCoC-H and Y5SiC0.2-H, were examined. A relation between hydrogen occupation and the local arrangement of metal and carbon atoms surrounding the hydrogen sites was established. Several characteristic features of the compounds were noted in addition to solving the structure of the former unknown deuterideY5Si3C0.2D2.0 by the use of direct methods. Several carbon-nanomaterial containing samples were studied by means of transmission electron microscopy and powder diffraction, thus gaining knowledge concerning the structural aspects of nanomaterials. Based on these investigations, a specific sample containing a large amount of open-ended single-wall carbon nanotubes was chosen for subsequent hydrogen storage experiments. The latter experiments revealed moderate hydrogen storage capacities of the nanotubes not exceeding the values obtained for more conventional forms of carbon. These two different routes in investigating the hydrogen storage properties of carbon and

Cell complexes of transition metals in biochemistry and medicine

International Nuclear Information System (INIS)

Voloshin, Ya.Z.; Varzatskij, O.A.; Bubnov, Yu.N.

2007-01-01

Basic directions and prospects of use of cell complexes of transition metals in medicine and biochemistry are considered: incapsulation of radioactive metal ions for radiotherapy and diagnostics; preparation of contrast compounds for magnetic resonance tomography, antidotes and pharmaceutical preparation of prolonged effect, preparations for boron-neutron-capture therapy of neoplasms, antioxidants; membrane transport of metal ions; study of interaction of cell metal complexes with nucleic acids; possibility of use of self-assembly of cell complexes for imitation of ligases and use of clathrochelates as linkers; design of inhibitors of viruses for AIDS therapy [ru

Rational Design of Two-Dimensional Metallic and Semiconducting Spintronic Materials Based on Ordered Double-Transition-Metal MXenes

KAUST Repository

Dong, Liang

2016-12-30

Two-dimensional (2D) materials that display robust ferromagnetism have been pursued intensively for nanoscale spintronic applications, but suitable candidates have not been identified. Here we present theoretical predictions on the design of ordered double-transition-metal MXene structures to achieve such a goal. On the basis of the analysis of electron filling in transition-metal cations and first-principles simulations, we demonstrate robust ferromagnetism in Ti2MnC2Tx monolayers regardless of the surface terminations (T = O, OH, and F), as well as in Hf2MnC2O2 and Hf2VC2O2 monolayers. The high magnetic moments (3–4 μB/unit cell) and high Curie temperatures (495–1133 K) of these MXenes are superior to those of existing 2D ferromagnetic materials. Furthermore, semimetal-to-semiconductor and ferromagnetic-to-antiferromagnetic phase transitions are predicted to occur in these materials in the presence of small or moderate tensile in-plane strains (0–3%), which can be externally applied mechanically or internally induced by the choice of transition metals.

Formation of transition metal cluster adducts on the surface of single-walled carbon nanotubes: HRTEM studies

KAUST Repository

Kalinina, Irina V.

2014-01-01

We report the formation of chromium clusters on the outer walls of single-walled carbon nanotubes (SWNTs). The clusters were obtained by reacting purified SWNTs with chromium hexacarbonyl in dibutyl ether at 100°C. The functionalized SWNTs were characterized by thermogravimetic analysis, XPS, and high-resolution TEM. The curvature of the SWNTs and the high mobility of the chromium moieties on graphitic surfaces allow the growth of the metal clusters and we propose a mechanism for their formation. © 2014 Taylor and Francis Group, LLC.

The atomic structure of transition metal clusters

International Nuclear Information System (INIS)

Riley, S.J.

1995-01-01

Chemical reactions are used to probe the atomic (geometrical) structure of isolated clusters of transition metal atoms. The number of adsorbate molecules that saturate a cluster, and/or the binding energy of molecules to cluster surfaces, are determined as a function of cluster size. Systematics in these properties often make it possible to propose geometrical structures consistent with the experimental observations. We will describe how studies of the reactions of cobalt and nickel clusters with ammonia, water, and nitrogen provide important and otherwise unavailable structural information. Specifically, small (less than 20 atoms) clusters of cobalt and nickel atoms adopt entirely different structures, the former having packing characteristic of the bulk and the latter having pentagonal symmetry. These observations provide important input for model potentials that attempt to describe the local properties of transition metals. In particular, they point out the importance of a proper treatment of d-orbital binding in these systems, since cobalt and nickel differ so little in their d-orbital occupancy

Lattice Location of Transition Metals in Semiconductors

CERN Multimedia

2002-01-01

%IS366 %title\\\\ \\\\Transition metals (TMs) in semiconductors have been the subject of considerable research for nearly 40 years. This is due both to their role as important model impurities for deep centers in semiconductors, and to their technological impact as widespread contaminants in Si processing, where the miniaturization of devices requires to keep their sheet concentration below 10$^{10}$ cm$^{-2}$. As a consequence of the low TM solubility, conventional ion beam methods for direct lattice location have failed completely in identifying the lattice sites of isolated transition metals. Although electron paramagnetic resonance (EPR) has yielded valuable information on a variety of TM centers, it has been unable to detect certain defects considered by theory, e.g., isolated interstitial or substitutional Cu in Si. The proposed identity of other EPR centers such as substitutional Fe in Si, still needs confirmation by additional experimental methods. As a consequence, the knowledge on the structural propert...

Metal non-metal transitions in doped semiconductors

International Nuclear Information System (INIS)

Brezini, A.

1989-12-01

A disordered Hubbard model with diagonal disorder is used to examine the electron localization effects associated with both disorder and electron-electron interaction. Extensive results are reported on the ground state properties and compared with other theories. In particular two regimes are observed; when the electron-electron interaction U is greater than the disorder parameter and when is smaller. Furthermore the effect of including conduction-band minima into the calculation of metal-insulator transitions in doped Si and Ge is investigated with use of Berggren approach. Good agreement with experiments are found when both disorder and interactions are included. (author). 37 refs, 7 figs, 3 tabs

Thermodynamics of carbon deoxidation and aluminium deoxidation of refractory metals

International Nuclear Information System (INIS)

Garg, S.P.; Sundaram, C.V.

1975-01-01

Carbon has been used for removing the last traces of oxygen from many refractory metals by evaporation of CO at high temperature and vacuum. Similar purification can also be achieved employing aluminium deoxidation by evaporation of Al 2 Osub(g). In the present paper a theoretical thermodynamic approach has been attempted to evaluate the deoxidation tendencies of refractory metals of groups IV to VI by these two processes. Expressions have been theoretically derived, relating the concentration product of carbon and oxygen in the metal (which is a measure of the carbon deoxidation tendency of the metal) with temperature and pressure, for various M-C-O systems. Similarly the relative vapour pressure values of Alsub(2)Osub(g),Alsub(g)andMO(g) (suboxide of the metal) over various M-Al-O systems have been calculated as a function of aluminium and oxygen contents of the metal. From these analyses, it has been shown that a substantial amount of oxygen can be removed from M-Al-O alloys by aluminium deoxidation. The estimated values are compared with the reported values based on experiment. (author)

Band gap tuning in transition metal oxides by site-specific substitution

Science.gov (United States)

Lee, Ho Nyung; Chisholm, Jr., Matthew F; Jellison, Jr., Gerald Earle; Singh, David J; Choi, Woo Seok

2013-12-24

A transition metal oxide insulator composition having a tuned band gap includes a transition metal oxide having a perovskite or a perovskite-like crystalline structure. The transition metal oxide includes at least one first element selected form the group of Bi, Ca, Ba, Sr, Li, Na, Mg, K, Pb, and Pr; and at least one second element selected from the group of Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Hf, Ta, W, Re, Os, Ir, and Pt. At least one correlated insulator is integrated into the crystalline structure, including REMO.sub.3, wherein RE is at least one Rare Earth element, and wherein M is at least one element selected from the group of Co, V, Cr, Ni, Mn, and Fe. The composition is characterized by a band gap of less of 4.5 eV.

First-principles study of hydrogen dissociation and diffusion on transition metal-doped Mg(0 0 0 1) surfaces

International Nuclear Information System (INIS)

Wang, Zhiwen; Guo, Xinjun; Wu, Mingyi; Sun, Qiang; Jia, Yu

2014-01-01

First-principles calculations within the density functional theory (DFT) have been carried out to study hydrogen molecules dissociation and diffusion on clean and transition metals (TMs) doped Mg(0 0 0 1) surfaces following Pozzo et al. work. Firstly, the stability of Mg(0 0 0 1) surface doped with transition metals atom has been studied. The results showed that transition metals on the left of the table tend to substitute Mg in the second layer, while the other transition metals prefer to substitute Mg in the first layer. Secondly, we studied hydrogen molecules dissociation and diffusion on clean and Mg(0 0 0 1) surfaces which the transition metal atoms substituted both in the first layer and second layer. When transition metal atoms substitute in the first layer, the results agree with the Pozzo et al. result; when transition metal atoms substitute in the second layer, the results showed that the transition metals on the left of the periodic table impact on the dissociation barriers is less. However, for the transition metals (Mn, Fe, Co, Ni) on the right, there is a great impact on the barriers. The transition metals doped surfaces bind the dissociated H atoms loosely, making them easily diffused. The results further reveal that the Fe dopant on the Mg surface is the best choice for H 2 dissociation and hydrogen storage.

Development of dissimilar metal transition joint by hot bond rolling

International Nuclear Information System (INIS)

Kurokawa, Hiroyuki; Nakasuji, Kazuyuki; Kajimura, Haruhiko; Nagai, Takayuki; Takeda, Seiichiro.

1997-01-01

Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) to stainless steel piping are required for nuclear fuel reprocessing plants. The authors have developed dissimilar transition joints made of stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot bond rolling process of clad bars and clad pipes, using a newly developed mill called 'rotary reduction mill'. This report presents the manufacturing process of dissimilar transition joints produced from the clad pipe with three layers by the hot bond rolling. First, the method of hot bond rolling of clad pipe is proposed. Then, the mechanical and corrosion properties of the dissimilar transition joints are evaluated in detail by carrying out various tests. Finally, the rolling properties in the clad pipe method are discussed. (author)

Ternary alkali-metal and transition metal or metalloid acetylides as alkali-metal intercalation electrodes for batteries

Science.gov (United States)

Nemeth, Karoly; Srajer, George; Harkay, Katherine C; Terdik, Joseph Z

2015-02-10

Novel intercalation electrode materials including ternary acetylides of chemical formula: A.sub.nMC.sub.2 where A is alkali or alkaline-earth element; M is transition metal or metalloid element; C.sub.2 is reference to the acetylide ion; n is an integer that is 0, 1, 2, 3 or 4 when A is alkali element and 0, 1, or 2 when A is alkaline-earth element. The alkali elements are Lithium (Li), Sodium (Na), Potassium (K), Rubidium (Rb), Cesium (Cs) and Francium (Fr). The alkaline-earth elements are Berilium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba), and Radium (Ra). M is a transition metal that is any element in groups 3 through 12 inclusive on the Periodic Table of Elements (elements 21 (Sc) to element 30 (Zn)). In another exemplary embodiment, M is a metalloid element.

Janus monolayers of transition metal dichalcogenides

KAUST Repository

Lu, Ang-Yu

2017-05-15

Structural symmetry-breaking plays a crucial role in determining the electronic band structures of two-dimensional materials. Tremendous efforts have been devoted to breaking the in-plane symmetry of graphene with electric fields on AB-stacked bilayers or stacked van der Waals heterostructures. In contrast, transition metal dichalcogenide monolayers are semiconductors with intrinsic in-plane asymmetry, leading to direct electronic bandgaps, distinctive optical properties and great potential in optoelectronics. Apart from their in-plane inversion asymmetry, an additional degree of freedom allowing spin manipulation can be induced by breaking the out-of-plane mirror symmetry with external electric fields or, as theoretically proposed, with an asymmetric out-of-plane structural configuration. Here, we report a synthetic strategy to grow Janus monolayers of transition metal dichalcogenides breaking the out-of-plane structural symmetry. In particular, based on a MoS2 monolayer, we fully replace the top-layer S with Se atoms. We confirm the Janus structure of MoSSe directly by means of scanning transmission electron microscopy and energy-dependent X-ray photoelectron spectroscopy, and prove the existence of vertical dipoles by second harmonic generation and piezoresponse force microscopy measurements.

The recent development of efficient Earth-abundant transition-metal nanocatalysts.

Science.gov (United States)

Wang, Dong; Astruc, Didier

2017-02-06

Whereas noble metal compounds have long been central in catalysis, Earth-abundant metal-based catalysts have in the same time remained undeveloped. Yet the efficacy of Earth-abundant metal catalysts was already shown at the very beginning of the 20th century with the Fe-catalyzed Haber-Bosch process of ammonia synthesis and later in the Fischer-Tropsch reaction. Nanoscience has revolutionized the world of catalysis since it was observed that very small Au nanoparticles (NPs) and other noble metal NPs are extraordinarily efficient. Therefore the development of Earth-abundant metals NPs is more recent, but it has appeared necessary due to their "greenness". This review highlights catalysis by NPs of Earth-abundant transition metals that include Mn, Fe, Co, Ni, Cu, early transition metals (Ti, V, Cr, Zr, Nb and W) and their nanocomposites with emphasis on basic principles and literature reported during the last 5 years. A very large spectrum of catalytic reactions has been successfully disclosed, and catalysis has been examined for each metal starting with zero-valent metal NPs followed by oxides and other nanocomposites. The last section highlights the catalytic activities of bi- and trimetallic NPs. Indeed this later family is very promising and simultaneously benefits from increased stability, efficiency and selectivity, compared to monometallic NPs, due to synergistic substrate activation.

Defect-Tolerant Monolayer Transition Metal Dichalcogenides

DEFF Research Database (Denmark)

Pandey, Mohnish; Rasmussen, Filip Anselm; Kuhar, Korina

2016-01-01

Localized electronic states formed inside the band gap of a semiconductor due to crystal defects can be detrimental to the material's optoelectronic properties. Semiconductors with a lower tendency to form defect induced deep gap states are termed defect-tolerant. Here we provide a systematic first...... the gap. These ideas are made quantitative by introducing a descriptor that measures the degree of similarity of the conduction and valence band manifolds. Finally, the study is generalized to nonpolar nanoribbons of the TMDs where we find that only the defect sensitive materials form edge states within......-principles investigation of defect tolerance in 29 monolayer transition metal dichalcogenides (TMDs) of interest for nanoscale optoelectronics. We find that the TMDs based on group VI and X metals form deep gap states upon creation of a chalcogen (S, Se, Te) vacancy, while the TMDs based on group IV metals form only...

Carbon pricing. A lever for energy transition

International Nuclear Information System (INIS)

2016-01-01

The international community has set itself the target of limiting the global temperature rise to 2 deg. C. In today's world, the challenge is to invent new ways of manufacturing goods, producing food, travelling and keeping ourselves warm, without emitting more greenhouse gases (GHG) into the atmosphere than what we are technically able to remove from it. Climate action can be considered as an insurance for our societies against unacceptable costs generated by the risk of increasingly frequent climate-triggered natural disasters, irreversible damage to ecosystems and mass population migrations. In addition to avoid climate damage there are many benefits of climate action, including greater energy autonomy, reduced atmospheric pollution, which is harmful for human health, and the economic benefits of new green growth sectors. However, the efforts needed to make the transition to economies that emit fewer greenhouse gases must not be underestimated. This transition requires the mass redirection of investments into clean transport, renewable energy sources, building insulation and the development of agro-ecology, in a highly restricted financial and budgetary context. The economic and financial tools used for explicit or implicit carbon pricing give clear messages about the benefits of emitting less carbon, or alternatively the cost of greenhouse gas emissions for society. Consequently, they make it possible to accelerate the energy transition. 74 countries and over 1,000 businesses formed a coalition for carbon pricing during the United Nations Climate Summit in September 2014, held at the invitation of the UN Secretary-General. The goal of the coalition is to promote productive dialogue between public and private decision-makers concerning opportunities to extend carbon pricing policies. It has been officially launched on November 30, 2015, on the opening day of COP21. It has been officially launched on November 30, 2015, on the opening day of COP21. Members of the

Metal-insulator transition and superconductivity in heavily boron-doped diamond and related materials

Energy Technology Data Exchange (ETDEWEB)

Achatz, Philipp

2009-05-15

During this PhD project, the metal-insulator transition and superconductivity of highly boron-doped single crystal diamond and related materials have been investigated. The critical boron concentration n{sub c} for the metal-insulator transition was found to be the same as for the normal-superconductor transition. All metallic samples have been found to be superconducting and we were able to link the occurence of superconductivity to the proximity to the metal-insulator transition. For this purpose, a scaling law approach based on low temperature transport was proposed. Furthermore, we tried to study the nature of the superconductivity in highly boron doped single crystal diamond. Raman spectroscopy measurements on the isotopically substituted series suggest that the feature occuring at low wavenumbers ({approx} 500 cm{sup -1}) is the A1g vibrational mode associated with boron dimers. Usual Hall effect measurements yielded a puzzling situation in metallic boron-doped diamond samples, leading to carrier concentrations up to a factor 10 higher than the boron concentration determined by secondary ion mass spectroscopy (SIMS). The low temperature transport follows the one expected for a granular metal or insulator, depending on the interplay of intergranular and intragranular (tunneling) conductance. The metal-insulator transition takes place at a critical conductance g{sub c}. The granularity also influences significantly the superconducting properties by introducing the superconducting gap {delta} in the grain and Josephson coupling J between superconducting grains. A peak in magnetoresistance is observed which can be explained by superconducting fluctuations and the granularity of the system. Additionally we studied the low temperature transport of boron-doped Si samples grown by gas immersion laser doping, some of which yielded a superconducting transition at very low temperatures. Furthermore, preliminary results on the LO-phonon-plasmon coupling are shown for the

Metal-insulator transition and superconductivity in heavily boron-doped diamond and related materials

International Nuclear Information System (INIS)

Achatz, Philipp

2009-01-01

During this PhD project, the metal-insulator transition and superconductivity of highly boron-doped single crystal diamond and related materials have been investigated. The critical boron concentration n c for the metal-insulator transition was found to be the same as for the normal-superconductor transition. All metallic samples have been found to be superconducting and we were able to link the occurence of superconductivity to the proximity to the metal-insulator transition. For this purpose, a scaling law approach based on low temperature transport was proposed. Furthermore, we tried to study the nature of the superconductivity in highly boron doped single crystal diamond. Raman spectroscopy measurements on the isotopically substituted series suggest that the feature occuring at low wavenumbers (∼ 500 cm -1 ) is the A1g vibrational mode associated with boron dimers. Usual Hall effect measurements yielded a puzzling situation in metallic boron-doped diamond samples, leading to carrier concentrations up to a factor 10 higher than the boron concentration determined by secondary ion mass spectroscopy (SIMS). The low temperature transport follows the one expected for a granular metal or insulator, depending on the interplay of intergranular and intragranular (tunneling) conductance. The metal-insulator transition takes place at a critical conductance g c . The granularity also influences significantly the superconducting properties by introducing the superconducting gap Δ in the grain and Josephson coupling J between superconducting grains. A peak in magnetoresistance is observed which can be explained by superconducting fluctuations and the granularity of the system. Additionally we studied the low temperature transport of boron-doped Si samples grown by gas immersion laser doping, some of which yielded a superconducting transition at very low temperatures. Furthermore, preliminary results on the LO-phonon-plasmon coupling are shown for the first time in aluminum

Carbon a support for sulfide catalysts

NARCIS (Netherlands)

Vissers, J.P.R.; Lensing, T.J.; Mercx, F.P.M.; Beer, de V.H.J.; Prins, R.

1983-01-01

Two types of carbon materials, carbon black composite and carbon covered alumina, were studied for-their use as support for sulfide catalysts. The following parameters were varied: type of carbon black, carbon coverage of the alumina and carbon pretreatment. Pore size distributions were determined

Phase-field model of insulator-to-metal transition in VO2 under an electric field

Science.gov (United States)

Shi, Yin; Chen, Long-Qing

2018-05-01

The roles of an electric field and electronic doping in insulator-to-metal transitions are still not well understood. Here we formulated a phase-field model of insulator-to-metal transitions by taking into account both structural and electronic instabilities as well as free electrons and holes in VO2, a strongly correlated transition-metal oxide. Our phase-field simulations demonstrate that in a VO2 slab under a uniform electric field, an abrupt universal resistive transition occurs inside the supercooling region, in sharp contrast to the conventional Landau-Zener smooth electric breakdown. We also show that hole doping may decouple the structural and electronic phase transitions in VO2, leading to a metastable metallic monoclinic phase which could be stabilized through a geometrical confinement and the size effect. This work provides a general mesoscale thermodynamic framework for understanding the influences of electric field, electronic doping, and stress and strain on insulator-to-metal transitions and the corresponding mesoscale domain structure evolution in VO2 and related strongly correlated systems.

A Facile Route to Metal Oxides/Single-Walled Carbon Nanotube Macrofilm Nanocomposites for Energy Storage

Science.gov (United States)

Cao, Zeyuan; Wei, Bingqing

2015-05-01

Nanocomposites consisting of transition-metal oxides and carbon nanomaterials with a desired size and structure are highly demanded for high performance energy storage devices. Here, a facile two-step and cost-efficient approach relying on directly thermal treatment of chemical-vapor-deposition products is developed as a general synthetic method to prepare a family of metal oxides (MxOy (M=Fe, Co, Ni))/single-walled carbon nanotube (SWNT) macrofilm nanocomposites. The MxOy nanoparticles obtained are of 3-17 nm in diameter and homogeneously anchor on the free-standing SWNT macrofilms. NiO/SWNT also exhibits a high specific capacitance of 400 F g-1 and fast charge-transfer Faradaic redox reactions to achieve asymmetric supercapacitors with a high power and energy density. All MxOy/SWNT nanocomposites could deliver a high capacity beyond 1000 mAh g-1 and show excellent cycling stability for lithium-ion batteries. The impressive results demonstrate the promise for energy storage devices and the general approach may pave the way to synthesize other functional nanocomposites.

A Facile Route to Metal Oxides/Single-Walled Carbon Nanotube Macrofilm Nanocomposites for Energy Storage

Directory of Open Access Journals (Sweden)

Zeyuan eCao

2015-05-01

Full Text Available Nanocomposites consisting of transition-metal oxides and carbon nanomaterials with a desired size and structure are highly demanded for high performance energy storage devices. Here, a facile two-step and cost-efficient approach relying on directly thermal treatment of chemical-vapor-deposition products is developed as a general synthetic method to prepare a family of metal oxides (MxOy (M=Fe, Co, Ni/single-walled carbon nanotube (SWNT macrofilm nanocomposites. The MxOy nanoparticles obtained are of 3-17 nm in diameter and homogeneously anchor on the free-standing SWNT macrofilms. NiO/SWNT also exhibits a high specific capacitance of 400 F g-1 and fast charge-transfer Faradaic redox reactions to achieve asymmetric supercapacitors with a high power and energy density. All MxOy/SWNT nanocomposites could deliver a high capacity beyond 1000 mAh g-1 and show excellent cycling stability for lithium-ion batteries. The impressive results demonstrate the promise for energy storage devices and the general approach may pave the way to synthesize other functional nanocomposites.

Universal Quantum Criticality in the Metal-Insulator Transition of Two-Dimensional Interacting Dirac Electrons

Directory of Open Access Journals (Sweden)

Yuichi Otsuka

2016-03-01

Full Text Available The metal-insulator transition has been a subject of intense research since Mott first proposed that the metallic behavior of interacting electrons could turn to an insulating one as electron correlations increase. Here, we consider electrons with massless Dirac-like dispersion in two spatial dimensions, described by the Hubbard models on two geometrically different lattices, and perform numerically exact calculations on unprecedentedly large systems that, combined with a careful finite-size scaling analysis, allow us to explore the quantum critical behavior in the vicinity of the interaction-driven metal-insulator transition. Thereby, we find that the transition is continuous, and we determine the quantum criticality for the corresponding universality class, which is described in the continuous limit by the Gross-Neveu model, a model extensively studied in quantum field theory. Furthermore, we discuss a fluctuation-driven scenario for the metal-insulator transition in the interacting Dirac electrons: The metal-insulator transition is triggered only by the vanishing of the quasiparticle weight, not by the Dirac Fermi velocity, which instead remains finite near the transition. This important feature cannot be captured by a simple mean-field or Gutzwiller-type approximate picture but is rather consistent with the low-energy behavior of the Gross-Neveu model.