C-C Coupling on Single-Atom-Based Heterogeneous Catalyst.

Science.gov (United States)

Zhang, Xiaoyan; Sun, Zaicheng; Wang, Bin; Tang, Yu; Nguyen, Luan; Li, Yuting; Tao, Franklin Feng

2018-01-24

Compared to homogeneous catalysis, heterogeneous catalysis allows for ready separation of products from the catalyst and thus reuse of the catalyst. C-C coupling is typically performed on a molecular catalyst which is mixed with reactants in liquid phase during catalysis. This homogeneous mixing at a molecular level in the same phase makes separation of the molecular catalyst extremely challenging and costly. Here we demonstrated that a TiO 2 -based nanoparticle catalyst anchoring singly dispersed Pd atoms (Pd 1 /TiO 2 ) is selective and highly active for more than 10 Sonogashira C-C coupling reactions (R≡CH + R'X → R≡R'; X = Br, I; R' = aryl or vinyl). The coupling between iodobenzene and phenylacetylene on Pd 1 /TiO 2 exhibits a turnover rate of 51.0 diphenylacetylene molecules per anchored Pd atom per minute at 60 °C, with a low apparent activation barrier of 28.9 kJ/mol and no cost of catalyst separation. DFT calculations suggest that the single Pd atom bonded to surface lattice oxygen atoms of TiO 2 acts as a site to dissociatively chemisorb iodobenzene to generate an intermediate phenyl, which then couples with phenylacetylenyl bound to a surface oxygen atom. This coupling of phenyl adsorbed on Pd 1 and phenylacetylenyl bound to O ad of TiO 2 forms the product molecule, diphenylacetylene.

Catalysis on singly dispersed bimetallic sites

Science.gov (United States)

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

2015-08-01

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

Single site porphyrine-like structures advantages over metals for selective electrochemical CO2 reduction

DEFF Research Database (Denmark)

Bagger, Alexander; Ju, Wen; Varela, Ana Sofia

2017-01-01

Currently, no catalysts are completely selective for the electrochemical CO2 Reduction Reaction (CO2RR). Based on trends in density functional theory calculations of reaction intermediates we find that the single metal site in a porphyrine-like structure has a simple advantage of limiting...... the competing Hydrogen Evolution Reaction (HER). The single metal site in a porphyrine-like structure requires an ontop site binding of hydrogen, compared to the hollow site binding of hydrogen on a metal catalyst surface. The difference in binding site structure gives a fundamental energy-shift in the scaling...... relation of ∼0.3eV between the COOH* vs. H* intermediate (CO2RR vs. HER). As a result, porphyrine-like catalysts have the advantage over metal catalyst of suppressing HER and enhancing CO2RR selectivity....

Exploiting nanospace for asymmetric catalysis: confinement of immobilized, single-site chiral catalysts enhances enantioselectivity.

Science.gov (United States)

Thomas, John Meurig; Raja, Robert

2008-06-01

In the mid-1990s, it became possible to prepare high-area silicas having pore diameters controllably adjustable in the range ca. 20-200 Å. Moreover, the inner walls of these nanoporous solids could be functionalized to yield single-site, chiral, catalytically active organometallic centers, the precise structures of which could be determined using in situ X-ray absorption and FTIR and multinuclear magic angle spinning (MAS) NMR spectroscopy. This approach opened up the prospect of performing heterogeneous enantioselective conversions in a novel manner, under the spatial restrictions imposed by the nanocavities within which the reactions occur. In particular, it suggested an alternative method for preparing pharmaceutically and agrochemically useful asymmetric products by capitalizing on the notion, initially tentatively perceived, that spatial confinement of prochiral reactants (and transition states formed at the chiral active center) would provide an altogether new method of boosting the enantioselectivity of the anchored chiral catalyst. Initially, we anchored chiral single-site heterogeneous catalysts to nanopores covalently via a ligand attached to Pd(II) or Rh(I) centers. Later, we employed a more convenient and cheaper electrostatic method, relying in part on strong hydrogen bonding. This Account provides many examples of these processes, encompassing hydrogenations, oxidations, and aminations. Of particular note is the facile synthesis from methyl benzoylformate of methyl mandelate, which is a precursor in the synthesis of pemoline, a stimulant of the central nervous system; our procedure offers several viable methods for reducing ketocarboxylic acids. In addition to relying on earlier (synchrotron-based) in situ techniques for characterizing catalysts, we have constructed experimental procedures involving robotically controlled catalytic reactors that allow the kinetics of conversion and enantioselectivity to be monitored continually, and we have access to

Regeneration of LOHC dehydrogenation catalysts: In-situ IR spectroscopy on single crystals, model catalysts, and real catalysts from UHV to near ambient pressure

International Nuclear Information System (INIS)

Amende, Max; Kaftan, Andre; Bachmann, Philipp; Brehmer, Richard; Preuster, Patrick; Koch, Marcus

2016-01-01

Graphical abstract: - Highlights: • We examine the regeneration of Pt-based catalysts poisoned by LOHC degradation. • A microscopic mechanism of the removal of degradation products from Pt is proposed. • Results of our UHV studies on model catalysts are transferred to real catalysis. • Oxidative regeneration of Pt/alumina is possible under mild conditions (600 K). • The degree and temperature regime of regeneration depends on the catalyst morphology. - Abstract: The Liquid Organic Hydrogen Carrier (LOHC) concept offers an efficient route to store hydrogen using organic compounds that are reversibly hydrogenated and dehydrogenated. One important challenge towards application of the LOHC technology at a larger scale is to minimize degradation of Pt-based dehydrogenation catalysts during long-term operation. Herein, we investigate the regeneration of Pt/alumina catalysts poisoned by LOHC degradation. We combine ultrahigh vacuum (UHV) studies on Pt(111), investigations on well-defined Pt/Al_2O_3 model catalysts, and near-ambient pressure (NAP) measurements on real core–shell Pt/Al_2O_3 catalyst pellets. The catalysts were purposely poisoned by reaction with the LOHC perhydro-dibenzyltoluene (H18-MSH) and with dicyclohexylmethane (DCHM) as a simpler model compound. We focus on oxidative regeneration under conditions that may be applied in real dehydrogenation reactors. The degree of poisoning and regeneration under oxidative reaction conditions was quantified using CO as a probe molecule and measured by infrared reflection-absorption spectroscopy (IRAS) and diffuse reflectance Fourier transform IR spectroscopy (DRIFTS) for planar model systems and real catalysts, respectively. We find that regeneration strongly depends on the composition of the catalyst surface. While the clean surface of a poisoned Pt(111) single crystal is fully restored upon thermal treatment in oxygen up to 700 K, contaminated Pt/Al_2O_3 model catalyst and core–shell pellet were only

Regeneration of LOHC dehydrogenation catalysts: In-situ IR spectroscopy on single crystals, model catalysts, and real catalysts from UHV to near ambient pressure

Energy Technology Data Exchange (ETDEWEB)

Amende, Max, E-mail: max.amende@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Kaftan, Andre, E-mail: andre.kaftan@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Bachmann, Philipp, E-mail: philipp.bachmann@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Brehmer, Richard, E-mail: richard.brehmer@fau.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Preuster, Patrick, E-mail: patrick.preuster@fau.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Koch, Marcus, E-mail: marcus.koch@crt.cbi.uni-erlangen.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); and others

2016-01-01

Graphical abstract: - Highlights: • We examine the regeneration of Pt-based catalysts poisoned by LOHC degradation. • A microscopic mechanism of the removal of degradation products from Pt is proposed. • Results of our UHV studies on model catalysts are transferred to real catalysis. • Oxidative regeneration of Pt/alumina is possible under mild conditions (600 K). • The degree and temperature regime of regeneration depends on the catalyst morphology. - Abstract: The Liquid Organic Hydrogen Carrier (LOHC) concept offers an efficient route to store hydrogen using organic compounds that are reversibly hydrogenated and dehydrogenated. One important challenge towards application of the LOHC technology at a larger scale is to minimize degradation of Pt-based dehydrogenation catalysts during long-term operation. Herein, we investigate the regeneration of Pt/alumina catalysts poisoned by LOHC degradation. We combine ultrahigh vacuum (UHV) studies on Pt(111), investigations on well-defined Pt/Al{sub 2}O{sub 3} model catalysts, and near-ambient pressure (NAP) measurements on real core–shell Pt/Al{sub 2}O{sub 3} catalyst pellets. The catalysts were purposely poisoned by reaction with the LOHC perhydro-dibenzyltoluene (H18-MSH) and with dicyclohexylmethane (DCHM) as a simpler model compound. We focus on oxidative regeneration under conditions that may be applied in real dehydrogenation reactors. The degree of poisoning and regeneration under oxidative reaction conditions was quantified using CO as a probe molecule and measured by infrared reflection-absorption spectroscopy (IRAS) and diffuse reflectance Fourier transform IR spectroscopy (DRIFTS) for planar model systems and real catalysts, respectively. We find that regeneration strongly depends on the composition of the catalyst surface. While the clean surface of a poisoned Pt(111) single crystal is fully restored upon thermal treatment in oxygen up to 700 K, contaminated Pt/Al{sub 2}O{sub 3} model catalyst and

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

Silica-supported, single-site titanium catalysts for olefin epoxidation. A molecular precursor strategy for control of catalyst structure.

Science.gov (United States)

Jarupatrakorn, Jonggol; Don Tilley, T

2002-07-17

A molecular precursor approach involving simple grafting procedures was used to produce site-isolated titanium-supported epoxidation catalysts of high activity and selectivity. The tris(tert-butoxy)siloxy titanium complexes Ti[OSi(O(t)Bu)(3)](4) (TiSi4), ((i)PrO)Ti[OSi(O(t)Bu)(3)](3) (TiSi3), and ((t)BuO)(3)TiOSi(O(t)Bu)(3) (TiSi) react with the hydroxyl groups of amorphous Aerosil, mesoporous MCM-41, and SBA-15 via loss of HO(t)Bu and/or HOSi(O(t)Bu)(3) and introduction of titanium species onto the silica surface. Powder X-ray diffraction, nitrogen adsorption/desorption, infrared, and diffuse reflectance ultraviolet spectroscopies were used to investigate the structures and chemical natures of the surface-bound titanium species. The titanium species exist mainly in isolated, tetrahedral coordination environments. Increasing the number of siloxide ligands in the molecular precursor decreases the amount of titanium that can be introduced this way, but also enhances the catalytic activity and selectivity for the epoxidation of cyclohexene with cumene hydroperoxide as oxidant. In addition, the high surface area mesoporous silicas (MCM-41 and SBA-15) are more effective than amorphous silica as supports for these catalysts. Supporting TiSi3 on the SBA-15 affords highly active cyclohexene epoxidation catalysts (0.25-1.77 wt % Ti loading) that provide turnover frequencies (TOFs) of 500-1500 h(-1) after 1 h (TOFs are reduced by about half after calcination). These results demonstrate that oxygen-rich siloxide complexes of titanium are useful as precursors to supported epoxidation catalysts.

Single-Atom Catalysts of Precious Metals for Electrochemical Reactions.

Science.gov (United States)

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

2018-01-10

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

Production of propylene from 1-butene on highly active "bi-functional single active site" catalyst: Tungsten carbene-hydride supported on alumina

KAUST Repository

Mazoyer, Etienne

2011-12-02

1-Butene is transformed in a continuous flow reactor over tungsten hydrides precursor W-H/Al2O3, 1, giving a promising yield into propylene at 150 °C and different pressures. Tungsten carbene-hydride single active site operates as a "bi-functional catalyst" through 1-butene isomerization on W-hydride and 1-butene/2-butenes cross-metathesis on W-carbene. This active moiety is generated in situ at the initiation steps by insertion of 1-butene on tungsten hydrides precursor W-H/Al2O3, 1 followed by α-H and β-H abstraction. © 2011 American Chemical Society.

Real-Time Visualization of Active Species in a Single-Site Metal–Organic Framework Photocatalyst

Energy Technology Data Exchange (ETDEWEB)

Yang, Sizhuo [Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201, United States; Pattengale, Brian [Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201, United States; Lee, Sungsik [X-ray Science Division, Argonne National Laboratory, Argonne, Illinois 60349, United States; Huang, Jier [Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201, United States

2018-02-06

In this work, we report a new single-site photocatalyst (Co-Ru-UIO- 67(bpy)) based on a metal-organic framework platform with incorporated molecular photosensitizer and catalyst. We show that this catalyst not only demonstrates exceptional activity for light-driven H2 production but also can be recycled without loss of activity. Using the combination of optical transient absorption spectroscopy and in situ X-ray absorption spectroscopy, we not only captured the key CoI intermediate species formed after ultrafast charge transfer from the incorporated photosensitizer but also identified the rate-limiting step in the catalytic cycle, providing insight into the catalysis mechanism of these single-site metal-organic framework photocatalysts.

Hydrogenation active sites of unsupported molybdenum sulfide catalysts for hydroprocessing heavy oils

Energy Technology Data Exchange (ETDEWEB)

Iwata, Y.; Araki, Y.; Honna, K. [Tsukuba-branch, Advanced Catalyst Research Laboratory, Petroleum Energy Center, 1-1 Higashi, Tsukuba, 305-8565 Ibaraki (Japan); Miki, Y.; Sato, K.; Shimada, H. [National Institute of Materials and Chemical Research, 1-1 Higashi, Tsukuba, 305-8565 Ibaraki (Japan)

2001-02-20

The purpose of the present study was to elucidate the nature of the hydrogenation active sites on unsupported molybdenum sulfide catalysts, aimed at the improvement of the catalysts for the slurry processes. The number of hydrogenation active sites was found to relate to the 'inflection' on the basal plane of the catalyst particles. The comparison of the catalytic activity to that of an oil-soluble catalyst in the hydroprocessing of heavy oils suggests that the performance of the oil-soluble catalyst was near the maximum, unless another component such as Ni or Co was incorporated.

Microwave effects on NiMoS and CoMoS single-sheet catalysts.

Science.gov (United States)

Borges, I; Silva, Alexander M; Modesto-Costa, Lucas

2018-05-04

Single-sheet nanoclusters of MoS 2 , NiMoS or CoMoS are widely used in hydrodesulfurization (HDS) catalysis in the petroleum industry. In HDS reactions under microwave irradiation, experiments indirectly pointed out that for pristine MoS 2 reaction rates are accelerated because hot spots are generated on the catalyst bed. In this work, we investigated NiMoS and CoMoS isolated single-sheet substituted catalysts before and after thiophene adsorption focusing on quantifying the effect of microwave irradiation. For that purpose, density functional theory (DFT) molecular charge densities of each system were decomposed according to the distributed multipole analysis (DMA) of Stone. Site dipole values of each system were directly associated with a larger or smaller interaction with the microwave field according to a proposed general approach. We showed that microwave enhancement of HDS reaction rates can occur more efficiently in the CoMoS and NiMoS promoted clusters compared to pristine MoS 2 in the following order: CoMoS > NiMoS > MoS 2 . The atomic origin of the catalyst hot spots induced by microwaves was clearly established in the promoted clusters.

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

Science.gov (United States)

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

2017-08-09

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

Ionic Exchange of Metal-Organic Frameworks to Access Single Nickel Sites for Efficient Electroreduction of CO2.

Science.gov (United States)

Zhao, Changming; Dai, Xinyao; Yao, Tao; Chen, Wenxing; Wang, Xiaoqian; Wang, Jing; Yang, Jian; Wei, Shiqiang; Wu, Yuen; Li, Yadong

2017-06-21

Single-atom catalysts often exhibit unexpected catalytic activity for many important chemical reactions because of their unique electronic and geometric structures with respect to their bulk counterparts. Herein we adopt metal-organic frameworks (MOFs) to assist the preparation of a catalyst containing single Ni sites for efficient electroreduction of CO 2 . The synthesis is based on ionic exchange between Zn nodes and adsorbed Ni ions within the cavities of the MOF. This single-atom catalyst exhibited an excellent turnover frequency for electroreduction of CO 2 (5273 h -1 ), with a Faradaic efficiency for CO production of over 71.9% and a current density of 10.48 mA cm -2 at an overpotential of 0.89 V. Our findings present some guidelines for the rational design and accurate modulation of nanostructured catalysts at the atomic scale.

Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO2.

Science.gov (United States)

DeRita, Leo; Dai, Sheng; Lopez-Zepeda, Kimberly; Pham, Nicholas; Graham, George W; Pan, Xiaoqing; Christopher, Phillip

2017-10-11

Oxide-supported precious metal nanoparticles are widely used industrial catalysts. Due to expense and rarity, developing synthetic protocols that reduce precious metal nanoparticle size and stabilize dispersed species is essential. Supported atomically dispersed, single precious metal atoms represent the most efficient metal utilization geometry, although debate regarding the catalytic activity of supported single precious atom species has arisen from difficulty in synthesizing homogeneous and stable single atom dispersions, and a lack of site-specific characterization approaches. We propose a catalyst architecture and characterization approach to overcome these limitations, by depositing ∼1 precious metal atom per support particle and characterizing structures by correlating scanning transmission electron microscopy imaging and CO probe molecule infrared spectroscopy. This is demonstrated for Pt supported on anatase TiO 2 . In these structures, isolated Pt atoms, Pt iso , remain stable through various conditions, and spectroscopic evidence suggests Pt iso species exist in homogeneous local environments. Comparing Pt iso to ∼1 nm preoxidized (Pt ox ) and prereduced (Pt metal ) Pt clusters on TiO 2 , we identify unique spectroscopic signatures of CO bound to each site and find CO adsorption energy is ordered: Pt iso ≪ Pt metal atoms bonded to TiO 2 and that Pt iso exhibits optimal reactivity because every atom is exposed for catalysis and forms an interfacial site with TiO 2 . This approach should be generally useful for studying the behavior of supported precious metal atoms.

FCC catalyst technologies expand limits of process capability

International Nuclear Information System (INIS)

Leiby, S.

1992-01-01

This paper reports that over the past 30 or so years, many improvements in fluid catalytic cracking (FCC) operation have been achieved as the result of innovations in catalyst formulation. During the 1990s, new environmental regulations on issues such as reformulated gasoline will place new demands on both the refining industry and catalyst suppliers. An overview of cracking catalyst technology therefore seems in order. Today, high-technology innovations by catalyst manufacturers are rapid, but profit margins are slim. Catalyst formulations are shrouded in secrecy and probably depend almost as much on art as on science. Special formulations for specific cracking applications get the greatest emphasis today. To illustrate this point, OGJ's Worldwide Catalyst Report lists over 200 FCC catalyst designations. Catalysts containing components to enhance gasoline octane now account for about 70% of total U.S. FCC catalyst usage

Directing reaction pathways by catalyst active-site selection using self-assembled monolayers.

Science.gov (United States)

Pang, Simon H; Schoenbaum, Carolyn A; Schwartz, Daniel K; Medlin, J Will

2013-01-01

One key route for controlling reaction selectivity in heterogeneous catalysis is to prepare catalysts that exhibit only specific types of sites required for desired product formation. Here we show that alkanethiolate self-assembled monolayers with varying surface densities can be used to tune selectivity to desired hydrogenation and hydrodeoxygenation products during the reaction of furfural on supported palladium catalysts. Vibrational spectroscopic studies demonstrate that the selectivity improvement is achieved by controlling the availability of specific sites for the hydrogenation of furfural on supported palladium catalysts through the selection of an appropriate alkanethiolate. Increasing self-assembled monolayer density by controlling the steric bulk of the organic tail ligand restricts adsorption on terrace sites and dramatically increases selectivity to desired products furfuryl alcohol and methylfuran. This technique of active-site selection simultaneously serves both to enhance selectivity and provide insight into the reaction mechanism.

Single Turnover at Molecular Polymerization Catalysts Reveals Spatiotemporally Resolved Reactions.

Science.gov (United States)

Easter, Quinn T; Blum, Suzanne A

2017-10-23

Multiple active individual molecular ruthenium catalysts have been pinpointed within growing polynorbornene, thereby revealing information on the reaction dynamics and location that is unavailable through traditional ensemble experiments. This is the first single-turnover imaging of a molecular catalyst by fluorescence microscopy and allows detection of individual monomer reactions at an industrially important molecular ruthenium ring-opening metathesis polymerization (ROMP) catalyst under synthetically relevant conditions (e.g. unmodified industrial catalyst, ambient pressure, condensed phase, ca. 0.03 m monomer). These results further establish the key fundamentals of this imaging technique for characterizing the reactivity and location of active molecular catalysts even when they are the minor components. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Performance Testing of Hydrodesulfurization Catalysts Using a Single-Pellet-String Reactor

NARCIS (Netherlands)

Moonen, Roel; Ras, Erik Jan; Harvey, Clare; Alles, Jeroen; Moulijn, J.A.

2017-01-01

Small-scale parallel trickle-bed reactors were used to evaluate the performance of a commercial hydrodesulfurization catalyst under industrially relevant conditions. Catalyst extrudates were loaded as a single string in reactor tubes. It is demonstrated that product sulfur levels and densities

Single-atom catalysts for CO2 electroreduction with significant activity and selectivity improvements.

Science.gov (United States)

Back, Seoin; Lim, Juhyung; Kim, Na-Young; Kim, Yong-Hyun; Jung, Yousung

2017-02-01

A single-atom catalyst (SAC) has an electronic structure that is very different from its bulk counterparts, and has shown an unexpectedly high specific activity with a significant reduction in noble metal usage for CO oxidation, fuel cell and hydrogen evolution applications, although physical origins of such performance enhancements are still poorly understood. Herein, by means of density functional theory (DFT) calculations, we for the first time investigate the great potential of single atom catalysts for CO 2 electroreduction applications. In particular, we study a single transition metal atom anchored on defective graphene with single or double vacancies, denoted M@sv-Gr or M@dv-Gr, where M = Ag, Au, Co, Cu, Fe, Ir, Ni, Os, Pd, Pt, Rh or Ru, as a CO 2 reduction catalyst. Many SACs are indeed shown to be highly selective for the CO 2 reduction reaction over a competitive H 2 evolution reaction due to favorable adsorption of carboxyl (*COOH) or formate (*OCHO) over hydrogen (*H) on the catalysts. On the basis of free energy profiles, we identified several promising candidate materials for different products; Ni@dv-Gr (limiting potential U L = -0.41 V) and Pt@dv-Gr (-0.27 V) for CH 3 OH production, and Os@dv-Gr (-0.52 V) and Ru@dv-Gr (-0.52 V) for CH 4 production. In particular, the Pt@dv-Gr catalyst shows remarkable reduction in the limiting potential for CH 3 OH production compared to any existing catalysts, synthesized or predicted. To understand the origin of the activity enhancement of SACs, we find that the lack of an atomic ensemble for adsorbate binding and the unique electronic structure of the single atom catalysts as well as orbital interaction play an important role, contributing to binding energies of SACs that deviate considerably from the conventional scaling relation of bulk transition metals.

Pt Single Atoms Embedded in the Surface of Ni Nanocrystals as Highly Active Catalysts for Selective Hydrogenation of Nitro Compounds.

Science.gov (United States)

Peng, Yuhan; Geng, Zhigang; Zhao, Songtao; Wang, Liangbing; Li, Hongliang; Wang, Xu; Zheng, Xusheng; Zhu, Junfa; Li, Zhenyu; Si, Rui; Zeng, Jie

2018-06-13

Single-atom catalysts exhibit high selectivity in hydrogenation due to their isolated active sites, which ensure uniform adsorption configurations of substrate molecules. Compared with the achievement in catalytic selectivity, there is still a long way to go in exploiting the catalytic activity of single-atom catalysts. Herein, we developed highly active and selective catalysts in selective hydrogenation by embedding Pt single atoms in the surface of Ni nanocrystals (denoted as Pt 1 /Ni nanocrystals). During the hydrogenation of 3-nitrostyrene, the TOF numbers based on surface Pt atoms of Pt 1 /Ni nanocrystals reached ∼1800 h -1 under 3 atm of H 2 at 40 °C, much higher than that of Pt single atoms supported on active carbon, TiO 2 , SiO 2 , and ZSM-5. Mechanistic studies reveal that the remarkable activity of Pt 1 /Ni nanocrystals derived from sufficient hydrogen supply because of spontaneous dissociation of H 2 on both Pt and Ni atoms as well as facile diffusion of H atoms on Pt 1 /Ni nanocrystals. Moreover, the ensemble composed of the Pt single atom and nearby Ni atoms in Pt 1 /Ni nanocrystals leads to the adsorption configuration of 3-nitrostyrene favorable for the activation of nitro groups, accounting for the high selectivity for 3-vinylaniline.

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

DEFF Research Database (Denmark)

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

2017-01-01

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

Formic acid decomposition on Pt1/Cu (111) single platinum atom catalyst: Insights from DFT calculations and energetic span model analysis

Science.gov (United States)

Wang, Ying-Fan; Li, Kun; Wang, Gui-Chang

2018-04-01

Inspired by the recent surface experimental results that the monatomic Pt catalysts has more excellent hydrogen production that Cu(111) surface, the mechanism of decomposition of formic acid on Cu(111) and single atom Pt1/Cu(111) surface was studied by periodic density functional theory calculations in the present work. The results show that the formic acid tends to undergo dehydrogenation on both surfaces to obtain the hydrogen product of the target product, and the selectivity and catalytic activity of Pt1/Cu (111) surface for formic acid dehydrogenation are better. The reason is that the single atom Pt1/Cu(111) catalyst reduces the reaction energy barrier (i.e., HCOO → CO2 + H) of the critical step of the dehydrogenation reaction due to the fact that the single atom Pt1/Cu(111) catalyst binds formate weakly compared to that of Cu (111) one. Moreover, it was found that the Pt1/Cu (111) binds CO more strongly than that of Cu (111) one and thus leading to the difficult for the formation of CO. These two factors would make the single Pt atom catalyst had the high selectivity for the H2 production. It is hoped that the present work may help people to design the efficient H2 production from HCOOH decomposition by reduce the surface binding strength of HCOO species, for example, using the low coordination number active site like single atom or other related catalytic system.

Preparation of ethylene/1-hexene copolymers from ethylene using a fully silica-supported tandem catalyst system

NARCIS (Netherlands)

Karbach, Fabian F.; Macko, Tibor; Duchateau, Robbert

2016-01-01

A silica-supported tandem catalyst system, capable of producing ethylene/1-hexene copolymers from ethylene being the single monomer, has been investigated. As tandem couple a phenoxyimine titanium catalyst for ethylene trimerization was combined with a metallocene catalyst for α-olefin

Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

International Nuclear Information System (INIS)

Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

2015-01-01

A successive anchoring of Ti(NMe 2 ) 4 , cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, 13 C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands. - Graphical abstract: The ligand-tailored silica supported “single site” titanium complexes were synthesized by SOMC strategy and fully characterized. Their catalytic activity were evaluated by benzaldehyde silylcyanation. - Highlights: • Single-site silica supported Ti active species was prepared by SOMC technique. • O-donor ligand tailored Ti surface species was synthesized. • The surface species was characterized by XPS, 13 C CP-MAS NMR, XANES etc. • Catalytic activity of the Ti active species in silylcyanation reaction was evaluated

Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

Energy Technology Data Exchange (ETDEWEB)

Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang, E-mail: gfzhang@snnu.edu.cn; Gao, Ziwei, E-mail: zwgao@snnu.edu.cn

2015-01-15

A successive anchoring of Ti(NMe{sub 2}){sub 4}, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, {sup 13}C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands. - Graphical abstract: The ligand-tailored silica supported “single site” titanium complexes were synthesized by SOMC strategy and fully characterized. Their catalytic activity were evaluated by benzaldehyde silylcyanation. - Highlights: • Single-site silica supported Ti active species was prepared by SOMC technique. • O-donor ligand tailored Ti surface species was synthesized. • The surface species was characterized by XPS, {sup 13}C CP-MAS NMR, XANES etc. • Catalytic activity of the Ti active species in silylcyanation reaction was evaluated.

Water Adsorption and Dissociation on Ceria-Supported Single-Atom Catalysts: A First-Principles DFT+U Investigation.

Science.gov (United States)

Han, Zhong-Kang; Gao, Yi

2016-02-01

Single-atom catalysts have attracted wide attention owing to their extremely high atom efficiency and activities. In this paper, we applied density functional theory with the inclusion of the on-site Coulomb interaction (DFT+U) to investigate water adsorption and dissociation on clean CeO 2 (111) surfaces and single transition metal atoms (STMAs) adsorbed on the CeO 2 (111) surface. It is found that the most stable water configuration is molecular adsorption on the clean CeO 2 (111) surface and dissociative adsorption on STMA/CeO 2 (111) surfaces, respectively. In addition, our results indicate that the more the electrons that transfer from STMA to the ceria substrate, the stronger the binding energies between the STMA and ceria surfaces. A linear relationship is identified between the water dissociation barriers and the d band centers of STMA, known as the generalized Brønsted-Evans-Polanyi principle. By combining the oxygen spillovers, single-atom dispersion stabilities, and water dissociation barriers, Zn, Cr, and V are identified as potential candidates for the future design of ceria-supported single-atom catalysts for reactions in which the dissociation of water plays an important role, such as the water-gas shift reaction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single-Atom Pt as Co-Catalyst for Enhanced Photocatalytic H2 Evolution.

Science.gov (United States)

Li, Xiaogang; Bi, Wentuan; Zhang, Lei; Tao, Shi; Chu, Wangsheng; Zhang, Qun; Luo, Yi; Wu, Changzheng; Xie, Yi

2016-03-23

Isolated single-atom platinum (Pt) embedded in the sub-nanoporosity of 2D g-C3 N4 as a new form of co-catalyst is reported. The highly stable single-atom co-catalyst maximizes the atom efficiency and alters the surface trap states of g-C3 N4 , leading to significantly enhanced photocatalytic H2 evolution activity, 8.6 times higher than that of Pt nanoparticles and up to 50 times that for bare g-C3 N4 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Broadening of molecular weight distribution of polymers synthesized by metallocene-based dual-site catalysts; Alargamento da distribuicao de massa molar de polimeros sintetizados com catalisadores metalocenicos dual-site

Energy Technology Data Exchange (ETDEWEB)

Santos, Joao H.Z. dos [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica]. E-mail: jhzds@iq.ufrgs.br; Fisch, Adriano G.; Cardozo, Nilo S.M.; Secchi, Argimiro R. [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Dept. de Engenharia Quimica

2008-07-01

The main topics related to the use of dual-site catalysts in the production of polymers with broad molecular weight distribution are reviewed. The polymerization using dual-site catalysts is more economical and allows to produce a higher quality product than other processes, such as polymer blend and multistage reactors. However, the formulation of these catalysts is quite complicated since the same catalyst must produce distinct polymer grades. In addition, the release of patents concerning the combination of metallocenes and new technologies for polymerization shows that polymerization processes using dual-site catalysts are of current industrial interest. (author)

An efficient hybrid, nanostructured, epoxidation catalyst: titanium silsesquioxane-polystyrene copolymer supported on SBA-15

NARCIS (Netherlands)

Santen, van R.A.; Zhang, Lei; Abbenhuis, H.C.L.; Gerritsen, G.; Ní Bhriain, N.M.; Magusin, P.C.M.M.; Mezari, B.; Han, W.; Yang, Q.; Li, Can

2007-01-01

A novel interfacial hybrid epoxidation catalyst was designed with a new immobilization method for homogeneous catalysts by coating an inorganic support with an organic polymer film containing active sites. The titanium silsesquioxane (TiPOSS) complex, which contains a single-site titanium active

Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction.

Science.gov (United States)

Yang, Liu; Cheng, Daojian; Xu, Haoxiang; Zeng, Xiaofei; Wan, Xin; Shui, Jianglan; Xiang, Zhonghua; Cao, Dapeng

2018-06-26

It is still a grand challenge to develop a highly efficient nonprecious-metal electrocatalyst to replace the Pt-based catalysts for oxygen reduction reaction (ORR). Here, we propose a surfactant-assisted method to synthesize single-atom iron catalysts (SA-Fe/NG). The half-wave potential of SA-Fe/NG is only 30 mV less than 20% Pt/C in acidic medium, while it is 30 mV superior to 20% Pt/C in alkaline medium. Moreover, SA-Fe/NG shows extremely high stability with only 12 mV and 15 mV negative shifts after 5,000 cycles in acidic and alkaline media, respectively. Impressively, the SA-Fe/NG-based acidic proton exchange membrane fuel cell (PEMFC) exhibits a high power density of 823 mW cm -2 Combining experimental results and density-functional theory (DFT) calculations, we further reveal that the origin of high-ORR activity of SA-Fe/NG is from the Fe-pyrrolic-N species, because such molecular incorporation is the key, leading to the active site increase in an order of magnitude which successfully clarifies the bottleneck puzzle of why a small amount of iron in the SA-Fe catalysts can exhibit extremely superior ORR activity.

Breaking the Fischer–Tropsch synthesis selectivity : Direct conversion of syngas to gasoline over hierarchical Co/H-ZSM-5 catalysts

NARCIS (Netherlands)

Sartipi, S.; Parashar, K.; Makkee, M.; Gascon, J.; Kapteijn, F.

2012-01-01

We report the combination of Fischer–Tropsch catalyst with acid functionality in one single catalyst particle. The resulting bifunctional catalyst is capable of producing gasoline range hydrocarbons from synthesis gas in one catalytic step with outstanding activities and selectivities.

Enhancing the performance of single-chambered microbial fuel cell using manganese/palladium and zirconium/palladium composite cathode catalysts.

Science.gov (United States)

Jadhav, Dipak A; Deshpande, Parag A; Ghangrekar, Makarand M

2017-08-01

Application of ZrO 2 , MnO 2 , palladium, palladium-substituted-zirconium oxide (Zr 0.98 Pd 0.02 O 2 ) and palladium-substituted-manganese oxide (Mn 0.98 Pd 0.02 O 2 ) cathode catalysts in a single-chambered microbial fuel cell (MFC) was explored. The highest power generation (1.28W/m 3 ) was achieved in MFC with Mn 0.98 Pd 0.02 O 2 catalyst, which was higher than that with MnO 2 (0.58W/m 3 ) alone; whereas, MFC having Zr 0.98 Pd 0.02 O 2 catalyzed cathode and non-catalyzed cathode produced powers of 1.02 and 0.23W/m 3 , respectively. Also, low-cost zirconium-palladium-composite showed better catalytic activity and capacitance over ZrO 2 with 20A/m 3 current production and demonstrated its suitability for MFC applications. Cyclic voltammetry analyses showed higher well-defined redox peaks in composite catalysts (Mn/Zr-Pd-C) over other catalyzed MFCs containing MnO 2 or ZrO 2 . Electrochemical behaviour of composite catalysts on cathode showed higher availability of adsorption sites for oxygen reduction and, hence, enhanced the rate of cathodic reactions. Thus, Mn/Zr-Pd-C-based composite catalysts exhibited superior cathodic performance and could be proposed as alternatives to costly Pd-catalyst for field applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Staining of fluid-catalytic cracking catalysts: Localising Brønsted acidity within a single catalyst particle

NARCIS (Netherlands)

Buurmans, I.L.C.; Ruiz Martinez, J.; van Leeuwen, S.L.; van der Beek, D.; Bergwerff, J.A.; Knowles, W.V.; Vogt, Eelco; Weckhuysen, B.M.

2012-01-01

A time-resolved in situ micro-spectroscopic approach has been used to investigate the Brønsted acidic properties of fluid-catalytic-cracking (FCC) catalysts at the single particle level by applying the acid-catalysed styrene oligomerisation probe reaction. The reactivity of individual FCC components

Selective alkane activation with single-site atoms on amorphous support

Science.gov (United States)

Hock, Adam S.; Schweitzer, Neil M.; Miller, Jeffrey T.; Hu, Bo

2015-11-24

The present invention relates generally to catalysts and methods for use in olefin production. More particularly, the present invention relates to novel amorphously supported single-center, Lewis acid metal ions and use of the same as catalysts.

Oxidation catalyst

Science.gov (United States)

Ceyer, Sylvia T.; Lahr, David L.

2010-11-09

The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

Science.gov (United States)

Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

2015-01-01

A successive anchoring of Ti(NMe2)4, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1‧-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, 13C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands.

Support effects on adsorption and catalytic activation of O2 in single atom iron catalysts with graphene-based substrates.

Science.gov (United States)

Gao, Zheng-Yang; Yang, Wei-Jie; Ding, Xun-Lei; Lv, Gang; Yan, Wei-Ping

2018-03-07

The adsorption and catalytic activation of O 2 on single atom iron catalysts with graphene-based substrates were investigated systematically by density functional theory calculation. It is found that the support effects of graphene-based substrates have a significant influence on the stability of the single atom catalysts, the adsorption configuration, the electron transfer mechanism, the adsorption energy and the energy barrier. The differences in the stable adsorption configuration of O 2 on single atom iron catalysts with different graphene-based substrates can be well understood by the symmetrical matching principle based on frontier molecular orbital analysis. There are two different mechanisms of electron transfer, in which the Fe atom acts as the electron donor in single vacancy graphene-based substrates while the Fe atom mainly acts as the bridge for electron transfer in double vacancy graphene-based substrates. The Fermi softness and work function are good descriptors of the adsorption energy and they can well reveal the relationship between electronic structure and adsorption energy. This single atom iron catalyst with single vacancy graphene modified by three nitrogen atoms is a promising non-noble metal single atom catalyst in the adsorption and catalytic oxidation of O 2 . Furthermore, the findings can lay the foundation for the further study of graphene-based support effects and provide a guideline for the development and design of new non-noble-metal single atom catalysts.

Novel Catalyst for the Chirality Selective Synthesis of Single Walled Carbon Nanotubes

Science.gov (United States)

2015-05-12

Final 3. DATES COVERED (From - To) 03-April-2013 to 02-April-2015 4. TITLE AND SUBTITLE Novel Catalyst for the Chirality Selective...Distribution is unlimited. 13. SUPPLEMENTARY NOTES 14. ABSTRACT Chiral single walled carbon nanotubes (SWCNTs) are known to possess unique... chirality control in SWCNT synthesis. A model catalyst based on CoSO4/SiO2 was developed that showed good selectivity to (9,8) nanotubes. Remote plasma

Unraveling the Nature of Sites Active toward Hydrogen Peroxide Reduction in Fe?N?C Catalysts

OpenAIRE

Choi, Chang Hyuck; Choi, Won Seok; Kasian, Olga; Mechler, Anna K.; Sougrati, Moulay Tahar; Br?ller, Sebastian; Strickland, Kara; Jia, Qingying; Mukerjee, Sanjeev; Mayrhofer, Karl J. J.; Jaouen, Fr?d?ric

2017-01-01

Abstract Fe?N?C catalysts with high O2 reduction performance are crucial for displacing Pt in low?temperature fuel cells. However, insufficient understanding of which reaction steps are catalyzed by what sites limits their progress. The nature of sites were investigated that are active toward H2O2 reduction, a key intermediate during indirect O2 reduction and a source of deactivation in fuel cells. Catalysts comprising different relative contents of FeN x C y moieties and Fe particles encapsu...

Heterogeneous Single-Atom Catalyst for Visible-Light-Driven High-Turnover CO2 Reduction: The Role of Electron Transfer.

Science.gov (United States)

Gao, Chao; Chen, Shuangming; Wang, Ying; Wang, Jiawen; Zheng, Xusheng; Zhu, Junfa; Song, Li; Zhang, Wenkai; Xiong, Yujie

2018-03-01

Visible-light-driven conversion of CO 2 into chemical fuels is an intriguing approach to address the energy and environmental challenges. In principle, light harvesting and catalytic reactions can be both optimized by combining the merits of homogeneous and heterogeneous photocatalysts; however, the efficiency of charge transfer between light absorbers and catalytic sites is often too low to limit the overall photocatalytic performance. In this communication, it is reported that the single-atom Co sites coordinated on the partially oxidized graphene nanosheets can serve as a highly active and durable heterogeneous catalyst for CO 2 conversion, wherein the graphene bridges homogeneous light absorbers with single-atom catalytic sites for the efficient transfer of photoexcited electrons. As a result, the turnover number for CO production reaches a high value of 678 with an unprecedented turnover frequency of 3.77 min -1 , superior to those obtained with the state-of-the-art heterogeneous photocatalysts. This work provides fresh insights into the design of catalytic sites toward photocatalytic CO 2 conversion from the angle of single-atom catalysis and highlights the role of charge kinetics in bridging the gap between heterogeneous and homogeneous photocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly dispersed metal catalyst

Science.gov (United States)

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

2016-11-08

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

Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts.

Science.gov (United States)

Yin, Peiqun; Yao, Tao; Wu, Yuen; Zheng, Lirong; Lin, Yue; Liu, Wei; Ju, Huanxin; Zhu, Junfa; Hong, Xun; Deng, Zhaoxiang; Zhou, Gang; Wei, Shiqiang; Li, Yadong

2016-08-26

A new strategy for achieving stable Co single atoms (SAs) on nitrogen-doped porous carbon with high metal loading over 4 wt % is reported. The strategy is based on a pyrolysis process of predesigned bimetallic Zn/Co metal-organic frameworks, during which Co can be reduced by carbonization of the organic linker and Zn is selectively evaporated away at high temperatures above 800 °C. The spherical aberration correction electron microscopy and extended X-ray absorption fine structure measurements both confirm the atomic dispersion of Co atoms stabilized by as-generated N-doped porous carbon. Surprisingly, the obtained Co-Nx single sites exhibit superior ORR performance with a half-wave potential (0.881 V) that is more positive than commercial Pt/C (0.811 V) and most reported non-precious metal catalysts. Durability tests revealed that the Co single atoms exhibit outstanding chemical stability during electrocatalysis and thermal stability that resists sintering at 900 °C. Our findings open up a new routine for general and practical synthesis of a variety of materials bearing single atoms, which could facilitate new discoveries at the atomic scale in condensed materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic activity of Pd-doped Cu nanoparticles for hydrogenation as a single-atom-alloy catalyst.

Science.gov (United States)

Cao, Xinrui; Fu, Qiang; Luo, Yi

2014-05-14

The single atom alloy of extended surfaces is known to provide remarkably enhanced catalytic performance toward heterogeneous hydrogenation. Here we demonstrate from first principles calculations that this approach can be extended to nanostructures, such as bimetallic nanoparticles. The catalytic properties of the single-Pd-doped Cu55 nanoparticles have been systemically examined for H2 dissociation as well as H atom adsorption and diffusion, following the concept of single atom alloy. It is found that doping a single Pd atom at the edge site of the Cu55 shell can considerably reduce the activation energy of H2 dissociation, while the single Pd atom doped at the top site or in the inner layers is much less effective. The H atom adsorption on Cu55 is slightly stronger than that on the Cu(111) surface; however, a larger nanoparticle that contains 147 atoms could effectively recover the weak binding of the H atoms. We have also investigated the H atom diffusion on the 55-atom nanoparticle and found that spillover of the produced H atoms could be a feasible process due to the low diffusion barriers. Our results have demonstrated that facile H2 dissociation and weak H atom adsorption could be combined at the nanoscale. Moreover, the effects of doping one more Pd atom on the H2 dissociation and H atom adsorption have also been investigated. We have found that both the doping Pd atoms in the most stable configuration could independently exhibit their catalytic activity, behaving as two single-atom-alloy catalysts.

Assessing Contractor Capabilities for Streamlined Site Investigations

Science.gov (United States)

The purpose of this document is to familiarize and encourage brownfields decision makers to investigate and employ innovative methods for characterizing their sites, to assist brownfields decision makers in assessing contractors' capabilities.

Operators guide: Atmospheric Release Advisory Capability (ARAC) site facility

International Nuclear Information System (INIS)

Lawver, B.S.

1977-01-01

In this report capabilities and services are described for the Atmospheric Release Advisory Capability (ARAC). The ARAC site system and its operating procedures and interactions with the ARAC central facility located at LLL is outlined. ARAC is designed to help officials at designated ERDA sites and other locations in estimating the effects of atmospheric releases of radionuclides or other hazardous materials by issuing real-time advisories to guide them in their planning

Operators guide: Atmospheric Release Advisory Capability (ARAC) site facility

International Nuclear Information System (INIS)

Cassaro, E.; Lomonaco, L.

1979-01-01

The Atmospheric Release Advisory Capability (ARAC) is designed to help officials at designated DOE sites and other locations in estimating the effects of atmospheric releases of radionuclides or other hazardous materials by issuing real-time advisories to guide them in their planning. This report outlines the capabilities and sources of ARAC, and in more detail describes an ARAC Site Facility, its operating procedures and interactions with the ARAC Central Facility (ACF) located at LLL

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

Energy Technology Data Exchange (ETDEWEB)

Zhang, Hanguang [Department; Hwang, Sooyeon [Center; Wang, Maoyu [School; Feng, Zhenxing [School; Karakalos, Stavros [Department; Luo, Langli [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Qiao, Zhi [Department; Xie, Xiaohong [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Wang, Chongmin [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Su, Dong [Center; Shao, Yuyan [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Wu, Gang [Department

2017-09-26

To significantly reduce the cost of proton exchange membrane (PEM) fuel cells, current Pt must be replaced by platinum-metal-group (PGM)-free catalysts for the oxygen reduction reaction (ORR) in acid. We report here a new class of high-performance atomic iron dispersed carbon catalysts through controlled chemical doping of iron ions into zinc-zeolitic imidazolate framework (ZIF), a type of metal-organic framework (MOF). The novel synthetic chemistry enables accurate size control of Fe-doped ZIF catalyst particles with a wide range from 20 to 1000 nm without changing chemical properties, which provides a great opportunity to increase the density of active sites that is determined by the particle size. We elucidated the active site formation mechanism by correlating the chemical and structural changes with thermal activation process for the conversion from Fe-N4 complex containing hydrocarbon networks in ZIF to highly active FeNx sites embedded into carbon. A temperature of 800oC was identified as the critical point to start forming pyridinic nitrogen doping at the edge of the graphitized carbon planes. Further increasing heating temperature to 1100oC leads to increase of graphitic nitrogen, generating possible synergistic effect with FeNx sites to promote ORR activity. The best performing catalyst, which has well-defined particle size around 50 nm and abundance of atomic FeNx sites embedded into carbon structures, achieve a new performance milestone for the ORR in acid including a half-wave potential of 0.85 V vs RHE and only 20 mV loss after 10,000 cycles in O2 saturated H2SO4 electrolyte. The new class PGM-free catalyst with approaching activity to Pt holds great promise for future PEM fuel cells.

New insights into Cu/SSZ-13 SCR catalyst acidity. Part I: Nature of acidic sites probed by NH 3 titration

Energy Technology Data Exchange (ETDEWEB)

Luo, Jinyong; Gao, Feng; Kamasamudram, Krishna; Currier, Neal; Peden, Charles H. F.; Yezerets, Aleksey

2017-04-01

In this work we investigated an unusual acidity feature of a Cu/SSZ-13 catalyst used in selective catalytic reduction of NOx with NH3 (NH3-SCR). In particular, this catalyst showed two distinct NH3 desorption peaks in NH3-TPD measurements, in contrast to single, unresolved desorption peaks observed for other Cu-exchanged zeolites conventionally used in the SCR studies, including its isostructural but chemically different analogue Cu/SAPO-34. We further observed that the intensities of the two TPD peaks, which represented the amount of stored NH3, changed in opposite directions in response to progressive mild hydrothermal aging, while the total storage capacity was preserved. We proposed an explanation for this remarkable behavior, by using model reference samples and additional characterization techniques. At least three NH3 storage sites were identified: two distinct populations of Cu sites responsible for low-temperature NH3 storage, and Brønsted acid sites responsible for high-temperature NH3 storage. Contrary to the commonly accepted mechanism that Brønsted acid site loss during hydrothermal aging is driven by dealumination, we concluded that the decline in the number of Brønsted acid sites upon mild hydrothermal aging for Cu/SSZ-13 was not due to dealumination, but rather transformation of Cu sites, i.e., gradual conversion of ZCuOH (Cu2+ singly coordinated with Zeolite) to Z2Cu (Cu2+ doubly coordinated with Zeolite). This transformation was responsible for the increased low-temperature desorption peak in NH3-TPD since each ZCuOH adsorbed ~1 NH3 molecule while each Z2Cu adsorbed ~2 NH3 molecules under the conditions used here. These findings were used in Part II of this series of studies to develop a method for quantifying hydrothermal ageing of industrial Cu/SSZ-13 SCR catalysts. Authors would like to thank Randall Jines for his help with collecting the reactor data, Nancy W. Washton for measuring the NMR data and Tamas Varga for in-situ XRD measurements

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

Science.gov (United States)

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

2018-03-01

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

Interaction of water, alkyl hydroperoxide, and allylic alcohol with a single-site homogeneous Ti-Si epoxidation catalyst: A spectroscopic and computational study.

Science.gov (United States)

Urakawa, Atsushi; Bürgi, Thomas; Skrabal, Peter; Bangerter, Felix; Baiker, Alfons

2005-02-17

Tetrakis(trimethylsiloxy)titanium (TTMST, Ti(OSiMe3)4) possesses an isolated Ti center and is a highly active homogeneous catalyst in epoxidation of various olefins. The structure of TTMST resembles that of the active sites in some heterogeneous Ti-Si epoxidation catalysts, especially silylated titania-silica mixed oxides. Water cleaves the Ti-O-Si bond and deactivates the catalyst. An alkyl hydroperoxide, TBHP (tert-butyl hydroperoxide), does not cleave the Ti-O-Si bond, but interacts via weak hydrogen-bonding as supported by NMR, DOSY, IR, and computational studies. ATR-IR spectroscopy combined with computational investigations shows that more than one, that is, up to four, TBHP can undergo hydrogen-bonding with TTMST, leading to the activation of the O-O bond of TBHP. The greater the number of TBHP molecules that form hydrogen bonds to TTMST, the more electrophilic the O-O bond becomes, and the more active the complex is for epoxidation. An allylic alcohol, 2-cyclohexen-1-ol, does not interact strongly with TTMST, but the interaction is prominent when it interacts with the TTMST-TBHP complex. On the basis of the experimental and theoretical findings, a hydrogen-bond-assisted epoxidation mechanism of TTMST is suggested.

Design of high-activity single-atom catalysts via n-p codoping

Science.gov (United States)

Wang, Xiaonan; Zhou, Haiyan; Zhang, Xiaoyang; Jia, Jianfeng; Wu, Haishun

2018-03-01

The large-scale synthesis of stable single-atom catalysts (SACs) in experiments remains a significant challenge due to high surface free energy of metal atom. Here, we propose a concise n-p codoping approach, and find it can not only disperse the relatively inexpensive metal, copper (Cu), onto boron (B)-doped graphene, but also result in high-activity SACs. We use CO oxidation on B/Cu codoped graphene as a prototype example, and demonstrate that: (1) a stable SAC can be formed by stronger electrostatic attraction between the metal atom (n-type Cu) and support (p-type B-doped graphene). (2) the energy barrier of the prototype CO oxidation on B/Cu codoped graphene is 0.536 eV by the Eley-Rideal mechanism. Further analysis shows that the spin selection rule can provide well theoretical insight into high activity of our suggested SAC. The concept of n-p codoping may lead to new strategy in large-scale synthesis of stable single-atom catalysts.

Development of a Catalyst/Sorbent for Methane Reforming

Energy Technology Data Exchange (ETDEWEB)

B.H. Shans; T.D. Wheelock; Justinus Satrio; Karl Albrecht; Tanya Harris Janine Keeley; Ben Silva; Aaron Shell; Molly Lohry; Zachary Beversdorf

2008-12-31

This project led to the further development of a combined catalyst and sorbent for improving the process technology required for converting CH{sub 4} and/or CO into H{sub 2} while simultaneously separating the CO{sub 2} byproduct all in a single step. The new material is in the form of core-in-shell pellets such that each pellet consists of a CaO core surrounded by an alumina-based shell capable of supporting a Ni catalyst. The Ni is capable of catalyzing the reactions of steam with CH{sub 4} or CO to produce H{sub 2} and CO{sub 2}, whereas the CaO is capable of absorbing the CO{sub 2} as it is produced. The absorption of CO{sub 2} eliminates the reaction inhibiting effects of CO{sub 2} and provides a means for recovering the CO{sub 2} in a useful form. The present work showed that the lifecycle performance of the sorbent can be improved either by incorporating a specific amount of MgO in the material or by calcining CaO derived from limestone at 1100 C for an extended period. It also showed how to prepare a strong shell material with a large surface area required for supporting an active Ni catalyst. The method combines graded particles of {alpha}-alumina with noncrystalline alumina having a large specific surface area together with a strength promoting additive followed by controlled calcination. Two different additives produced good results: 3 {micro}m limestone and lanthanum nitrate which were converted to their respective oxides upon calcination. The oxides partially reacted with the alumina to form aluminates which probably accounted for the strength enhancing properties of the additives. The use of lanthanum made it possible to calcine the shell material at a lower temperature, which was less detrimental to the surface area, but still capable of producing a strong shell. Core-in-shell pellets made with the improved shell materials and impregnated with a Ni catalyst were used for steam reforming CH{sub 4} at different temperatures and pressures. Under all

Catalysts, methods of making catalysts, and methods of use

KAUST Repository

Renard, Laetitia; El Eter, Mohamad; Caps, Valerie; Basset, Jean-Marie

2014-01-01

Embodiments of the present disclosure provide for catalysts, methods of making catalysts, methods of using catalysts, and the like. In an embodiment, the method of making the catalysts can be performed in a single step with a metal nanoparticle precursor and a metal oxide precursor, where a separate stabilizing agent is not needed.

Catalysts, methods of making catalysts, and methods of use

KAUST Repository

Renard, Laetitia

2014-03-06

Embodiments of the present disclosure provide for catalysts, methods of making catalysts, methods of using catalysts, and the like. In an embodiment, the method of making the catalysts can be performed in a single step with a metal nanoparticle precursor and a metal oxide precursor, where a separate stabilizing agent is not needed.

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

Energy Technology Data Exchange (ETDEWEB)

Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu; Feng, Zhenxing; Karakalos, Stavros; Luo, Langli; Qiao, Zhi; Xie, Xiaohong; Wang, Chongmin; Su, Dong; Shao, Yuyan; Wu, Gang (BNL); (Oregon State U.); (SC); (PNNL); (Buffalo)

2017-09-26

It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). Here, we report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunable through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. Using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe3+ to Fe2+) likely bonded with pyridinic N (FeN4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H2SO4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μgPt/cm2). Enhanced stability

Growth Mechanism of Single-Walled Carbon Nanotubes on Iron–Copper Catalyst and Chirality Studies by Electron Diffraction

DEFF Research Database (Denmark)

He, Maoshuai; Liu, Bilu; Chernov, Alexander I.

2012-01-01

Chiralities of single-walled carbon nanotubes grown on an atomic layer deposition prepared bimetallic FeCu/MgO catalyst were evaluated quantitatively using nanobeam electron diffraction. The results reveal that the growth yields nearly 90% semiconducting tubes, 45% of which are of the (6,5) type...... by impregnation, showing similar catalytic performance as the atomic layer deposition-prepared catalyst, yielding single-walled carbon nanotubes with a similar narrow chirality distribution....

On the activation of Pt/Al2O3 catalysts in HC-SCR by sintering. Determination of redox-active sites using Multitrack

International Nuclear Information System (INIS)

Vaccaro, A.R.; Mul, G.; Moulijn, J.A.; Perez-Ramirez, J.

2003-01-01

A highly dispersed Pt/Al 2 O 3 catalyst was used for the selective catalytic reduction of NO x using propene (HC-SCR). Contact with the reaction gas mixture led to a significant activation of the catalyst at temperatures above 523K. According to CO chemisorption data and HRTEM analysis, Pt particles on the activated catalyst had sintered. The redox behavior of the fresh and sintered catalysts was investigated using Multitrack, a TAP-like pulse reactor. If Pt particles on the catalyst are highly dispersed (average size below =2nm), only a small part (=10%) of the total number of Pt surface sites as determined by CO chemisorption (Pt surf ) participates in H 2 /O 2 redox cycles (Pt surf,redox ) in Multitrack conditions. For a sintered catalyst, with an average particle size of 2.7nm, the number of Pt surf and Pt surf,redox sites are in good agreement. Similar results were obtained for both catalysts using NO as the oxidant. The low number of Pt surf,redox sites on highly dispersed Pt/Al 2 O 3 is explained by the presence of a kinetically more stable-probably ionic-form of Pt-O bonds on all surface sites of the smaller Pt particles, including corner, edge and terrace sites. When the average particle size shifts to =2.7nm, the kinetic stability of all Pt-O bonds is collectively decreased, enabling the participation of all Pt surface sites in the redox cycles. A linear correlation between the NO x conversion in HC-SCR, and the amount of Pt surf,redox was found. This suggests that redox-active Pt sites are necessary for catalytic activity. In addition, the correlation could be significantly improved by assuming that Pt surf,terrace sites of the particles larger than 2.7nm are mainly responsible for HC-SCR activity in steady state conditions. Implications of these results for the pathway of HC-SCR over Pt catalysts are discussed

Robotic single-site pelvic lymphadenectomy.

Science.gov (United States)

Tateo, Saverio; Nozza, Arrigo; Del Pezzo, Chiara; Mereu, Liliana

2014-09-01

To examine the feasibility of performing pelvic lymphadenectomy with robotic single site approach. Recent papers described the feasibility of robotic-single site hysterectomy [1-3] for benign and malign pathologies but only with the development of new single site 5mm instruments as the bipolar forceps, robotic single site platform can be safely utilized also for lymphadenectomy. A 65 year-old, multiparous patient with a body mass index of 22.5 and diagnosed with well differentiated adenocarcinoma of the endometrium underwent a robotic single-site peritoneal washing, total hysterectomy, bilateral adnexectomy and pelvic lymphadenectomy. The procedure was performed using the da Vinci Si Surgical System (Intuitive Surgical, Sunnyvale, CA) through a single 2,5 cm umbilical incision, with a multi-channel system and two single site robotic 5mm instruments. A 3-dimensional, HD 8.5mm endoscope and a 5mm accessory instrument were also utilized. Type I lymphonodes dissection for external iliac and obturator regions was performed [4]. Total operative time was 210 min; incision, trocar placement and docking time occurring in 12 min. Total console time was 183 min, estimated blood loss was 50 ml, no intra-operative or post-operative complications occurred. Hospital discharge occurred on post operative day 2 and total number of lymphnodes removed was 33. Difficulties in term of instrument's clashing and awkward motions have been encountered. Robotic single-site pelvic lymphadenectomy using bipolar forceps and monopolar hook is feasible. New developments are needed to improve surgical ergonomics and additional studies should be performed to explore possible benefits of this procedure. Copyright © 2014 Elsevier Inc. All rights reserved.

Active sites of ligand-protected Au25 nanoparticle catalysts for CO2 electroreduction to CO

Science.gov (United States)

Alfonso, Dominic R.; Kauffman, Douglas; Matranga, Christopher

2016-05-01

Recent experimental studies have reported the electrochemical reduction of carbon dioxide (CO2) into CO at atomically precise negatively charged Au25- nanoclusters. The studies showed CO2 conversion at remarkably low overpotentials, but the exact mechanisms and nature of the active sites remain unclear. We used first-principles density functional theory and continuum solvation models to examine the role of the cluster during electrochemical CO2 reduction and analyze the free energies of proposed intermediate species. Contrary to previous assumptions, our results show that the fully ligand protected cluster is not an active CO2 reduction catalyst because formation of the crucial carboxyl intermediate required very high electrochemical potentials. Instead, our calculations suggest that the reduction process likely occurs on a dethiolated gold site, and adsorbed carboxyl intermediate formation was significantly stabilized at dethiolated gold sites. These findings point to the crucial role of exposed metal sites during electrochemical CO2 reduction at gold nanocluster catalysts.

Single-Atom Mn Active Site in a Triol-Stabilized β-Anderson Manganohexamolybdate for Enhanced Catalytic Activity towards Adipic Acid Production

Directory of Open Access Journals (Sweden)

Jianhui Luo

2018-03-01

Full Text Available Adipic acid is an important raw chemical for the commercial production of polyamides and polyesters. The traditional industrial adipic acid production utilizes nitric acid to oxidize KA oil (mixtures of cyclohexanone and cyclohexanol, leading to the emission of N2O and thus causing ozone depletion, global warming, and acid rain. Herein, we reported an organically functionalized β-isomer of Anderson polyoxometalates (POMs nanocluster with single-atom Mn, β-{[H3NC(CH2O3]2MnMo6O18}− (1, as a highly active catalyst to selectively catalyze the oxidation of cyclohexanone, cyclohexanol, or KA oil with atom economy use of 30% H2O2 for the eco-friendly synthesis of adipic acid. The catalyst has been characterized by single crystal and powder XRD, XPS, ESI-MS, FT-IR, and NMR. A cyclohexanone (cyclohexanol conversion of >99.9% with an adipic acid selectivity of ~97.1% (~85.3% could be achieved over catalyst 1 with high turnover frequency of 2427.5 h−1 (2132.5 h−1. It has been demonstrated that the existence of Mn3+ atom active site in catalyst 1 and the special butterfly-shaped topology of POMs both play vital roles in the enhancement of catalytic activity.

Solid Catalyst Nanoparticles derived from Oil-Palm Empty Fruit Bunches (OP-EFB) as a Renewable Catalyst for Biodiesel Production

Science.gov (United States)

Husin, H.; Asnawi, T. M.; Firdaus, A.; Husaini, H.; Ibrahim, I.; Hasfita, F.

2018-05-01

Solid nanocatalyst derived from oil-palm empty fruit bunches (OP-EFB) fiber was successfully synthesized and its application for biodiesel production was investigated. The OPEFB was treated by burning, milling and heating methods to generate ashes in a nanoparticle size. The nanoparticle palm-bunch ash was characterized by scanning electron microscopy (SEM) and x-ray diffraction (XRD). The effects of the calcination temperature and catalyst amounts for transesterification reactions were investigated. XRD analysis of palm bunch ash exhibited that the highest composition of peaks characteristic were potassium oxide (K2O). SEM analysis showed that the nano palm bunch ash have a particle size ranging of 150-400 nm. The highest conversion of palm-oil to biodiesel reach to 97.90% was observed by using of palm bunch ash nanocatalyst which heated at 600°C, 3 h reaction time and 1% catalyst amount. Reusability of palm bunch ash catalysts was also examined. It was found that of its high active sites, reusable solid catalyst was obtained by just heating of palm bunch ash. It has a capability to reduce not only the amount of catalyst consumption but also reduce the reaction time of transesterification process.

Fe-Ti-O based catalyst for large-chiral-angle single-walled carbon nanotube growth

DEFF Research Database (Denmark)

He, Maoshuai; Zhang, Lili; Jiang, Hua

2016-01-01

Catalyst selection is very crucial for controlled growth of single-walled carbon nanotubes (SWNTs). Here we introduce a well-designed Fe-Ti-O solid solution for SWNT growth with a high preference to large chiral angles. The Fe-Ti-O catalyst was prepared by combining Ti layer deposition onto premade...... Fe nanoparticles with subsequent high-temperature air calcination, which favours the formation of a homogeneous Fe-Ti-O solid solution. Using CO as the carbon feedstock, chemical vapour deposition growth of SWNTs at 800 °C was demonstrated on the Fe-Ti-O catalyst. Nanobeam electron diffraction...... characterization on a number of individual SWNTs revealed that more than 94% of SWNTs have chiral angles larger than 15°. In situ environmental transmission electron microscopy study was carried out to reveal the catalyst dynamics upon reduction. Our results identify that the phase segregation through reducing Fe...

Competing reaction processes on a lattice as a paradigm for catalyst deactivation

Science.gov (United States)

Abad, E.; Kozak, J. J.

2015-02-01

We mobilize both a generating function approach and the theory of finite Markov processes to compute the probability of irreversible absorption of a randomly diffusing species on a lattice with competing reaction centers. We consider an N-site lattice populated by a single deep trap, and N -1 partially absorbing traps (absorption probability 0 characteristic Ω =0 and Ω =2 . The results obtained allow a characterization of catalyst deactivation processes on planar surfaces and on catalyst pellets where only a single catalytic site remains fully active (deep trap), the other sites being only partially active as a result of surface poisoning. The central result of our study is that the predicted dependence of the reaction efficiency on system size N and on s is in qualitative accord with previously reported experimental results, notably catalysts exhibiting selective poisoning due to surface sites that have different affinities for chemisorption of the poisoning agent (e.g., acid zeolite catalysts). Deviations from the efficiency of a catalyst with identical sites are quantified, and we find that such deviations display a significant dependence on the topological details of the surface (for fixed values of N and s we find markedly different results for, say, a planar surface and for the polyhedral surface of a catalyst pellet). Our results highlight the importance of surface topology for the efficiency of catalytic conversion processes on inhomogeneous substrates, and in particular for those aimed at industrial applications. From our exact analysis we extract results for the two limiting cases s ≈1 and s ≈0 , corresponding respectively to weak and strong catalyst poisoning (decreasing s leads to a monotonic decrease in the efficiency of catalytic conversion). The results for the s ≈0 case are relevant for the dual problem of light-energy conversion via trapping of excitations in the chlorophyll antenna network. Here, decreasing the probability of excitation

Approaches to single-nanoparticle catalysis.

Science.gov (United States)

Sambur, Justin B; Chen, Peng

2014-01-01

Nanoparticles are among the most important industrial catalysts, with applications ranging from chemical manufacturing to energy conversion and storage. Heterogeneity is a general feature among these nanoparticles, with their individual differences in size, shape, and surface sites leading to variable, particle-specific catalytic activity. Assessing the activity of individual nanoparticles, preferably with subparticle resolution, is thus desired and vital to the development of efficient catalysts. It is challenging to measure the activity of single-nanoparticle catalysts, however. Several experimental approaches have been developed to monitor catalysis on single nanoparticles, including electrochemical methods, single-molecule fluorescence microscopy, surface plasmon resonance spectroscopy, X-ray microscopy, and surface-enhanced Raman spectroscopy. This review focuses on these experimental approaches, the associated methods and strategies, and selected applications in studying single-nanoparticle catalysis with chemical selectivity, sensitivity, or subparticle spatial resolution.

Mesoporous zeolite single crystal catalysts: Diffusion and catalysis in hierarchical zeolites

DEFF Research Database (Denmark)

Christensen, Christina Hviid; Johannsen, Kim; Toernqvist, Eric

2007-01-01

During the last years, several new routes to produce zeolites with controlled mesoporosity have appeared. Moreover, an improved catalytic performance of the resulting mesoporous zeolites over conventional zeolites has been demonstrated in several reactions. In most cases, the mesoporous zeolites...... exhibit higher catalytic activity, but in some cases also improved selectivity and longer catalyst lifetime has been reported. The beneficial effects of introducing mesopores into the zeolites has in most instances been attributed to improved mass transport to and from the active sites located...... in the zeolite micropores. Here, we briefly discuss the most important ways of introducing mesopores into zeolites and, for the first time, we show experimentally that the presence of mesopores dramatically increases the rate of diffusion in zeolite catalysts. This is done by studying the elution of iso...

Deactivation-resistant catalyst for selective catalyst reduction of NOx

DEFF Research Database (Denmark)

2011-01-01

The present invention relates to a catalyst for selective catalytic reduction of NOx in alkali metal containing flue gas using ammonia as reductant, the catalyst comprising a surface with catalytically active sites, wherein the surface is at least partly coated with a coating comprising at least...... one metal oxide. In another aspect the present invention relates to the use of said catalyst and to a method of producing said catalyst. In addition, the present invention relates to a method of treating an catalyst for conferring thereon an improved resistance to alkali poisoning....

Enhancement of alkylation catalysts for improved supercritical fluid regeneration

Science.gov (United States)

Ginosar, Daniel M.; Petkovic, Lucia M.

2010-12-28

A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

NANOSTRUCTURED METAL OXIDE CATALYSTS VIA BUILDING BLOCK SYNTHESES

Energy Technology Data Exchange (ETDEWEB)

Craig E. Barnes

2013-03-05

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

Final Technical Report: Metal—Organic Surface Catalyst for Low-temperature Methane Oxidation: Bi-functional Union of Metal—Organic Complex and Chemically Complementary Surface

Energy Technology Data Exchange (ETDEWEB)

Tait, Steven L. [Indiana Univ., Bloomington, IN (United States)

2016-10-01

Stabilization and chemical control of transition metal centers is a critical problem in the advancement of heterogeneous catalysts to next-generation catalysts that exhibit high levels of selectivity, while maintaining strong activity and facile catalyst recycling. Supported metal nanoparticle catalysts typically suffer from having a wide range of metal sites with different coordination numbers and varying chemistry. This project is exploring new possibilities in catalysis by combining features of homogeneous catalysts with those of heterogeneous catalysts to develop new, bi-functional systems. The systems are more complex than traditional heterogeneous catalysts in that they utilize sequential active sites to accomplish the desired overall reaction. The interaction of metal—organic catalysts with surface supports and their interactions with reactants to enable the catalysis of critical reactions at lower temperatures are at the focus of this study. Our work targets key fundamental chemistry problems. How do the metal—organic complexes interact with the surface? Can those metal center sites be tuned for selectivity and activity as they are in the homogeneous system by ligand design? What steps are necessary to enable a cooperative chemistry to occur and open opportunities for bi-functional catalyst systems? Study of these systems will develop the concept of bringing together the advantages of heterogeneous catalysis with those of homogeneous catalysis, and take this a step further by pursuing the objective of a bi-functional system. The use of metal-organic complexes in surface catalysts is therefore of interest to create well-defined and highly regular single-site centers. While these are not likely to be stable in the high temperature environments (> 300 °C) typical of industrial heterogeneous catalysts, they could be applied in moderate temperature reactions (100-300 °C), made feasible by lowering reaction temperatures by better catalyst control. They also

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

Directory of Open Access Journals (Sweden)

James F. Brazdil

2018-03-01

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

Synthesis of cobalt-containing mesoporous catalysts using the ultrasonic-assisted “pH-adjusting” method: Importance of cobalt species in styrene oxidation

Energy Technology Data Exchange (ETDEWEB)

Li, Baitao, E-mail: btli@scut.edu.cn; Zhu, Yanrun; Jin, Xiaojing

2015-01-15

Cobalt-containing SBA-15 and MCM-41 (Co-SBA-15 and Co-MCM-41) mesoporous catalysts were prepared via ultrasonic-assisted “pH-adjusting” technique in this study. Their physiochemical structures were comprehensively characterized and correlated with catalytic activity in oxidation of styrene. The nature of cobalt species depended on the type of mesoporous silica as well as pH values. The different catalytic performance between Co-SBA-15 and Co-MCM-41 catalysts originated from cobalt species. Cobalt species were homogenously incorporated into the siliceous framework of Co-SBA-15 in single-site Co(II) state, while Co{sub 3}O{sub 4} particles were loaded on Co-MCM-41 catalysts. The styrene oxidation tests showed that the single-site Co(II) state was more beneficial to the catalytic oxidation of styrene. The higher styrene conversion and benzaldehyde selectivity over Co-SBA-15 catalysts were mainly attributed to single-site Co(II) state incorporated into the framework of SBA-15. The highest conversion of styrene (34.7%) with benzaldehyde selectivity of 88.2% was obtained over Co-SBA-15 catalyst prepared at pH of 7.5, at the mole ratio of 1:1 (styrene to H{sub 2}O{sub 2}) at 70 °C. - Graphical abstract: Cobalt-containing mesoporous silica catalysts were developed via ultrasonic-assisted “pH-adjusting” technique. Compared with Co{sub 3}O{sub 4} in Co-MCM-41, the single-site Co(II) state in Co-SBA-15 was more efficient for the styrene oxidation. - Highlights: • Fast and cost-effective ultrasonic technique for preparing mesoporous materials. • Incorporation of Co via ultrasonic irradiation and “pH-adjusting”. • Physicochemical comparison between Co-SBA-15 and Co-MCM-41. • Correlation of styrene oxidation activity and catalyst structural property.

Communicating catalysts

Science.gov (United States)

Weckhuysen, Bert M.

2018-06-01

The beauty and activity of enzymes inspire chemists to tailor new and better non-biological catalysts. Now, a study reveals that the active sites within heterogeneous catalysts actively cooperate in a fashion phenomenologically similar to, but mechanistically distinct, from enzymes.

Integrated Transmission Electron and Single-Molecule Fluorescence Microscopy Correlates Reactivity with Ultrastructure in a Single Catalyst Particle

OpenAIRE

Hendriks, Frank C.; Mohammadian, Sajjad; Ristanovic, Zoran; Kalirai, Samanbir; Meirer, Florian; Vogt, Eelco T. C.; Bruijnincx, Pieter C. A.; Gerritsen, Hans; Weckhuysen, Bert M.

2018-01-01

Establishing structure–activity relationships in complex, hierarchically structured nanomaterials, such as fluid catalytic cracking (FCC) catalysts, requires characterization with complementary, correlated analysis techniques. An integrated setup has been developed to perform transmission electron microscopy (TEM) and single-molecule fluorescence (SMF) microscopy on such nanostructured samples. Correlated structure–reactivity information was obtained for 100 nm thin, microtomed sections of a ...

Laser-Induced Fluorescence Detection in High-Throughput Screening of Heterogeneous Catalysts and Single Cells Analysis

Energy Technology Data Exchange (ETDEWEB)

Su, Hui [Iowa State Univ., Ames, IA (United States)

2001-01-01

Laser-induced fluorescence detection is one of the most sensitive detection techniques and it has found enormous applications in various areas. The purpose of this research was to develop detection approaches based on laser-induced fluorescence detection in two different areas, heterogeneous catalysts screening and single cell study. First, the author introduced laser-induced imaging (LIFI) as a high-throughput screening technique for heterogeneous catalysts to explore the use of this high-throughput screening technique in discovery and study of various heterogeneous catalyst systems. This scheme is based on the fact that the creation or the destruction of chemical bonds alters the fluorescence properties of suitably designed molecules. By irradiating the region immediately above the catalytic surface with a laser, the fluorescence intensity of a selected product or reactant can be imaged by a charge-coupled device (CCD) camera to follow the catalytic activity as a function of time and space. By screening the catalytic activity of vanadium pentoxide catalysts in oxidation of naphthalene, they demonstrated LIFI has good detection performance and the spatial and temporal resolution needed for high-throughput screening of heterogeneous catalysts. The sample packing density can reach up to 250 x 250 subunits/cm² for 40-μm wells. This experimental set-up also can screen solid catalysts via near infrared thermography detection. In the second part of this dissertation, the author used laser-induced native fluorescence coupled with capillary electrophoresis (LINF-CE) and microscope imaging to study the single cell degranulation. On the basis of good temporal correlation with events observed through an optical microscope, they have identified individual peaks in the fluorescence electropherograms as serotonin released from the granular core on contact with the surrounding fluid.

Investigation of heterogeneous solid acid catalyst performance on low grade feedstocks for biodiesel production: A review

International Nuclear Information System (INIS)

Mansir, Nasar; Taufiq-Yap, Yun Hin; Rashid, Umer; Lokman, Ibrahim M.

2017-01-01

Highlights: • Solid acid catalysts are proficient to esterifying high free fatty acid feedstocks to biodiesel. • Heterogeneous catalysts have the advantage of easy separation and reusability. • Heterogeneous basic catalysts have limitations due to high FFA of low cost feedstocks. • Solid catalysts having acid and base sites reveal better catalyst for biodiesel production. - Abstract: The conventional fossil fuel reserves are continually declining worldwide and therefore posing greater challenges to the future of the energy sources. Biofuel alternatives were found promising to replace the diminishing fossil fuels. However, conversion of edible vegetable oils to biodiesel using homogeneous acids and base catalysts is now considered as indefensible for the future particularly due to food versus fuel competition and other environmental problems related to catalyst system and feedstock. This review has discussed the progression in research and growth related to heterogeneous catalysts used for biodiesel production for low grade feedstocks. The heterogeneous base catalysts have revealed effective way to produce biodiesel, but it has the limitation of being sensitive to high free fatty acid (FFA) or low grade feedstocks. Alternatively, solid acid catalysts are capable of converting the low grade feedstocks to biodiesel in the presence of active acid sites. The paper presents a comprehensive review towards the investigation of solid acid catalyst performance on low grade feedstock, their category, properties, advantages, limitations and possible remedy to their drawbacks for biodiesel production.

High utilization platinum deposition on single-walled carbon nanotubes as catalysts for direct methanol fuel cell

International Nuclear Information System (INIS)

Wang, J.J.; Yin, G.P.; Zhang, J.; Wang, Z.B.; Gao, Y.Z.

2007-01-01

This research aims to enhance the activity of Pt catalysts, thus to lower the loading of Pt metal in fuel cell. Highly dispersed platinum supported on single-walled carbon nanotubes (SWNTs) as catalyst was prepared by ion exchange method. The homemade Pt/SWNTs underwent a repetition of ion exchange and reduction process in order to achieve an increase of the metal loading. For comparison, the similar loading of Pt catalyst supported on carbon nanotubes was prepared by borohydride reduction method. The catalysts were characterized by using energy dispersive analysis of X-ray (EDAX), transmission electron micrograph (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectrum (XPS). Compared with the Pt/SWNTs catalyst prepared by borohydride method, higher Pt utilization was achieved on the SWNTs by ion exchange method. Furthermore, in comparison to the E-TEK 20 wt.% Pt/C catalyst with the support of carbon black, the results from electrochemical measurement indicated that the Pt/SWNTs prepared by ion exchange method displayed a higher catalytic activity for methanol oxidation and higher Pt utilization, while no significant increasing in the catalytic activity of the Pt/SWNTs catalyst obtained by borohydride method

Efficient Dual-Site Carbon Monoxide Electro-Catalysts via Interfacial Nano-Engineering

Science.gov (United States)

Liu, Zhen; Huang, Zhongyuan; Cheng, Feifei; Guo, Zhanhu; Wang, Guangdi; Chen, Xu; Wang, Zhe

2016-01-01

Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal−air batteries. Herein, we report the novel system of nickel−aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis (trifluoromethylsulfonyl)imide (NTf2) anion of ionic liquid electrolyte was selected to enhance the CO/O2 adsorption and to facilitate electro-catalyzed oxidation of Ni (OH)2 to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was much higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Moreover, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles. PMID:27650532

Synthesis of subnanometer-diameter vertically aligned single-walled carbon nanotubes with copper-anchored cobalt catalysts

Science.gov (United States)

Cui, Kehang; Kumamoto, Akihito; Xiang, Rong; An, Hua; Wang, Benjamin; Inoue, Taiki; Chiashi, Shohei; Ikuhara, Yuichi; Maruyama, Shigeo

2016-01-01

We synthesize vertically aligned single-walled carbon nanotubes (VA-SWNTs) with subnanometer diameters on quartz (and SiO2/Si) substrates by alcohol CVD using Cu-anchored Co catalysts. The uniform VA-SWNTs with a nanotube diameter of 1 nm are synthesized at a CVD temperature of 800 °C and have a thickness of several tens of μm. The diameter of SWNTs was reduced to 0.75 nm at 650 °C with the G/D ratio maintained above 24. Scanning transmission electron microscopy energy-dispersive X-ray spectroscopy (EDS-STEM) and high angle annular dark field (HAADF-STEM) imaging of the Co/Cu bimetallic catalyst system showed that Co catalysts were captured and anchored by adjacent Cu nanoparticles, and thus were prevented from coalescing into a larger size, which contributed to the small diameter of SWNTs. The correlation between the catalyst size and the SWNT diameter was experimentally clarified. The subnanometer-diameter and high-quality SWNTs are expected to pave the way to replace silicon for next-generation optoelectronic and photovoltaic devices.We synthesize vertically aligned single-walled carbon nanotubes (VA-SWNTs) with subnanometer diameters on quartz (and SiO2/Si) substrates by alcohol CVD using Cu-anchored Co catalysts. The uniform VA-SWNTs with a nanotube diameter of 1 nm are synthesized at a CVD temperature of 800 °C and have a thickness of several tens of μm. The diameter of SWNTs was reduced to 0.75 nm at 650 °C with the G/D ratio maintained above 24. Scanning transmission electron microscopy energy-dispersive X-ray spectroscopy (EDS-STEM) and high angle annular dark field (HAADF-STEM) imaging of the Co/Cu bimetallic catalyst system showed that Co catalysts were captured and anchored by adjacent Cu nanoparticles, and thus were prevented from coalescing into a larger size, which contributed to the small diameter of SWNTs. The correlation between the catalyst size and the SWNT diameter was experimentally clarified. The subnanometer-diameter and high

Growth of vertically aligned single-walled carbon nanotubes with metallic chirality through faceted FePt-Au catalysts

Science.gov (United States)

Ohashi, Toshiyuki; Iwama, Hiroki; Shima, Toshiyuki

2016-02-01

Direct synthesis of vertically aligned metallic single-walled carbon nanotubes (m-SWCNT forests) is a difficult challenge. We have successfully synthesized m-SWCNT forests using faceted iron platinum-gold catalysts epitaxially grown on a single crystalline magnesium oxide substrate. The metallic content of the forests estimated by Raman spectroscopy reaches 90%. From the standpoint of growth rate of the forests, the growth mechanism is probably based on the catalyst of solid state. It is suggested that preferential growth of m-SWCNTs is achieved when both factors are satisfied, namely, {111} dominant octahedral facet and ideal size (fine particles) of FePt particles.

Activation of surface lattice oxygen in single-atom Pt/CeO ₂ for low-temperature CO oxidation

Energy Technology Data Exchange (ETDEWEB)

Nie, Lei; Mei, Donghai; Xiong, Haifeng; Peng, Bo; Ren, Zhibo; Pereira Hernandez, Xavier I.; DelaRiva, Andrew; Wang, Meng; Engelhard, Mark H.; Kovarik, Libor; Datye, Abhaya K.; Wang, Yong

2017-12-14

While single-atom catalysts can provide high catalytic activity and selectivity, application in industrial catalysts demands long term performance and the ability to regenerate the catalysts. We have investigated the factors that lead to improved catalytic activity of a Pt/CeO2 catalyst for low temperature CO oxidation. Single-atom Pt/CeO2 becomes active for CO oxidation under lean condition only at elevated temperatures, because CO is strongly bound to ionic Pt sites. Reducing the catalyst, even under mild conditions, leads to onset of CO oxidation activity even at room temperature. This high activity state involves the transformation of mononuclear Pt species to sub-nanometer sized Pt particles. Under oxidizing conditions, the Pt can be restored to its stable, single-atom state. The key to facile regeneration is the ability to create mobile Pt species and suitable trapping sites on the support, making this a prototypical catalyst system for industrial application of single-atom catalysis.

Energetic Mapping of Ni Catalysts by Detailed Kinetic Modeling

DEFF Research Database (Denmark)

Bjørgum, Erlend; Chen, De; Bakken, Mari G.

2005-01-01

Temperature-programmed desorption (TPD) of CO has been performed on supported and unsupported nickel catalysts. The unsupported Ni catalyst consists of a Ni(14 13 13) single crystal which has been studied under ultrahigh vacuum conditions. The desorption energy for CO at low CO surface coverage...... was found to be 119 kJ/mol, and the binding energy of C to the Ni(111) surface of the crystal was 703 kJ/mol. The supported catalysts consist of nickel supported on hydrotalcite-like compounds with three different Mg2+/Al3+ ratios. The experimental results show that for the supported Ni catalysts TPD of CO...... precursor seems to result in more steplike sites, kinks, and defects for carbon monoxide dissociation. A detailed kinetic modeling of the TPO results based on elementary reaction steps has been conducted to give an energetic map of supported Ni catalysts. Experimental results from the ideal Ni surface fit...

On-site and off-site forensic analysis capabilities for proliferation and terrorism prevention

International Nuclear Information System (INIS)

Whipple, R.E.; Nunes, P.J.; Reynolds, J.G.; Alcaraz, A.; Hart, B.R.

2004-01-01

Full text: We will present current on-site technologies that can be utilized for the screening of explosives, chemical agents, and environmental contaminants. These techniques must have the capability to detect various hazardous materials at very low levels, since they pose a major challenge for first responders. Specifically, the technology must detect concealed explosives or chemical agents on-site rapidly. Lawrence Livermore National Laboratory (LLNL) is currently developing several different high explosive screening and detection technologies for field use. Two technologies that have demonstrated an ability to screen for explosives at low levels are colorimetric spot tests and thin layer chromatography (TLC). Another technology that has demonstrated usefulness for the on-site analysis of unknowns is portable gas chromatography-mass spectrometry (GC-MS) with solid phase micro-extraction (SPME) sampling. Several examples utilizing these technologies and their usefulness will be presented. In addition to developing on-site screening methods, LLNL is an Organization for the Prohibition of Chemical Weapons (OPCW) designated laboratory and is certified to accept CW suspect samples. Currently, LLNL is expanding its ISO-17025 certification to include nuclear forensics and explosives. These off-site forensic analysis capabilities and certified procedures will support the needs for homeland security. We will highlight some of the ISO-17025 requirements to accredit procedures, handle samples, and reports. Work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under contract W-7405-ENG-48

On-site and off-site forensic analysis capabilities for proliferation and terrorism prevention

International Nuclear Information System (INIS)

Hart, B.R.; Whipple, R.E.; Nunes, P.J.; Reynolds, J.G.; Alcaraz, A.

2004-01-01

We present current on-site technologies that can be utilized for the screening of explosives, chemical agents, and environmental contaminants. These techniques must have the capability to detect various hazardous materials at very low levels, since they pose a major challenge for first responders. Specifically, the technology must detect concealed explosives or chemical agents on-site rapidly. Lawrence Livermore National Laboratory (LLNL) is currently developing several different high explosive screening and detection technologies for field use. Two technologies that have demonstrated an ability to screen for explosives at low levels are colorimetric spot tests and thin layer chromatography (TLC). Another technology that has demonstrated usefulness for the on-site analysis of unknowns is portable gas chromatography-mass spectrometry (GC-MS) with solid phase micro-extraction (SPME) sampling. Several examples utilizing these technologies and their usefulness will be presented. In addition to developing on-site screening methods, LLNL is an Organization for the Prohibition of Chemical Weapons (OPCW) designated laboratory and is certified to accept CW suspect samples. Currently, LLNL is expanding its ISO-17025 certification to include nuclear forensics and explosives. These off-site forensic analysis capabilities and certified procedures will support the needs for homeland security. We will highlight some of the ISO-17025 requirements to accredit procedures, handle samples, and reports. Work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under contract W-7405-ENG-48. (author)

Rational Catalyst Design of Titanium-Silica Materials Aided by Site-Specific Titration Tools

Science.gov (United States)

Eaton, Todd Robert

Silica-supported titanium materials are widely used for thermocatalytic applications such as hydroxylation of alkanes and aromatics, oxidation of alcohols and ethers, ammoximation of carbonyls, and sulfoxidations, while Ti-based materials are widely studied for photocatalytic applications such as photo-oxidation of organic substrates and photo-reduction of CO 2. However, the underlying phenomena of how to synthesize, identify, and control the active structures in these materials is not well understood because of the narrow scope of previous work. Studies of titanium-based catalysts typically focus on materials where the metal is present as either highly-dispersed Ti cations or in bulk crystalline TiO2 form, neglecting the numerous and potentially useful intermediate structures. Furthermore, these works typically focus on a single synthesis technique and rely upon bulk characterization techniques to understand the materials. Here rigorous titanium-silica synthesis-structure-function relationships are established by examining several different synthetic method and utilizing characterization techniques that enable an atomic-level understanding of the materials. The materials studied span the range from isolated Ti cations to clustered TiOx domains, polymeric TiO x domains, anatase-like 2D TiO2 domains, and 3D crystalline TiO2. Tools to quantify accessible TiO x and tetrahedral Ti sites are developed, utilizing the selective titration of titanium with phenylphosphonic acid (PPA). Catalytic properties are probed with the photocatalytic oxidation of benzyl alcohol and the thermocatalytic epoxidation of cis-cyclooctene with H2O2 . PPA titration data indicate that the rate of benzyl alcohol photo-oxidation is independent of titanium coordination, while the rate of alkene epoxidation with H2O2 is proportional to the number of tetrahedral titanium sites on the catalyst. PPA titration data also enables the estimation of TiO2 particle size and reveals an important distinction

The Atmospheric Release Advisory Capability Site Workstation System

International Nuclear Information System (INIS)

Foster, K.T.; Sumikawa, D.A.; Foster, C.S.; Baskett, R.L.

1993-01-01

The Atmospheric Release Advisory Capability (ARAC) is a centralized emergency response service that assesses the consequences that may result from an atmospheric release of toxic material. ARAC was developed by the Lawrence Livermore National Laboratory (LLNL) for the Departments of Energy (DOE) and Defense (DOD) and responds principally to radiological accidents. ARAC provides radiological health and safety guidance to decision makers in the form of computer-generated estimates of the effects of an actual, or potential release of radioactive material into the atmosphere. Upon receipt of the release scenario, the ARAC assessment staff extracts meteorological, topographic, and geographic data from resident world-wide databases for use in complex, three-dimensional transport and diffusion models. These dispersion models generate air concentration (or dose) and ground deposition contour plots showing estimates of the contamination patterns produced as the toxic material is carried by the prevailing winds. To facilitate the ARAC response to a release from specific DOE and DOD sites and to provide these sites with a local emergency response tool, a remote Site Workstation System (SWS) is being placed at various ARAC-supported facilities across the country.. This SWS replaces the existing antiquated ARAC Site System now installed at many of these sites. The new system gives users access to complex atmospheric dispersion models that may be run either by the ARAC staff at LLNL, or (in a later phase of the system) by site personnel using the computational resources of the SWS. Supporting this primary function are a variety of SWS-resident supplemental capabilities that include meteorological data acquisition, manipulation of release-specific databases, computer-based communications, and the use of a simpler Gaussian trajectory puff model that is based on Environmental Protection Agency's INPUFF code

Self-Anchored Catalyst Interface Enables Ordered Via Array Formation from Submicrometer to Millimeter Scale for Polycrystalline and Single-Crystalline Silicon.

Science.gov (United States)

Kim, Jeong Dong; Kim, Munho; Kong, Lingyu; Mohseni, Parsian K; Ranganathan, Srikanth; Pachamuthu, Jayavel; Chim, Wai Kin; Chiam, Sing Yang; Coleman, James J; Li, Xiuling

2018-03-14

Defying text definitions of wet etching, metal-assisted chemical etching (MacEtch), a solution-based, damage-free semiconductor etching method, is directional, where the metal catalyst film sinks with the semiconductor etching front, producing 3D semiconductor structures that are complementary to the metal catalyst film pattern. The same recipe that works perfectly to produce ordered array of nanostructures for single-crystalline Si (c-Si) fails completely when applied to polycrystalline Si (poly-Si) with the same doping type and level. Another long-standing challenge for MacEtch is the difficulty of uniformly etching across feature sizes larger than a few micrometers because of the nature of lateral etching. The issue of interface control between the catalyst and the semiconductor in both lateral and vertical directions over time and over distance needs to be systematically addressed. Here, we present a self-anchored catalyst (SAC) MacEtch method, where a nanoporous catalyst film is used to produce nanowires through the pinholes, which in turn physically anchor the catalyst film from detouring as it descends. The systematic vertical etch rate study as a function of porous catalyst diameter from 200 to 900 nm shows that the SAC-MacEtch not only confines the etching direction but also enhances the etch rate due to the increased liquid access path, significantly delaying the onset of the mass-transport-limited critical diameter compared to nonporous catalyst c-Si counterpart. With this enhanced mass transport approach, vias on multistacks of poly-Si/SiO 2 are also formed with excellent vertical registry through the polystack, even though they are separated by SiO 2 which is readily removed by HF alone with no anisotropy. In addition, 320 μm square through-Si-via (TSV) arrays in 550 μm thick c-Si are realized. The ability of SAC-MacEtch to etch through poly/oxide/poly stack as well as more than half millimeter thick silicon with excellent site specificity for a wide

Laser-Induced Fluorescence Detection in High-Throughput Screening of Heterogeneous Catalysts and Single Cells Analysis

Energy Technology Data Exchange (ETDEWEB)

Su, Hui [Iowa State Univ., Ames, IA (United States)

2001-01-01

Laser-induced fluorescence detection is one of the most sensitive detection techniques and it has found enormous applications in various areas. The purpose of this research was to develop detection approaches based on laser-induced fluorescence detection in two different areas, heterogeneous catalysts screening and single cell study. First, we introduced laser-induced imaging (LIFI) as a high-throughput screening technique for heterogeneous catalysts to explore the use of this high-throughput screening technique in discovery and study of various heterogeneous catalyst systems. This scheme is based on the fact that the creation or the destruction of chemical bonds alters the fluorescence properties of suitably designed molecules. By irradiating the region immediately above the catalytic surface with a laser, the fluorescence intensity of a selected product or reactant can be imaged by a charge-coupled device (CCD) camera to follow the catalytic activity as a function of time and space. By screening the catalytic activity of vanadium pentoxide catalysts in oxidation of naphthalene, we demonstrated LIFI has good detection performance and the spatial and temporal resolution needed for high-throughput screening of heterogeneous catalysts. The sample packing density can reach up to 250 x 250 subunits/cm₂ for 40-μm wells. This experimental set-up also can screen solid catalysts via near infrared thermography detection.

Laser-Induced Fluorescence Detection in High-Throughput Screening of Heterogeneous Catalysts and Single Cells Analysis

International Nuclear Information System (INIS)

Hui Su

2001-01-01

Laser-induced fluorescence detection is one of the most sensitive detection techniques and it has found enormous applications in various areas. The purpose of this research was to develop detection approaches based on laser-induced fluorescence detection in two different areas, heterogeneous catalysts screening and single cell study. First, we introduced laser-induced imaging (LIFI) as a high-throughput screening technique for heterogeneous catalysts to explore the use of this high-throughput screening technique in discovery and study of various heterogeneous catalyst systems. This scheme is based on the fact that the creation or the destruction of chemical bonds alters the fluorescence properties of suitably designed molecules. By irradiating the region immediately above the catalytic surface with a laser, the fluorescence intensity of a selected product or reactant can be imaged by a charge-coupled device (CCD) camera to follow the catalytic activity as a function of time and space. By screening the catalytic activity of vanadium pentoxide catalysts in oxidation of naphthalene, we demonstrated LIFI has good detection performance and the spatial and temporal resolution needed for high-throughput screening of heterogeneous catalysts. The sample packing density can reach up to 250 x 250 subunits/cm(sub 2) for 40-(micro)m wells. This experimental set-up also can screen solid catalysts via near infrared thermography detection

Hydroprocessing catalysts utilization and regeneration schemes

Energy Technology Data Exchange (ETDEWEB)

Furimsky, E.

The catalyst reactor inventory represents an important part of the cost of hydroprocessing operation. The selection of a suitable catalyst and reactor is influenced by feedstock properties. Processes ensuring an uninterrupted operation during catalyst addition and withdrawal are preferred for processing high asphaltene and metal content feedstocks. The spent catalyst can be regenerated and returned to the operation if the extent of its deactivation is not high. The regeneration may be performed either in-situ or off-site. The former is suitable for fixed bed reactors whereas the catalyst from ebullated bed reactors must be regenerated off-site. The regeneration of spent catalysts heavily loaded with metals such as V, Ni and Fe may not be economic. Such catalysts may be suitable for metal reclamation. An environmentally safe method for catalyst disposal must be found if neither regeneration nor metal reclamation from spent catalysts can be performed.

Single-site SBA-15 supported zirconium catalysts. Synthesis, characterization and toward cyanosilylation reaction

Science.gov (United States)

Xu, Wei; Yu, Bo; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

2015-01-01

A successive anchoring of Zr(NMe2)4, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1‧-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on dehydroxylated SBA-15 pretreated at 500 °C for 16 h (SBA-15-500) was conducted by SOMC strategy in moderate conditions. The dehydoxylation of SBA-15 was monitored by in situ Fourier transform infrared spectroscopy (in situ FT-IR). The ligand-modified SBA-15-500 supported zirconium complexes were characterized by in situ FT-IR, 13C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MAS) and elemental analysis in detail, verifying that the surface zirconium species are single-sited. The catalytic activity of these complexes was evaluated by cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the structure of surface species and the configuration of the ligands.

Redox-active on-surface polymerization of single-site divalent cations from pure metals by a ketone-functionalized phenanthroline

Energy Technology Data Exchange (ETDEWEB)

Skomski, Daniel; Tempas, Christopher D.; Bukowski, Gregory S.; Smith, Kevin A.; Tait, Steven L., E-mail: tait@indiana.edu [Department of Chemistry, Indiana University, 800 E. Kirkwood Ave., Bloomington, Indiana 47405 (United States)

2015-03-14

Metallic iron, chromium, or platinum mixing with a ketone-functionalized phenanthroline ligand on a single crystal gold surface demonstrates redox activity to a well-defined oxidation state and assembly into thermally stable, one dimensional, polymeric chains. The diverging ligand geometry incorporates redox-active sub-units and bi-dentate binding sites. The gold surface provides a stable adsorption environment and directs growth of the polymeric chains, but is inert with regard to the redox chemistry. These systems are characterized by scanning tunnelling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy under ultra-high vacuum conditions. The relative propensity of the metals to interact with the ketone group is examined, and it is found that Fe and Cr more readily complex the ligand than Pt. The formation and stabilization of well-defined transition metal single-sites at surfaces may open new routes to achieve higher selectivity in heterogeneous catalysts.

Productions of palm oil bio diesel whit heterogeneous basic catalysts compared to conventional homogeneous catalysts

International Nuclear Information System (INIS)

Rios, Luis A; Franco C, Alexander; Zuleta S, Ernesto

2009-01-01

The conventional process to produce biodiesel involves the presence of homogeneous basic catalysts. However, these catalysts have disadvantages associated to the need of purification steps, which increase the cost of the final product and generate pollution problems caused by the effluents. This paper compares different homogeneous and heterogeneous catalysts for the biodiesel production from palm oil. For this, heterogeneous catalysts supported on alumina were prepared and characterized by nitrogen adsorption, scanning electron microscopy, energy dispersive X ray spectroscopy and X ray diffraction. Transesterification of palm oil with methanol was accomplished at 60 celsius degrade and one hour, varying methanol/oil ratio, the type of catalyst and its concentration. Yields of the reaction and purity of the so obtained biodiesel were evaluated. Comparing the catalysts performance, based on the amount, was found that sodium methoxide (CH 3 ONa) and potassium carbonate supported on alumina (K 2 CO 3 /Al 2 O 3 ) were the catalysts that give the higher purity of biodiesel (96.8 and 95.85% respectively). When was determined the active site quality, by dividing the performance by each mole of active sites, it was found that calcined Na 2 SO 4 /Al 2 O 3 has the most active sites.

Support effects in single atom iron catalysts on adsorption characteristics of toxic gases (NO2, NH3, SO3 and H2S)

Science.gov (United States)

Gao, Zhengyang; Yang, Weijie; Ding, Xunlei; Lv, Gang; Yan, Weiping

2018-04-01

The effects of support on gas adsorption is crucial for single atom catalysts design and optimization. To gain insight into support effects on gas adsorption characteristics, a comprehensive theoretical study was performed to investigate the adsorption characteristics of toxic gases (NO2, NH3, SO3 and H2S) by utilizing single atom iron catalysts with three graphene-based supports. The adsorption geometry, adsorption energy, electronic and magnetic properties of the adsorption system have been explored. Additionally, the support effects have been analyzed through d-band center and Fermi softness, and thermodynamic analysis has been performed to consider the effect of temperature on gas adsorption. The support effects have a remarkable influence on the adsorption characteristics of four types of toxic gases which is determined by the electronic structure of graphene-based support, and the electronic structure can be characterized by Fermi softness of catalysts. Fermi softness and uplift height of Fe atom could be good descriptors for the adsorption activity of single atom iron catalysts with graphene-based supports. The findings can lay a foundation for the further study of graphene-based support effects in single atom catalysts and provide a guideline for development and design of new graphene-based support materials utilizing the idea of Fermi softness.

Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst

Science.gov (United States)

Chung, Hoon T.; Cullen, David A.; Higgins, Drew; Sneed, Brian T.; Holby, Edward F.; More, Karren L.; Zelenay, Piotr

2017-08-01

Platinum group metal-free (PGM-free) metal-nitrogen-carbon catalysts have emerged as a promising alternative to their costly platinum (Pt)-based counterparts in polymer electrolyte fuel cells (PEFCs) but still face some major challenges, including (i) the identification of the most relevant catalytic site for the oxygen reduction reaction (ORR) and (ii) demonstration of competitive PEFC performance under automotive-application conditions in the hydrogen (H2)-air fuel cell. Herein, we demonstrate H2-air performance gains achieved with an iron-nitrogen-carbon catalyst synthesized with two nitrogen precursors that developed hierarchical porosity. Current densities recorded in the kinetic region of cathode operation, at fuel cell voltages greater than ~0.75 V, were the same as those obtained with a Pt cathode at a loading of 0.1 milligram of Pt per centimeter squared. The proposed catalytic active site, carbon-embedded nitrogen-coordinated iron (FeN4), was directly visualized with aberration-corrected scanning transmission electron microscopy, and the contributions of these active sites associated with specific lattice-level carbon structures were explored computationally.

Structure, Mobility, and Composition of Transition Metal Catalyst Surfaces. High-Pressure Scanning Tunneling Microscopy and Ambient-Pressure X-ray Photoelectron Spectroscopy Studies

Energy Technology Data Exchange (ETDEWEB)

Zhu, Zhongwei [Univ. of California, Berkeley, CA (United States)

2013-12-06

Surface structure, mobility, and composition of transition metal catalysts were studied by high-pressure scanning tunneling microscopy (HP-STM) and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) at high gas pressures. HP-STM makes it possible to determine the atomic or molecular rearrangement at catalyst surfaces, particularly at the low-coordinated active surface sites. AP-XPS monitors changes in elemental composition and chemical states of catalysts in response to variations in gas environments. Stepped Pt and Cu single crystals, the hexagonally reconstructed Pt(100) single crystal, and Pt-based bimetallic nanoparticles with controlled size, shape and composition, were employed as the model catalysts for experiments in this thesis.

Extended Catalyst Longevity Via Supercritical Isobutane Regeneration of a Partially Deactivated USY Alkylation Catalyst

Energy Technology Data Exchange (ETDEWEB)

Daniel M. Ginosar; David N. Thompson; Kyle C. Burch; David J. Zalewski

2005-05-01

Off-line, in situ activity recovery of a partially deactivated USY zeolite catalyst used for isobutane/butene alkylation was examined in a continuous-flow reaction system employing supercritical isobutane. Catalyst samples were deactivated in a controlled manner by running them to either to a fixed butene conversion level of 95% or a fixed time on stream of three hours, and then exposing the catalyst to supercritical isobutane to restore activity. Activity recovery was determined by comparing alkylation activity before and after the regeneration step. Both single and multiple regenerations were performed. Use of a 95% butene conversion level criterion to terminate the reaction step afforded 86% activity recovery for a single regeneration and provided nine sequential reaction steps for the multiple regeneration studies. Employing a fixed 3 h time on stream criterion resulted in nearly complete activity recovery for a single regeneration, and 24 reaction steps were demonstrated in sequence for the multiple regeneration process, producing only minor product yield declines per step. This resulted in a 12-fold increase in catalyst longevity versus unregenerated catalyst.

The amyloid architecture provides a scaffold for enzyme-like catalysts.

Science.gov (United States)

Al-Garawi, Z S; McIntosh, B A; Neill-Hall, D; Hatimy, A A; Sweet, S M; Bagley, M C; Serpell, L C

2017-08-03

Natural biological enzymes possess catalytic sites that are generally surrounded by a large three-dimensional scaffold. However, the proportion of the protein molecule that participates in the catalytic reaction is relatively small. The generation of artificial or miniature enzymes has long been a focus of research because enzyme mimetics can be produced with high activity at low cost. These enzymes aim to mimic the active sites without the additional architecture contributed by the protein chain. Previous work has shown that amyloidogenic peptides are able to self-assemble to create an active site that is capable of binding zinc and catalysing an esterase reaction. Here, we describe the structural characterisation of a set of designed peptides that form an amyloid-like architecture and reveal that their capability to mimic carbonic anhydrase and serve as enzyme-like catalysts is related to their ability to self-assemble. These amyloid fibril structures can bind the metal ion Zn 2+ via a three-dimensional arrangement of His residues created by the amyloid architecture. Our results suggest that the catalytic efficiency of amyloid-like assembly is not only zinc-dependent but also depends on an active centre created by the peptides which is, in turn, dependent on the ordered architecture. These fibrils have good esterase activity, and they may serve as good models for the evolution of modern-day enzymes. Furthermore, they may be useful in designing self-assembling fibrils for applications as metal ion catalysts. This study also demonstrates that the ligands surrounding the catalytic site affect the affinity of the zinc-binding site to bind the substrate contributing to the enzymatic activity of the assembled peptides.

On multi-site damage identification using single-site training data

Science.gov (United States)

Barthorpe, R. J.; Manson, G.; Worden, K.

2017-11-01

This paper proposes a methodology for developing multi-site damage location systems for engineering structures that can be trained using single-site damaged state data only. The methodology involves training a sequence of binary classifiers based upon single-site damage data and combining the developed classifiers into a robust multi-class damage locator. In this way, the multi-site damage identification problem may be decomposed into a sequence of binary decisions. In this paper Support Vector Classifiers are adopted as the means of making these binary decisions. The proposed methodology represents an advancement on the state of the art in the field of multi-site damage identification which require either: (1) full damaged state data from single- and multi-site damage cases or (2) the development of a physics-based model to make multi-site model predictions. The potential benefit of the proposed methodology is that a significantly reduced number of recorded damage states may be required in order to train a multi-site damage locator without recourse to physics-based model predictions. In this paper it is first demonstrated that Support Vector Classification represents an appropriate approach to the multi-site damage location problem, with methods for combining binary classifiers discussed. Next, the proposed methodology is demonstrated and evaluated through application to a real engineering structure - a Piper Tomahawk trainer aircraft wing - with its performance compared to classifiers trained using the full damaged-state dataset.

Effect of the solvent in the catalyst ink preparation on the properties and performance of unsupported PtRu catalyst layers in direct methanol fuel cells

International Nuclear Information System (INIS)

Alcaide, Francisco; Álvarez, Garbiñe; Cabot, Pere L.; Genova-Koleva, Radostina; Grande, Hans-Jürgen; Miguel, Oscar

2017-01-01

The effect of the organic solvent polarity on the properties of unsupported PtRu catalyst inks and on the performance of the catalyst layers prepared with them for the methanol electrooxidation, has been studied. The light scattering results indicate that the PtRu-Nafion ® aggregates in the inks prepared with n-butyl acetate (NBA) are larger than those prepared with 2-propanol (IPA). The lower polarity of the former favours the aggregation of Nafion ® and nanoparticles. The electron microscopy images and porosimetry measurements of the catalyst layers show that the secondary pore volume between the agglomerates is larger for NBA. The linear sweep voltammetry and eis results for the methanol electrooxidation in the three-electrode cell denote the higher active surface area for NBA and comparable specific oxidation rates of the intermediates in both catalysts layers. The current densities for PtRu anode catalyst layers in single DMFC are higher when the solvent is NBA, the mass transport limitations being much more apparent with IPA. The adapted transmission line equivalent circuit to interpret the impedance results in single DMFC indicates that the proton resistance for NBA is significantly lower than for IPA, thus suggesting that the greater number of accessible active sites for methanol oxidation in the former are well connected to the Nafion ® ionomers and easier transported to the membrane.

Hierarchical zeolites: progress on synthesis and characterization of mesoporous zeolite single crystal catalysts

DEFF Research Database (Denmark)

Kustova, Marina; Egeblad, Kresten; Christensen, Claus H.

2007-01-01

Recently, a new family of crystalline zeolitic materials was reported, the so-called mesoporous zeolite single crystals featuring individual zeolite single crystals with an additional noncrystalline mesopore system interconnected with the usual micropore system of the zeolite, resulting...... measurements. Additionally, the results of diffusion of n-hexadecane in conventional and mesoporous zeolites are presented. Isomerization and cracking of n-hexadecane was chosen as model test reaction for these materials. All results support that mesoporous zeolites are superior catalysts due to improved mass...... transport. Importantly, the mesoporous zeolites show significant improved resistance to poisoning by carbon formation....

Pt based anode catalysts for direct ethanol fuel cells

Energy Technology Data Exchange (ETDEWEB)

Zhou, Weijiang; Zhou, Zhenhua; Song, Shuqin; Li, Wenzhen; Sun, Gongquan; Xin, Qin [Direct Alcohol Fuel Cell Laboratory, Dalian Institute of Chemical Physics, CAS, P.O. Box 110, Dalian 116023 (China); Tsiakaras, Panagiotis [Department of Mechanical and Industrial Engineering, University of Thessalia, Pedion Areos, GR 38334 Volos (Greece) 7

2003-11-10

In the present work several Pt-based anode catalysts supported on carbon XC-72R were prepared with a novel method and characterized by means of XRD, TEM and XPS analysis. It was found that all these catalysts are consisted of uniform nanosized particles with sharp distribution and Pt lattice parameter decreases with the addition of Ru or Pd and increases with the addition of Sn or W. Cyclic voltammetry (CV) measurements and single direct ethanol fuel cell (DEFC) tests jointly showed that the presence of Sn, Ru and W enhances the activity of Pt towards ethanol electro-oxidation in the following order: Pt{sub 1}Sn{sub 1}/C>Pt{sub 1}Ru{sub 1}/C>Pt{sub 1}W{sub 1}/C>Pt{sub 1}Pd{sub 1}/C>Pt/C. Moreover, Pt{sub 1}Ru{sub 1}/C further modified by W and Mo showed improved ethanol electro-oxidation activity, but its DEFC performance was found to be inferior to that measured for Pt{sub 1}Sn{sub 1}/C. Under this respect, several PtSn/C catalysts with different Pt/Sn atomic ratio were also identically prepared and characterized and their direct ethanol fuel cell performances were evaluated. It was found that the single direct ethanol fuel cell having Pt{sub 1}Sn{sub 1}/C or Pt{sub 3}Sn{sub 2}/C or Pt{sub 2}Sn{sub 1}/C as anode catalyst showed better performances than those with Pt{sub 3}Sn{sub 1}/C or Pt{sub 4}Sn{sub 1}/C. It was also found that the latter two cells exhibited higher performances than the single cell using Pt{sub 1}Ru{sub 1}/C, which is exclusively used in PEMFC as anode catalyst for both methanol electro-oxidation and CO-tolerance. This distinct difference in DEFC performance between the catalysts examined here would be attributed to the so-called bifunctional mechanism and to the electronic interaction between Pt and additives. It is thought that an amount of -OH{sub ads}, an amount of surface Pt active sites and the conductivity effect of PtSn/C catalysts would determine the activity of PtSn/C with different Pt/Sn ratios. At lower temperature values or at low

Potential of Transition Metal Atoms Embedded in Buckled Monolayer g-C3N4 as Single-Atom Catalysts

KAUST Repository

Li, Shu-Long; Kan, Xiang; Yin, Hui; Gan, Li-Yong; Schwingenschlö gl, Udo; Zhao, Yong

2017-01-01

We use first-principles calculations to systematically explore the potential of transition metal atoms (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) embedded in buckled monolayer g-C3N4 as single-atom catalysts. We show that clustering of Sc and Ti on g-C3N4 is thermodynamically impeded and that V, Cr, Mn, and Cu are much less susceptible to clustering than the other TM atoms under investigation. Strong bonding of the transition metal atoms in the cavities of g-C3N4 and high diffusion barriers together are responsible for single-atom fixation. Analysis of the CO oxidation process indicates that embedding of Cr and Mn in g-C3N4 gives rise to promising single-atom catalysts at low temperature.

Potential of Transition Metal Atoms Embedded in Buckled Monolayer g-C3N4 as Single-Atom Catalysts

KAUST Repository

Li, Shu-Long

2017-10-27

We use first-principles calculations to systematically explore the potential of transition metal atoms (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) embedded in buckled monolayer g-C3N4 as single-atom catalysts. We show that clustering of Sc and Ti on g-C3N4 is thermodynamically impeded and that V, Cr, Mn, and Cu are much less susceptible to clustering than the other TM atoms under investigation. Strong bonding of the transition metal atoms in the cavities of g-C3N4 and high diffusion barriers together are responsible for single-atom fixation. Analysis of the CO oxidation process indicates that embedding of Cr and Mn in g-C3N4 gives rise to promising single-atom catalysts at low temperature.

An efficient hybrid, nanostructured, epoxidation catalyst: titanium silsesquioxane-polystyrene copolymer supported on SBA-15.

Science.gov (United States)

Zhang, Lei; Abbenhuis, Hendrikus C L; Gerritsen, Gijsbert; Bhriain, Nollaig Ní; Magusin, Pieter C M M; Mezari, Brahim; Han, Wei; van Santen, Rutger A; Yang, Qihua; Li, Can

2007-01-01

A novel interfacial hybrid epoxidation catalyst was designed with a new immobilization method for homogeneous catalysts by coating an inorganic support with an organic polymer film containing active sites. The titanium silsesquioxane (TiPOSS) complex, which contains a single-site titanium active center, was immobilized successfully by in-situ copolymerization on a mesoporous SBA-15-supported polystyrene polymer. The resulting hybrid materials exhibit attractive textural properties (highly ordered mesostructure, large specific surface area (>380 m2 g-1) and pore volume (>or==0.46 cm3 g-1)), and high activity in the epoxidation of alkenes. In the epoxidation of cyclooctene with tert-butyl hydrogen peroxide (TBHP), the hybrid catalysts have rate constants comparable with that of their homogeneous counterpart, and can be recycled at least seven times. They can also catalyze the epoxidation of cyclooctene with aqueous H2O2 as the oxidant. In two-phase reaction media, the catalysts show much higher activity than their homogeneous counterpart due to the hydrophobic environment around the active centers. They behave as interfacial catalysts due to their multifunctionality, that is, the hydrophobicity of polystyrene and the polyhedral oligomeric silsesquioxanes (POSS), and the hydrophilicity of the silica and the mesoporous structure. Combination of the immobilization of homogeneous catalysts on two conventional supports, inorganic solid and organic polymer, is demonstrated to achieve novel heterogeneous catalytic ensembles with the merits of attractive textural properties, tunable surface properties, and optimized environments around the active sites.

Comparative study of activated carbon, natural zeolite, and green sand supports for CuOX and ZnO sites as ozone decomposition catalyst

Science.gov (United States)

Azhariyah, A. S.; Pradyasti, A.; Dianty, A. G.; Bismo, S.

2018-03-01

This research was based on ozone decomposition in industrial environment. Ozone is harmful to human. Therefore, catalysts were made as a mask filter to decompose ozone. Comparison studies of catalyst supports were done using Granular Activated Carbon (GAC), Natural Zeolite (NZ), and Green Sand (GS). GAC showed the highest catalytic activity compared to other supports with conversion of 98%. Meanwhile, the conversion using NZ was only 77% and GS had been just 27%. GAC had the highest catalytic activity because it had the largest pore volume, which is 0.478 cm3/g. So GAC was used as catalyst supports. To have a higher conversion in ozone decomposition, GAC was impregnated with metal oxide as the active site of the catalyst. Active site comparison was made using CuOX and ZnO as the active site. Morphology, composition, and crystal phase were analyzed using SEM-EDX, XRF, and XRD methods. Mask filter, which contained catalysts for ozone decomposition, was tested using a fixed bed reactor at room temperature and atmospheric pressure. The result of conversion was analyzed using iodometric method. CuOX/GAC and ZnO/GAC 2%-w showed the highest catalytic activity and conversion reached 100%. From the durability test, CuOX/GAC 2%-w was better than ZnO/GAC 2%-w because the conversion of ozone to oxygen reached 100% with the lowest conversion was 70% for over eight hours.

Pt-Fe catalyst nanoparticles supported on single-wall carbon nanotubes: Direct synthesis and electrochemical performance for methanol oxidation

Science.gov (United States)

Ma, Xiaohui; Luo, Liqiang; Zhu, Limei; Yu, Liming; Sheng, Leimei; An, Kang; Ando, Yoshinori; Zhao, Xinluo

2013-11-01

Single-wall carbon nanotubes (SWCNTs) supported Pt-Fe nanoparticles have been prepared by one-step hydrogen arc discharge evaporation of carbon electrode containing both Pt and Fe metal elements. The formation of SWCNTs and Pt-Fe nanoparticles occur simultaneously during the evaporation process. High-temperature hydrogen treatment and hydrochloric acid soaking have been carried out to purify and activate those materials in order to obtain a new type of Pt-Fe/SWCNTs catalyst for methanol oxidation. The Pt-Fe/SWCNTs catalyst performs much higher electrocatalytic activity for methanol oxidation, better stability and better durability than a commercial Pt/C catalyst according to the electrochemical measurements, indicating that it has a great potential for applications in direct methanol fuel cells.

Studies on recycling and utilization of spent catalysts. Preparation of active hydrodemetallization catalyst compositions from spent residue hydroprocessing catalysts

Energy Technology Data Exchange (ETDEWEB)

Marafi, Meena; Stanislaus, Antony [Petroleum Refining Department, Petroleum Research and Studies Center, Kuwait Institute for Scientific Research, P.O. Box 24885, Safat (Kuwait)

2007-02-15

Spent catalysts form a major source of solid wastes in the petroleum refining industries. Due to environmental concerns, increasing emphasis has been placed on the development of recycling processes for the waste catalyst materials as much as possible. In the present study the potential reuse of spent catalysts in the preparation of active new catalysts for residual oil hydrotreating was examined. A series of catalysts were prepared by mixing and extruding spent residue hydroprocessing catalysts that contained C, V, Mo, Ni and Al{sub 2}O{sub 3} with boehmite in different proportions. All prepared catalysts were characterized by chemical analysis and by surface area, pore volume, pore size and crushing strength measurements. The hydrodesulfurization (HDS) and hydrodemetallization (HDM) activities of the catalysts were evaluated by testing in a high pressure fixed-bed microreactor unit using Kuwait atmospheric residue as feed. A commercial HDM catalyst was also tested under similar operating conditions and their HDS and HDM activities were compared with that of the prepared catalysts. The results revealed that catalyst prepared with addition of up to 40 wt% spent catalyst to boehmite had fairly high surface area and pore volume together with large pores. The catalyst prepared by mixing and extruding about 40 wt% spent catalyst with boehmite was relatively more active for promoting HDM and HDS reactions than a reference commercial HDM catalyst. The formation of some kind of new active sites from the metals (V, Mo and Ni) present in the spent catalyst is suggested to be responsible for the high HDM activity of the prepared catalyst. (author)

From fundamental studies of reactivity on single crystals to the design of catalysts

Science.gov (United States)

H. Larsen, Jane; Chorkendorff, Ib

One of the prominent arguments for performing surface science studies have for many years been to improve and design new and better catalysts. Although surface science has provided the fundamental framework and tools for understanding heterogeneous catalysis until now there have been extremely few examples of actually designing new catalysts based solely on surface science studies. In this review, we shall demonstrate how a close collaboration between different fundamental disciplines like structural-, theoretical-and reactivity-studies of surfaces as well as a strong interaction with industry can have strong synergetic effects and how this was used to develop a new catalyst. As so often before the studies reviewed here were not initiated with the objective to solve a specific problem, but realizing that a new class of very stable two-dimensional alloys could be synthesized from otherwise immiscible metals made it possible to present a new solution to a specific problem in the industrial catalysis relating to methane activation in the steam reforming process. Methane is the main constituent of natural gas and it is an extremely important raw material for many large scale chemical processes such as production of hydrogen, ammonia, and methanol. In the steam reforming process methane and water are converted into a mixture of mainly hydrogen and carbon monoxide, the so-called synthesis gas. Industrially the steam reforming process usually takes place over a catalyst containing small nickel crystallites highly dispersed on a porous support material like aluminum/magnesium oxides in order to achieve a high active metal area. There is a general consensus that the rate limiting step of this process is the dissociative sticking of methane on the nickel surface. Driven by the desire to understand this step and hopefully be able to manipulate the reactivity, a large number of investigations of the methane/nickel interaction have been performed using nickel single crystals as

Dual-band infrared capabilities for imaging buried object sites

Energy Technology Data Exchange (ETDEWEB)

Del Grande, N.K.; Durbin, P.F.; Gorvad, M.R.; Perkins, D.E.; Clark, G.A.; Hernandez, J.E.; Sherwood, R.J.

1993-04-02

We discuss dual-band infrared (DBIR) capabilities for imaging buried object sizes. We identify physical features affecting thermal contrast needed to distinguish buried object sites from undisturbed sites or surface clutter. Apart from atmospheric transmission and system performance, these features include: object size, shape, and burial depth; ambient soil, disturbed soil and object site thermal diffusivity differences; surface temperature, emissivity, plant-cover, slope, albedo and roughness variations; weather conditions and measurement times. We use good instrumentation to measure the time-varying temperature differences between buried object sites and undisturbed soil sites. We compare near surface soil temperature differences with radiometric infrared (IR) surface temperature differences recorded at 4.7 {plus_minus} 0.4 {mu}m and at 10.6 {plus_minus} 1.0 {mu}m. By producing selective DBIR image ratio maps, we distinguish temperature-difference patterns from surface emissivity effects. We discuss temperature differences between buried object sites, filled hole site (without buried objects), cleared (undisturbed) soil sites, and grass-covered sites (with and without different types of surface clutter). We compare temperature, emissivity-ratio, visible and near-IR reflectance signatures of surface objects, leafy plants and sod. We discuss the physical aspects of environmental, surface and buried target features affecting interpretation of buried targets, surface objects and natural backgrounds.

Thermally oxidized aluminum as catalyst-support layer for vertically aligned single-walled carbon nanotube growth using ethanol

Energy Technology Data Exchange (ETDEWEB)

Azam, Mohd Asyadi, E-mail: asyadi@jaist.ac.jp [School of Materials Science, Japan Advanced Institute of Science and Technology (JAIST), 1-1 Asahidai, Nomi, Ishikawa 923-1292 (Japan); Fujiwara, Akihiko [Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI), 1-1-1, Kouto, Sayo-cho, Sayo, Hyogo 679-5198 (Japan); Shimoda, Tatsuya [School of Materials Science, Japan Advanced Institute of Science and Technology (JAIST), 1-1 Asahidai, Nomi, Ishikawa 923-1292 (Japan)

2011-11-01

Characteristics and role of Al oxide (Al-O) films used as catalyst-support layer for vertical growth of single-walled carbon nanotubes (SWCNTs) were studied. EB-deposited Al films (20 nm) were thermally oxidized at 400 deg. C (10 min, static air) to produce the most appropriate surface structure of Al-O. Al-O catalyst-support layers were characterized using various analytical measurements, i.e., atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and spectroscopy ellipsometry (SE). The thermally oxidized Al-O has a highly roughened surface, and also has the most suitable surface chemical states compared to other type of Al-O support layers. We suggest that the surface of thermally oxidized Al-O characterized in this work enhanced Co catalyst activity to promote the vertically aligned SWCNT growth.

Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network

Science.gov (United States)

Shui, Jianglan; Chen, Chen; Grabstanowicz, Lauren; Zhao, Dan; Liu, Di-Jia

2015-01-01

Fuel cell vehicles, the only all-electric technology with a demonstrated >300 miles per fill travel range, use Pt as the electrode catalyst. The high price of Pt creates a major cost barrier for large-scale implementation of polymer electrolyte membrane fuel cells. Nonprecious metal catalysts (NPMCs) represent attractive low-cost alternatives. However, a significantly lower turnover frequency at the individual catalytic site renders the traditional carbon-supported NPMCs inadequate in reaching the desired performance afforded by Pt. Unconventional catalyst design aiming at maximizing the active site density at much improved mass and charge transports is essential for the next-generation NPMC. We report here a method of preparing highly efficient, nanofibrous NPMC for cathodic oxygen reduction reaction by electrospinning a polymer solution containing ferrous organometallics and zeolitic imidazolate framework followed by thermal activation. The catalyst offers a carbon nanonetwork architecture made of microporous nanofibers decorated by uniformly distributed high-density active sites. In a single-cell test, the membrane electrode containing such a catalyst delivered unprecedented volumetric activities of 3.3 A⋅cm−3 at 0.9 V or 450 A⋅cm−3 extrapolated at 0.8 V, representing the highest reported value in the literature. Improved fuel cell durability was also observed. PMID:26261338

Active sites and mechanisms for H2O2 decomposition over Pd catalysts

Science.gov (United States)

Plauck, Anthony; Stangland, Eric E.; Dumesic, James A.; Mavrikakis, Manos

2016-01-01

A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2. We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O–O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O–O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

Non-PGM cell catalysts

Energy Technology Data Exchange (ETDEWEB)

Colon-Mercado, H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Elvington, M. [Savannah River Consulting, Aiken, SC (United States); Ganesan, P. [Savannah River Consulting, Aiken, SC (United States)

2017-09-27

A unique approach has been developed to probe the non-PGM catalyst active site for the Oxygen Reduction Reaction (ORR) for PEMFCs. Iron based functionalities have been engineered into a variety of catalysts to evaluate their impact on activity for the ORR. A series of high surface area catalysts were synthesized and the impact of the chemical structure on the electrochemical and electrocatalytic properties was investigated. Elemental and surface analyses of the prepared catalysts reveal the incorporation of iron in a targeted and controlled manner. A high surface area framework catalyst was prepared that shows exceptional activity, comparable to state-of-the-art materials. The results of this research project provided critical seed data for the newly awarded ElectroCat project, which focuses on rationally designed framework catalysts for the oxygen reduction reaction.

40 CFR 90.329 - Catalyst thermal stress test.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Catalyst thermal stress test. 90.329... Equipment Provisions § 90.329 Catalyst thermal stress test. (a) Oven characteristics. The oven used for thermally stressing the test catalyst must be capable of maintaining a temperature of 500 ±5 °C and 1000 ±10...

40 CFR 91.329 - Catalyst thermal stress test.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Catalyst thermal stress test. 91.329....329 Catalyst thermal stress test. (a) Oven characteristics. The oven used for termally stressing the test catalyst must be capable of maintaining a temperature of 500 ±5 °C and 1000 ±10 °C. (b) Evaluation...

Robotic-assisted single-port donor nephrectomy using the da Vinci single-site platform.

Science.gov (United States)

LaMattina, John C; Alvarez-Casas, Josue; Lu, Irene; Powell, Jessica M; Sultan, Samuel; Phelan, Michael W; Barth, Rolf N

2018-02-01

Although single-port donor nephrectomy offers improved cosmetic outcomes, technical challenges have limited its application to selected centers. Our center has performed over 400 single-port donor nephrectomies. The da Vinci single-site robotic platform was utilized in an effort to overcome the steric, visualization, ergonomic, and other technical limitations associated with the single-port approach. Food and Drug Administration device exemption was obtained. Selection criteria for kidney donation included body mass index da Vinci single-site platform. Our experience supported the safety of this approach but found that the technology added cost and complexity without tangible benefit. Development of articulating instruments, energy, and stapling devices will be necessary for increased application of robotic single-site surgery for donor nephrectomy. Copyright © 2017 Elsevier Inc. All rights reserved.

Ethylbenzene dehydrogenation over FeOx/(Mg,Zn)(Al)O catalysts derived from hydrotalcites: Role of MgO as basic sites

KAUST Repository

Balasamy, Rabindran J.; Tope, Balkrishna B.; Khurshid, Alam; Al-Ali, Ali A S; Atanda, Luqman A.; Sagata, Kunimasa; Asamoto, Makiko; Yahiro, Hidenori; Nomura, Kiyoshi; Sano, Tsuneji; Takehira, Katsuomi; Al-Khattaf, Sulaiman S.

2011-01-01

A series of Mg3-xZnxFe0.5Al0.5 mixed oxide catalysts derived from hydrotalcites were tested in the ethylbenzene dehydrogenation to styrene in He atmosphere at 550 °C. The catalysts were prepared by coprecipitation from the nitrates of metal components followed by calcination to mixed oxides at 550 °C. A part of Mg2+ in Mg 3Fe0.5Al0.5 mixed oxide was replaced with Zn2+ to test the effect of MgO as the support. The mixed oxides were composed of periclase and spinel-type compounds with a high surface area of 100-180m2gcat-1. Mössbauer and XPS measurements indicated the presence of Fe3+ on the catalysts and H2-TPR measurement suggested that the dehydrogenation reaction is catalyzed by the reduction-oxidation between Fe3+/Fe2+. The activity of Mg3-xZnxFe0.5Al0.5 mixed oxide decreased with increasing x, indicating an important role of MgO on the activity. Both CO2-TPD measurements as well as IR measurements of adsorbed CO2 clearly indicated the presence of basic sites of Mg 2+O2- on the catalysts. It seems that the combination of Mg2+O2- and Fe3+ was essential for the catalytic activity. It is concluded that the surface base sites generated on O2- bound Mg2+ near Fe3+ sites are responsible for H+-abstraction; the dehydrogenation of ethylbenzene was initiated by the H+ abstraction on Mg2+O2- basic sites, and accelerated by the reduction-oxidation of Fe3+/Fe2+ active species. © 2011 Elsevier B.V.

Ethylbenzene dehydrogenation over FeOx/(Mg,Zn)(Al)O catalysts derived from hydrotalcites: Role of MgO as basic sites

KAUST Repository

Balasamy, Rabindran J.

2011-05-01

A series of Mg3-xZnxFe0.5Al0.5 mixed oxide catalysts derived from hydrotalcites were tested in the ethylbenzene dehydrogenation to styrene in He atmosphere at 550 °C. The catalysts were prepared by coprecipitation from the nitrates of metal components followed by calcination to mixed oxides at 550 °C. A part of Mg2+ in Mg 3Fe0.5Al0.5 mixed oxide was replaced with Zn2+ to test the effect of MgO as the support. The mixed oxides were composed of periclase and spinel-type compounds with a high surface area of 100-180m2gcat-1. Mössbauer and XPS measurements indicated the presence of Fe3+ on the catalysts and H2-TPR measurement suggested that the dehydrogenation reaction is catalyzed by the reduction-oxidation between Fe3+/Fe2+. The activity of Mg3-xZnxFe0.5Al0.5 mixed oxide decreased with increasing x, indicating an important role of MgO on the activity. Both CO2-TPD measurements as well as IR measurements of adsorbed CO2 clearly indicated the presence of basic sites of Mg 2+O2- on the catalysts. It seems that the combination of Mg2+O2- and Fe3+ was essential for the catalytic activity. It is concluded that the surface base sites generated on O2- bound Mg2+ near Fe3+ sites are responsible for H+-abstraction; the dehydrogenation of ethylbenzene was initiated by the H+ abstraction on Mg2+O2- basic sites, and accelerated by the reduction-oxidation of Fe3+/Fe2+ active species. © 2011 Elsevier B.V.

Tunable, Chemo- and Site-Selective Nitrene Transfer Reactions through the Rational Design of Silver(I) Catalysts.

Science.gov (United States)

Alderson, Juliet M; Corbin, Joshua R; Schomaker, Jennifer M

2017-09-19

Carbon-nitrogen (C-N) bonds are ubiquitous in pharmaceuticals, agrochemicals, diverse bioactive natural products, and ligands for transition metal catalysts. An effective strategy for introducing a new C-N bond into a molecule is through transition metal-catalyzed nitrene transfer chemistry. In these reactions, a metal-supported nitrene can either add across a C═C bond to form an aziridine or insert into a C-H bond to furnish the corresponding amine. Typical catalysts for nitrene transfer include Rh 2 L n and Ru 2 L n complexes supported by bridging carboxylate and related ligands, as well as complexes based on Cu, Co, Ir, Fe, and Mn supported by porphyrins and related ligands. A limitation of metal-catalyzed nitrene transfer is the ability to predictably select which specific site will undergo amination in the presence of multiple reactive groups; thus, many reactions rely primarily on substrate control. Achieving true catalyst-control over nitrene transfer would open up exciting possibilities for flexible installation of new C-N bonds into hydrocarbons, natural product-inspired scaffolds, existing pharmaceuticals or biorenewable building blocks. Silver-catalyzed nitrene transfer enables flexible control over the position at which a new C-N bond is introduced. Ag(I) supported by simple N-donor ligands accommodates a diverse range of coordination geometries, from linear to tetrahedral to seesaw, enabling the electronic and steric parameters of the catalyst to be tuned independently. In addition, the ligand, Ag salt counteranion, Ag/ligand ratio and the solvent all influence the fluxional and dynamic behavior of Ag(I) complexes in solution. Understanding the interplay of these parameters to manipulate the behavior of Ag-nitrenes in a predictable manner is a key design feature of our work. In this Account, we describe successful applications of a variety of design principles to tunable, Ag-catalyzed aminations, including (1) changing Ag/ligand ratios to influence

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

Science.gov (United States)

Liu, Lichen; Corma, Avelino

2018-05-23

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

Rejuvenation of the SCR catalyst at Mehrum

Energy Technology Data Exchange (ETDEWEB)

Nagai, Y.; Inatsume, Y.; Morita, I.; Kato, Y.; Yokoyama, K.; Ito, K. [Babcock Hitachi K.K., Kure-shi, Hiroshima-ken (Japan)

2004-07-01

Babcock Hitachi K.K. (BHK) received the contract of the rejuvenation of the SCR catalyst at the 750 MW coal-fired Mehrum Power Station (in Hohenhameln, Germany) in March 2003. The contractual coverage was 160 m{sup 3} of the entire catalyst layer. The catalyst, which had been in operation for 16 years since 1987, was originally supplied by BHK. The rejuvenation process developed for the Mehrum project consisted of two major steps: the first is to dust off the catalyst and remove the catalyst poison, and the second step is to add active material to enhance the catalyst activity. The catalyst must be dried after each washing. In order to minimize transportation cost and time, the rejuvenation work was done at the Mehrum station site. The scope of the rejuvenation work was shared between the owner and BHK. It took about one and a half months to complete the (total) on-site rejuvenation worked. The performance of the rejuvenated catalyst was superior to show the same level of activity as the unused catalyst and maintain the same SO{sub 2} conversion rate as the spent catalyst. This paper gives the details of the spent coal-fired SCR catalyst rejuvenation work. 13 figs., 1 tab.

exchanged Mg-Al hydrotalcite catalyst

Indian Academy of Sciences (India)

) catalysts, ... The catalyst can be easily separated by simple filtration ... surface area by the single-point N2 adsorption method ... concentration of carbonate anions (by treating the cat- .... hydrotalcite phase along with copper hydroxide and.

Process of activation of a palladium catalyst system

Science.gov (United States)

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-08-02

Improved processes for activating a catalyst system used for the reduction of nitrogen oxides are provided. In one embodiment, the catalyst system is activated by passing an activation gas stream having an amount of each of oxygen, water vapor, nitrogen oxides, and hydrogen over the catalyst system and increasing a temperature of the catalyst system to a temperature of at least 180.degree. C. at a heating rate of from 1-20.degree./min. Use of activation processes described herein leads to a catalyst system with superior NOx reduction capabilities.

Active catalytic sites in the ammoxidation of propane and propene over V-Sb-O catalysts

Energy Technology Data Exchange (ETDEWEB)

Buchholz, S.A.; Zanthoff, H.W. [Bochum Univ. (Germany). Lehrstuhl fuer Technische Chemie

1998-12-31

The ammoxidation of propane over VSb{sub y}O{sub x} catalysts (y=1, 2, 5) was investigated with respect to the role of different oxygen species in the selective and non selective reaction steps using transient experiments in the Temporal Analysis of Products (TAP) reactor. Only lattice oxygen is involved in the oxidation reactions. Using isotopic labelled oxygen it is shown that two different active sites exist on the surface. On site A, which can be reoxidized faster by gas phase oxygen compared to site B, mainly CO is formed. On site B CO{sub 2} and acrolein as well as NO and N{sub 2}O in the presence of ammonia in the feed gas are formed and reoxidation mainly occurs with bulk lattice oxygen. (orig.)

An overview on the applications of 'Doyle catalysts' in asymmetric ...

Indian Academy of Sciences (India)

Administrator

Johnson Matthey has recently obtained a worldwide exclusive licence to manufacture and sell a unique class of chiral dirhodium(II) carboxamidate catalysts called 'Doyle catalysts'. These homogeneous catalysts are capable of producing chiral cyclopropanes, cyclopropenes and C–H insertion products of very high ...

On factors controlling activity of submonolayer bimetallic catalysts: Nitrogen desorption

Energy Technology Data Exchange (ETDEWEB)

Guo, Wei; Vlachos, Dionisios G., E-mail: vlachos@udel.edu [Center for Catalytic Science and Technology, Catalysis Center for Energy Innovation, Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, Delaware 19716 (United States)

2014-01-07

We model N{sub 2} desorption on submonolayer bimetallic surfaces consisting of Co clusters on Pt(111) via first-principles density functional theory-based kinetic Monte Carlo simulations. We find that submonolayer structures are essential to rationalize the high activity of these bimetallics in ammonia decomposition. We show that the N{sub 2} desorption temperature on Co/Pt(111) is about 100 K higher than that on Ni/Pt(111), despite Co/Pt(111) binding N weaker at low N coverages. Co/Pt(111) has substantially different lateral interactions than single metals and Ni/Pt. The lateral interactions are rationalized with the d-band center theory. The activity of bimetallic catalysts is the result of heterogeneity of binding energies and reaction barriers among sites, and the most active site can differ on various bimetallics. Our results are in excellent agreement with experimental data and demonstrate for the first time that the zero-coverage descriptor, used until now, for catalyst activity is inadequate due not only to lacking lateral interactions but importantly to presence of multiple sites and a complex interplay of thermodynamics (binding energies, occupation) and kinetics (association barriers) on those sites.

Laparoendoscopic single site in pelvic surgery

Science.gov (United States)

Sanchez-Salas, Rafael; Clavijo, Rafael; Barret, Eric; Sotelo, Rene

2012-01-01

Laparoendoscopic single site (LESS) has recently gained momentum as feasible techniques for minimal access surgery. Our aim is to describe the current status of laparoendoscopic single site (LESS) in pelvic surgery. A comprehensive revision of the literature in LESS pelvic surgery was performed. References for this manuscript were obtained by performing a review of the available literature in PubMed from 01-01-01 to 30-11-11. References outside the search period were obtained selected manuscript΄s bibliography. Search terms included: pelvic anatomy, less in gynecology, single port colectomy, urological less, single port, single site, NOTES, LESS and single incision. 314 manuscripts were initially identified. Out of these, 46 manuscripts were selected based in their pelvic anatomy or surgical content; including experimental experience, clinical series and literature reviews. LESS drastically limit the surgeon's ability to perform in the operative field and the latter becomes hardened by the lack of space in anatomical location like the pelvis. Potential advantages of LESS are gained with the understanding that the surgical procedure is more technically challenging. Pelvic surgical procedures related to colorectal surgery, gynecology and urology have been performed with LESS technique and information available is mostly represented by case reports and short case series. Comparative series remain few. LESS pelvic surgery remain in its very beginning and due to the very specific anatomical conditions further development of LESS surgery in the mentioned area can be clearly be facilitated by using robotic technology. Standardization ad reproducibility of techniques are mandatory to further develop LESS in the surgical arena.. PMID:22557719

Laparoendoscopic single site in pelvic surgery

Directory of Open Access Journals (Sweden)

Rafael Sanchez-Salas

2012-01-01

Full Text Available Laparoendoscopic single site (LESS has recently gained momentum as feasible techniques for minimal access surgery. Our aim is to describe the current status of laparoendoscopic single site (LESS in pelvic surgery. A comprehensive revision of the literature in LESS pelvic surgery was performed. References for this manuscript were obtained by performing a review of the available literature in PubMed from 01-01-01 to 30-11-11. References outside the search period were obtained selected manuscript΄s bibliography. Search terms included: pelvic anatomy, less in gynecology, single port colectomy, urological less, single port, single site, NOTES, LESS and single incision. 314 manuscripts were initially identified. Out of these, 46 manuscripts were selected based in their pelvic anatomy or surgical content; including experimental experience, clinical series and literature reviews. LESS drastically limit the surgeon′s ability to perform in the operative field and the latter becomes hardened by the lack of space in anatomical location like the pelvis. Potential advantages of LESS are gained with the understanding that the surgical procedure is more technically challenging. Pelvic surgical procedures related to colorectal surgery, gynecology and urology have been performed with LESS technique and information available is mostly represented by case reports and short case series. Comparative series remain few. LESS pelvic surgery remain in its very beginning and due to the very specific anatomical conditions further development of LESS surgery in the mentioned area can be clearly be facilitated by using robotic technology. Standardization ad reproducibility of techniques are mandatory to further develop LESS in the surgical arena..

Reversible conversion of valence-tautomeric copper metal-organic frameworks dependent single-crystal-to-single-crystal oxidation/reduction: a redox-switchable catalyst for C-H bonds activation reaction.

Science.gov (United States)

Huang, Chao; Wu, Jie; Song, Chuanjun; Ding, Ran; Qiao, Yan; Hou, Hongwei; Chang, Junbiao; Fan, Yaoting

2015-06-28

Upon single-crystal-to-single-crystal (SCSC) oxidation/reduction, reversible structural transformations take place between the anionic porous zeolite-like Cu(I) framework and a topologically equivalent neutral Cu(I)Cu(II) mixed-valent framework. The unique conversion behavior of the Cu(I) framework endowed it as a redox-switchable catalyst for the direct arylation of heterocycle C-H bonds.

Production of propylene from 1-butene on highly active "bi-functional single active site" catalyst: Tungsten carbene-hydride supported on alumina

KAUST Repository

Mazoyer, Etienne; Szeto, Kaï Chung; Norsic, Sé bastien; Garron, Anthony; Basset, Jean-Marie; Nicholas, Christopher P.; Taoufik, Mostafa

2011-01-01

1-Butene is transformed in a continuous flow reactor over tungsten hydrides precursor W-H/Al2O3, 1, giving a promising yield into propylene at 150 °C and different pressures. Tungsten carbene-hydride single active site operates as a "bi

Catalysts for conversion of syngas to liquid motor fuels

Science.gov (United States)

Rabo, Jule A.; Coughlin, Peter K.

1987-01-01

Synthesis gas comprising carbon monoxide and hydrogen is converted to C.sub.5.sup.+ hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst composition capable of ensuring the production of only relatively minor amounts of heavy products boiling beyond the diesel oil range. The catalyst composition, having desirable stability during continuous production operation, employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component. The latter component is a steam-stabilized zeolite Y catalyst of hydrophobic character, desirably in acid-extracted form.

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

Directory of Open Access Journals (Sweden)

Wei-Wen Liu

2013-01-01

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

Electrocatalytic Activity and Stability of M-Fe Catalysts Synthesized by Polymer Complex Method for PEFC Cathode

KAUST Repository

Ou, Yiwei

2011-11-01

The polymerized complex (PC) method was used to synthesize highly dispersed iron-based catalysts for the oxygen reduction reaction (ORR). The catalysts were prepared with an addition of 1,10-phenanthroline (Phen) and transition metals (M), such as Ta, Ti, and W, in an attempt to enhance the ORR activity and durability of the catalysts. The composition and properties of the catalysts were characterized by thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The catalyst components, after extensive dissolution in a strong acid solution, were characterized by inductively coupled plasma mass spectroscopy and ultraviolet-visible spectroscopy. It was found that the Ti-Fe catalyst showed improved ORR performance, and the Ta-Fe catalyst showed enhanced stability towards ORR in acidic solution. The catalytic activity and stability for ORR was observed by adding Ti or Ta into the catalyst formulation, suggesting that the interaction between added hetero-ions (Ti and Ta) and ionic Fe active sites was beneficial for the ORR. A single-cell test with the synthesized catalyst in the cathode initially generated a high power density, but the low stability remains an issue to be solved.

Electrocatalytic Activity and Stability of M-Fe Catalysts Synthesized by Polymer Complex Method for PEFC Cathode

KAUST Repository

Ou, Yiwei; Kumagai, Hiromu; Yin, Fengxiang; Okada, Saori; Hatasawa, Haruna; Morioka, Hiroyuki; Takanabe, Kazuhiro; Kubota, Jun; Domen, Kazunari

2011-01-01

The polymerized complex (PC) method was used to synthesize highly dispersed iron-based catalysts for the oxygen reduction reaction (ORR). The catalysts were prepared with an addition of 1,10-phenanthroline (Phen) and transition metals (M), such as Ta, Ti, and W, in an attempt to enhance the ORR activity and durability of the catalysts. The composition and properties of the catalysts were characterized by thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The catalyst components, after extensive dissolution in a strong acid solution, were characterized by inductively coupled plasma mass spectroscopy and ultraviolet-visible spectroscopy. It was found that the Ti-Fe catalyst showed improved ORR performance, and the Ta-Fe catalyst showed enhanced stability towards ORR in acidic solution. The catalytic activity and stability for ORR was observed by adding Ti or Ta into the catalyst formulation, suggesting that the interaction between added hetero-ions (Ti and Ta) and ionic Fe active sites was beneficial for the ORR. A single-cell test with the synthesized catalyst in the cathode initially generated a high power density, but the low stability remains an issue to be solved.

Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C-H activation

Science.gov (United States)

Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei; Wimble, Joshua M.; Lucci, Felicia R.; Lee, Sungsik; Michaelides, Angelos; Flytzani-Stephanopoulos, Maria; Stamatakis, Michail; Sykes, E. Charles H.

2018-03-01

The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards the synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu-based catalysts are not practical due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Using Pt/Cu single-atom alloys (SAAs), we examine C-H activation in a number of systems including methyl groups, methane and butane using a combination of simulations, surface science and catalysis studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke-resistant C-H activation chemistry, with the added economic benefit that the precious metal is diluted at the atomic limit.

Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation

Energy Technology Data Exchange (ETDEWEB)

Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei; Wimble, Joshua M.; Lucci, Felicia R.; Lee, Sungsik; Michaelides, Angelos; Flytzani-Stephanopoulos, Maria; Stamatakis, Michail; Sykes, E. Charles H.

2018-01-08

The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu- based catalysts are not practical for this chemistry due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Utilizing Pt/Cu single atom alloys (SAAs) we examine C-H activation in a number of systems including methyl groups, methane, and butane using a combination of simulations, surface science, and catalysis studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke resistant C-H activation chemistry with the added economic benefit that the precious metal is diluted at the atomic limit.

Synthesis of Dicyclopentadiene Oligomer Over Nanoporous Al-MCM-41 Catalysts.

Science.gov (United States)

Park, Eunseo; Kim, Jinhan; Yim, Jin-Heong; Han, Jeongsik; Kwon, Tae Soo; Park, Y K; Jeon, Jong-Ki

2016-05-01

One step reaction composed of DCPD oligomerization and DCPD oligomer isomerization was investigated over nanoporous Al-MCM-41 catalysts. The effects of aluminum grafting over MCM-41 on the catalyst characteristics were studied with respect to the synthesis of TCPD isomer. Physical and chemical properties of the catalysts were analyzed by N2 adsorption, temperature-programmed desorption of ammonia, and infrared spectroscopy of adsorbed pyridine. The overall number of acid sites as well as the number of Lewis acid sites increased with increasing of aluminum content over MCM-41. When utilizing MCM-41 and Al-MCM-41 as the catalyst, DCPD oligomerization reaction activity greatly increased compared to the thermal reaction. The highest TCPD isomer selectivity over the Al-MCM-41 catalyst with the highest aluminum content could be ascribed to the largest amount of acid sites. This study showed an increased level of TCPD isomer selectivity by an increasing level of Lewis acid sites through aluminum addition over MCM-41.

Single versus Two-Site Phacoemulsification and Mitomycin-C Trabeculectomy

Directory of Open Access Journals (Sweden)

Alireza Baradaran-Rafiee

2008-11-01

Full Text Available

PURPOSE: To compare the outcomes of single-site versus two-site mitomycin-C (MMC augmented phacotrabeculectomy. METHODS: This matched randomized clinical trial included 34 eyes of 30 patients with visually significant cataracts and poorly controlled glaucoma. Equal numbers of eyes were randomly assigned to the single-site and two-site groups. In the single-site approach, phacoemulsification was performed under a superior scleral tunnel followed by trabeculectomy. The two-site approach included a temporal clear corneal phaco-emulsification combined with a separate superior trabeculectomy. MMC 0.2 mg/ml was similarly applied for one minute in both groups. RESULTS: Patients were followed for a mean period of 13±1.4 (range, 12 to 15 months. Mean best corrected visual acuity one year after surgery was 0.6±0.4 LogMAR in the single-site group and 0.4±0.28 LogMAR in the two-site group (P=0.12. In the single-site group, mean preoperative intraocular pressure (IOP was 26.4±6.6 mmHg which was decreased to 14.8±2.5 mmHg, one year after the operation (P < 0.001. Corresponding figures for the two-site group were 22.9±3.3 and 13.6±1.7 mmHg respectively (P < 0.001. At final follow up no significant difference in IOP existed between the study groups. Mean number of anti-glaucoma medications was 0.06±0.24 in the two-site group vs 0

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

Science.gov (United States)

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

2011-10-01

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

Anti-site defected MoS2 sheet-based single electron transistor as a gas sensor

Science.gov (United States)

Sharma, Archana; Husain, Mushahid; Srivastava, Anurag; Khan, Mohd. Shahid

2018-05-01

To prevent harmful and poisonous CO gas molecules, catalysts are needed for converting them into benign substances. Density functional theory (DFT) calculations have been used to study the adsorption of CO and CO2 gas molecules on the surface of MoS2 monolayer with Mo atom embedded at S-vacancy site (MoS). The strong interaction between Mo metal with pristine MoS2 sheet suggests its strong binding nature. Doping Mo into MoS2 sheet enhances CO and CO2 adsorption strength. The sensing response of MoS-doped MoS2 system to CO and CO2 gas molecules is obtained in the single electron transistor (SET) environment by varying bias voltage. Doping reduces charging energy of the device which results in fast switching of the device from OFF to ON state.

Economically viable production of biodiesel from a rural feedstock from eastern India, P. pinnata oil using a recyclable laboratory synthesized heterogeneous catalyst

International Nuclear Information System (INIS)

Singh, Veena; Hameed, Bassim H.; Sharma, Yogesh Chandra

2016-01-01

Graphical abstract: Barium zirconate was synthesized by co-precipitation method using nitrates of barium and zirconia and was applied for biodiesel production using karanja oil as feedstock through transesterification reaction. - Highlights: • Barium zirconate have been used as a heterogeneous catalyst for biodiesel production. • Effect of calcination time on stability of catalyst was studied. • 98.79 ± 0.5% of FAME conversion from karanja oil was attained. • Catalyst is stable and can be reused up to nine cycles with conversion up to >65%. • Glycerol obtained as a byproduct was easily purified for better use. - Abstract: Barium zirconate was synthesized by co-precipitation method and its feasibility as a heterogeneous catalyst for production of biodiesel (fatty acid methyl ester) was assessed. Fatty acid methyl ester (FAME) was synthesized through transesterification of karanja oil with methanol. Synthesized barium zirconate was characterized by Thermogravimetric analysis (TGA), Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray diffractometry (XRD), Energy dispersive X-ray spectroscopy (EDS), and Scanning Electron Microscope (SEM). Specific surface area and basicity of the catalyst were also deliberated. Catalyst characterization indicated formation of single phase of barium zirconate which was capable of catalyzing the transesterification of esterified karanja oil with methanol. Feedstock was characterized by Gas Chromatography Mass Spectrometry (GC–MS). Reaction conditions such as molar ratio (oil:methanol), catalyst concentration, temperature, time, stirring speed and catalyst reusability were optimized. Calcination temperature and time significantly affected the catalytic activity of the catalyst because of variation in availability of basic sites. FAME conversion of 98.79 ± 0.5% was obtained at catalyst concentration of 1.0 wt%, 1:27 M ratio (oil:methanol), 65 °C for a 3 h contact time. The catalyst could be

Supported rhodium catalysts for ammonia-borane hydrolysis. Dependence of the catalytic activity on the highest occupied state of the single rhodium atoms

Energy Technology Data Exchange (ETDEWEB)

Wang, Liangbing; Li, Hongliang; Zhang, Wenbo; Zhao, Xiao; Qiu, Jianxiang; Li, Aowen; Zheng, Xusheng; Zeng, Jie [Hefei National Lab. for Physical Sciences at the Microscale, Key Lab. of Strongly-Coupled Quantum Matter Physics, Chinese Academy of Sciences, Hefei, Anhui(China); Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui (China); Hu, Zhenpeng [School of Physics, Nankai University, Tianjin (China); Si, Rui [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences (China)

2017-04-18

Supported metal nanocrystals have exhibited remarkable catalytic performance in hydrogen generation reactions, which is influenced and even determined by their supports. Accordingly, it is of fundamental importance to determine the direct relationship between catalytic performance and metal-support interactions. Herein, we provide a quantitative profile for exploring metal-support interactions by considering the highest occupied state in single-atom catalysts. The catalyst studied consisted of isolated Rh atoms dispersed on the surface of VO{sub 2} nanorods. It was observed that the activation energy of ammonia-borane hydrolysis changed when the substrate underwent a phase transition. Mechanistic studies indicate that the catalytic performance depended directly on the highest occupied state of the single Rh atoms, which was determined by the band structure of the substrates. Other metal catalysts, even with non-noble metals, that exhibited significant catalytic activity towards NH{sub 3}BH{sub 3} hydrolysis were rationally designed by adjusting their highest occupied states. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

A Single-step Process to Convert Karanja Oil to Fatty Acid Methyl Esters Using Amberlyst15 as a Catalyst

Directory of Open Access Journals (Sweden)

Arun K. Gupta

2018-03-01

Full Text Available Karanja oil was successfully converted to fatty acid methyl esters (FAME in a single- step process using Amberlyst15 as a catalyst. A methanol to oil ratio of 6 was required to retain the physical structure of the Amberlyst15 catalyst. At higher methanol to oil ratios, the Amberlyst15 catalyst disintegrated. Disintegration of Amberlyst15 caused an irreversible loss in catalytic activity. This loss in activity was due to a decrease in surface area of Amberlyst15, which was caused by a decrease in its mesoporous volume. It appeared that the chemical nature of Amberlyst15 was unaffected. Reuse of Amberlyst15 with a methanol to oil ratio of 6:1 also revealed a loss in FAME yield. However, this loss in activity was recovered by heating the used Amberlyst15 catalyst to 393 K. The kinetic parameters of a power law model were successfully determined for a methanol to oil ratio of 6:1. An activation energy of 54.9 kJ mol–1 was obtained.

In situ Ru K-edge EXAFS of CO adsorption on a Ru modified Pt/C fuel cell catalyst

International Nuclear Information System (INIS)

Rose, Abigail; Bilsborrow, Robert; King, Colin R.; Ravikumar, M.K.; Qian Yangdong; Wiltshire, Richard J.K.; Crabb, Eleanor M.; Russell, Andrea E.

2009-01-01

The Ru-CO bond of CO adsorbed on a Ru modified Pt/C fuel cell catalyst has been directly probed by in situ EXAFS at the Ru K-edge, providing evidence of a CO:metal surface atom ratio greater than 1:1 and that CO is adsorbed at bridging sites associated with Ru atoms at the surface of the catalyst nanoparticles. This result illustrates the limitations of single crystal models as representations of the bonding of adsorbed species at nanoparticle surfaces.

Robotic single-access splenectomy using the Da Vinci Single-Site® platform: a case report.

Science.gov (United States)

Corcione, Francesco; Bracale, Umberto; Pirozzi, Felice; Cuccurullo, Diego; Angelini, Pier Luigi

2014-03-01

Single-access laparoscopic splenectomy can offer patients some advantages. It has many difficulties, such as instrument clashing, lack of triangulation, odd angles and lack of space. The Da Vinci Single-Site® robotic surgery platform could decrease these difficulties. We present a case of single-access robotic splenectomy using this device. A 37 year-old female with idiopathic thrombocytopenic purpura was operated on with a single-site approach, using the Da Vinci Single-Site robotic surgery device. The procedure was successfully completed in 140 min. No intraoperative and postoperative complications occurred. The patient was discharged from hospital on day 3. Single-access robotic splenectomy seems to be feasible and safe using the new robotic single-access platform, which seems to overcome certain limits of previous robotic or conventional single-access laparoscopy. We think that additional studies should also be performed to explore the real cost-effectiveness of the platform. Copyright © 2013 John Wiley & Sons, Ltd.

Effect of temperature for synthesizing single-walled carbon nanotubes by catalytic chemical vapor deposition over Mo-Co-MgO catalyst

International Nuclear Information System (INIS)

Niu Zhiqiang; Fang Yan

2008-01-01

The influence of temperature on synthesizing single-walled carbon nanotubes (SWCNTs) by catalytic chemical vapor deposition of methane over Mo-Co-MgO catalyst was studied by Transmission Electron Microscope (TEM) and Raman scattering. The Mo-Co-MgO bimetallic catalyst was prepared by decomposing the mixture of magnesium nitrate, ammonium molybdate, citric acid, and cobalt nitrate. The results show that Mo-Co-MgO bimetallic catalyst is effective to synthesize SWCNTs. By using Mo-Co-MgO bimetallic catalyst, generation of SWCNTs even at 940 K was demonstrated. The optimum temperature of synthesizing SWCNTs over Mo-Co-MgO bimetallic catalyst may be about 1123 K. At 1123 K, the diameters of SWCNTs are in the range of 0.75-1.65 nm. The content of SWCNTs is increased with the increase of temperature below 1123 K and the carbon yield rate is also increased with the increase of synthesis temperature. Therefore, the amount of SWCNTs increases with the increase of temperature below 1123 K. However, above 1123 K, the content of SWCNTs is decreased with the increase of temperature; therefore, it is not effective to increase the amount of SWCNTs through increasing synthesis temperature above 1123 K

Low Voltage Ride-Through Capability of a Single-Stage Single-Phase Photovoltaic System Connected to the Low-Voltage Grid

DEFF Research Database (Denmark)

Yang, Yongheng; Blaabjerg, Frede

2013-01-01

The progressively growing of single-phase photovoltaic (PV) systems makes the Distribution System Operators (DSO) to update or revise the existing grid codes in order to guarantee the availability, quality and reliability of the electrical system. It is expected that the future PV systems connected...... to the low-voltage grid will be more active with functionalities of low voltage ride-through (LVRT) and the grid support capability, which is not the case today. In this paper, the operation principle is demonstrated for a single-phase grid-connected PV system in low voltage ride through operation in order...... to map future challenges. The system is verified by simulations and experiments. Test results show that the proposed power control method is effective and the single-phase PV inverters connected to low-voltage networks are ready to provide grid support and ride-through voltage fault capability...

A Combined Probe-Molecule, Mössbauer, Nuclear Resonance Vibrational Spectroscopy, and Density Functional Theory Approach for Evaluation of Potential Iron Active Sites in an Oxygen Reduction Reaction Catalyst

Energy Technology Data Exchange (ETDEWEB)

Kneebone, Jared L. [Univ. of Rochester, Rochester, NY (United States); Daifuku, Stephanie L. [Univ. of Rochester, Rochester, NY (United States); Kehl, Jeffrey A. [Univ. of Rochester, Rochester, NY (United States); Wu, Gang [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Chung, Hoon T. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Hu, Michael Y. [Argonne National Lab. (ANL), Argonne, IL (United States); Alp, E. Ercan [Argonne National Lab. (ANL), Argonne, IL (United States); More, Karren L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Zelenay, Piotr [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Holby, Edward F. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Neidig, Michael L. [Univ. of Rochester, Rochester, NY (United States)

2017-07-06

While non-precious metal M-N-C (M = Fe or Co) catalysts have been developed that are effective for the oxygen reduction reaction in polymer electrolyte fuel cells, no consensus has yet been reached regarding the nature of the M sites in these heterogeneous catalysts that are responsible for reaction with dioxygen (O₂). While multiple studies have developed correlations between Fe distributions in as-prepared catalysts and ORR activity, the direct identification of sites reactive towards O₂ or O₂-analog molecules remains a significant challenge. In the present study, we demonstrate a new approach to identifying and characterizing potential Fe active sites in complex ORR catalysts that combines an effective probe molecule (NO_(g)) Mössbauer spectroscopy and nuclear resonance vibrational spectroscopy (NRVS) with density functional theory (DFT) calculations. Mössbauer spectroscopic studies demonstrate that NO_(g) treatment of electrochemically reduced PANI-57Fe-C leads to selective reaction with only a sub-set of the Fe species present. Nuclear resonance vibrational spectroscopic studies identified new Fe-ligand vibrations associated with the site reactive towards NO_(g). DFT calculations of vibrational properties of a small selection of previously proposed active site structures suggest that graphene zig-zag edge hosted Fe-N structures may be responsible for the observed vibrational behavior with NO_(g) probe molecules. Moreover, such sites are likely also reactive to O₂, possibly serving as the ORR active sites in the synthesized materials.

A Synthetic Single-Site Fe Nitrogenase: High Turnover, Freeze-Quench (57)Fe Mössbauer Data, and a Hydride Resting State.

Science.gov (United States)

Del Castillo, Trevor J; Thompson, Niklas B; Peters, Jonas C

2016-04-27

The mechanisms of the few known molecular nitrogen-fixing systems, including nitrogenase enzymes, are of much interest but are not fully understood. We recently reported that Fe-N2 complexes of tetradentate P3(E) ligands (E = B, C) generate catalytic yields of NH3 under an atmosphere of N2 with acid and reductant at low temperatures. Here we show that these Fe catalysts are unexpectedly robust and retain activity after multiple reloadings. Nearly an order of magnitude improvement in yield of NH3 for each Fe catalyst has been realized (up to 64 equiv of NH3 produced per Fe for P3(B) and up to 47 equiv for P3(C)) by increasing acid/reductant loading with highly purified acid. Cyclic voltammetry shows the apparent onset of catalysis at the P3(B)Fe-N2/P3(B)Fe-N2(-) couple and controlled-potential electrolysis of P3(B)Fe(+) at -45 °C demonstrates that electrolytic N2 reduction to NH3 is feasible. Kinetic studies reveal first-order rate dependence on Fe catalyst concentration (P3(B)), consistent with a single-site catalyst model. An isostructural system (P3(Si)) is shown to be appreciably more selective for hydrogen evolution. In situ freeze-quench Mössbauer spectroscopy during turnover reveals an iron-borohydrido-hydride complex as a likely resting state of the P3(B)Fe catalyst system. We postulate that hydrogen-evolving reaction activity may prevent iron hydride formation from poisoning the P3(B)Fe system. This idea may be important to consider in the design of synthetic nitrogenases and may also have broader significance given that intermediate metal hydrides and hydrogen evolution may play a key role in biological nitrogen fixation.

One-step production of long-chain hydrocarbons from waste-biomass-derived chemicals using bi-functional heterogeneous catalysts.

Science.gov (United States)

Wen, Cun; Barrow, Elizabeth; Hattrick-Simpers, Jason; Lauterbach, Jochen

2014-02-21

In this study, we demonstrate the production of long-chain hydrocarbons (C8+) from 2-methylfuran (2MF) and butanal in a single step reactive process by utilizing a bi-functional catalyst with both acid and metallic sites. Our approach utilizes a solid acid for the hydroalkylation function and as a support as well as a transition metal as hydrodeoxygenation catalyst. A series of solid acids was screened, among which MCM-41 demonstrated the best combination of activity and stability. Platinum nanoparticles were then incorporated into the MCM-41. The Pt/MCM-41 catalyst showed 96% yield for C8+ hydrocarbons and the catalytic performance was stable over four reaction cycles of 20 hour each. The reaction pathways for the production of long-chain hydrocarbons is probed with a combination of infrared spectroscopy and steady-state reaction experiments. It is proposed that 2MF and butanal go through hydroalkylation first on the acid site followed by hydrodeoxygenation to produce the hydrocarbon fuels.

Intermetallic Alloys as CO Electroreduction Catalysts-Role of Isolated Active Sites

DEFF Research Database (Denmark)

Karamad, Mohammadreza; Tripkovic, Vladimir; Rossmeisl, Jan

2014-01-01

One of the main challenges associated with the electrochemical CO or CO2 reduction is poor selectivity toward energetically rich products. In order to promote selectivity toward hydrocarbons and alcohols, most notably, the hydrogen evolution reaction (HER) should be suppressed. To achieve this goal...... potentially selective intermetallic surfaces on which CO can be reduced to methanol at potentials comparable to or even slightly positive than those for CO/CO2 reduction to methane on Cu. Common features shared by most of the selective alloys are single TM sites. The role of single sites is to block parasitic...... HER and thereby promote CO reduction....

Autothermal reforming catalyst having perovskite structure

Science.gov (United States)

Krumpel, Michael [Naperville, IL; Liu, Di-Jia [Naperville, IL

2009-03-24

The invention addressed two critical issues in fuel processing for fuel cell application, i.e. catalyst cost and operating stability. The existing state-of-the-art fuel reforming catalyst uses Rh and platinum supported over refractory oxide which add significant cost to the fuel cell system. Supported metals agglomerate under elevated temperature during reforming and decrease the catalyst activity. The catalyst is a perovskite oxide or a Ruddlesden-Popper type oxide containing rare-earth elements, catalytically active firs row transition metal elements, and stabilizing elements, such that the catalyst is a single phase in high temperature oxidizing conditions and maintains a primarily perovskite or Ruddlesden-Popper structure under high temperature reducing conditions. The catalyst can also contain alkaline earth dopants, which enhance the catalytic activity of the catalyst, but do not compromise the stability of the perovskite structure.

Conversion of actual flue gas CO 2 via cycloaddition to propylene oxide catalyzed by a single-site, recyclable zirconium catalyst

KAUST Repository

Kelly, Michael J.

2017-06-12

A reusable zirconium-based catalyst for the cycloaddition of CO2 to propylene oxide (PO) was prepared by the surface organometallic chemistry (SOMC) methodology. Accordingly, well-defined amounts of the ZrCl4·(OEt2)2 precursor were grafted on the surface of silica dehydroxylated at 700°C (SiO2-700) and at 200°C (SiO2-200) in order to afford surface coordination compounds with different podality and chemical environment. The identity of the surface complexes was thoroughly investigated by FT-IR, elemental microanalysis and solid state NMR and applied as a recoverable and reusable heterogeneous catalyst for the title reaction using pure CO2 and flue gas samples from a cement factory. The observed catalytic activity for the isolated zirconium complexes is rationalized by means of systematic DFT calculations.

Conversion of actual flue gas CO 2 via cycloaddition to propylene oxide catalyzed by a single-site, recyclable zirconium catalyst

KAUST Repository

Kelly, Michael J.; Barthel, Alexander; Maheu, Clement; Sodpiban, Ounjit; Dega, Frank-Blondel; Vummaleti, Sai V.C.; Abou-Hamad, Edy; Pelletier, Jeremie; Cavallo, Luigi; D'Elia, Valerio; Basset, Jean-Marie

2017-01-01

A reusable zirconium-based catalyst for the cycloaddition of CO2 to propylene oxide (PO) was prepared by the surface organometallic chemistry (SOMC) methodology. Accordingly, well-defined amounts of the ZrCl4·(OEt2)2 precursor were grafted on the surface of silica dehydroxylated at 700°C (SiO2-700) and at 200°C (SiO2-200) in order to afford surface coordination compounds with different podality and chemical environment. The identity of the surface complexes was thoroughly investigated by FT-IR, elemental microanalysis and solid state NMR and applied as a recoverable and reusable heterogeneous catalyst for the title reaction using pure CO2 and flue gas samples from a cement factory. The observed catalytic activity for the isolated zirconium complexes is rationalized by means of systematic DFT calculations.

Characterization of alumina supported molybdenum catalysts

Energy Technology Data Exchange (ETDEWEB)

Pastura, N M; Carmo, L M.P.M.; Sachett, C M.M.; Lam, Y L [Instituto Militar de Engenharia, Rio de Janeiro (Brazil). Secao de Quimica

1983-10-01

In order to optimize a bifunctional catalyst (acid and hydrogenating) of Mo/Al/sub 2/O/sub 3/, oxygen adsorption at 195 K and ethanol dehydration at 480-520 K were carried out using a series of these catalysts. The increase of Mo content increased the quantity of adsorbed oxygen, thus indicating that the number of hydrogenating sites also increased. The specific activity of ethanol dehydration varied slightly, indicating that the number of acid sites remains almost constant. On the other hand, the selectivity in ethylene (versus ether) increased markedly. This may be attributed to the increase in acid force of the acid sites.

Characterization of alumina supported molybdenum catalysts

International Nuclear Information System (INIS)

Pastura, N.M.; Carmo, L.M.P.M.; Sachett, C.M.M.; Lam, Y.L.

1983-01-01

In order to optimize a bifunctional catalyst (acid and hydrogenating) of Mo/Al 2 O 3 , oxygen adsorption at 195 K and ethanol dehydration at 480-520 K were carried out using a series of these catalysts. The increase of Mo content increased the quantity of adsorbed oxygen, thus indicating that the number of hydrogenating sites also increased. The specific activity of ethanol dehydration varied slightly, indicating that the number of acid sites remains almost constant. On the other hand, the selectivity in ethylene (versus ether) increased markedly. This may be attributed to the increase in acid force of the acid sites. (C.L.B.) [pt

Activation of molecular catalysts using semiconductor quantum dots

Science.gov (United States)

Meyer, Thomas J [Chapel Hill, NC; Sykora, Milan [Los Alamos, NM; Klimov, Victor I [Los Alamos, NM

2011-10-04

Photocatalytic materials based on coupling of semiconductor nanocrystalline quantum dots (NQD) and molecular catalysts. These materials have capability to drive or catalyze non-spontaneous chemical reactions in the presence of visible radiation, ultraviolet radiation, or both. The NQD functions in these materials as a light absorber and charge generator. Following light absorption, the NQD activates a molecular catalyst adsorbed on the surface of the NQD via transfer of one or more charges (either electrons or electron-holes) from the NQD to the molecular catalyst. The activated molecular catalyst can then drive a chemical reaction. A photoelectrolytic device that includes such photocatalytic materials is also described.

Performance evaluation of the technical capabilities of DOE sites for disposal of mixed low-level waste: Volume 3, Site evaluations

Energy Technology Data Exchange (ETDEWEB)

Waters, R.D.; Gruebel, M.M. [eds.

1996-03-01

A team of analysts designed and conducted a performance evaluation to estimate the technical capabilities of fifteen Department of Energy sites for disposal of mixed low-level waste (i.e., waste that contains both low-level radioactive materials and hazardous constituents). Volume 1 summarizes the process for selecting the fifteen sites, the methodology used in the evaluation, and the conclusions derived from the evaluation. Volume 2 provides details about the site-selection process, the performance-evaluation methodology, and the overall results of the analysis. Volume 3 contains detailed evaluations of the fifteen sites and discussion of the results for each site.

Performance evaluation of the technical capabilities of DOE sites for disposal of mixed low-level waste: Volume 3, Site evaluations

International Nuclear Information System (INIS)

Waters, R.D.; Gruebel, M.M.

1996-03-01

A team of analysts designed and conducted a performance evaluation to estimate the technical capabilities of fifteen Department of Energy sites for disposal of mixed low-level waste (i.e., waste that contains both low-level radioactive materials and hazardous constituents). Volume 1 summarizes the process for selecting the fifteen sites, the methodology used in the evaluation, and the conclusions derived from the evaluation. Volume 2 provides details about the site-selection process, the performance-evaluation methodology, and the overall results of the analysis. Volume 3 contains detailed evaluations of the fifteen sites and discussion of the results for each site

Quantitative 3D Fluorescence Imaging of Single Catalytic Turnovers Reveals Spatiotemporal Gradients in Reactivity of Zeolite H-ZSM-5 Crystals upon Steaming

NARCIS (Netherlands)

Ristanovic, Zoran|info:eu-repo/dai/nl/328233005; Hofmann, Jan P.|info:eu-repo/dai/nl/355351110; De Cremer, Gert; Kubarev, Alexey V.; Rohnke, Marcus; Meirer, Florian; Hofkens, Johan; Roeffaers, Maarten B. J.; Weckhuysen, Bert M.|info:eu-repo/dai/nl/285484397

2015-01-01

Optimizing the number, distribution, and accessibility of Bronsted acid sites in zeolite-based catalysts is of a paramount importance to further improve their catalytic performance. However, it remains challenging to measure real-time changes in reactivity of single zeolite catalyst particles by

Direct instrumental identification of catalytically active surface sites

Science.gov (United States)

Pfisterer, Jonas H. K.; Liang, Yunchang; Schneider, Oliver; Bandarenka, Aliaksandr S.

2017-09-01

The activity of heterogeneous catalysts—which are involved in some 80 per cent of processes in the chemical and energy industries—is determined by the electronic structure of specific surface sites that offer optimal binding of reaction intermediates. Directly identifying and monitoring these sites during a reaction should therefore provide insight that might aid the targeted development of heterogeneous catalysts and electrocatalysts (those that participate in electrochemical reactions) for practical applications. The invention of the scanning tunnelling microscope (STM) and the electrochemical STM promised to deliver such imaging capabilities, and both have indeed contributed greatly to our atomistic understanding of heterogeneous catalysis. But although the STM has been used to probe and initiate surface reactions, and has even enabled local measurements of reactivity in some systems, it is not generally thought to be suited to the direct identification of catalytically active surface sites under reaction conditions. Here we demonstrate, however, that common STMs can readily map the catalytic activity of surfaces with high spatial resolution: we show that by monitoring relative changes in the tunnelling current noise, active sites can be distinguished in an almost quantitative fashion according to their ability to catalyse the hydrogen-evolution reaction or the oxygen-reduction reaction. These data allow us to evaluate directly the importance and relative contribution to overall catalyst activity of different defects and sites at the boundaries between two materials. With its ability to deliver such information and its ready applicability to different systems, we anticipate that our method will aid the rational design of heterogeneous catalysts.

Hydroisomerization of n-dodecane over Pt/Al-MCM-48 catalysts.

Science.gov (United States)

Yun, Soyoung; Park, Young-Kwon; Jeong, Soon-Yong; Han, Jeongsik; Jeon, Jong-Ki

2014-04-01

The objective of this study is to evaluate the catalytic potential of Pt/Al-MCM-48 catalysts in hydroisomerization of n-dodecane. The effects of the Si/Al ratio and platinum loading on the acid characteristics of Al-MCM-48 and the catalytic performance in n-dodecane hydroisomerization were analyzed. The catalysts were characterized by X-ray diffraction, nitrogen adsorption, infrared spectroscopy of pyridine adsorption, and temperature programmed desorption of ammonia. The number of weak strength acid sites on Al-MCM-48 increased with 0.5 wt% platinum loading. The weak strength acid sites of Pt/Al-MCM-48 catalysts were ascribed to Lewis acid sites, which can be confirmed by NH3-TPD and FTIR spectra of pyridine adsorption. Iso-dodecane can be produced with high selectivity in n-dodecane hydrosisomerization over Pt/Al-MCM-48 catalysts. This is attributed to the mild acidic properties of Pt/Al-MCM-48 catalysts.

Cooperative communication within and between single nanocatalysts

Science.gov (United States)

Zou, Ningmu; Zhou, Xiaochun; Chen, Guanqun; Andoy, Nesha May; Jung, Won; Liu, Guokun; Chen, Peng

2018-06-01

Enzymes often show catalytic allostery in which reactions occurring at different sites communicate cooperatively over distances of up to a few nanometres. Whether such effects can occur with non-biological nanocatalysts remains unclear, even though these nanocatalysts can undergo restructuring and molecules can diffuse over catalyst surfaces. Here we report that phenomenologically similar, but mechanistically distinct, cooperative effects indeed exist for nanocatalysts. Using spatiotemporally resolved single-molecule catalysis imaging, we find that catalytic reactions on a single Pd or Au nanocatalyst can communicate with each other, probably via hopping of positively charged holes on the catalyst surface, over 102 nanometres and with a temporal memory of 101 to 102 seconds, giving rise to positive cooperativity among its surface active sites. Similar communication is also observed between individual nanocatalysts, however it operates via a molecular diffusion mechanism involving negatively charged product molecules, and its communication distance is many micrometres. Generalization of these long-range intra- and interparticle catalytic communication mechanisms may introduce a novel conceptual framework for understanding nanoscale catalysis.

AN/FSY-3 Space Fence System – Sensor Site One/Operations Center Integration Status and Sensor Site Two Planned Capability

Science.gov (United States)

Fonder, G. P.; Hack, P. J.; Hughes, M. R.

This paper covers two topics related to Space Fence System development: Sensor Site One / Operations Center construction and integration status including risk reduction integration and test efforts at the Moorestown, NJ Integrated Test Bed (ITB); and the planned capability of Sensor Site Two. The AN/FSY-3 Space Fence System is a ground-based system of S-band radars integrated with an Operations Center designed to greatly enhance the Air Force Space Surveillance network. The radar architecture is based on Digital Beam-forming. This capability permits tremendous user-defined flexibility to customize volume surveillance and track sectors instantaneously without impacting routine surveillance functions. Space Fence provides unprecedented sensitivity, coverage and tracking accuracy, and contributes to key mission threads with the ability to detect, track and catalog small objects in LEO, MEO and GEO. The system is net-centric and will seamlessly integrate into the existing Space Surveillance Network, providing services to external users—such as JSpOC—and coordinating handoffs to other SSN sites. Sensor Site One construction on the Kwajalein Atoll is in progress and nearing completion. The Operations Center in Huntsville, Alabama has been configured and will be integrated with Sensor Site One in the coming months. System hardware, firmware, and software is undergoing integration testing at the Mooretown, NJ ITB and will be deployed at Sensor Site One and the Operations Center. The preliminary design for Sensor Site Two is complete and will provide critical coverage, timeliness, and operational flexibility to the overall system.

Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons

Science.gov (United States)

Zecevic, Jovana; Vanbutsele, Gina; de Jong, Krijn P.; Martens, Johan A.

2015-12-01

The ability to control nanoscale features precisely is increasingly being exploited to develop and improve monofunctional catalysts. Striking effects might also be expected in the case of bifunctional catalysts, which are important in the hydrocracking of fossil and renewable hydrocarbon sources to provide high-quality diesel fuel. Such bifunctional hydrocracking catalysts contain metal sites and acid sites, and for more than 50 years the so-called intimacy criterion has dictated the maximum distance between the two types of site, beyond which catalytic activity decreases. A lack of synthesis and material-characterization methods with nanometre precision has long prevented in-depth exploration of the intimacy criterion, which has often been interpreted simply as ‘the closer the better’ for positioning metal and acid sites. Here we show for a bifunctional catalyst—comprising an intimate mixture of zeolite Y and alumina binder, and with platinum metal controllably deposited on either the zeolite or the binder—that closest proximity between metal and zeolite acid sites can be detrimental. Specifically, the selectivity when cracking large hydrocarbon feedstock molecules for high-quality diesel production is optimized with the catalyst that contains platinum on the binder, that is, with a nanoscale rather than closest intimacy of the metal and acid sites. Thus, cracking of the large and complex hydrocarbon molecules that are typically derived from alternative sources, such as gas-to-liquid technology, vegetable oil or algal oil, should benefit especially from bifunctional catalysts that avoid locating platinum on the zeolite (the traditionally assumed optimal location). More generally, we anticipate that the ability demonstrated here to spatially organize different active sites at the nanoscale will benefit the further development and optimization of the emerging generation of multifunctional catalysts.

Catalyst growth of single crystal aligned ZnO nanorods on ZnO thin films

Energy Technology Data Exchange (ETDEWEB)

Zhao, Dongxu; Andreazza, Caroline; Andreazza, Pascal [Centre de Recherche sur la Matiere Divisee, CNRS-Universite d' Orleans, 1b rue de la Ferollerie, 45071 Orleans cedex 2 (France)

2005-02-01

One dimensional ZnO nanorods were successfully fabricated on Si substrates via a simple physical vapor-phase transport method at 950 C. A ZnO shell covered Au/Zn alloy is assumed as the nucleation site, then ZnO nanorods grow following a vapor-solid (VS) process. In order to guide the nanorod growth a c-axis oriented ZnO thin film and Au catalyst were first deposited on Si (100) surface. SEM images show nanorods grown on this substrate are vertical to the substrate surface. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Water Oxidation by Ru-Polyoxometalate Catalysts: Overpotential Dependency on the Number and Charge of the Metal Centers

Directory of Open Access Journals (Sweden)

Simone Piccinin

2015-09-01

Full Text Available Water oxidation is efficiently catalyzed by several Ru-based polyoxometalate (POM molecular catalysts differing in the number, local atomistic environment and oxidation state of the Ru sites. We employ density functional theory calculations to rationalize the dependency of the reaction overpotential on the main structural and electronic molecular properties. In particular, we compare the thermodynamics of the water oxidation cycle for single-site Ru-POM and multiple-site Ru4-POM complexes. For the Ru-POM case, we also investigate the reaction free energy as a function of the Ru oxidation state. We find that the overpotential of these molecular catalysts is primarily determined by the oxidation state of the metal center and is minimum for Ru(IV. In solution, the number of active sites is shown to play a minor role on the reaction energetics. The results are rationalized and discussed in terms of the local structure around the active sites and of the electrostatic screening due to the molecular structure or the solvent.

Conversion of Methane into Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

Energy Technology Data Exchange (ETDEWEB)

Okolie, Chukwuemeka [School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA; Belhseine, Yasmeen F. [School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA; Lyu, Yimeng [School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA; Yung, Matthew M. [National Renewable Energy Laboratory, Golden CO 80401 USA; Engelhard, Mark H. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Lab, Richland WA 99354 USA; Kovarik, Libor [Environmental Molecular Sciences Laboratory, Pacific Northwest National Lab, Richland WA 99354 USA; Stavitski, Eli [National Synchrotron Light Source II, Brookhaven National Laboratory, Upton NY 11973 USA; Sievers, Carsten [School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA

2017-09-26

Direct conversion of methane into alcohols is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can selectively oxidize methane to methanol and ethanol in a single, steady-state process at 723 K using O2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to the synergy between the small Lewis acidic NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.

Cerium-containing catalysts for obtaining ethylene from ethanol

Directory of Open Access Journals (Sweden)

Kusman Dossumov

2014-10-01

Full Text Available The catalysts Се/γ-Al2O3 и Се-La/γ-Al2O3 were studied by methods of electron microscopy (EM and temperature-programmed desorption (TPD of ammonia. Their activity was studied in reaction of ethanol dehydration with formation of ethylene. Modification of Се/γ-Al2O3 catalyst by Lanthanum promotes dispersion of the catalyst and increases the amount of acidic sites. This modification positively affects the catalyst activity.

Catalyst design for clean and efficient fuels

DEFF Research Database (Denmark)

Šaric, Manuel

cobalt promoted MoS2 catalyst. Reactivity of a series of model molecules, found in oil prior to desulfurization, is studied on cobalt promoted MoS2. Such an approach has the potential to explain the underlying processes involved in the removal of sulfur at each specific site of the catalyst. The goal...... is to identify which sites are active towards specific molecules and in getting insight to what the ideal catalyst should look like in terms of morphology. Dimethyl carbonate is an environmentally benign compound that can be used as a solvent and precursor in chemical synthesis or as a fuel and fuel additive...... processes currently used. It is found that noble metals can be used as electrocatalysts for the synthesis of dimethyl carbonate, significantly lowering the potential when using copper instead of gold. Besides being active, copper was found to be selective towards dimethyl carbonate. A non-selective catalyst...

Deactivation of molybdate catalysts by nitrogen bases

Energy Technology Data Exchange (ETDEWEB)

Furimsky, E.

1982-10-01

Nitrogen bases present in petroleum deactivate the surface of molybdate catalysts. The detrimental effect is attributed either to interactions of the bases with Lewis sites via unpaired electrons on nitrogen or to their ability to remove proton from the surface. The later effect results in a decrease of concentration of Bronsted sites known to be active in catalytic reactions. This enhances rate of coke forming reactions. Resistence of molybdate catalysts to coke formation depends on the form and redistribution of active ingredients on the surface. This can be effected by conditions applied during preparation and pretreatment of the catalysts. Processing parameters used during catalytic hydrotreatment are also important; i.e., the coke formation is slow under conditions ensuring high rate of removal of basic nitrogen containing compounds.

EXAFS characterization of supported metal catalysts in chemically dynamic environments

International Nuclear Information System (INIS)

Robota, H.J.

1991-01-01

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

Heterogeneous Metal Catalysts for Oxidation Reactions

Directory of Open Access Journals (Sweden)

Md. Eaqub Ali

2014-01-01

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

Step sites in syngas catalysis

DEFF Research Database (Denmark)

Rostrup-Nielsen, J.; Nørskov, Jens Kehlet

2006-01-01

Step sites play an important role in many catalytic reactions. This paper reviews recent results on metal catalysts for syngas reactions with emphasis on steam reforming. Modern characterization techniques (STEM, HREM...) and theoretical calculations (DFT) has allowed a more quantitative explanat......Step sites play an important role in many catalytic reactions. This paper reviews recent results on metal catalysts for syngas reactions with emphasis on steam reforming. Modern characterization techniques (STEM, HREM...) and theoretical calculations (DFT) has allowed a more quantitative...... explanation of the impact of step sites on catalyst activity and side reactions such as carbon formation. This leads to a discussion of principles for catalyst promotion....

Idaho National Laboratory Ten-year Site Plan (2012 through 2021) -- DOE-NE's National Nuclear Capability -- Developing and Maintaining the INL Infrastructure

Energy Technology Data Exchange (ETDEWEB)

Cal Ozaki

2010-06-01

To meet long-term objectives to transform the Idaho National Laboratory (INL), we are providing an integrated, long-term vision of infrastructure requirements that support research, development and demonstration (RD&D) goals outlined in the DOE strategic plans, including the NE Roadmap and reports such as Facilities for the Future of Nuclear Energy Research: A Twenty-year Outlook. The goal of the INL Ten-year Site Plan (TYSP) is to clearly link RD&D mission goals and INL core capabilities with infrastructure requirements (single and multi-program), establish the 10-year end-state vision for INL complexes, identify and prioritize infrastructure and capability gaps, as well as the most efficient and economic approaches to closing those gaps.

Heterogenization of Homogeneous Catalysts: the Effect of the Support

Energy Technology Data Exchange (ETDEWEB)

Earl, W.L.; Ott, K.C.; Hall, K.A.; de Rege, F.M.; Morita, D.K.; Tumas, W.; Brown, G.H.; Broene, R.D.

1999-06-29

We have studied the influence of placing a soluble, homogeneous catalyst onto a solid support. We determined that such a 'heterogenized' homogeneous catalyst can have improved activity and selectivity for the asymmetric hydrogenation of enamides to amino acid derivatives. The route of heterogenization of RhDuPhos(COD){sup +} cations occurs via electrostatic interactions with anions that are capable of strong hydrogen bonding to silica surfaces. This is a novel approach to supported catalysis. Supported RhDuPhos(COD){sup +} is a recyclable, non-leaching catalyst in non-polar media. This is one of the few heterogenized catalysts that exhibits improved catalytic performance as compared to its homogeneous analog.

Compact teleoperated laparoendoscopic single-site robotic surgical system: Kinematics, control, and operation.

Science.gov (United States)

Isaac-Lowry, Oran Jacob; Okamoto, Steele; Pedram, Sahba Aghajani; Woo, Russell; Berkelman, Peter

2017-12-01

To date a variety of teleoperated surgical robotic systems have been developed to improve a surgeon's ability to perform demanding single-port procedures. However typical large systems are bulky, expensive, and afford limited angular motion, while smaller designs suffer complications arising from limited motion range, speed, and force generation. This work was to develop and validate a simple, compact, low cost single site teleoperated laparoendoscopic surgical robotic system, with demonstrated capability to carry out basic surgical procedures. This system builds upon previous work done at the University of Hawaii at Manoa and includes instrument and endoscope manipulators as well as compact articulated instruments designed to overcome single incision geometry complications. A robotic endoscope holder was used for the base, with an added support frame for teleoperated manipulators and instruments fabricated mostly from 3D printed parts. Kinematics and control methods were formulated for the novel manipulator configuration. Trajectory following results from an optical motion tracker and sample task performance results are presented. Results indicate that the system has successfully met the goal of basic surgical functionality while minimizing physical size, complexity, and cost. Copyright © 2017 John Wiley & Sons, Ltd.

Templating Routes to Supported Oxide Catalysts by Design

Energy Technology Data Exchange (ETDEWEB)

Notestein, Justin M. [Northwestern Univ., Evanston, IL (United States)

2016-09-08

The rational design and understanding of supported oxide catalysts requires at least three advancements, in order of increasing complexity: the ability to quantify the number and nature of active sites in a catalytic material, the ability to place external controls on the number and structure of these active sites, and the ability to assemble these active sites so as to carry out more complex functions in tandem. As part of an individual investigator research program that is integrated with the Northwestern University Institute for Catalysis in Energy Processes (ICEP) as of 2015, significant advances were achieved in these three areas. First, phosphonic acids were utilized in the quantitative assessment of the number of active and geometrically-available sites in MO_x-SiO₂ catalysts, including nanocrystalline composites, co-condensed materials, and grafted structures, for M=Ti, Zr, Hf, Nb, and Ta. That work built off progress in understanding supported Fe, Cu, and Co oxide catalysts from chelating and/or multinuclear precursors to maximize surface reactivity. Secondly, significant progress was made in the new area of using thin oxide overcoats containing ‘nanocavities’ from organic templates as a method to control the dispersion and thermal stability of subsequently deposited metal nanoparticles or other catalytic domains. Similar methods were used to control surface reactivity in SiO₂-Al₂O₃ acid catalysts and to control reactant selectivity in Al₂O₃-TiO₂ photocatalysts. Finally, knowledge gained from the first two areas has been combined to synthesize a tandem catalyst for hydrotreating reactions and an orthogonal tandem catalyst system where two subsequent reactions in a reaction network are independently controlled by light and heat. Overall, work carried out under this project significantly advanced the knowledge of synthesis-structure-function relationships in supported

Preferential synthesis of (6,4) single-walled carbon nanotubes by controlling oxidation degree of Co catalyst.

Science.gov (United States)

Xu, Bin; Kaneko, Toshiro; Shibuta, Yasushi; Kato, Toshiaki

2017-09-11

Chirality-selective synthesis of single-walled carbon nanotubes (SWNTs) has been a research goal for the last two decades and is still challenging due to the difficulty in controlling the atomic structure in the one-dimensional material. Here, we develop an optimized approach for controlling the chirality of species by tuning the oxidation degree of Co catalyst. Predominant synthesis of (6,4) SWNTs is realized for the first time. The detailed mechanism is investigated through a systematic experimental study combined with first-principles calculations, revealing that the independent control of tube diameter and chiral angle achieved by changing the binding energy between SWNTs (cap and tube edge) and catalyst causes a drastic transition of chirality of SWNTs from (6,5) to (6,4). Since our approach of independently controlling the diameter and chiral angle can be applied to other chirality species, our results can be useful in achieving the on-demand synthesis of specific-chirality SWNTs.

Single cobalt sites in mesoporous N-doped carbon matrix for selective catalytic hydrogenation of nitroarenes

KAUST Repository

Sun, Xiaohui

2017-11-20

A supported cobalt catalyst with atomically dispersed Co-Nx sites (3.5 wt% Co) in a mesoporous N-doped carbon matrix (named Co@mesoNC) is synthesized by hydrolysis of tetramethyl orthosilicate (TMOS) in a Zn/Co bimetallic zeolitic imidazolate framework (BIMZIF(Co,Zn)), followed by high-temperature pyrolysis and SiO2 leaching. A combination of TEM, XRD XPS and X-ray absorption spectroscopy studies confirm the absence of cobalt nanoparticles and indicate that these highly dispersed cobalt species are present in the form of Co-Nx. The exclusive formation of Co-Nx sites in the carbon matrix is attributed to the presence of a large amount of Zn and N in the BIMZIF precursor together with the presence of SiO2 in the pore space of this framework, extending the initial spatial distance between cobalt atoms and thereby impeding their agglomeration. The presence of SiO2 during high-temperature pyrolysis is proven crucial to create mesoporosity and a high BET area and pore volume in the N-doped carbon support (1780 m2 g−1, 1.54 cm3 g−1). This heterogeneous Co@mesoNC catalyst displays high activity and selectivity (>99%) for the selective hydrogenation of nitrobenzene to aniline at mild conditions (0.5–3 MPa, 343–383 K). When more challenging substrates (functionalized nitroarenes) are hydrogenated, the catalyst Co@mesoNC displays an excellent chemoselectivity to the corresponding substituted anilines.The presence of mesoporosity improves mass transport of reactants and/or products and the accessibility of the active Co-Nx sites, and greatly reduces deactivation due to fouling.

Single cobalt sites in mesoporous N-doped carbon matrix for selective catalytic hydrogenation of nitroarenes

KAUST Repository

Sun, Xiaohui; Olivos-Suarez, Alma I.; Osadchii, Dmitrii; Romero, Maria Jose Valero; Kapteijn, Freek; Gascon, Jorge

2017-01-01

A supported cobalt catalyst with atomically dispersed Co-Nx sites (3.5 wt% Co) in a mesoporous N-doped carbon matrix (named Co@mesoNC) is synthesized by hydrolysis of tetramethyl orthosilicate (TMOS) in a Zn/Co bimetallic zeolitic imidazolate framework (BIMZIF(Co,Zn)), followed by high-temperature pyrolysis and SiO2 leaching. A combination of TEM, XRD XPS and X-ray absorption spectroscopy studies confirm the absence of cobalt nanoparticles and indicate that these highly dispersed cobalt species are present in the form of Co-Nx. The exclusive formation of Co-Nx sites in the carbon matrix is attributed to the presence of a large amount of Zn and N in the BIMZIF precursor together with the presence of SiO2 in the pore space of this framework, extending the initial spatial distance between cobalt atoms and thereby impeding their agglomeration. The presence of SiO2 during high-temperature pyrolysis is proven crucial to create mesoporosity and a high BET area and pore volume in the N-doped carbon support (1780 m2 g−1, 1.54 cm3 g−1). This heterogeneous Co@mesoNC catalyst displays high activity and selectivity (>99%) for the selective hydrogenation of nitrobenzene to aniline at mild conditions (0.5–3 MPa, 343–383 K). When more challenging substrates (functionalized nitroarenes) are hydrogenated, the catalyst Co@mesoNC displays an excellent chemoselectivity to the corresponding substituted anilines.The presence of mesoporosity improves mass transport of reactants and/or products and the accessibility of the active Co-Nx sites, and greatly reduces deactivation due to fouling.

Therapeutic benefits of carbon dioxide (CO2) laser on single-site HPV lesions in the lower female genital tract

Science.gov (United States)

Urru, Giovanni; Moretti, Gianfranco

1998-01-01

Numerous studies have shown contradictory variable percentages of recurrent HPV lesions, after various therapies. The present study therefore evaluates the effectiveness of CO2 laser vaporization in the treatment of single-site HPV lesions of the lower female genital tract in order to confirm the conviction that physical therapy alone, in agreement with some findings reported in the literature, is capable of guaranteeing a high cure rate in selected patients. From January 1995 to June 1996, seventy- five female patients were treated with CO2 laser vaporization for single-site genital HPV lesions, some of which were associated with low-grade intra-epithelial neoplasia. The success rate after 12 months proved to be 97%. The pre-existing clinical symptoms disappeared in all the patients treated. No complication in the vaporization procedure was encountered.

Mo-Co catalyst nanoparticles: Comparative study between TiN and Si surfaces for single-walled carbon nanotube growth

Energy Technology Data Exchange (ETDEWEB)

Morant, C., E-mail: c.morant@uam.es [Departamento de Fisica Aplicada, C-XII, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain); Campo, T. [Departamento de Fisica Aplicada, C-XII, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain); Marquez, F. [School of Science and Technology, University of Turabo, 00778-PR (United States); Domingo, C. [Instituto de Estructura de la Materia, CSIC, Serrano 123, 28006 Madrid (Spain); Sanz, J.M.; Elizalde, E. [Departamento de Fisica Aplicada, C-XII, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain)

2012-06-01

Highly pure single-walled carbon nanotubes (SWNT) were synthesized by alcohol catalytic chemical vapor deposition on silicon substrates partially covered by a thin layer of TiN. The TiN coating selectively prevented the growth of carbon nanotubes. Field emission scanning electron microscopy and Raman spectroscopy revealed the formation of high purity vertically aligned SWNT in the Si region. X-ray Photoelectron Spectroscopy and Atomic Force Microscopy indicated that Co nanoparticles are present on the Si regions, and not on the TiN regions. This clearly explains the obtained experimental results: the SWNT only grow where the Co is presented as nanoparticles, i.e. on the Si regions. - Highlights: Black-Right-Pointing-Pointer Single-wall carbon nanotubes (SWNT) ontained by catalytic chemical vapor-deposition. Black-Right-Pointing-Pointer Substrate/Co-Mo catalyst behaviour plays a key role in the SWNT growth. Black-Right-Pointing-Pointer Co nanoparticles (the effective catalyst) have been only observed on the Si region. Black-Right-Pointing-Pointer High purity SWNT were spatially confined in specific locations (Si regions). Black-Right-Pointing-Pointer TiN-coated surfaces, adjacent to a Si oxide region, prevent the growth of SWNT.

Novel synthesis of highly durable and active Pt catalyst encapsulated in nitrogen containing carbon for polymer electrolyte membrane fuel cell

Science.gov (United States)

Lee, Hyunjoon; Sung, Yung-Eun; Choi, Insoo; Lim, Taeho; Kwon, Oh Joong

2017-09-01

Novel synthesis of a Pt catalyst encapsulated in a N-containing carbon layer for use in a polymer electrolyte membrane fuel cell is described in this study. A Pt-aniline complex, formed by mixing Pt precursor and aniline monomer, was used as the source of Pt, C, and N. Heat treatment of the Pt-aniline complex with carbon black yielded 5 nm Pt nanoparticles encapsulated by a N-containing carbon layer originating from aniline carbonization. The synthesized Pt catalyst exhibited higher mass specific activity to oxygen reduction reaction than that shown by conventional Pt/C catalyst because pyridinic N with graphitic carbon in the carbon layer provided active sites for oxygen reduction reaction in addition to those provided by Pt. In single cell testing, initial performance of the synthesized catalyst was limited because the thick catalyst layer increased resistance related to mass transfer. However, it was observed that the carbon layer successfully prevented Pt nanoparticles from growing via agglomeration and Ostwald ripening under fuel cell operation, thereby improving durability. Furthermore, a mass specific performance of the synthesized catalyst higher than that of a conventional Pt/C catalyst was achieved by modifying the synthesized catalyst's layer thickness.

Metal-​based catalysts for controlled ring-​opening polymerization of macrolactones : high molecular weight and well-​defined copolymer architectures

NARCIS (Netherlands)

Bouyahyi, M.; Duchateau, R.

2014-01-01

This contribution describes our recent results regarding the metal-¿catalyzed ring-¿opening polymn. of pentadecalactone and its copolymn. with e-¿caprolactone involving single-¿site metal complexes based on aluminum, zinc, and calcium. Under the right conditions (i.e., monomer concn., catalyst type,

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

International Nuclear Information System (INIS)

Lim, Steven S.; Haller, Gary L.

2013-01-01

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

Bimetallic magnetic PtPd-nanoparticles as efficient catalyst for PAH removal from liquid media

Science.gov (United States)

Zanato, A. F. S.; Silva, V. C.; Lima, D. A.; Jacinto, M. J.

2017-11-01

Monometallic Pd- and bimetallic PtPd-nanoparticles supported on a mesoporous magnetic magnetite@silica matrix resembling a core-shell structure (Fe3O4@mSiO2) have been fabricated. The material was characterized by transmission electron microscope (TEM), high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), X-ray photoelectron spectra (XPS), energy dispersive spectroscopy (EDS) and inductively coupled plasma mass spectrometry (ICP-MS). The catalysts were applied in the removal of anthracene from liquid phase via catalytic hydrogenation. It was found that anthracene as a model compound could be completely converted into the partially hydrogenated species by the monometallic and bimetallic solids. However, during the recycling study the bimetallic material (Fe3O4@mSiO2PtPd-) showed an enhanced activity towards anthracene removal compared with the monometallic materials. A single portion of the PtPd-based catalyst can be used up to 11 times in the hydrogenation of anthracene under mild conditions (6 atm of H2, 75 °C, 20 min). Thanks to the presence of a dense magnetic core, the catalysts were capable of responding to an applied external magnetic field and once the reaction was completed, catalyst/product separation was straightforward.

Dynamics of Catalyst Nanoparticles

DEFF Research Database (Denmark)

Hansen, Thomas Willum; Cavalca, Filippo; Wagner, Jakob Birkedal

and pharmaceuticals, and the cleanup of exhaust from automobiles and stationary power plants. Sintering, or thermal deactivation, is an important mechanism for the loss of catalyst activity. In order to initiate a systematic study of the dynamics and sintering of nanoparticles, various catalytic systems have been...... under gas exposure, dynamic phenomena such as sintering and growth can be observed with sub-Ångstrøm resolution. Metal nanoparticles contain the active sites in heterogeneous catalysts, which are important for many industrial applications including the production of clean fuels, chemicals...

Radio-Frequency-Controlled Urea Dosing for NH₃-SCR Catalysts: NH₃ Storage Influence to Catalyst Performance under Transient Conditions.

Science.gov (United States)

Dietrich, Markus; Hagen, Gunter; Reitmeier, Willibald; Burger, Katharina; Hien, Markus; Grass, Philippe; Kubinski, David; Visser, Jaco; Moos, Ralf

2017-11-28

Current developments in exhaust gas aftertreatment led to a huge mistrust in diesel driven passenger cars due to their NO x emissions being too high. The selective catalytic reduction (SCR) with ammonia (NH₃) as reducing agent is the only approach today with the capability to meet upcoming emission limits. Therefore, the radio-frequency-based (RF) catalyst state determination to monitor the NH₃ loading on SCR catalysts has a huge potential in emission reduction. Recent work on this topic proved the basic capability of this technique under realistic conditions on an engine test bench. In these studies, an RF system calibration for the serial type SCR catalyst Cu-SSZ-13 was developed and different approaches for a temperature dependent NH₃ storage were determined. This paper continues this work and uses a fully calibrated RF-SCR system under transient conditions to compare different directly measured and controlled NH₃ storage levels, and NH₃ target curves. It could be clearly demonstrated that the right NH₃ target curve, together with a direct control on the desired level by the RF system, is able to operate the SCR system with the maximum possible NO x conversion efficiency and without NH₃ slip.

Iridium-catalyst-based autonomous bubble-propelled graphene micromotors with ultralow catalyst loading.

Science.gov (United States)

Wang, Hong; Sofer, Zdeněk; Eng, Alex Yong Sheng; Pumera, Martin

2014-11-10

A novel concept of an iridium-based bubble-propelled Janus-particle-type graphene micromotor with very high surface area and with very low catalyst loading is described. The low loading of Ir catalyst (0.54 at %) allows for fast motion of graphene microparticles with high surface area of 316.2 m(2)  g(-1). The micromotor was prepared with a simple and scalable method by thermal exfoliation of iridium-doped graphite oxide precursor composite in hydrogen atmosphere. Oxygen bubbles generated from the decomposition of hydrogen peroxide at the iridium catalytic sites provide robust propulsion thrust for the graphene micromotor. The high surface area and low iridium catalyst loading of the bubble-propelled graphene motors offer great possibilities for dramatically enhanced cargo delivery. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bifunctional catalysts for the direct production of liquid fuels from syngas

NARCIS (Netherlands)

Sartipi, S.

2014-01-01

Design and development of catalyst formulations that maximize the direct production of liquid fuels by combining Fischer-Tropsch synthesis (FTS), hydrocarbon cracking, and isomerization into one single catalyst particle (bifunctional FTS catalyst) have been investigated in this thesis. To achieve

Rudimentary simple, single step fabrication of nano-flakes like AgCd alloy electro-catalyst for oxygen reduction reaction in alkaline fuel cell

International Nuclear Information System (INIS)

Bhandary, Nimai; Basu, Suddhasatwa; Ingole, Pravin P.

2016-01-01

In this work, for the first time, we report rudimentary simple, single step fabrication of an electro-catalyst based on AgCd alloy nanoparticles with flakes like geometry which shows highly efficient activity towards oxygen reduction reaction (ORR). A simple potentiostatic deposition method has been employed for co-depositing AgCd alloy nanostructures with flakes like shapes along with dendrites on the surface of carbon fibre paper. The chemico-physical properties of the catalyst are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDXS). Electro-catalytic activity of AgCd alloy based electro-catalyst towards ORR is studied in alkaline medium by cyclic voltammetry and rotating ring disk electrode (RRDE) technique. Electrochemical in-situ FTIR measurements are also performed to identify the species generated during ORR process. Based on the results from electro-catalysis experiment, it is concluded that nano-alloyed AgCd electrodeposited on carbon paper shows excellent activity for ORR, following four electron pathways with H_2O_2 yield less than 15%. The combination of low cost of Ag and Cd, fast and facile method of its fabrication and higher activity towards ORR makes the AgCd electro-catalyst an attractive catalyst of choice for alkaline fuel cell.

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

International Nuclear Information System (INIS)

Britton, M.D.

1995-01-01

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

Site-Selection in Single-Molecule Junction for Highly Reproducible Molecular Electronics.

Science.gov (United States)

Kaneko, Satoshi; Murai, Daigo; Marqués-González, Santiago; Nakamura, Hisao; Komoto, Yuki; Fujii, Shintaro; Nishino, Tomoaki; Ikeda, Katsuyoshi; Tsukagoshi, Kazuhito; Kiguchi, Manabu

2016-02-03

Adsorption sites of molecules critically determine the electric/photonic properties and the stability of heterogeneous molecule-metal interfaces. Then, selectivity of adsorption site is essential for development of the fields including organic electronics, catalysis, and biology. However, due to current technical limitations, site-selectivity, i.e., precise determination of the molecular adsorption site, remains a major challenge because of difficulty in precise selection of meaningful one among the sites. We have succeeded the single site-selection at a single-molecule junction by performing newly developed hybrid technique: simultaneous characterization of surface enhanced Raman scattering (SERS) and current-voltage (I-V) measurements. The I-V response of 1,4-benzenedithiol junctions reveals the existence of three metastable states arising from different adsorption sites. Notably, correlated SERS measurements show selectivity toward one of the adsorption sites: "bridge sites". This site-selectivity represents an essential step toward the reliable integration of individual molecules on metallic surfaces. Furthermore, the hybrid spectro-electric technique reveals the dependence of the SERS intensity on the strength of the molecule-metal interaction, showing the interdependence between the optical and electronic properties in single-molecule junctions.

A phenyl-sulfonic acid anchored carbon-supported platinum catalyst for polymer electrolyte fuel cell electrodes

International Nuclear Information System (INIS)

Selvarani, G.; Sahu, A.K.; Choudhury, N.A.; Sridhar, P.; Pitchumani, S.; Shukla, A.K.

2007-01-01

A method, to anchor phenyl-sulfonic acid functional groups with the platinum catalyst supported onto a high surface-area carbon substrate, is reported. The use of the catalyst in the electrodes of a polymer electrolyte fuel cell (PEFC) helps enhancing its performance. Characterization of the catalyst by Fourier transform infra red (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and point-of-zero-charge (PZC) studies suggests that the improvement in performance of the PEFC is facilitated not only by enlarging the three-phase boundary in the catalyst layer but also by providing ionic-conduction paths as well as by imparting negative charge to platinum sites with concomitant oxidation of sulfur present in the carbon support. It is argued that the negatively charged platinum sites help repel water facilitating oxygen to access the catalyst sites. The PEFC with modified carbon-supported platinum catalyst electrodes exhibits 40% enhancement in its power density as compared to the one with unmodified carbon-supported platinum catalyst electrodes

Magnetic properties of carbon nanotubes with and without catalyst

Energy Technology Data Exchange (ETDEWEB)

Lipert, Kamil; Ritschel, Manfred; Leonhardt, Albrecht; Krupskaya, Yulia; Buechner, Bernd; Klingeler, Ruediger, E-mail: k.lipert@ifw-dresden.d [Leibniz Institute for Solid State and Materials Research (IFW) Dresden (Germany)

2010-01-01

In this paper we report on the magnetic properties of single- and multiwalled carbon nanotubes synthesized using different chemical vapour deposition methods and with variety of catalyst materials (ferromagnetic Fe, FeCo and diamagnetic Re). Different methods yield carbon nanotubes with different morphologies and different quantity of residual catalyst material. Catalyst particles are usually encapsulated in the nanotubes and influence the magnetic respond of the samples. Varying ferromagnetic properties depending on the shape, size and type of catalyst are discussed in detail. The data are compared with M(H) characteristics of carbon nanotubes without catalysts and with nonmagnetic rhenium, as a reference.

Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts.

Science.gov (United States)

Easter, Quinn T; Blum, Suzanne A

2018-02-05

Catalytic cycles are typically depicted as possessing time-invariant steps with fixed rates. Yet the true behavior of individual catalysts with respect to time is unknown, hidden by the ensemble averaging inherent to bulk measurements. Evidence is presented for variable chemical kinetics at individual catalysts, with a focus on ring-opening metathesis polymerization catalyzed by the second-generation Grubbs' ruthenium catalyst. Fluorescence microscopy is used to probe the chemical kinetics of the reaction because the technique possesses sufficient sensitivity for the detection of single chemical reactions. Insertion reactions in submicron regions likely occur at groups of many (not single) catalysts, yet not so many that their unique kinetic behavior is ensemble averaged. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Off-Site Regeneration of Hydroprocessing Catalysts Régénération hors-site de catalyseurs d'hydrotraitement

Directory of Open Access Journals (Sweden)

Dufresne P.

2006-11-01

Full Text Available This paper describes the basic phenomena occurring during oxidative regeneration of hydroprocessing catalysts, as well as laboratory experiments studying the removal of carbon and sulfur as a function of temperature. In addition, the evolution of Surface Area (SA and Dynamic Oxygen Chemisorption (DOC values versus regeneration temperature applied is discussed. DOC is used to evaluate the dispersion of the active metal-sulfide phase. DOC and SA measurements are complementary techniques for quality assurance of the regeneration process. A substantial loss of SA is found above 600°C while DOC values begin to decrease at lower temperatures. As regards combustion of C and S, it was found that carbon is readily eliminated in a single step between 300 and 450°C. The elimination of sulfur starts as low as 150°C and is terminated only at high temperatures (>600°C. The combustion of C and S, however, seems to be limited by an oxygen diffusion effect into the pores of the catalyst. The EURECAT regeneration process is described as well as an example of an industrial regeneration. Finally, the regulation aspects concerning handling and transport of spent hydroprocessing catalyst are discussed. The safety aspects for unregenerated catalysts are covered by ADR and IMDG codes, but new European legislation exists concerning waste transport including spent catalyst transport. This may result in stricter regulations concerning the transport of spent catalyst from refinery to regeneration facilities in the very near future. Les phénomènes principaux auxquels sont soumis les catalyseurs d'hydrotraitement pendant une régénération oxydante sont décrits, ainsi que des études laboratoires de l'enlèvement du carbone et du soufre en fonction de la température. La qualité du catalyseur est suivie par mesure de la surface spécifique et de la chimisorption d'oxygène (Dynamic Oxygen Chemisorption, DOC. Les mesures de DOC et de surface sont des techniques compl

Single-site neural tube closure in human embryos revisited.

Science.gov (United States)

de Bakker, Bernadette S; Driessen, Stan; Boukens, Bastiaan J D; van den Hoff, Maurice J B; Oostra, Roelof-Jan

2017-10-01

Since the multi-site closure theory was first proposed in 1991 as explanation for the preferential localizations of neural tube defects, the closure of the neural tube has been debated. Although the multi-site closure theory is much cited in clinical literature, single-site closure is most apparent in literature concerning embryology. Inspired by Victor Hamburgers (1900-2001) statement that "our real teacher has been and still is the embryo, who is, incidentally, the only teacher who is always right", we decided to critically review both theories of neural tube closure. To verify the theories of closure, we studied serial histological sections of 10 mouse embryos between 8.5 and 9.5 days of gestation and 18 human embryos of the Carnegie collection between Carnegie stage 9 (19-21 days) and 13 (28-32 days). Neural tube closure was histologically defined by the neuroepithelial remodeling of the two adjoining neural fold tips in the midline. We did not observe multiple fusion sites in neither mouse nor human embryos. A meta-analysis of case reports on neural tube defects showed that defects can occur at any level of the neural axis. Our data indicate that the human neural tube fuses at a single site and, therefore, we propose to reinstate the single-site closure theory for neural tube closure. We showed that neural tube defects are not restricted to a specific location, thereby refuting the reasoning underlying the multi-site closure theory. Clin. Anat. 30:988-999, 2017. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

The role of reaction pathways and support interactions in the development of high activity hydrotreating catalysts

DEFF Research Database (Denmark)

Topsøe, Henrik; Hinnemann, Berit; Nørskov, Jens Kehlet

2005-01-01

structures may be present as single sulfide sheets. Thus, stacking is not an essential feature of Type II catalysts. The article illustrates how the new scientific insight has aided the introduction of the new high activity BRIM (TM) type catalysts for FCC pre-treatment and production of ultra low sulfur...... exhibiting a metallic character are observed to be involved in adsorption, hydrogenation and C-S bond cleavage. The insight is seen to provide a new framework for understanding the DDS and HYD pathways and the role of steric hindrance and poisons. Density functional theory (DFT) calculations have illustrated...... how support interactions may influence the activity of sulfided catalysts. The brim sites and the tendency to form vacancies are seen to differ in types I and II Co-Mo-S. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) studies show that the high activity Type II...

Use of ionic liquids as coordination ligands for organometallic catalysts

Science.gov (United States)

Li, Zaiwei [Moreno Valley, CA; Tang, Yongchun [Walnut, CA; Cheng,; Jihong, [Arcadia, CA

2009-11-10

Aspects of the present invention relate to compositions and methods for the use of ionic liquids with dissolved metal compounds as catalysts for a variety of chemical reactions. Ionic liquids are salts that generally are liquids at room temperature, and are capable of dissolving a many types of compounds that are relatively insoluble in aqueous or organic solvent systems. Specifically, ionic liquids may dissolve metal compounds to produce homogeneous and heterogeneous organometallic catalysts. One industrially-important chemical reaction that may be catalyzed by metal-containing ionic liquid catalysts is the conversion of methane to methanol.

Controlling Structural Characteristics of Single-Walled Carbon Nanotubes (SWNT) by Tailoring Catalyst Composition and Synthesis Conditions

International Nuclear Information System (INIS)

Resasco, Daniel E.

2010-01-01

This report shows the extensive research on the mechanism responsible for the formation of single walled carbon nanotubes in order to get control over their structural parameters (diameter and chirality). Catalyst formulations, pre-treatment conditions, and reaction conditions are described in detail as well as mechanisms to produce nanotubes structures of specific arrays (vertical forest, nanotube pillars). Applications of SWNT in different fields are also described in this report. In relation to this project five students have graduated (3 PhD and 2 MS) and 35 papers have been published.

Catalyst Design Using Nanoporous Iron for the Chemical Vapor Deposition Synthesis of Single-Walled Carbon Nanotubes

Directory of Open Access Journals (Sweden)

Tarek M. Abdel-Fattah

2013-01-01

Full Text Available Single-walled carbon nanotubes (SWNTs have been synthesized via a novel chemical vapor deposition (CVD approach utilizing nanoporous, iron-supported catalysts. Stable aqueous dispersions of the CVD-grown nanotubes using an anionic surfactant were also obtained. The properties of the as-produced SWNTs were characterized through atomic force microscopy and Raman spectroscopy and compared with purified SWNTs produced via the high-pressure CO (HiPCO method as a reference, and the nanotubes were observed with greater lengths than those of similarly processed HiPCO SWNTs.

The acidic properties of mixed tin and antimony oxide catalysts

Energy Technology Data Exchange (ETDEWEB)

Irving, E.A.; Taylor, D.

1978-01-01

The acidic properties of mixed tin + antimony oxide catalysts were studied in the isomerization of 3,3-dimethyl-1-butene, cyclopropane, 1-butene, and cis-2-butene and the dehydration of isopropanol over the mixed oxides outgassed at room temperature and 698/sup 0/K. Only the zero-order portions of the reaction were used for calculations. With catalysts outgassed at room temperature, weakly acidic sites were present, and all the reactions probably occurred by a carbonium ion mechanism with Broensted acid sites as a source of protons. The rates increased with increasing antimony content to a maximum at approx. 50 at. % and then decreased with further increase in the antimony content. Outgassing of the catalysts at 698/sup 0/K increased the isomerization rate of 3,3-dimethyl-1-butene, but decreased those for cyclopropane and isopropanol due to poisoning by the propylene produced. For 1-butene and cis-2-butene and catalysts outgassed at 698/sup 0/K, only catalysts with less than 50Vertical Bar3< antimony were active. The catalysts were poisoned by treatment with bases or with sodium acetate. A proposed correlation between rates and acidity led to the conclusion that the catalyst composition corresponding to maximum acidity differs from that for maximum selective oxidation activity. Graphs and 10 references.

Surface tailored single walled carbon nanotubes as catalyst support for direct methanol fuel cell

Science.gov (United States)

Kireeti, Kota V. M. K.; Jha, Neetu

2017-10-01

A strategy for tuning the surface property of Single Walled Carbon Nanotubes (SWNTs) for enhanced methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) along with methanol tolerance is presented. The surface functionality is tailored using controlled acid and base treatment. Acid treatment leads to the attachment of carboxylic carbon (CC) fragments to SWNT making it hydrophilic (P3-SWNT). Base treatment of P3-SWNT with 0.05 M NaOH reduces the CCs and makes it hydrophobic (P33-SWNT). Pt catalyst supported on the P3-SWNT possesses enhanced MOR whereas that supported on P33-SWNT not only enhances ORR kinetics but also possess good tolerance towards methanol oxidation as verified by the electrochemical technique.

Time-over-threshold readout to enhance the high flux capabilities of single-photon-counting detectors

International Nuclear Information System (INIS)

Bergamaschi, Anna; Dinapoli, Roberto; Greiffenberg, Dominic; Henrich, Beat; Johnson, Ian; Mozzanica, Aldo; Radicci, Valeria; Schmitt, Bernd; Shi, Xintian; Stoppani, Laura

2011-01-01

The MYTHEN photon-counting ASIC operated in time-over-threshold mode shows an innovative approach towards the development of a detector operating with very high photon intensities while maintaining the single-photon sensitivity for synchrotron radiation experiments. The MYTHEN single-photon-counting (SPC) detector has been characterized using the time-over-threshold (ToT) readout method, i.e. measuring the time that the signal produced by the detected X-rays remains above the comparator threshold. In the following it is shown that the ToT readout preserves the sensitivity, dynamic range and capability of background suppression of the SPC mode, while enhancing the count-rate capability, which is the main limitation of state-of-the-art SPC systems

Time-over-threshold readout to enhance the high flux capabilities of single-photon-counting detectors

Energy Technology Data Exchange (ETDEWEB)

Bergamaschi, Anna, E-mail: anna.bergamaschi@psi.ch; Dinapoli, Roberto; Greiffenberg, Dominic; Henrich, Beat; Johnson, Ian; Mozzanica, Aldo; Radicci, Valeria; Schmitt, Bernd; Shi, Xintian; Stoppani, Laura [Paul Scherrer Institut, CH-5232 Villigen (Switzerland)

2011-11-01

The MYTHEN photon-counting ASIC operated in time-over-threshold mode shows an innovative approach towards the development of a detector operating with very high photon intensities while maintaining the single-photon sensitivity for synchrotron radiation experiments. The MYTHEN single-photon-counting (SPC) detector has been characterized using the time-over-threshold (ToT) readout method, i.e. measuring the time that the signal produced by the detected X-rays remains above the comparator threshold. In the following it is shown that the ToT readout preserves the sensitivity, dynamic range and capability of background suppression of the SPC mode, while enhancing the count-rate capability, which is the main limitation of state-of-the-art SPC systems.

Single-Step Electrophoretic Deposition of Non-noble Metal Catalyst Layer with Low Onset Voltage for Ethanol Electro-oxidation.

Science.gov (United States)

Ahmadi Daryakenari, Ahmad; Hosseini, Davood; Ho, Ya-Lun; Saito, Takumi; Apostoluk, Aleksandra; Müller, Christoph R; Delaunay, Jean-Jacques

2016-06-29

A single-step electrophoretic deposition (EPD) process is used to fabricate catalyst layers which consist of nickel oxide nanoparticles attached on the surface of nanographitic flakes. Magnesium ions present in the colloid charge positively the flake's surface as they attach on it and are also used to bind nanographitic flakes together. The fabricated catalyst layers showed a very low onset voltage (-0.2 V vs Ag/AgCl) in the electro-oxidation of ethanol. To clarify the occurring catalytic mechanism, we performed annealing treatment to produce samples having a different electrochemical behavior with a large onset voltage. Temperature dependence measurements of the layer conductivity pointed toward a charge transport mechanism based on hopping for the nonannealed layers, while the drift transport is observed in the annealed layers. The hopping charge transport is responsible for the appearance of the low onset voltage in ethanol electro-oxidation.

Confined-interface-directed synthesis of Palladium single-atom catalysts on graphene/amorphous carbon

DEFF Research Database (Denmark)

Xi, Jiangbo; Sun, Hongyu; Zhang, Zheye

2018-01-01

The maximized atomic efficiency of supported catalysts is highly desired in heterogeneous catalysis. Therefore, the design and development of active, stable, and atomic metal-based catalysts remains a formidable challenge. To tackle these problems, it is necessary to investigate the interaction b...

Dehydration of alcohols using solid acid catalysts

OpenAIRE

Cholerton, Mary

2014-01-01

Solid acid catalysts were prepared through silicon substitution into aluminophosphate frameworks. Silicon incorporation was confirmed using solid state nuclear magnetic resonance spectroscopy. The nature of the acid sites generated was determined using Fourier Transform infrared spectroscopy. These materials were tested as catalysts for the dehydration of ethanol to ethylene at low operating temperatures. The materials were active for dehydration of ethanol to ethylene with significant differ...

Single-atom catalysts for CO2 electroreduction with significant activity and selectivity improvements† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc03911a Click here for additional data file.

Science.gov (United States)

Back, Seoin; Lim, Juhyung; Kim, Na-Young; Kim, Yong-Hyun

2017-01-01

A single-atom catalyst (SAC) has an electronic structure that is very different from its bulk counterparts, and has shown an unexpectedly high specific activity with a significant reduction in noble metal usage for CO oxidation, fuel cell and hydrogen evolution applications, although physical origins of such performance enhancements are still poorly understood. Herein, by means of density functional theory (DFT) calculations, we for the first time investigate the great potential of single atom catalysts for CO2 electroreduction applications. In particular, we study a single transition metal atom anchored on defective graphene with single or double vacancies, denoted M@sv-Gr or M@dv-Gr, where M = Ag, Au, Co, Cu, Fe, Ir, Ni, Os, Pd, Pt, Rh or Ru, as a CO2 reduction catalyst. Many SACs are indeed shown to be highly selective for the CO2 reduction reaction over a competitive H2 evolution reaction due to favorable adsorption of carboxyl (*COOH) or formate (*OCHO) over hydrogen (*H) on the catalysts. On the basis of free energy profiles, we identified several promising candidate materials for different products; Ni@dv-Gr (limiting potential U L = –0.41 V) and Pt@dv-Gr (–0.27 V) for CH3OH production, and Os@dv-Gr (–0.52 V) and Ru@dv-Gr (–0.52 V) for CH4 production. In particular, the Pt@dv-Gr catalyst shows remarkable reduction in the limiting potential for CH3OH production compared to any existing catalysts, synthesized or predicted. To understand the origin of the activity enhancement of SACs, we find that the lack of an atomic ensemble for adsorbate binding and the unique electronic structure of the single atom catalysts as well as orbital interaction play an important role, contributing to binding energies of SACs that deviate considerably from the conventional scaling relation of bulk transition metals. PMID:28451248

Advanced Simulation Capability for Environmental Management (ASCEM): Early Site Demonstration

International Nuclear Information System (INIS)

Meza, Juan; Hubbard, Susan; Freshley, Mark D.; Gorton, Ian; Moulton, David; Denham, Miles E.

2011-01-01

The U.S. Department of Energy Office of Environmental Management, Technology Innovation and Development (EM-32), is supporting development of the Advanced Simulation Capability for Environmental Management (ASCEM). ASCEM is a state-of-the-art scientific tool and approach for understanding and predicting contaminant fate and transport in natural and engineered systems. The modular and open source high performance computing tool will facilitate integrated approaches to modeling and site characterization that enable robust and standardized assessments of performance and risk for EM cleanup and closure activities. As part of the initial development process, a series of demonstrations were defined to test ASCEM components and provide feedback to developers, engage end users in applications, and lead to an outcome that would benefit the sites. The demonstration was implemented for a sub-region of the Savannah River Site General Separations Area that includes the F-Area Seepage Basins. The physical domain included the unsaturated and saturated zones in the vicinity of the seepage basins and Fourmile Branch, using an unstructured mesh fit to the hydrostratigraphy and topography of the site. The calculations modeled variably saturated flow and the resulting flow field was used in simulations of the advection of non-reactive species and the reactive-transport of uranium. As part of the demonstrations, a new set of data management, visualization, and uncertainty quantification tools were developed to analyze simulation results and existing site data. These new tools can be used to provide summary statistics, including information on which simulation parameters were most important in the prediction of uncertainty and to visualize the relationships between model input and output.

Pt Nanostructures/N-Doped Carbon hybrid, an Efficient Catalyst for Hydrogen Evolution/Oxidation Reactions: Enhancing its Base Media Activity through Bifunctionality of the Catalyst.

Science.gov (United States)

Barman, Sudip; Kundu, Manas; Bhowmik, Tanmay; Mishra, Ranjit

2018-06-04

Design and synthesis of active catalyst for HER/HOR are important for the development of hydrogen based renewable technologies. We report synthesis of Pt nanostructures-N-doped carbon hybrid (Pt-(PtO2)-NSs/C) for HER/HOR applications. The HER activity of this Pt-(PtOx)-NSs/C catalyst is 4 and 6.5 times better than commercial Pt/C in acid and base. The catalyst exhibits a current density of 10 mA/cm2 at overpotentials of 5 and 51 mV with tafel slopes of 29 and 64mV/dec in in 0.5 M H2SO4 and 0.5 M KOH. This catalyst also showed superior HOR activity at all pH values. The HER/HOR activity of Pt-(PtOx)-NSs/C and PtOx-free Pt-Nanostructures/C (PtNSs/C) catalysts are comparable in acid. The presence of PtOx in Pt-(PtOx)-NSs/C makes this Pt-catalyst more HER/HOR active in base media. The activity of Pt-(PtOx)NSs/C catalyst is 5 fold higher than that of PtNSs/C catalyst in basic medium although their activity is comparable in acid. Hydrogen binding energy and oxophilicity are the two equivalent descriptors for HER/HOR in basic media. We propose a bi-functional mechanism for the enhanced alkaline HER/HOR activity of Pt(PtOx)-NSs/C catalyst. In bi-functional Pt-(PtOx)-NSs/C catalyst, PtOx provide an active site for OH- adsorption to form OHads which reacts with hydrogen intermediate (Hads), present at neighbouring Pt sites to form H2O leading to enhancement of HOR activity in basic medium This work may provide opportunity to develop catalysts for various renewable energy technologies. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coke formation on hydrodesulphurization catalysts. [Including effects of different promoters

Energy Technology Data Exchange (ETDEWEB)

Ternan, M.; Furimsky, E.; Parsons, B.I.

1979-02-01

The extent of coke formation was measured on a number of different hydrodesulfurization catalysts, primarily as a function of the catalyst chemical composition. Variations in the concentration of MoO/sub 3/ on the alumina, the type of catalyst promoter, the promoter/MoO/sub 3/ ratio, the presulfiding material and the reaction temperature were made. Increases in the reaction rate caused by either changes in the catalyst composition or by moderate changes in the reaction temperature were compared to the catalyst coke content. It was suggested that two types of coke were present on the catalyst, a reactive coke which is subsequently converted to reaction products and an unreactive coke which blocks catalytic sites.

Critical Surface Parameters for the Oxidative Coupling of Methane over the Mn-Na-W/SiO2 Catalyst.

Science.gov (United States)

Hayek, Naseem S; Lucas, Nishita S; Warwar Damouny, Christine; Gazit, Oz M

2017-11-22

The work here presents a thorough evaluation of the effect of Mn-Na-W/SiO 2 catalyst surface parameters on its performance in the oxidative coupling of methane (OCM). To do so, we used microporous dealuminated β-zeolite (Zeo), or mesoporous SBA-15 (SBA), or macroporous fumed silica (Fum) as precursors for catalyst preparation, together with Mn nitrate, Mn acetate and Na 2 WO 4 . Characterizing the catalysts by inductively coupled plasma-optical emission spectroscopy, N 2 physisorption, X-ray diffraction, high-resolution scanning electron microscopy-energy-dispersive spectroscopy, X-ray photoelectron spectroscopy, and catalytic testing enabled us to identify critical surface parameters that govern the activity and C 2 selectivity of the Mn-Na-W/SiO 2 catalyst. Although the current paradigm views the phase transition of silica to α-cristobalite as the critical step in obtaining dispersed and stable metal sites, we show that the choice of precursors is equally or even more important with respect to tailoring the right surface properties. Specifically, the SBA-based catalyst, characterized by relatively closed surface porosity, demonstrated low activity and low C 2 selectivity. By contrast, for the same composition, the Zeo-based catalyst showed an open surface pore structure, which translated up to fourfold higher activity and enhanced selectivity. By varying the overall composition of the Zeo catalysts, we show that reducing the overall W concentration reduces the size of the Na 2 WO 4 species and increases the catalytic activity linearly as much as fivefold higher than the SBA catalyst. This linear dependence correlates well to the number of interfaces between the Na 2 WO 4 and Mn 2 O 3 species. Our results combined with prior studies lead us to single out the interface between Na 2 WO 4 and Mn 2 O 3 as the most probable active site for OCM using this catalyst. Synergistic interactions between the various precursors used and the phase transition are discussed in

CO Reduction to CH3OSiMe3: Electrophile-Promoted Hydride Migration at a Single Fe Site.

Science.gov (United States)

Deegan, Meaghan M; Peters, Jonas C

2017-02-22

One of the major challenges associated with developing molecular Fischer-Tropsch catalysts is the design of systems that promote the formation of C-H bonds from H 2 and CO while also facilitating the release of the resulting CO-derived organic products. To this end, we describe the synthesis of reduced iron-hydride/carbonyl complexes that enable an electrophile-promoted hydride migration process, resulting in the reduction of coordinated CO to a siloxymethyl (L n Fe-CH 2 OSiMe 3 ) group. Intramolecular hydride-to-CO migrations are extremely rare, and to our knowledge the system described herein is the first example where such a process can be accessed from a thermally stable M(CO)(H) complex. Further addition of H 2 to L n Fe-CH 2 OSiMe 3 releases CH 3 OSiMe 3 , demonstrating net four-electron reduction of CO to CH 3 OSiMe 3 at a single Fe site.

Stability investigation of a high number density Pt1/Fe2O3 single-atom catalyst under different gas environments by HAADF-STEM

Science.gov (United States)

Duan, Sibin; Wang, Rongming; Liu, Jingyue

2018-05-01

Catalysis by supported single metal atoms has demonstrated tremendous potential for practical applications due to their unique catalytic properties. Unless they are strongly anchored to the support surfaces, supported single atoms, however, are thermodynamically unstable, which poses a major obstacle for broad applications of single-atom catalysts (SACs). In order to develop strategies to improve the stability of SACs, we need to understand the intrinsic nature of the sintering processes of supported single metal atoms, especially under various gas environments that are relevant to important catalytic reactions. We report on the synthesis of high number density Pt1/Fe2O3 SACs using a facial strong adsorption method and the study of the mobility of these supported Pt single atoms at 250 °C under various gas environments that are relevant to CO oxidation, water–gas shift, and hydrogenation reactions. Under the oxidative gas environment, Fe2O3 supported Pt single atoms are stable even at high temperatures. The presence of either CO or H2 molecules in the gas environment, however, facilitates the movement of the Pt atoms. The strong interaction between CO and Pt weakens the binding between the Pt atoms and the support, facilitating the movement of the Pt single atoms. The dissociation of H2 molecules on the Pt atoms and their subsequent interaction with the oxygen species of the support surfaces dislodge the surface oxygen anchored Pt atoms, resulting in the formation of Pt clusters. The addition of H2O molecules to the CO or H2 significantly accelerates the sintering of the Fe2O3 supported Pt single atoms. An anchoring-site determined sintering mechanism is further proposed, which is related to the metal–support interaction.

Synthesis and characterization of Cu-MFI catalyst for the direct medium temperature range NO decomposition

Directory of Open Access Journals (Sweden)

Valkaj Karolina Maduna

2016-03-01

Full Text Available In this study the physico-chemical and catalytic properties of copper bearing MFI zeolites (Cu-MFI with different Si/Al and Si/Cu ratios were investigated. Two different methods for incorporation of metal ions into the zeolite framework were used: the ion exchange from the solution of copper acetate and the direct hydrothermal synthesis. Direct synthesis of a zeolite in the presence of copper-phosphate complexes was expected to generate more active copper species necessary for the desired reaction than the conventional ion exchange method. Direct decomposition of NO was used as a model reaction, because this reaction still offers a very attractive approach to NOX removal. The catalytic properties of zeolite samples were studied using techniques, such as XRD, SEM, EPR and nitrogen adsorption/desorption measurements at 77 K. Results of the kinetic investigation revealed that both methods are applicable for the preparation of the catalysts with active sites capable of catalyzing the NO decomposition. It was found out that Cu-MFI zeolites obtained through direct synthesis are promising catalysts for NO decomposition, especially at lower reaction temperatures. The efficiency of the catalysts prepared by both methods is compared and discussed.

Intrinsic Activity of MnOx-CeO2 Catalysts in Ethanol Oxidation

Directory of Open Access Journals (Sweden)

Dimitrios Delimaris

2017-11-01

Full Text Available MnOx-CeO2 mixed oxides are considered efficient oxidation catalysts superior to the corresponding single oxides. Although these oxides have been the subject of numerous studies, their fundamental performance indicators, such as turnover frequency (TOF or specific activity, are scarcely reported. The purpose of the present work is to investigate the effect of catalyst composition on the concentration of active sites and intrinsic activity in ethanol oxidation by the employment of temperature-programmed desorption and oxidation of isotopically-labelled ethanol, 12CH313CH2OH. The transformation pathways of preadsorbed ethanol in the absence of gaseous oxygen refer to dehydrogenation to acetaldehyde followed by its dissociation combined with oxidation by lattice oxygen. In the presence of gaseous oxygen, lattice oxygen is rapidly restored and the main products are acetaldehyde, CO2, and water. CO2 forms less easily on mixed oxides than on pure MnOx. The TOF of ethanol oxidation has been calculated assuming that the amount of adsorbed ethanol and CO2 produced during temperature-programmed oxidation (TPO is a reliable indicator of the concentration of the active sites.

Single site laparoscopic right hemicolectomy: an oncological feasible option

Directory of Open Access Journals (Sweden)

Lim Yon Kuei

2010-09-01

Full Text Available Abstract Introduction We present the first 7 cases of single site right hemicolectomy in Asia using the new Single Site Laparoscopy (SSL access system from Ethicon Endo-surgery. Methods Right hemicolectomy was performed using the new Single Site Laparoscopy (SSL access system. Patient demographics, operative time, histology and post operative recovery and complications were collected and analysed. Results The median operative time was 90 mins (range 60 - 150 mins and a median wound size of 2.5 cm (range 2 to 4.5 cm. The median number of lymph nodes harvested was 24 (range 20 to 34 lymph nodes. The median length of proximal margin was 70 mm (range 30 to 145 mm and that of distal margin was 50 mm (35 to 120 mm. All patients had a median hospital stay of 7 days (range 5 to 11 and there were no significant perioperative complications except for 1 patient who had a minor myocardial event. Conclusion Right hemicolectomy using SSL access system is feasible and safe for oncologic surgery.

Esterification of Palmitic Acid with Methanol in the Presence of Macroporous Ion Exchange Resin as Catalyst

Directory of Open Access Journals (Sweden)

Amelia Qarina Yaakob and Subhash Bhatia

2012-10-01

Full Text Available The esterification of palmitic acid with methanol was studied in a batch reactor using macro porous ion exchange resin Amberlyst 15 as a catalyst. Methyl palmitate was produced from the reaction between palmitic acid and methanol in the presence of catalyst. The effects of processing parameters, molar ratio of alcohol to acid M, (4-10, catalyst loading (0-10 g cat/liter, water inhibition (0-2 mol/liter, agitator speed (200-800 rpm and reaction temperature (343-373K were studied. The experimental kinetic data were correlated using homogenous as well as heterogeneous models (based on single as well as dual site mechanisms. The activation energy of the reaction was 11.552 kJ/mol for forward reaction whilst 5.464 kJ/mol for backward reaction. The experimental data fitted well with the simulated data obtained from the kinetic models. Keywords: Palmitic Acid, Methanol, Esterification, Ion Exchange Resin, Kinetics.

In-situ environmental (scanning) transmission electron microscopy of catalysts at the atomic level

International Nuclear Information System (INIS)

Gai, P L; Boyes, E D

2014-01-01

Observing reacting single atoms on the solid catalyst surfaces under controlled reaction conditions is a key goal in understanding and controlling heterogeneous catalytic reactions. In-situ real time aberration corrected environmental (scanning) transmission electron microscopy (E(S)TEM permit the direct imaging of dynamic surface and sub-surface structures of reacting catalysts. In this paper in-situ AC ETEM and AC ESTEM studies under controlled reaction environments of oxide catalysts and supported metal nanocatalysts important in chemical industry are presented. They provide the direct evidence of dynamic processes at the oxide catalyst surface at the atomic scale and single atom dynamics in catalytic reactions. The ESTEM studies of single atom dynamics in controlled reaction environments show that nanoparticles act as reservoirs of ad-atoms. The results have important implications in catalysis and nanoparticle studies

Graphene Carbon Nanotube Carpets Grown Using Binary Catalysts for High-Performance Lithium-Ion Capacitors.

Science.gov (United States)

Salvatierra, Rodrigo Villegas; Zakhidov, Dante; Sha, Junwei; Kim, Nam Dong; Lee, Seoung-Ki; Raji, Abdul-Rahman O; Zhao, Naiqin; Tour, James M

2017-03-28

Here we show that a versatile binary catalyst solution of Fe 3 O 4 /AlO x nanoparticles enables homogeneous growth of single to few-walled carbon nanotube (CNT) carpets from three-dimensional carbon-based substrates, moving past existing two-dimensional limited growth methods. The binary catalyst is composed of amorphous AlO x nanoclusters over Fe 3 O 4 crystalline nanoparticles, facilitating the creation of seamless junctions between the CNTs and the underlying carbon platform. The resulting graphene-CNT (GCNT) structure is a high-density CNT carpet ohmically connected to the carbon substrate, an important feature for advanced carbon electronics. As a demonstration of the utility of this approach, we use GCNTs as anodes and cathodes in binder-free lithium-ion capacitors, producing stable devices with high-energy densities (∼120 Wh kg -1 ), high-power density capabilities (∼20,500 W kg -1 at 29 Wh kg -1 ), and a large operating voltage window (4.3 to 0.01 V).

Uncooled Radiation Hard SiC Schottky VUV Detectors Capable of Single Photon Sensing, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — This project seeks to design, fabricate, characterize and commercialize very large area, uncooled and radiative hard 4H-SiC VUV detectors capable of near single...

Advanced Aqueous Phase Catalyst Development using Combinatorial Methods, Phase II

Data.gov (United States)

National Aeronautics and Space Administration — Combinatorial methods are proposed to develop advanced Aqueous Oxidation Catalysts (AOCs) with the capability to mineralize organic contaminants present in effluents...

Characterization of three-way automotive catalysts

Energy Technology Data Exchange (ETDEWEB)

Kenik, E.A.; More, K.L. [Oak Ridge National Lab., TN (United States); LaBarge, W. [Delphi Automotive Systems, Flint, MI (United States)] [and others

1997-04-01

The CRADA between Delphi Automotive Systems (Delphi; formerly General Motors - AC Delco, Systems) and Lockheed Martin Energy Research (LMER) on automotive catalysts was completed at the end of FY96, after a ten month, no-cost extension. The CRADA was aimed at improved performance and lifetime of noble metal based three-way-catalysts (TWC), which are the primary catalytic system for automotive emission control systems. While these TWC can meet the currently required emission standards, higher than optimum noble metal loadings are often required to meet lifetime requirements. In addition, more stringent emission standards will be imposed in the near future, demanding improved performance and service life from these catalysts. Understanding the changes of TWC conversion efficiency with ageing is a critical need in improving these catalysts. Initially in a fresh catalyst, the active material is often distributed on a very fine scale, approaching single atoms or small atomic clusters. As such, a wide range of analytical techniques have been employed to provide high spatial resolution characterization of the evolving state of the catalytic material.

High aspect ratio catalytic reactor and catalyst inserts therefor

Science.gov (United States)

Lin, Jiefeng; Kelly, Sean M.

2018-04-10

The present invention relates to high efficient tubular catalytic steam reforming reactor configured from about 0.2 inch to about 2 inch inside diameter high temperature metal alloy tube or pipe and loaded with a plurality of rolled catalyst inserts comprising metallic monoliths. The catalyst insert substrate is formed from a single metal foil without a central supporting structure in the form of a spiral monolith. The single metal foil is treated to have 3-dimensional surface features that provide mechanical support and establish open gas channels between each of the rolled layers. This unique geometry accelerates gas mixing and heat transfer and provides a high catalytic active surface area. The small diameter, high aspect ratio tubular catalytic steam reforming reactors loaded with rolled catalyst inserts can be arranged in a multi-pass non-vertical parallel configuration thermally coupled with a heat source to carry out steam reforming of hydrocarbon-containing feeds. The rolled catalyst inserts are self-supported on the reactor wall and enable efficient heat transfer from the reactor wall to the reactor interior, and lower pressure drop than known particulate catalysts. The heat source can be oxygen transport membrane reactors.

Relating FTS Catalyst Properties to Performance

Science.gov (United States)

Ma, Wenping; Ramana Rao Pendyala, Venkat; Gao, Pei; Jermwongratanachai, Thani; Jacobs, Gary; Davis, Burton H.

2016-01-01

During the reporting period June 23, 2011 to August 31, 2013, CAER researchers carried out research in two areas of fundamental importance to the topic of cobalt-based Fischer-Tropsch Synthesis (FTS): promoters and stability. The first area was research into possible substitute promoters that might be used to replace the expensive promoters (e.g., Pt, Re, and Ru) that are commonly used. To that end, three separate investigations were carried out. Due to the strong support interaction of ?-Al2O3 with cobalt, metal promoters are commonly added to commercial FTS catalysts to facilitate the reduction of cobalt oxides and thereby boost active surface cobalt metal sites. To date, the metal promoters examined have been those up to and including Group 11. Because two Group 11 promoters (i.e., Ag and Au) were identified to exhibit positive impacts on conversion, selectivity, or both, research was undertaken to explore metals in Groups 12 - 14. The three metals selected for this purpose were Cd, In, and Sn. At a higher loading of 25%Co on alumina, 1% addition of Cd, In, or Sn was found to-on average-facilitate reduction by promoting a heterogeneous distribution of cobalt consisting of larger lesser interacting cobalt clusters and smaller strongly interacting cobalt species. The lesser interacting species were identified in TPR profiles, where a sharp low temperature peak occurred for the reduction of larger, weakly interacting, CoO species. In XANES, the Cd, In, and Sn promoters were found to exist as oxides, whereas typical promoters (e.g., Re, Ru, Pt) were previously determined to exist in an metallic state in atomic coordination with cobalt. The larger cobalt clusters significantly decreased the active site density relative to the unpromoted 25%Co/Al2O3 catalyst. Decreasing the cobalt loading to 15%Co eliminated the large non-interacting species. The TPR peak for reduction of strongly interacting CoO in the Cd promoted catalyst occurred at a measurably lower temperature

Synthesis of MoVTeNb Oxide Catalysts with Tunable Particle Dimensions

DEFF Research Database (Denmark)

Kolenko, Yury V.; Zhang, Wei; d'Alnoncourt, Raoul Naumann

2011-01-01

Reliable procedures for the controlled synthesis of phase-pure MoVTeNb mixed oxides with M1 structure (ICSD 55097) and tunable crystal dimensions were developed to study the structure sensitivity of the selective oxidation of propane to acrylic acid. A series of powdered M1 catalysts...... catalysts were studied in the selective oxidation of propane to acrylic acid, revealing that active sites appear on the entire M1 surface and illustrating the high sensitivity of catalyst performance on the catalyst synthesis method....

Overcoming the Instability of Nanoparticle-Based Catalyst Films in Alkaline Electrolyzers by using Self-Assembling and Self-Healing Films

NARCIS (Netherlands)

Barwe, Stefan; Masa, Justus; Andronescu, Corina; Mei, Bastian; Schuhmann, Wolfgang; Ventosa, Edgar

2017-01-01

Engineering stable electrodes using highly active catalyst nanopowders for electrochemical water splitting remains a challenge. We report an innovative and general approach for attaining highly stable catalyst films with self-healing capability based on the in situ self-assembly of catalyst

CATALYTIC PERFORMANCES OF Fe2O3/TS-1 CATALYST IN PHENOL HYDROXYLATION REACTION

Directory of Open Access Journals (Sweden)

Didik Prasetyoko

2010-07-01

Full Text Available Hydroxylation reaction of phenol into diphenol, such as hydroquinone and catechol, has a great role in many industrial applications. Phenol hydroxylation reaction can be carried out using Titanium Silicalite-1 (TS-1 as catalyst and H2O2 as an oxidant. TS-1 catalyst shows high activity and selectivity for phenol hydroxylation reaction. However, its hydrophobic sites lead to slow H2O2 adsorption toward the active site of TS-1. Consequently, the reaction rate of phenol hydroxylation reaction is tends to be low. Addition of metal oxide Fe2O3 enhanced hydrophilicity of TS-1 catalyst. Liquid phase catalytic phenol hydroxylation using hydrogen peroxide as oxidant was carried out over iron (III oxide-modified TS-1 catalyst (Fe2O3/TS-1, that were prepared by impregnation method using iron (III nitrate as precursor and characterized by X-ray diffraction, infrared spectroscopy, nitrogen adsorption, pyridine adsorption, and hydrophilicity techniques. Catalysts 1Fe2O3/TS-1 showed maximum catalytic activity of hydroquinone product. In this research, the increase of hydroquinone formation rate is due to the higher hydrophilicity of Fe2O3/TS-1 catalysts compare to the parent catalyst, TS-1.   Keywords: Fe2O3/TS-1, hydrophilic site, phenol hydroxylation

Catalytic hydroprocessing of simulated coal tars. 2. Effect of acid catalysts on the hydroconversion of model compounds on a sulphided Ni-Mo/Al/sub 2/O/sub 3/ catalyst

Energy Technology Data Exchange (ETDEWEB)

Lemberton, J.L.; Touzeyidio, M.; Guisnet, M. (Laboratoire de Catalyse en Chimie Organique CNRS, Poitiers (France))

1989-09-15

Acid catalysts were added to sulphided Ni-Mo/Al/sub 2/O/sub 3/ catalyst in order to obtain a higher hydrocracking activity. The hydroconversion of phenanthrene, alone or in the presence of carbazole and/or 1-naphthol, was chosen as a model reaction. The presence of acid catalysts greatly increases the conversion of phenanthrene and allows significant amounts of light products to be obtained. In the presence of carbazole or of 1-naphthol, acid catalysts create a small increase in phenanthrene conversion, but light products are no longer obtained as the acid sites are poisoned either by adsorption of ammonia from carbazole decomposition, or by extensive coke deposition generated from 1-naphthol. In the presence of carbazole and 1-naphthol, there is no longer any effect of the acid catalysts on the hydroconversion of phenanthrene, owing to complete inhibition of the acid sites. 12 refs., 5 tabs.

Sustainable Applications of Magnetic Nano-catalysts and Graphitic Carbon Nitrides (presentation)

Science.gov (United States)

Homogeneous catalysts, known for chemo-, regio- and enantioselectivity, have better contact with the reactants but the catalyst separation creates barriers. Heterogeneous systems enable better separation although at the cost of reduction in the availability of active sites. Becau...

Electron beam application for regeneration of catalysts used in refinery cracking units

International Nuclear Information System (INIS)

Kondo, Fernando Mantovani; Duarte, Celina Lopes; Sato, Ivone Mulako; Salvador, Vera Lucia Ribeiro; Calvo, Wilson Aparecido Parejo

2013-01-01

A catalyst is a substance that alters the rate of a reaction. The process of catalysis is essential to the modern day manufacturing industry, mainly in Fluid Catalytic Cracking Process (FCC) units. However, long-term exploitation of oil and gas processing catalysts leads to formation of carbon-and sulfur-containing structures of coke and dense products on the catalyst surface. They block reactive catalyst sites and reduce the catalytic activity. The main advantage of radiation processing by electron beam (EB) and gamma rays is chain cracking reaction in crude oil. Otherwise, under exposure to ionic radiation, considerable structure modification of equilibrium silica-alumina catalyst from FCC process may occur, in addition to the removal of impurities. The conditions applied in the irradiation range (20-150 kGy) of gamma rays and electron beam were not sufficient to alter the structure of the catalyst, whether for removal of the contaminant nickel, a major contaminant of the FCC catalyst, either to rupture of the crystalline structure either for the future reutilization of chemical elements. Attenuated Total Reflectance - Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Energy Dispersive X-Ray Fluorescence Spectrometry (EDXRFS) analysis were used to characterize and evaluate effects of radiation processing on equilibrium catalysts purification. To evaluate and comprehend the reactive catalyst sites, Scanning Electron Microscopy (SEM) and particle size distribution analyses were carried out. (author)

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

Institute of Scientific and Technical Information of China (English)

李阳; 刘云龙; 穆曼曼; 陈立功

2015-01-01

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

Titanium Dioxide as a Catalyst Support in Heterogeneous Catalysis

Science.gov (United States)

Bagheri, Samira; Muhd Julkapli, Nurhidayatullaili; Bee Abd Hamid, Sharifah

2014-01-01

The lack of stability is a challenge for most heterogeneous catalysts. During operations, the agglomeration of particles may block the active sites of the catalyst, which is believed to contribute to its instability. Recently, titanium oxide (TiO2) was introduced as an alternative support material for heterogeneous catalyst due to the effect of its high surface area stabilizing the catalysts in its mesoporous structure. TiO2 supported metal catalysts have attracted interest due to TiO2 nanoparticles high activity for various reduction and oxidation reactions at low pressures and temperatures. Furthermore, TiO2 was found to be a good metal oxide catalyst support due to the strong metal support interaction, chemical stability, and acid-base property. The aforementioned properties make heterogeneous TiO2 supported catalysts show a high potential in photocatalyst-related applications, electrodes for wet solar cells, synthesis of fine chemicals, and others. This review focuses on TiO2 as a support material for heterogeneous catalysts and its potential applications. PMID:25383380

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.

Liquefaction of kraft lignin by hydrocracking with simultaneous use of a novel dual acid-base catalyst and a hydrogenation catalyst.

Science.gov (United States)

Wang, Jindong; Li, Wenzhi; Wang, Huizhen; Ma, Qiaozhi; Li, Song; Chang, Hou-Min; Jameel, Hasan

2017-11-01

In this study, a novel catalyst, S 2 O 8 2- -KNO 3 /TiO 2 , which has active acidic and basic sites, was prepared and used in lignin hydrocracking with a co-catalyst, Ru/C. Ru/C is an efficient hydrogenation catalyst and S 2 O 8 2- -KNO 3 /TiO 2 is a dual catalyst, which could efficiently degrade lignin. This catalytic hydrogenation system can reduce solid products to less than 1%, while giving a high liquid product yield of 93%. Catalytic hydrocracking of kraft lignin at 320°C for 6h gave 93% liquid product with 0.5% solid product. Most of this liquid product was soluble in petroleum ether (60% of 93%), which is a clear liquid and comprises mainly of monomeric and dimeric degradation products. These results demonstrated that the combination of the two catalysts is an efficient catalyst for liquefaction of lignin, with little char formation (∼1%). This concept has the potential to produce valuable chemicals and fuels from lignin under moderate conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

The dual role of local sites in assisting firms with developing technological capabilities: Evidence from China

DEFF Research Database (Denmark)

Wang, Yuandi; Zhou, Zhao

2013-01-01

.g., knowledge, human capital) and the role of motivating multinational companies (MNCs) to upgrade their local operations in developing countries so as to perform more innovation activities. Few articles are presented that examine the role of local sites in the learning and technological-capability building......, and the collaborations with local industrial community firms positively influence the relationship between firms' international inward technology licensing and technological capabilities. (C) 2012 Elsevier Ltd. All rights reserved....

Hanford Site Welding Program Successfully Providing A Single Site Function For Use By Multiple Contractors

International Nuclear Information System (INIS)

Cannell, G.R.

2009-01-01

The Department of Energy, Richland Operations (DOE-RL) recently restructured its Hanford work scope, awarding two new contracts over the past several months for a total of three contracts to manage the sites cleanup efforts. DOE-RL met with key contractor personnel prior to and during contract transition to ensure site welding activities had appropriate oversight and maintained code compliance. The transition also provided an opportunity to establish a single site-wide function that would provide welding and materials engineering services to the Hanford site contractors: CH2M HILL Plateau Remediation Company (CHPRC); Mission Support Alliance (MSA); Washington River Protection Solutions (WRPS); and Washington Closure Hanford (WCH). Over the years, multiple and separate welding programs (amongst the several contractors) existed at the Hanford site leading to inefficiencies resulting from duplication of administrative efforts, maintenance of welding procedures, welder performance certifications, etc. The new, single program eliminates these inefficiencies. The new program, co-managed by two of the sites' new contractors, the CHPRC ('owner' of the program and responsible for construction welding services) and the MSA (provides maintenance welding services), provides more than just the traditional construction and maintenance welding services. Also provided, are welding engineering, specialty welding development/qualification for the closure of radioactive materials containers and materials evaluation/failure analysis. The following describes the new Hanford site welding program.

Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers

Energy Technology Data Exchange (ETDEWEB)

Coan, Patrick D. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Ellis, Lucas D. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Griffin, Michael B. [National Bioenergy Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States; Schwartz, Daniel K. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Medlin, J. Will [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States

2018-03-01

Cooperative catalysts containing a combination of noble metal hydrogenation sites and Bronsted acid sites are critical for many reactions, including the deoxygenation (DO) of biomass-derived oxygenates in the upgrading of pyrolysis oil. One route toward the design of cooperative catalysts is to tether two different catalytically active functions so that they are in close proximity while avoiding undesirable interactions that can block active sites. Here, we deposited carboxylic acid (CA)-functionalized organophosphonate monolayers onto Al2O3-supported Pd nanoparticle catalysts to prepare bifunctional catalysts containing both Bronsted acid and metal sites. Modification with phosphonic acids (PAs) improved activity and selectivity for gas-phase DO reactions, but the degree of improvement was highly sensitive to both the presence and positioning of the CA group, suggesting a significant contribution from both the PA and CA sites. Short spacer lengths of 1-2 methylene groups between the phosphonate head and CA tail were found to yield the best DO rates and selectivities, whereas longer chains performed similarly to self-assembled monolayers having alkyl tails. Results from a combination of density functional theory and Fourier transform infrared spectroscopy suggested that the enhanced catalyst performance on the optimally positioned CAs was due to the generation of strong acid sites on the Al2O3 support adjacent to the metal. Furthermore, the high activity of these sites was found to result from a hydrogen-bonded cyclic structure involving cooperativity between the phosphonate head group and CA tail function. More broadly, these results indicate that functional groups tethered to supports via organic ligands can influence catalytic chemistry on metal nanoparticles.

Single-Phase Microgrid with Seamless Transition Capabilities between Modes of Operation

DEFF Research Database (Denmark)

Micallef, Alexander; Apap, Maurice; Spiteri-Staines, Cyril

2015-01-01

with the secondary control loops that are used to synchronize the microgrid as a single unit to the grid. Simulation results are given that show the seamless transitions between the two modes without any disconnection times for the CC-VSIs and VC-VSIs connected to the microgrid.......Microgrids are an effective way to increase the penetration of DG into the grid. They are capable of operating either in grid-connected or in islanded mode thereby increasing the supply reliability for the end user. This paper focuses on achieving seamless transitions from islanded to grid-connected...

A Study of Iron-Nitrogen-Carbon Fuel Cell Catalysts: Chemistry - Nanostructure - Performance

Science.gov (United States)

Workman, Michael J., Jr.

Fuel cells have the potential to be a pollution-free, low-cost, and energy efficient alternative to the internal combustion engine for transportation and small-scale stationary power applications. The current state of fuel cell technology has already achieved two of these three lofty goals. The remaining barrier to wide-scale deployment is the high cost, which is primarily caused by dependence on large amounts of platinum to catalyze the energy conversion reactions. To overcome this barrier and facilitate the integration of fuel cells into mainstream applications, research into a new class of catalyst materials that do not require platinum is needed. There has been a significant amount of research effort directed toward the development of platinum-group metal free (PGM-free) catalysts, yet there is a lack of consensus on both the engineering parameters necessary to improve the technology and the fundamental science that would facilitate rational design. I have engaged in research on PGM-free catalysts based on inexpensive and abundant reagents, specifically: nicarbazin and iron. Catalysts made from these precursors have previously proven to be among the best PGM-free catalysts, but their continued advancement suffered from the same lack of understanding that besets all catalysts in this class. The work I have performed address both engineering concerns and fundamental underlying principles. I present results demonstrating correlations between physical structure, chemical speciation, and synthesis parameters, as well as addressing active site chemistry and likely locations. My research presented herein introduces new morphology analysis techniques and elucidates several key structure-to-property characteristics of catalysts derived from iron and nicarbazin. I discuss the development and application of a new length-scale specific surface analysis technique that allows for analysis of well-defined size ranges from a few nm to several microns. The existing technique of

Quick Guide to Flash Catalyst

CERN Document Server

Elmansy, Rafiq

2011-01-01

How do you transform user interface designs created in Photoshop or Illustrator into interactive web pages? It's easier than you think. This guide shows you how to use Adobe Flash Catalyst to create interactive UIs and website wireframes for Rich Internet Applications-without writing a single line of code. Ideal for web designers, this book introduces Flash Catalyst basics with detailed step-by-step instructions and screenshots that illustrate every part of the process. You'll learn hands-on how to turn your static design or artwork into working user interfaces that can be implemented in Fla

Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase

Energy Technology Data Exchange (ETDEWEB)

Shan, Junjun [Department; Department; Zhang, Shiran [Department; Department; Choksi, Tej [Department; Nguyen, Luan [Department; Department; Bonifacio, Cecile S. [Department; Li, Yuanyuan [Department; Zhu, Wei [Department; Department; College; Tang, Yu [Department; Department; Zhang, Yawen [College; Yang, Judith C. [Department; Greeley, Jeffrey [Department; Frenkel, Anatoly I. [Department; Tao, Franklin [Department; Department

2016-12-05

Catalytic performance of a bimetallic catalyst is determined by geometric structure and electronic state of the surface or even the near-surface region of the catalyst. Here we report that single and sequential postsynthesis reactions of an as-synthesized bimetallic nanoparticle catalyst in one or more gas phases can tailor surface chemistry and structure of the catalyst in a gas phase, by which catalytic performance of this bimetallic catalyst can be tuned. Pt–Cu regular nanocube (Pt–Cu RNC) and concave nanocube (Pt–Cu CNC) are chosen as models of bimetallic catalysts. Surface chemistry and catalyst structure under different reaction conditions and during catalysis were explored in gas phase of one or two reactants with ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The newly formed surface structures of Pt–Cu RNC and Pt–Cu CNC catalysts strongly depend on the reactive gas(es) used in the postsynthesis reaction(s). A reaction of Pt–Cu RNC-as synthesized with H2 at 200 °C generates a near-surface alloy consisting of a Pt skin layer, a Cu-rich subsurface, and a Pt-rich deep layer. This near-surface alloy of Pt–Cu RNC-as synthesized-H2 exhibits a much higher catalytic activity in CO oxidation in terms of a low activation barrier of 39 ± 4 kJ/mol in contrast to 128 ± 7 kJ/mol of Pt–Cu RNC-as synthesized. Here the significant decrease of activation barrier demonstrates a method to tune catalytic performances of as-synthesized bimetallic catalysts. A further reaction of Pt–Cu RNC-as synthesized-H2 with CO forms a Pt–Cu alloy surface, which exhibits quite different catalytic performance in CO oxidation. It suggests the capability of generating a different surface by using another gas. The capability of tuning surface chemistry and structure of bimetallic catalysts was also demonstrated in restructuring of Pt–Cu CNC-as synthesized.

Ganoderma-Like MoS2 /NiS2 with Single Platinum Atoms Doping as an Efficient and Stable Hydrogen Evolution Reaction Catalyst.

Science.gov (United States)

Guan, Yongxin; Feng, Yangyang; Wan, Jing; Yang, Xiaohui; Fang, Ling; Gu, Xiao; Liu, Ruirui; Huang, Zhengyong; Li, Jian; Luo, Jun; Li, Changming; Wang, Yu

2018-05-27

Herein, a unique ganoderma-like MoS 2 /NiS 2 hetero-nanostructure with isolated Pt atoms anchored is reported. This novel ganoderma-like heterostructure can not only efficiently disperse and confine the few-layer MoS 2 nanosheets to fully expose the edge sites of MoS 2 , and provide more opportunity to capture the Pt atoms, but also tune the electronic structure to modify the catalytic activity. Because of the favorable dispersibility and exposed large specific surface area, single Pt atoms can be easily anchored on MoS 2 nanosheets with ultrahigh loading of 1.8 at% (the highest is 1.3 at% to date). Owing to the ganoderma-like structure and platinum atoms doping, this catalyst shows Pt-like catalytic activity for the hydrogen evolution reaction with an ultralow overpotential of 34 mV and excellent durability of only 2% increase in overpotential for 72 h under the constant current density of 10 mA cm -2 . © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pulsed laser dewetting of nickel catalyst for carbon nanofiber growth

International Nuclear Information System (INIS)

Guan, Y F; Pearce, R C; Simpson, M L; Rack, P D; Melechko, A V; Hensley, D K

2008-01-01

We present a pulsed laser dewetting technique that produces single nickel catalyst particles from lithographically patterned disks for subsequent carbon nanofiber growth through plasma enhanced chemical vapor deposition. Unlike the case for standard heat treated Ni catalyst disks, for which multiple nickel particles and consequently multiple carbon nanofibers (CNFs) are observed, single vertically aligned CNFs could be obtained from the laser dewetted catalyst. Different laser dewetting parameters were tested in this study, such as the laser energy density and the laser processing time measured by the total number of laser pulses. Various nickel disk radii and thicknesses were attempted and the resultant number of carbon nanofibers was found to be a function of the initial disk dimension and the number of laser pulses

Robotic right colectomy using the Da Vinci Single-Site® platform: case report.

Science.gov (United States)

Morelli, Luca; Guadagni, Simone; Caprili, Giovanni; Di Candio, Giulio; Boggi, Ugo; Mosca, Franco

2013-09-01

While single-port laparoscopy for abdominal surgery is technically challenging, the Da Vinci Single-Site® robotic surgery platform may help to overcome some of the difficulties of this rapidly evolving technique. The authors of this article present a case of single-incision, robotic right colectomy using this device. A 74-year-old female with malignant polyp of caecum was operated on with a single-site approach using the Da Vinci Single-Site® robotic surgery device. Resection and anastomosis were performed extra-corporeally after undocking the robot. The procedure was successfully completed in 200 min. No surgical complications occurred during the intervention and the post-operative stay and no conversion to laparotomy or additional trocars were required. To the best of our knowledge, this is the first case of right colectomy using the Da Vinci Single-Site® robotic surgery platform to be reported. The procedure is feasible and safe and its main advantages are restoration of triangulation and reduced instrument clashes. Copyright © 2013 John Wiley & Sons, Ltd.

"Hydro-metathesis" of olefins: A catalytic reaction using a bifunctional single-site tantalum hydride catalyst supported on fibrous silica (KCC-1) nanospheres

KAUST Repository

Polshettiwar, Vivek

2011-02-18

Tantalizing hydrocarbons: Tantalum hydride supported on fibrous silica nanospheres (KCC-1) catalyzes, in the presence of hydrogen, the direct conversion of olefins into alkanes that have higher and lower numbers of carbon atoms (see scheme). This catalyst shows remarkable catalytic activity and stability, with excellent potential of regeneration. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

"Hydro-metathesis" of olefins: A catalytic reaction using a bifunctional single-site tantalum hydride catalyst supported on fibrous silica (KCC-1) nanospheres

KAUST Repository

Polshettiwar, Vivek; Thivolle-Cazat, Jean; Taoufik, Mostafa; Stoffelbach, Franç ois; Norsic, Sé bastien; Basset, Jean-Marie

2011-01-01

Tantalizing hydrocarbons: Tantalum hydride supported on fibrous silica nanospheres (KCC-1) catalyzes, in the presence of hydrogen, the direct conversion of olefins into alkanes that have higher and lower numbers of carbon atoms (see scheme). This catalyst shows remarkable catalytic activity and stability, with excellent potential of regeneration. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic wet air oxidation of coke-plant wastewater on ruthenium-based eggshell catalysts in a bubbling bed reactor.

Science.gov (United States)

Yang, M; Sun, Y; Xu, A H; Lu, X Y; Du, H Z; Sun, C L; Li, C

2007-07-01

Catalytic wet air of coke-plant wastewater was studied in a bubbling bed reactor. Two types of supported Ru-based catalysts, eggshell and uniform catalysts, were employed. Compared with the results in the wet air oxidation of coke-plant wastewater, supported Ru uniform catalysts showed high activity for chemical oxygen demand (COD) and ammonia/ammonium compounds (NH3-N) removal at temperature of 250 degrees C and pressure of 4.8 MPa, and it has been demonstrated that the catalytic activity of uniform catalyst depended strongly on the distribution of active sites of Ru on catalyst. Compared to the corresponding uniform catalysts with the same Ru loading (0.25 wt.% and 0.1 wt.%, respectively), the eggshell catalysts showed higher activities for CODcr removal and much higher activities for NH3-N degradation. The high activity of eggshell catalyst for treatment of coke-plant wastewater can be attributed to the higher density of active Ru sites in the shell layer than that of the corresponding uniform catalyst with the same Ru loading. It has been also evidenced that the active Ru sites in the internal core of uniform catalyst have very little or no contribution to CODcr and NH3-N removal in the total oxidation of coke-plant wastewater.

Well-Defined Silica Supported Aluminum Hydride: Another Step Towards the Utopian Single Site Dream?

KAUST Repository

Werghi, Baraa; Bendjeriou-Sedjerari, Anissa; Sofack-Kreutzer, Julien; Jedidi, Abdesslem; Abou-Hamad, Edy; Cavallo, Luigi; Basset, Jean-Marie

2015-01-01

Reaction of triisobutylaluminum with SBA15700 at room temperature occurs by two parallel pathways involving either silanol or siloxane bridges. It leads to the formation of a well-defined bipodal [(≡SiO)2Al-CH2CH(CH3)2] 1a, silicon isobutyl [≡Si-CH2CH(CH3)2] 1b and a silicon hydride [≡Si-H] 1c. Their structural identity was characterized by FT-IR and advance solid-state NMR spectroscopies (1H, 13C, 29Si, 27Al and 2D multiple quantum), elemental and gas phase analysis, and DFT calculations. The reaction involves the formation of a highly reactive monopodal intermediate: [≡SiO-Al-[CH2CH(CH3)2]2], with evolution of isobutane. This intermediate undergoes two parallel routes: Transfer of either one isobutyl fragment or of one hydride to an adjacent silicon atom. Both processes occur by opening of a strained siloxane bridge, ≡Si-O-Si≡ but with two different mechanisms, showing that the reality of “single site” catalyst may be an utopia: DFT calculations indicate that isobutyl transfer occurs via a simple metathesis between the Al-isobutyl and O-Si bonds, while hydride transfer occurs via a two steps mechanism, the first one is a ß-H elimination to Al with elimination of isobutene, whereas the second is a metathesis step between the formed Al-H bond and a O-Si bond. Thermal treatment of 1a (at 250 °C) under high vacuum (10-5 mbar) generates Al-H through a ß-H elimination of isobutyl fragment. These supported well-defined Al-H which are highly stable with time, are tetra, penta and octa coordinated as demonstrated by IR and 27Al–1H J-HMQC NMR spectroscopy. All these observations indicate that surfaces atoms around the site of grafting play a considerable role in the reactivity of a single site system.

Well-Defined Silica Supported Aluminum Hydride: Another Step Towards the Utopian Single Site Dream?

KAUST Repository

Werghi, Baraa

2015-07-17

Reaction of triisobutylaluminum with SBA15700 at room temperature occurs by two parallel pathways involving either silanol or siloxane bridges. It leads to the formation of a well-defined bipodal [(≡SiO)2Al-CH2CH(CH3)2] 1a, silicon isobutyl [≡Si-CH2CH(CH3)2] 1b and a silicon hydride [≡Si-H] 1c. Their structural identity was characterized by FT-IR and advance solid-state NMR spectroscopies (1H, 13C, 29Si, 27Al and 2D multiple quantum), elemental and gas phase analysis, and DFT calculations. The reaction involves the formation of a highly reactive monopodal intermediate: [≡SiO-Al-[CH2CH(CH3)2]2], with evolution of isobutane. This intermediate undergoes two parallel routes: Transfer of either one isobutyl fragment or of one hydride to an adjacent silicon atom. Both processes occur by opening of a strained siloxane bridge, ≡Si-O-Si≡ but with two different mechanisms, showing that the reality of “single site” catalyst may be an utopia: DFT calculations indicate that isobutyl transfer occurs via a simple metathesis between the Al-isobutyl and O-Si bonds, while hydride transfer occurs via a two steps mechanism, the first one is a ß-H elimination to Al with elimination of isobutene, whereas the second is a metathesis step between the formed Al-H bond and a O-Si bond. Thermal treatment of 1a (at 250 °C) under high vacuum (10-5 mbar) generates Al-H through a ß-H elimination of isobutyl fragment. These supported well-defined Al-H which are highly stable with time, are tetra, penta and octa coordinated as demonstrated by IR and 27Al–1H J-HMQC NMR spectroscopy. All these observations indicate that surfaces atoms around the site of grafting play a considerable role in the reactivity of a single site system.

Raising distillate selectivity and catalyst life time in Fischer-Tropsch synthesis by using a novel dual-bed reactor

International Nuclear Information System (INIS)

Tavasoli, A.; Sadaghiani, K.; Khodadadi, A. A.; Mortazavi, Y.

2007-01-01

In a novel dual bed reactor Fischer-Tropsch synthesis was studied by using two diff rent cobalt catalysts. An alkali-promoted cobalt catalyst was used in the first bed of a fixed-bed reactor followed by a Raiment promoted cobalt catalyst in the second bed. The activity, product selectivity and accelerated deactivation of the system were assessed and compared with a conventional single bed reactor system. The methane selectivity in the dual-bed reactor was about 18.9% less compared to that of the single-bed reactor. The C 5+ selectivity for the dual-bed reactor was 10.9% higher than that of the single-bed reactor. Accelerated deactivation of the catalysts in the dual-bed reactor was 42% lower than that of the single-bed reactor. It was revealed that the amount of catalysts activity recovery after regeneration at 400 d eg C in the dual-bed system is higher than that of the single-bed system

Preparation of highly dispersed Ru-Sn bimetallic supported catalysts from the single source precursors Cp(PPh32Ru-SnX3 (X = Cl or Br

Directory of Open Access Journals (Sweden)

Ana Cláudia Bernardes Silva

2003-06-01

Full Text Available In this work highly dispersed Ru-Sn bimetallic catalysts have been prepared from organobimetallic Cp(PPh32Ru-SnX3 (X = Cl or Br complexes. These single source precursors can be easily impregnated in high surface area supports, such as activated carbon and sol-gel SiO2, and upon controlled thermal treatment the ligands are released as volatile products resulting in the formation of the bimetallic system Ru-Sn. Catalytic reactions, such as hydrodechlorination of CCl4 and chlorobenzene and TPR (Temperature Programmed Reduction experiments carried out with these RuSn catalysts suggested a strong interaction between Ruthenium and Tin. Mössbauer measurements showed that these materials when exposed to air are immediately oxidized to form Sn (IV. It was shown that upon controlled reduction conditions with H2 it is possible to reduce selectively Sn to different oxidation states and different phases. The Sn oxidation state showed significant effect on the catalytic hydrogenation of 1,5-cyclooctadiene. The use of these single source precursors with a controlled decomposition/reduction procedure allows the preparation of unique catalysts with an intimate interaction between the components ruthenium and tin and the possibility of varying the Sn oxidation state around the Ru metal.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-10-20

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

Hybrid modeling approach to improve the forecasting capability for the gaseous radionuclide in a nuclear site

International Nuclear Information System (INIS)

Jeong, Hyojoon; Hwang, Wontae; Kim, Eunhan; Han, Moonhee

2012-01-01

Highlights: ► This study is to improve the reliability of air dispersion modeling. ► Tracer experiments assumed gaseous radionuclides were conducted at a nuclear site. ► The performance of a hybrid modeling combined ISC with ANFIS was investigated.. ► Hybrid modeling approach shows better performance rather than a single ISC model. - Abstract: Predicted air concentrations of radioactive materials are important for an environmental impact assessment for the public health. In this study, the performance of a hybrid modeling combined with the industrial source complex (ISC) model and an adaptive neuro-fuzzy inference system (ANFIS) for predicting tracer concentrations was investigated. Tracer dispersion experiments were performed to produce the field data assuming the accidental release of radioactive material. ANFIS was trained in order that the outputs of the ISC model are similar to the measured data. Judging from the higher correlation coefficients between the measured and the calculated ones, the hybrid modeling approach could be an appropriate technique for an improvement of the modeling capability to predict the air concentrations for radioactive materials.

Graphite-supported platinum catalysts: Effects of gas and aqueous phase treatments

Energy Technology Data Exchange (ETDEWEB)

Vleeming, J.H.; Kuster, B.F.M.; Marin, G.B. [Eindhoven Univ. of Technology (Netherlands)] [and others

1997-03-01

The effects on the platinum particle diameter and the available platinum surface area of a graphite-supported platinum catalyst resulting from pretreatments and from performing a selective oxidation reaction are investigated. In the gas phase considerable catalyst sintering occurs only in the presence of oxygen at 773 K due to extensive carbon burn-off, whereas in an aqueous phase platinum particle growth is limited upon oxidative treatment. A hydrogen treatment in aqueous phase at 363 K causes platinum particle growth, aggregate formation, and covering of metal sites. These phenomena become more important with increasing pH. Platinum particle growth and aggregate formation are attributed to platinum particle rather than platinum adatom mobility and is caused by the destruction of the oxygen-containing surface groups on the graphite support, which serve as anchorage sites for the platinum particles. Site covering is caused by products originating from the graphite support, which are formed as a result of the reductive treatments. When performing the aqueous phase oxidation of methyl {alpha}-D-glucopyranoside at 323 K and a pH of 9, catalyst modifications are small under oxidative conditions. Exposure of the catalyst for several hours to methyl {alpha}-D-glucopyranoside under the same conditions but in the absence of oxygen causes site covering. 50 refs., 9 figs., 1 tab.

Catalysis Science Initiative: Catalyst Design by Discovery Informatics

Energy Technology Data Exchange (ETDEWEB)

Delgass, William Nicholas [Purdue Univ., West Lafayette, IN (United States). Chemical Engineering; Abu-Omar, Mahdi [Purdue Univ., West Lafayette, IN (United States) Department of Chemistry; Caruthers, James [Purdue Univ., West Lafayette, IN (United States). Chemical Engineering; Ribeiro, Fabio [Purdue Univ., West Lafayette, IN (United States). Chemical Engineering; Thomson, Kendall [Purdue Univ., West Lafayette, IN (United States). Chemical Engineering; Schneider, William [Univ. of Notre Dame, IN (United States)

2016-07-08

atoms in the interfacial region. Some of the first theoretical descriptions of this important chemistry and potential new source of control of catalyst properties are be in preparation for submission. On the homogeneous catalysis side, we have used single site olefin polymerization as the testbed. This system is important because changes in a single ligand bonded to the catalytically active metal site can alter the rates of individual steps in the polymerization sequence and thereby change the properties of the resulting polymer, potentially improving its value in a hundred million pound per year industry. We have made a major advance in understanding such systems by developing a population balance kinetic model that allows us to predict the molecular weight distribution (MWD) of the product. That, in turn, allows use of MWD data to fit kinetic parameters. By combining monomer loss data, MWD, measurement of the number of working active sites, and polymer end group analysis, we have a rich data set that is highly discriminating of kinetic mechanism. Thus, we have a robust tool for producing high quality, detailed kinetic parameters, which we have used to refine mechanisms presented in the literature and discover relationships between steric and electronic properties of group IV catalysts and individual rate constants in a number of systems. Our recent work on six-coordinate Zr, Ti, and Hf amine bis(phenolate) systems, we have shown that: • The sterics (bulkiness) of the ligands specifically affect the chain termination reaction • The electron density on the metal controls misinsertion (flipped orientation) of the olefin into the growing polymer • Steric effects related to the size of the ortho ligand on the catalyst have been shown to strongly affect its the degree of dormancy, i.e. tendency to stop reacting • Changes in the size of the amine pendent group on the catalyst can have such a strong effect on chain termination as to change the catalyst from one that

Pyrochlore-type catalysts for the reforming of hydrocarbon fuels

Science.gov (United States)

Berry, David A [Morgantown, WV; Shekhawat, Dushyant [Morgantown, WV; Haynes, Daniel [Morgantown, WV; Smith, Mark [Morgantown, WV; Spivey, James J [Baton Rouge, LA

2012-03-13

A method of catalytically reforming a reactant gas mixture using a pyrochlore catalyst material comprised of one or more pyrochlores having the composition A.sub.2-w-xA'.sub.wA''.sub.xB.sub.2-y-zB'.sub.yB''.sub.zO.sub.7-.DELTA.. Distribution of catalytically active metals throughout the structure at the B site creates an active and well dispersed metal locked into place in the crystal structure. This greatly reduces the metal sintering that typically occurs on supported catalysts used in reforming reactions, and reduces deactivation by sulfur and carbon. Further, oxygen mobility may also be enhanced by elemental exchange of promoters at sites in the pyrochlore. The pyrochlore catalyst material may be utilized in catalytic reforming reactions for the conversion of hydrocarbon fuels into synthesis gas (H.sub.2+CO) for fuel cells, among other uses.

Syntheses, Characterization and Kinetics of Nickel-Tungsten Nitride Catalysts for Hydrotreating of Gas Oil

Science.gov (United States)

Botchwey, Christian

This thesis summarizes the methods and major findings of Ni-W(P)/gamma-Al 2O3 nitride catalyst synthesis, characterization, hydrotreating activity, kinetic analysis and correlation of the catalysts' activities to their synthesis parameters and properties. The range of parameters for catalyst synthesis were W (15-40 wt%), Ni (0-8 wt%), P (0-5 wt%) and nitriding temperature (TN) (500-900 °C). Characterization techniques used included: N2 sorption studies, chemisorption, elemental analysis, temperature programmed studies, x-ray diffraction, scanning electron microscopy, energy dispersive x-ray, infrared spectroscopy, transmission electron microscopy and x-ray absorption near edge structure. Hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatization (HDA) were performed at: temperature (340-380 °C), pressure (6.2-9.0 MPa), liquid hourly space velocity (1-3 h-1) and hydrogen to oil ratio (600 ml/ml, STP). The predominant species on the catalyst surface were Ni3N, W2N and bimetallic Ni2W3N. The bimetallic Ni-W nitride species was more active than the individual activities of the Ni3N and W2N. P increased weak acid sites while nitriding temperature decreased amount of strong acid sites. Low nitriding temperature enhanced dispersion of metal particles. P interacted with Al 2O3 which increased the dispersion of metal nitrides on the catalyst surface. HDN activity increased with Ni and P loading but decreased with increase in nitriding temperature (optimum conversion; 60 wt%). HDS and HDA activities went through a maximum with increase in the synthesis parameters (optimum conversions; 88. wt% for HDS and 47 wt% for HDA). Increase in W loading led to increase in catalyst activity. The catalysts were stable to deactivation and had the nitride structure conserved during hydrotreating in the presence of hydrogen sulfide. The results showed good correlation between hydrotreating activities (HDS and HDN) and the catalyst nitrogen content, number of exposed

Performance comparison of low-temperature direct alcohol fuel cells with different anode catalysts

Science.gov (United States)

Zhou, W. J.; Zhou, B.; Li, W. Z.; Zhou, Z. H.; Song, S. Q.; Sun, G. Q.; Xin, Q.; Douvartzides, S.; Goula, M.; Tsiakaras, P.

Low-temperature polymer electrolyte membrane fuel cells directly fed by methanol and ethanol were investigated employing carbon supported Pt, PtSn and PtRu as anode catalysts, respectively. Employing Pt/C as anode catalyst, both direct methanol fuel cell (DMFC) and direct ethanol fuel cell (DEFC) showed poor performances even in presence of high Pt loading on anode. It was found that the addition of Ru or Sn to the Pt dramatically enhances the electro-oxidation of both methanol and ethanol. It was also found that the single cell adopting PtRu/C as anode shows better DMFC performance, while PtSn/C catalyst shows better DEFC performance. The single fuel cell using PtSn/C as anode catalyst at 90 °C shows similar power densities whenever fueled by methanol or ethanol. The cyclic voltammetry (CV) and single fuel cell tests indicated that PtRu is more suitable for DMFC while PtSn is more suitable for DEFC.

Catalyst-free site-specific surface modifications of nanocrystalline diamond films via microchannel cantilever spotting

Czech Academy of Sciences Publication Activity Database

Davydova, Marina; de los Santos Pereira, Andres; Bruns, M.; Kromka, Alexander; Ukraintsev, Egor; Hirtz, M.; Rodriguez-Emmenegger, Cesar

2016-01-01

Roč. 6, č. 63 (2016), s. 57820-57827 ISSN 2046-2069 R&D Projects: GA ČR(CZ) GP14-06054P Institutional support: RVO:68378271 ; RVO:61389013 Keywords : catalysts * nanocrystals * photonic devices * catalyst-free * functionalizations * high reproducibility * micropatterned * multicomponents Subject RIV: BO - Biophysics; CD - Macromolecular Chemistry (UMCH-V) Impact factor: 3.108, year: 2016

Power coordinated control method with frequency support capability for hybrid single/three-phase microgrid

DEFF Research Database (Denmark)

Zhou, Xiaoping; Chen, Yandong; Zhou, Leming

2018-01-01

storage unit (ESU) are added into hybrid single/three-phase microgrid, and a power coordinated control method with frequency support capability is proposed for hybrid single/three-phase microgrid in this study. PEU is connected with three single-phase microgrids to coordinate power exchange among three...... phases and provide frequency support for hybrid microgrid. Meanwhile, a power coordinated control method based on the droop control is proposed for PEU to alleviate three-phase power imbalance and reduce voltage fluctuation of hybrid microgrid. Besides, ESU is injected into the DC-link to buffer......Due to the intermittent output power of distributed generations (DGs) and the variability of loads, voltage fluctuation and three-phase power imbalance easily occur when hybrid single/three-phase microgrid operates in islanded mode. To address these issues, the power exchange unit (PEU) and energy...

Efficient oxygen electrocatalysis on special active sites

DEFF Research Database (Denmark)

Halck, Niels Bendtsen

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

Regeneration of Pt-catalysts deactivated in municipal waste flue gas with H2/N2 and the effect of regeneration step on the SCR catalyst

DEFF Research Database (Denmark)

Due-Hansen, Johannes; Rasmussen, Søren Brik; Kustov, Arkady

The deactivation performance of Pt-catalysts for CO oxidation has been studied in relation to use in sewage sludge municipal waste burners, where HMDS was found to poison the industrial catalyst in a similar way to the model Pt/TiO2 catalyst. A promising regeneration procedure was developed based...... on reduction with hydrogen. This procedure had negligible effect on the performance of the SCR catalyst. After treatment with 2% H2, 8% O2 in N2 for one hour, a slight better NO SCR activity was observed due to increase in the concentration V4+ sites. However, after exposure in normal NO SCR gases the activity...

Application of zeolite-based catalyst to hydrocracking of coal-derived liquids

Energy Technology Data Exchange (ETDEWEB)

Shimada, H.; Sato, T.; Yoshimura, Y.; Hinata, A.; Yoshitomi, S.; Castillo Mares, A.; Nishijima, A. (National Chemical Laboratory for Industry, Tsukuba (Japan))

1990-06-01

Y-zeolite supported catalysts were applied to the hydrocracking of coal-derived liquids. By the introduction of two-stage upgrading consisting of hydrotreating and hydrocracking, Wandoan coal-derived middle distillate was hydrocracked over Ni-Mo/Y-zeolite, producing a high gasoline fraction yield. Zeolite supported catalysts gave little hydrocracked compounds in the hydroprocessing of coal-derived heavy oils, even after hydrotreatment. The reaction inhibitors which seriously poison the active sites of zeolites were found to be small nitrogen-containing molecules. In the hydroprocessing of coal-derived heavy oils, zeolite supported catalysts were inferior to alumina supported catalysts. This is due to the high hydrocracking but low hydrogenation activity of zeolite supported catalysts. 22 refs., 5 figs., 11 tabs.

The nanosize catalysts role in the modern hydroprocesses

International Nuclear Information System (INIS)

Irisova, K N; Smirnov, V K; Talisman, E L

2011-01-01

Introduction of the modern technological procedures operating the catalytic systems with different nanosized characteristics is the only way to fabricate components of commercial oils that meet the current requirements. Specifications to the individual catalysts, which form a catalytic system, differ both in nanostructural features of the support porosity and in distribution of nanosized active site. These specifications are related to the purpose of the process and the role of the catalyst in the process.

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

Science.gov (United States)

Kim, In Soo; Li, Zhanyong; Zheng, Jian; Platero-Prats, Ana E; Mavrandonakis, Andreas; Pellizzeri, Steven; Ferrandon, Magali; Vjunov, Aleksei; Gallington, Leighanne C; Webber, Thomas E; Vermeulen, Nicolaas A; Penn, R Lee; Getman, Rachel B; Cramer, Christopher J; Chapman, Karena W; Camaioni, Donald M; Fulton, John L; Lercher, Johannes A; Farha, Omar K; Hupp, Joseph T; Martinson, Alex B F

2018-01-22

Single atoms and few-atom clusters of platinum are uniformly installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and X-ray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Dispersed Alloy Catalyst for Durability

Energy Technology Data Exchange (ETDEWEB)

Murthi, Vivek S.; Izzo, Elise; Bi, Wu; Guerrero, Sandra; Protsailo, Lesia

2013-01-08

Achieving DOE's stated 5000-hr durability goal for light-duty vehicles by 2015 will require MEAs with characteristics that are beyond the current state of the art. Significant effort was placed on developing advanced durable cathode catalysts to arrive at the best possible electrode for high performance and durability, as well as developing manufacturing processes that yield significant cost benefit. Accordingly, the overall goal of this project was to develop and construct advanced MEAs that will improve performance and durability while reducing the cost of PEMFC stacks. The project, led by UTC Power, focused on developing new catalysts/supports and integrating them with existing materials (membranes and gas diffusion layers (GDLs)) using state-of-the-art fabrication methods capable of meeting the durability requirements essential for automotive applications. Specifically, the project work aimed to lower platinum group metals (PGM) loading while increasing performance and durability. Appropriate catalysts and MEA configuration were down-selected that protects the membrane, and the layers were tailored to optimize the movements of reactants and product water through the cell to maximize performance while maintaining durability.

Single Pot Selective Hydrogenation of Furfural to 2-Methylfuran Over Carbon Supported Iridium Catalysts

KAUST Repository

Date, Nandan S; Hengne, Amol Mahalingappa; Huang, Kuo-Wei; Chikate, Rajeev C.; Rode, C. V.

2018-01-01

Various iridium supported carbon catalysts were prepared and screened for direct hydrogenation of furfural (FFR) to 2-methyl furan (2-MF). Amongest these, 5% Ir/C showed excellent results with complete FFR conversion and highest selectivity of 95% to 2-MF at very low H2 pressure of 100 psig. Metallic (Iro) and oxide ( IrO2) phases of Ir catalyzed first step hydrogenation involving FFR to FAL and subsequent hydrogenation to 2-MF,respecively. This was confirmed by XPS analysis and some controlled experiments. At low temperature of 140 oC, almost equal selectivities of FAL (42%) and 2-MF (43%) were observed, while higher temperature (220oC) favored selective hydrodeoxygenation. At optimized temperature, 2-MF formed selectively while higher pressure and higher catalyst loading favored ring hydrogenation of furfural rather than side chain hydrogenation. With combination of several control experimental results and detailed catalyst characterization, a plausible reaction pathway has been proposed for selective formation of 2-MF. The selectivity to various other products in FFR hydrogenation can be manipulated by tailoring the reaction conditions over the same catalyst.

Single Pot Selective Hydrogenation of Furfural to 2-Methylfuran Over Carbon Supported Iridium Catalysts

KAUST Repository

Date, Nandan S

2018-03-20

Various iridium supported carbon catalysts were prepared and screened for direct hydrogenation of furfural (FFR) to 2-methyl furan (2-MF). Amongest these, 5% Ir/C showed excellent results with complete FFR conversion and highest selectivity of 95% to 2-MF at very low H2 pressure of 100 psig. Metallic (Iro) and oxide ( IrO2) phases of Ir catalyzed first step hydrogenation involving FFR to FAL and subsequent hydrogenation to 2-MF,respecively. This was confirmed by XPS analysis and some controlled experiments. At low temperature of 140 oC, almost equal selectivities of FAL (42%) and 2-MF (43%) were observed, while higher temperature (220oC) favored selective hydrodeoxygenation. At optimized temperature, 2-MF formed selectively while higher pressure and higher catalyst loading favored ring hydrogenation of furfural rather than side chain hydrogenation. With combination of several control experimental results and detailed catalyst characterization, a plausible reaction pathway has been proposed for selective formation of 2-MF. The selectivity to various other products in FFR hydrogenation can be manipulated by tailoring the reaction conditions over the same catalyst.

Da Vinci single site© surgical platform in clinical practice: a systematic review.

Science.gov (United States)

Morelli, Luca; Guadagni, Simone; Di Franco, Gregorio; Palmeri, Matteo; Di Candio, Giulio; Mosca, Franco

2016-12-01

The Da Vinci single-site© surgical platform (DVSSP) is a set of single-site instruments and accessories specifically dedicated to robot-assisted single-site surgery. The PubMed database from inception to June 2015 was searched for English literature on the clinical use of DVSSP in general surgery, urology and gynecology. Twenty-nine articles involving the clinical application of DVSSP were identified; 15 articles on general surgery (561 procedures), four articles on urology (48 procedures) and 10 articles on gynecology (212 procedures). All studies have proven the safety and feasibility of the use of DVSSP. The principal reported advantage is the restoration of intra-abdominal triangulation, while the main reported limitation is the lack of the endowrist. Da Vinci systems have proven to be valuable assets in single-site surgery, owing to the combination of robot use with the dedicated single-incision platform. However, case-control or prospective trials are warranted to draw more definitive conc lusions. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Characterization and Regeneration of Pt-Catalysts Deactivated in Municipal Waste Flue Gas

DEFF Research Database (Denmark)

Rasmussen, Søren Birk; Kustov, Arkadii; Due-Hansen, Johannes

2006-01-01

Severe deactivation was observed for industrially aged catalysts used in waste incineration plants and tested in lab-scale. Possible compounds that cause deactivation of these Pt-based CO oxidation catalysts have been studied. Kinetic observations of industrial and model catalysts showed...... that siloxanes were the most severe catalyst poisons, although acidic sulfur compounds also caused deactivation. Furthermore, a method for on-site regeneration without shutdown of the catalytic flue gas cleaning system has been developed, i.e. an addition of H-2/N-2 gas to the off-gas can completely restore...... the activity of the deactivated catalysts. (c) 2006 Elsevier B.V. All rights reserved....

Life Support Catalyst Regeneration Using Ionic Liquids and In Situ Resources

Science.gov (United States)

Abney, Morgan B.; Karr, Laurel; Paley, Mark S.; Donovan, David N.

2016-01-01

Oxygen recovery from metabolic carbon dioxide is an enabling capability for long-duration manned space flight. Complete recovery of oxygen (100%) involves the production of solid carbon. Catalytic approaches for this purpose, such as Bosch technology, have been limited in trade analyses due in part to the mass penalty for high catalyst resupply caused by carbon fouling of the iron or nickel catalyst. In an effort to mitigate this challenge, several technology approaches have been proposed. These approaches have included methods to prolong the life of the catalysts by increasing the total carbon mass loading per mass catalyst, methods for simplified catalyst introduction and removal to limit the resupply container mass, methods of using in situ resources, and methods to regenerate catalyst material. Research and development into these methods is ongoing, but only use of in situ resources and/or complete regeneration of catalyst material has the potential to entirely eliminate the need for resupply. The use of ionic liquids provides an opportunity to combine these methods in a technology approach designed to eliminate the need for resupply of oxygen recovery catalyst. Here we describe the results of an initial feasibility study using ionic liquids and in situ resources for life support catalyst regeneration, we discuss the key challenges with the approach, and we propose future efforts to advance the technology.

PdRu/C catalysts for ethanol oxidation in anion-exchange membrane direct ethanol fuel cells

Science.gov (United States)

Ma, Liang; He, Hui; Hsu, Andrew; Chen, Rongrong

2013-11-01

Carbon supported PdRu catalysts with various Pd:Ru atomic ratios were synthesized by impregnation method, and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), electrochemical half-cell tests, and the anion-exchange membrane direct ethanol fuel cell (AEM-DEFC) tests. XRD results suggest that the PdRu metal exists on carbon support in an alloy form. TEM study shows that the bimetallic PdRu/C catalysts have slightly smaller average particle size than the single metal Pd/C catalyst. Lower onset potential and peak potential and much higher steady state current for ethanol oxidation in alkaline media were observed on the bimetallic catalysts (PdxRuy/C) than on the Pd/C, while the activity for ethanol oxidation on the pure Ru/C was not noticeable. By using Pd/C anode catalysts and MnO2 cathode catalysts, AEM-DEFCs free from the expensive Pt catalyst were assembled. The AEM DEFC using the bimetallic Pd3Ru/C anode catalyst showed a peak power density as high as 176 mW cm-2 at 80 °C, about 1.8 times higher than that using the single metal Pd/C catalyst. The role of Ru for enhancing the EOR activity of Pd/C catalysts is discussed.

The Evaluation of Novel Camphor-derived Ligands as Catalysts in ...

African Journals Online (AJOL)

The evaluation of a series of camphor-derived ligands as catalysts in the asymmetric Henry reaction is reported. The synthesis of two novel derivatives is detailed and these molecules are also screened as catalysts in this reaction. The single crystal X-ray structure of one of the novel compounds is reported. The reaction is ...

A Scalable Process for Production of Single-walled Carbon Nanotubes (SWNTs) by Catalytic Disproportionation of CO on a Solid Catalyst

International Nuclear Information System (INIS)

Resasco, D.E.; Alvarez, W.E.; Pompeo, F.; Balzano, L.; Herrera, J.E.; Kitiyanan, B.; Borgna, A.

2002-01-01

Existing single-walled carbon nanotube synthesis methods are not easily scalable, operate under severe conditions, and involve high capital and operating costs. The current cost of SWNT is exceedingly high. A catalytic method of synthesis has been developed that has shown potential advantages over the existing methods. This method is based on a catalyst formulation that inhibits the formation of undesired forms of carbon; it can be scaled-up and may result in lower production costs

Atmospheric pressure reaction cell for operando sum frequency generation spectroscopy of ultrahigh vacuum grown model catalysts

Science.gov (United States)

Roiaz, Matteo; Pramhaas, Verena; Li, Xia; Rameshan, Christoph; Rupprechter, Günther

2018-04-01

A new custom-designed ultrahigh vacuum (UHV) chamber coupled to a UHV and atmospheric-pressure-compatible spectroscopic and catalytic reaction cell is described, which allows us to perform IR-vis sum frequency generation (SFG) vibrational spectroscopy during catalytic (kinetic) measurements. SFG spectroscopy is an exceptional tool to study vibrational properties of surface adsorbates under operando conditions, close to those of technical catalysis. This versatile setup allows performing surface science, SFG spectroscopy, catalysis, and electrochemical investigations on model systems, including single crystals, thin films, and deposited metal nanoparticles, under well-controlled conditions of gas composition, pressure, temperature, and potential. The UHV chamber enables us to prepare the model catalysts and to analyze their surface structure and composition by low energy electron diffraction and Auger electron spectroscopy, respectively. Thereafter, a sample transfer mechanism moves samples under UHV to the spectroscopic cell, avoiding air exposure. In the catalytic cell, SFG spectroscopy and catalytic tests (reactant/product analysis by mass spectrometry or gas chromatography) are performed simultaneously. A dedicated sample manipulation stage allows the model catalysts to be examined from LN2 temperature to 1273 K, with gaseous reactants in a pressure range from UHV to atmospheric. For post-reaction analysis, the SFG cell is rapidly evacuated and samples are transferred back to the UHV chamber. The capabilities of this new setup are demonstrated by benchmark results of CO adsorption on Pt and Pd(111) single crystal surfaces and of CO adsorption and oxidation on a ZrO2 supported Pt nanoparticle model catalyst grown by atomic layer deposition.

Comparison of sample digestion techniques for the determination of trace and residual catalyst metal content in single-wall carbon nanotubes by inductively coupled plasma mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Grinberg, Patricia, E-mail: patricia.grinberg@nrc.ca [Measurement Science and Standards, National Research Council Canada, Ottawa (Canada); Sturgeon, Ralph E. [Measurement Science and Standards, National Research Council Canada, Ottawa (Canada); Diehl, Liange de O.; Bizzi, Cezar A. [Measurement Science and Standards, National Research Council Canada, Ottawa (Canada); Chemistry Department, Universidade Federal de Santa Maria, Santa Maria (Brazil); Flores, Erico M.M. [Chemistry Department, Universidade Federal de Santa Maria, Santa Maria (Brazil)

2015-03-01

A single-wall carbon nanotube material produced by laser ablation of renewable biochar in the presence of Ni and Co catalyst was characterized for residual catalyst (Co and Ni) as well as trace metal impurity content (Fe, Mo, Cr, Pb and Hg) by isotope dilution ICP-MS following sample digestion. Several matrix destruction procedures were evaluated, including a multi-step microwave-assisted acid digestion, dry ashing at 450 °C and microwave-induced combustion with oxygen. Results were benchmarked against those derived from neutron activation analysis and also supported by solid sampling continuum source GF-AAS for several of the elements. Although laborious to execute, the multi-step microwave-assisted acid digestion proved to be most reliable for recovery of the majority of the analytes, although content of Cr remained biased low for each approach, likely due to its presence as refractory carbide. - Highlights: • Determination of trace and residual catalyst metal content in Single-Wall Carbon Nanotubes by Inductively Coupled Plasma Mass Spectrometry. • Comparative study of digestion methodology combined with high precision isotope dilution ICP-MS for quantitation of elements of toxicologic relevance. • Results were benchmarked against those derived from neutron activation analysis and also supported by solid sampling continuum source GF-AAS for several of the elements.

Research advances in the catalysts for the selective oxidation of ethane to aldehydes

Institute of Scientific and Technical Information of China (English)

ZHANG Zhe; ZHAO Zhen; XU Chunming

2005-01-01

Selective oxidation of ethane to aldehydes is one of the most difficult processes in the catalysis researches of low alkanes. The development of selective oxidation of ethane to aldehydes (formaldehyde, acetaldehyde and acrolein) is discussed. The latest progress of the catalysts, including bulk or supported metal oxide catalysts, highly dispersed and isolated active sites catalysts, and the photo-catalytic ethane oxidation catalysts, partial oxidation of ethane in the gas phase, and the proposed reaction pathways from ethane to aldehydes are involved.

CATALYSTS NHI Thermochemical Systems FY 2009 Year-End Report

International Nuclear Information System (INIS)

Ginosar, Daniel M.

2009-01-01

, development and testing of metal oxide based H2SO4 catalysts, support of the ILS for catalyst studies, conducting a long term catalyst stability test at anticipated operating temperatures and pressures, and developing capabilities for conducting pressurized catalyst tests.

Catalyst deposition for the preparation of carbon nanotubes

DEFF Research Database (Denmark)

2013-01-01

patterned surface is configured to ensure that no more than a single island of catalyst is formed on each plateau, so that a sub sequent growth of carbon nanotubes from the deposited islands result in that no more than a single carbon nanotube is grown from each plateau....

Adsorption and desorption of hydrogen and carbon monoxide were studied on alumina-supported iridium catalysts

Energy Technology Data Exchange (ETDEWEB)

Etherton, B.P.

1980-01-01

The adsorption and desorption of hydrogen and carbon monoxide were studied on alumina-supported iridium catalysts which were examined by a scanning transmission electron microscope (STEM). The metal particle size and number of particles per area of catalyst increased with increasing metal loading. The particles were approx. 10 A. in diameter, cubo-octahedral shaped, and approx. 80-90% disperse. The STEM electron beam caused negligible damage to the samples. Hydrogen adsorption measurements showed that the hydrogen-iridium atom ratio was 1.2:1-1.3:1 and increased with decreasing metal loading. Temperature-programed desorption showed four types of adsorbed hydrogen desorbing at -90/sup 0/C (I), 15/sup 0/C (IV), 115/sup 0/C (II), and 245/sup 0/C (III). Types II and IV desorb from single atom sites and Types I and III from multiple atom sites. Type I is in rapid equilibrium with the gas phase. All desorption processes appear to be first order. Carbon monoxide adsorbed nondissociatively at 25/sup 0/C with approx. 0.7:1 CO/Ir atom ratio. It adsorbed primarily in linear forms at low coverage, but a bridged form appeared at high coverage.

Direct NO decomposition over conventional and mesoporous Cu-ZSM-5 and Cu-ZSM-11 catalysts

DEFF Research Database (Denmark)

Kustova, Marina; Rasmussen, Søren Birk; Kustov, Arkadii

2006-01-01

Conventional Cu-ZSM-5 has for many years been recognized as a unique catalyst for direct NO decomposition. Zeolite-based catalysts have a crystallographically well-defined microporous structure. In such microporous catalysts, the creation and accessibility of the active sites is often influenced...... that ZSM-11 has only straight microporous channels, while ZSNI-5 has both straight and sinusoidal channels. Apparently, there is a preferential formation of active sites and/or improved accessibility in the straight channels compared to the sinusoidal channels, which make the ZSM-11 material a better...

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

DEFF Research Database (Denmark)

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

2018-01-01

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

Catalyst Deactivation Simulation Through Carbon Deposition in Carbon Dioxide Reforming over Ni/CaO-Al2O3 Catalyst

Directory of Open Access Journals (Sweden)

Istadi Istadi

2011-11-01

Full Text Available Major problem in CO2 reforming of methane (CORM process is coke formation which is a carbonaceous residue that can physically cover active sites of a catalyst surface and leads to catalyst deactivation. A key to develop a more coke-resistant catalyst lies in a better understanding of the methane reforming mechanism at a molecular level. Therefore, this paper is aimed to simulate a micro-kinetic approach in order to calculate coking rate in CORM reaction. Rates of encapsulating and filamentous carbon formation are also included. The simulation results show that the studied catalyst has a high activity, and the rate of carbon formation is relatively low. This micro-kinetic modeling approach can be used as a tool to better understand the catalyst deactivation phenomena in reaction via carbon deposition. Copyright © 2011 BCREC UNDIP. All rights reserved.(Received: 10th May 2011; Revised: 16th August 2011; Accepted: 27th August 2011[How to Cite: I. Istadi, D.D. Anggoro, N.A.S. Amin, and D.H.W. Ling. (2011. Catalyst Deactivation Simulation Through Carbon Deposition in Carbon Dioxide Reforming over Ni/CaO-Al2O3 Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2: 129-136. doi:10.9767/bcrec.6.2.1213.129-136][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.2.1213.129-136 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/1213 ] | View in  |  

A feasible quantum optical experiment capable of refuting noncontextuality for single photons

International Nuclear Information System (INIS)

Cereceda, Jose L

2002-01-01

Elaborating on a previous work by Simon et al (2000 Phys. Rev. Lett. 85 1783) we propose a realizable quantum optical single-photon experiment using standard present day technology, capable of discriminating maximally between the predictions of quantum mechanics (QM) and noncontextual hidden variable theories (NCHV). Quantum mechanics predicts a gross violation (up to a factor of 2) of the noncontextual Bell-like inequality associated with the proposed experiment. An actual maximal violation of this inequality would demonstrate (modulo fair sampling) an all-or-nothing type contradiction between QM and NCHV

Direct dimethyl-ether (DME) synthesis by spatial patterned catalyst arrangement. A modeling and simulation study

Energy Technology Data Exchange (ETDEWEB)

McBride, K.; Turek, T.; Guettel, R. [Clausthal Univ. of Technology (Germany). Inst. of Chemical Process Engineering

2011-07-01

The effect of spatially patterned catalyst beds was investigated for direct DME synthesis from synthesis gas as an example. A layered arrangement of methanol synthesis and dehydration catalyst was chosen and studied by numerical simulation under typical operating conditions for single-step DME synthesis. It was revealed that catalyst layers significantly influence the DME productivity. With an increasing number of layers from 2 to 40, an increase in DME productivity was observed approaching the performance of a physical catalyst mixture for an infinite number of layers. The results prove that a physical mixture of methanol synthesis and dehydration catalyst achieves the highest DME productivity under operating conditions chosen in this study. This can be explained by the higher average methanol concentration for the layered catalyst arrangement and thus stronger equilibrium constraints for the methanol synthesis reaction. Essentially, the layered catalyst arrangement is comparable to a cascade model of the two-step process, which is less efficient in terms of DME yield than the single-step process. However, since a significant effect was found, the layered catalyst arrangement could be beneficial for other reaction systems. (orig.)

Integrated Transmission Electron and Single-Molecule Fluorescence Microscopy Correlates Reactivity with Ultrastructure in a Single Catalyst Particle

NARCIS (Netherlands)

Hendriks, Frank C.|info:eu-repo/dai/nl/412642697; Mohammadian, Sajjad|info:eu-repo/dai/nl/374721327; Ristanovic, Zoran|info:eu-repo/dai/nl/328233005; Kalirai, Samanbir; Meirer, Florian; Vogt, Eelco T. C.|info:eu-repo/dai/nl/073717398; Bruijnincx, Pieter C. A.|info:eu-repo/dai/nl/33799529X; Gerritsen, Hans|info:eu-repo/dai/nl/071548777; Weckhuysen, Bert M.|info:eu-repo/dai/nl/285484397

2018-01-01

Establishing structure–activity relationships in complex, hierarchically structured nanomaterials, such as fluid catalytic cracking (FCC) catalysts, requires characterization with complementary, correlated analysis techniques. An integrated setup has been developed to perform transmission electron

Regeneration of a deactivated USY alkylation catalyst using supercritical isobutane

Energy Technology Data Exchange (ETDEWEB)

Daniel M. Ginosar; David N. Ghompson; Kyle C. Burch

2005-01-01

Off-line, in-situ alkylation activity recovery from a completely deactivated solid acid catalyst was examined in a continuous-flow reaction system employing supercritical isobutane. A USY zeolite catalyst was initially deactivated during the liquid phase alkylation of butene with isobutane in a single-pass reactor and then varying amounts of alkylation activity were recovered by passing supercritical isobutane over the catalyst bed at different reactivation conditions. Temperature, pressure and regeneration time were found to play important roles in the supercritical isobutane regeneration process when applied to a completely deactivated USY zeolite alkylation catalyst. Manipulation of the variables that influence solvent strength, diffusivity, surface desorption, hydride transfer rates, and coke aging, strongly influence regeneration effectiveness.

New Trends in Gold Catalysts

Directory of Open Access Journals (Sweden)

Leonarda F. Liotta

2014-07-01

Full Text Available Gold is an element that has fascinated mankind for millennia. The catalytic properties of gold have been a source of debate, due to its complete chemical inertness when in a bulk form, while it can oxidize CO at temperatures as low as ~200 K when in a nanocrystalline state, as discovered by Haruta in the late 1980s [1]. Since then, extensive activity in both applied and fundamental research on gold has been initiated. The importance of the catalysis by gold represents one of the fasted growing fields in science and is proven by the promising applications in several fields, such as green chemistry and environmental catalysis, in the synthesis of single-walled carbon nanotubes, as modifiers of Ni catalysts for methane steam and dry reforming reactions and in biological and electrochemistry applications. The range of reactions catalyzed by gold, as well as the suitability of different supports and the influence of the preparation conditions have been widely explored and optimized in applied research [2]. Gold catalysts appeared to be very different from the other noble metal-based catalysts, due to their marked dependence on the preparation method, which is crucial for the genesis of the catalytic activity. Several methods, including deposition-precipitation, chemical vapor deposition and cation adsorption, have been applied for the preparation of gold catalysts over reducible oxides, like TiO2. Among these methods, deposition-precipitation has been the most frequently employed method for Au loading, and it involves the use of tetrachloroauric (III acid as a precursor. On the other hand, the number of articles dealing with Au-loaded acidic supports is smaller than that on basic supports, possibly because the deposition of [AuCl4]− or [AuOHxCl4−x]− species on acidic supports is difficult, due to their very low point of zero charge. Despite this challenge, several groups have reported the use of acidic zeolites as supports for gold. Zeolites

Single-site Lennard-Jones models via polynomial chaos surrogates of Monte Carlo molecular simulation

KAUST Repository

Kadoura, Ahmad Salim

2016-06-01

In this work, two Polynomial Chaos (PC) surrogates were generated to reproduce Monte Carlo (MC) molecular simulation results of the canonical (single-phase) and the NVT-Gibbs (two-phase) ensembles for a system of normalized structureless Lennard-Jones (LJ) particles. The main advantage of such surrogates, once generated, is the capability of accurately computing the needed thermodynamic quantities in a few seconds, thus efficiently replacing the computationally expensive MC molecular simulations. Benefiting from the tremendous computational time reduction, the PC surrogates were used to conduct large-scale optimization in order to propose single-site LJ models for several simple molecules. Experimental data, a set of supercritical isotherms, and part of the two-phase envelope, of several pure components were used for tuning the LJ parameters (ε, σ). Based on the conducted optimization, excellent fit was obtained for different noble gases (Ar, Kr, and Xe) and other small molecules (CH4, N2, and CO). On the other hand, due to the simplicity of the LJ model used, dramatic deviations between simulation and experimental data were observed, especially in the two-phase region, for more complex molecules such as CO2 and C2 H6.

Correlation between Fischer-Tropsch catalytic activity and composition of catalysts

Directory of Open Access Journals (Sweden)

Subbarao Duvvuri

2011-11-01

Full Text Available Abstract This paper presents the synthesis and characterization of monometallic and bimetallic cobalt and iron nanoparticles supported on alumina. The catalysts were prepared by a wet impregnation method. Samples were characterized using temperature-programmed reduction (TPR, temperature-programmed oxidation (TPO, CO-chemisorption, transmission electron microscopy (TEM, field emission scanning electron microscopy (FESEM-EDX and N2-adsorption analysis. Fischer-Tropsch synthesis (FTS was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/CO = 2 v/v and space velocity, SV = 12L/g.h. The physicochemical properties and the FTS activity of the bimetallic catalysts were analyzed and compared with those of monometallic cobalt and iron catalysts at similar operating conditions. H2-TPR analysis of cobalt catalyst indicated three temperature regions at 506°C (low, 650°C (medium and 731°C (high. The incorporation of iron up to 30% into cobalt catalysts increased the reduction, CO chemisorption and number of cobalt active sites of the catalyst while an opposite trend was observed for the iron-riched bimetallic catalysts. The CO conversion was 6.3% and 4.6%, over the monometallic cobalt and iron catalysts, respectively. Bimetallic catalysts enhanced the CO conversion. Amongst the catalysts studied, bimetallic catalyst with the composition of 70Co30Fe showed the highest CO conversion (8.1% while exhibiting the same product selectivity as that of monometallic Co catalyst. Monometallic iron catalyst showed the lowest selectivity for C5+ hydrocarbons (1.6%.

Vapour phase dehydration of glycerol to acrolein over tungstated zirconia catalysts

Science.gov (United States)

Rao Ginjupalli, Srinivasa; Mugawar, Sowmya; Rajan N., Pethan; Kumar Balla, Putra; Chary Komandur, V. R.

2014-08-01

Tetragonal (TZ) and monoclinic (MZ) polymorphs of zirconia supports were synthesised by sol-gel method followed by variation of the calcination temperature. Tungstated (10 wt% WO3) supported on the zirconia polymorphs were prepared by impregnation method by using ammonium metatungstate precursor. The physico-chemical properties of the calcined catalysts were characterised by X-ray diffraction, UV-vis diffused reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), surface area and pore size distribution measurements to gain insight into the effect of morphology of the catalyst textural properties, and structure. The surface acidic properties have been determined by NH3 TPD method and also with FT-IR spectra of pyridine adsorption. Vapour phase dehydration of glycerol to acrolein was employed to investigate the catalytic functionalities. Glycerol conversion and acrolein selectivity was mainly dependent on the fraction of moderate acid sites with majority of them are due to Brønsted acidic sites. Monoclinic zirconia based catalysts have shown the highest activity and acrolein selectivity compared to the corresponding tetragonal zirconia catalysts.

Vapour phase dehydration of glycerol to acrolein over tungstated zirconia catalysts

International Nuclear Information System (INIS)

Rao Ginjupalli, Srinivasa; Mugawar, Sowmya; Rajan, Pethan N.; Kumar Balla, Putra; Chary Komandur, V.R.

2014-01-01

Tetragonal (TZ) and monoclinic (MZ) polymorphs of zirconia supports were synthesised by sol–gel method followed by variation of the calcination temperature. Tungstated (10 wt% WO 3 ) supported on the zirconia polymorphs were prepared by impregnation method by using ammonium metatungstate precursor. The physico-chemical properties of the calcined catalysts were characterised by X-ray diffraction, UV–vis diffused reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), surface area and pore size distribution measurements to gain insight into the effect of morphology of the catalyst textural properties, and structure. The surface acidic properties have been determined by NH 3 TPD method and also with FT-IR spectra of pyridine adsorption. Vapour phase dehydration of glycerol to acrolein was employed to investigate the catalytic functionalities. Glycerol conversion and acrolein selectivity was mainly dependent on the fraction of moderate acid sites with majority of them are due to Brønsted acidic sites. Monoclinic zirconia based catalysts have shown the highest activity and acrolein selectivity compared to the corresponding tetragonal zirconia catalysts.

Vapour phase dehydration of glycerol to acrolein over tungstated zirconia catalysts

Energy Technology Data Exchange (ETDEWEB)

Rao Ginjupalli, Srinivasa; Mugawar, Sowmya; Rajan, Pethan N.; Kumar Balla, Putra; Chary Komandur, V.R., E-mail: kvrchary@iict.res.in

2014-08-01

Tetragonal (TZ) and monoclinic (MZ) polymorphs of zirconia supports were synthesised by sol–gel method followed by variation of the calcination temperature. Tungstated (10 wt% WO{sub 3}) supported on the zirconia polymorphs were prepared by impregnation method by using ammonium metatungstate precursor. The physico-chemical properties of the calcined catalysts were characterised by X-ray diffraction, UV–vis diffused reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), surface area and pore size distribution measurements to gain insight into the effect of morphology of the catalyst textural properties, and structure. The surface acidic properties have been determined by NH{sub 3} TPD method and also with FT-IR spectra of pyridine adsorption. Vapour phase dehydration of glycerol to acrolein was employed to investigate the catalytic functionalities. Glycerol conversion and acrolein selectivity was mainly dependent on the fraction of moderate acid sites with majority of them are due to Brønsted acidic sites. Monoclinic zirconia based catalysts have shown the highest activity and acrolein selectivity compared to the corresponding tetragonal zirconia catalysts.

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

Science.gov (United States)

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

2017-04-11

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

Performance of (CoPC)n catalyst in active lithium-thionyl chloride cells

Science.gov (United States)

Shah, Pinakin M.

1990-01-01

An experimental study was conducted with anode limited D size cells to characterize the performance of an active lithium-thionyl chloride (Li/SOCl2) system using the polymeric cobalt phthalocyanine, (CoPC)n, catalyst in carbon cathodes. The author describes the results of this experiment with respect to initial voltage delays, operating voltages, and capacities. The effectiveness of the preconditioning methods evolved to alleviate passivation effects on storage are also discussed. The results clearly demonstrated the superior high rate capability of cells with the catalyst. The catalyst did not adversely impact the performance of cells after active storage for up to 6 months, while retaining its beneficial influences.

Active Iron Sites of Disordered Mesoporous Silica Catalyst FeKIL-2 in the Oxidation of Volatile Organic Compounds (VOC

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Mojca Rangus

2014-05-01

Full Text Available Iron-functionalized disordered mesoporous silica (FeKIL-2 is a promising, environmentally friendly, cost-effective and highly efficient catalyst for the elimination of volatile organic compounds (VOCs from polluted air via catalytic oxidation. In this study, we investigated the type of catalytically active iron sites for different iron concentrations in FeKIL-2 catalysts using advanced characterization of the local environment of iron atoms by a combination of X-ray Absorption Spectroscopy Techniques (XANES, EXAFS and Atomic-Resolution Scanning Transmission Electron Microscopy (AR STEM. We found that the molar ratio Fe/Si ≤ 0.01 leads to the formation of stable, mostly isolated Fe3+ sites in the silica matrix, while higher iron content Fe/Si > 0.01 leads to the formation of oligonuclear iron clusters. STEM imaging and EELS techniques confirmed the existence of these clusters. Their size ranges from one to a few nanometers, and they are unevenly distributed throughout the material. The size of the clusters was also found to be similar, regardless of the nominal concentration of iron (Fe/Si = 0.02 and Fe/Si = 0.05. From the results obtained from sample characterization and model catalytic tests, we established that the enhanced activity of FeKIL-2 with the optimal Fe/Si = 0.01 ratio can be attributed to: (1 the optimal concentration of stable isolated Fe3+ in the silica support; and (2 accelerated diffusion of the reactants in disordered mesoporous silica (FeKIL-2 when compared to ordered mesoporous silica materials (FeSBA-15, FeMCM-41.

A General Catalyst for Site-Selective C(sp(3))-H Bond Amination of Activated Secondary over Tertiary Alkyl C(sp(3))-H Bonds.

Science.gov (United States)

Scamp, Ryan J; Jirak, James G; Dolan, Nicholas S; Guzei, Ilia A; Schomaker, Jennifer M

2016-06-17

The discovery of transition metal complexes capable of promoting general, catalyst-controlled and selective carbon-hydrogen (C-H) bond amination of activated secondary C-H bonds over tertiary alkyl C(sp(3))-H bonds is challenging, as substrate control often dominates when reactive nitrene intermediates are involved. In this letter, we report the design of a new silver complex, [(Py5Me2)AgOTf]2, that displays general and good-to-excellent selectivity for nitrene insertion into propargylic, benzylic, and allylic C-H bonds over tertiary alkyl C(sp(3))-H bonds.

Edge termination of MoS2 and CoMoS catalyst particles

DEFF Research Database (Denmark)

Byskov, Line Sjolte; Nørskov, Jens Kehlet; Clausen, B. S.

2000-01-01

The edge termination of MoS2 and CoMoS catalyst particles is studied by density functional calculations. We show that for structures without vacancies Mo-terminated edges have the lowest edge energies. Creation of vacancies, which are believed to be active sites in these catalyst systems, leads...

Electrochemical characterization of nano-sized Pd-based catalysts as cathode materials in direct methanol fuel cells.

Science.gov (United States)

Choi, M; Han, C; Kim, I T; An, J C; Lee, J J; Lee, H K; Shim, J

2011-01-01

To improve the catalytic activity of palladium (Pd) as a cathode catalyst in direct methanol fuel cells (DMFCs), we prepared palladium-titanium oxide (Pd-TiO2) catalysts which the Pd and TiO2 nanoparticles were simultaneously impregnated on carbon. We selected Pd and TiO2 as catalytic materials because of their electrochemical stability in acid solution. The crystal structure and the loading amount of Pd and TiO2 on carbon were characterized by X-ray diffraction (XRD) and energy dispersive X-ray microanalysis (EDX). The electrochemical characterization of Pd-TiO2/C catalysts for the oxygen reduction reaction was carried out in half and single cell systems. The catalytic activities of the Pd-TiO2 catalysts were strongly influenced by the TiO2 content. In the single cell test, the Pd-TiO2 catalysts showed very comparable performance to the Pt catalyst.

Site-controlled InGaN/GaN single-photon-emitting diode

Energy Technology Data Exchange (ETDEWEB)

Zhang, Lei; Deng, Hui, E-mail: dengh@umich.edu [Department of Physics, University of Michigan, 450 Church St., Ann Arbor, Michigan 48109 (United States); Teng, Chu-Hsiang; Ku, Pei-Cheng, E-mail: peicheng@umich.edu [Department of Electrical Engineering and Computer Science, University of Michigan, 1301 Beal Ave., Ann Arbor, Michigan 48109 (United States)

2016-04-11

We report single-photon emission from electrically driven site-controlled InGaN/GaN quantum dots. The device is fabricated from a planar light-emitting diode structure containing a single InGaN quantum well, using a top-down approach. The location, dimension, and height of each single-photon-emitting diode are controlled lithographically, providing great flexibility for chip-scale integration.

Basic study of catalyst aging in the H-coal process

Energy Technology Data Exchange (ETDEWEB)

Cable, T.L.; Massoth, F.E.; Thomas, M.G.

1985-04-01

Samples of CoMo/Al/sub 2/O/sub 3/ catalysts used in an H-coal process demonstration run were studied to determine causes of catalyst deactivation. Physical and surface properties of the aged and regenerated catalysts were examined. Model compounds were used to assess four catalyst activity functions, viz., hydrodesulfurization (HDS), hydrogenation, cracking and hydrodeoxygenation (HDO). Other tests were performed to study the effects of coke and metals separately on the four catalyst activity functions. Catalyst coke content and metal deposits first increased rapidly, then more gradually with exposure time in the process run. Surface area and pore volume markedly decreased with exposure time. Catalyst activities of aged catalysts showed a rapid decline with exposure time. One-day exposure to coal resulted in significant losses in HDS and hydrogenation activities and nearly complete loss in cracking and HDO activities. Although metal deposits caused some permanent catalyst deactivation, coke had a much greater effect. Regenerated catalysts showed less recovery of catalytic activity as processing time increased. These results agreed well with product inspections from the process run. Oxygen chemisorption on aged-regenerated catalysts decreased with catalyst exposure time, indicating a significant loss of active sites. However, ESCA results showed no evidence of extensive sintering of the active MoS/sub 2/ phase. Permanent deactivation of the longer-time exposed catalysts can be ascribed, at least partly, to lateral growth of the active molybdenum sulfide phase. In addition, some loss in cobalt promotion occurred early in the process, which may account for the rapid loss in HDS and HDO activity in regenerated catalysts. 24 references.

Part I: A Comparative Thermal Aging Study on the Regenerability of Rh/Al2O3 and Rh/CexOy-ZrO2 as Model Catalysts for Automotive Three Way Catalysts

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Qinghe Zheng

2015-10-01

Full Text Available The rhodium (Rh component in automotive three way catalysts (TWC experiences severe thermal deactivation during fuel shutoff, an engine mode (e.g., at downhill coasting used for enhancing fuel economy. In a subsequent switch to a slightly fuel rich condition, in situ catalyst regeneration is accomplished by reduction with H2 generated through steam reforming catalyzed by Rh0 sites. The present work reports the effects of the two processes on the activity and properties of 0.5% Rh/Al2O3 and 0.5% Rh/CexOy-ZrO2 (CZO as model catalysts for Rh-TWC. A very brief introduction of three way catalysts and system considerations is also given. During simulated fuel shutoff, catalyst deactivation is accelerated with increasing aging temperature from 800 °C to 1050 °C. Rh on a CZO support experiences less deactivation and faster regeneration than Rh on Al2O3. Catalyst characterization techniques including BET surface area, CO chemisorption, TPR, and XPS measurements were applied to examine the roles of metal-support interactions in each catalyst system. For Rh/Al2O3, strong metal-support interactions with the formation of stable rhodium aluminate (Rh(AlO2y complex dominates in fuel shutoff, leading to more difficult catalyst regeneration. For Rh/CZO, Rh sites were partially oxidized to Rh2O3 and were relatively easy to be reduced to active Rh0 during regeneration.

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

KAUST Repository

Al Mana, Noor

2016-01-01

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

Advances in X-ray Chemical Imaging of a Single Catalyst Particle

NARCIS (Netherlands)

Kalirai, S.

2016-01-01

Fluid Catalytic Cracking (FCC) catalyst particles are complex, hierarchical, multi-component systems that are used ubiquitously for the production of valuable hydrocarbons such as gasoline and propylene from crude oil feedstocks. In the FCC unit, high heat, steam and feedstocks contaminated with

Understanding the Performance and Stability of Supported Ni-Co-Based Catalysts in Phenol HDO

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Thuan M. Huynh

2016-11-01

Full Text Available Performances of bimetallic catalysts (Ni-Co supported on different acidic carriers (HZSM-5, HBeta, HY, ZrO2 and corresponding monometallic Ni catalysts in aqueous phase hydrodeoxygenation of phenol were compared in batch and continuous flow modes. The results revealed that the support acidity plays an important role in deoxygenation as it mainly controls the oxygen-removing steps in the reaction network. At the same time, sufficient hydrothermal stability of a solid catalyst is essential. Batch experiments revealed 10Ni10Co/HZSM-5 to be the best-performing catalyst in terms of conversion and cyclohexane yield. Complementary continuous runs provided more insights into the relationship between catalyst structure, efficiency and stability. After 24 h on-stream, the catalyst still reveals 100% conversion and a slight loss (from 100% to 90% in liquid hydrocarbon selectivity. The observed alloy of Co with Ni increased dispersion and stability of Ni-active sites, and combination with HZSM-5 resulted in a well-balanced ratio of metal and acid sites which promoted all necessary steps in preferred pathways. This was proved by studies of fresh and spent catalysts using various characterization techniques (N2 physisorption, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, transmission electron microscopy (TEM and infrared spectroscopy of adsorbed pyridine (pyr-IR.

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

KAUST Repository

Al-ShaikhAli, Anaam H.

2016-11-30

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

All-sky-imaging capabilities for ionospheric space weather research using geomagnetic conjugate point observing sites

Science.gov (United States)

Martinis, C.; Baumgardner, J.; Wroten, J.; Mendillo, M.

2018-04-01

Optical signatures of ionospheric disturbances exist at all latitudes on Earth-the most well known case being visible aurora at high latitudes. Sub-visual emissions occur equatorward of the auroral zones that also indicate periods and locations of severe Space Weather effects. These fall into three magnetic latitude domains in each hemisphere: (1) sub-auroral latitudes ∼40-60°, (2) mid-latitudes (20-40°) and (3) equatorial-to-low latitudes (0-20°). Boston University has established a network of all-sky-imagers (ASIs) with sites at opposite ends of the same geomagnetic field lines in each hemisphere-called geomagnetic conjugate points. Our ASIs are autonomous instruments that operate in mini-observatories situated at four conjugate pairs in North and South America, plus one pair linking Europe and South Africa. In this paper, we describe instrument design, data-taking protocols, data transfer and archiving issues, image processing, science objectives and early results for each latitude domain. This unique capability addresses how a single source of disturbance is transformed into similar or different effects based on the unique "receptor" conditions (seasonal effects) found in each hemisphere. Applying optical conjugate point observations to Space Weather problems offers a new diagnostic approach for understanding the global system response functions operating in the Earth's upper atmosphere.

American National Standard: criteria and guidelines for assessing capability for surface faulting at nuclear power plant sites

International Nuclear Information System (INIS)

Anon.

1982-01-01

This standard provides applicants and consultants with criteria and guidelines for investigations directed toward the assessment of the capability for surface faulting at nuclear power plant sites. Assessment of vibratory ground motion resulting from faulting is not treated in these guidelines

Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces

Science.gov (United States)

McBriarty, Martin E.

Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.

Metal-Catalyst-Free Synthesis and Characterization of Single-Crystalline Silicon Oxynitride Nanowires

Directory of Open Access Journals (Sweden)

Shuang Xi

2012-01-01

Full Text Available Large quantities of single-crystal silicon oxynitride nanowires with high N concentration have been synthesized directly on silicon substrate at 1200°C without using any metal catalyst. The diameter of these ternary nanowires is ranging from 10 to 180 nm with log-normal distribution, and the length of these nanowires varies from a few hundreds of micrometers to several millimeters. A vapor-solid mechanism was proposed to explain the growth of the nanowires. These nanowires are grown to form a disordered mat with an ultrabright white nonspecular appearance. The mat demonstrates highly diffusive reflectivity with the optical reflectivity of around 80% over the whole visible wavelength, which is comparable to the most brilliant white beetle scales found in nature. The whiteness might be resulted from the strong multiscattering of a large fraction of incident light on the disordered nanowire mat. These ultra-bright white nanowires could form as reflecting surface to meet the stringent requirements of bright-white light-emitting-diode lighting for higher optical efficiency. They can also find applications in diverse fields such as sensors, cosmetics, paints, and tooth whitening.

Perovskite Catalysts—A Special Issue on Versatile Oxide Catalysts

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Yu-Chuan Lin

2014-08-01

Full Text Available Perovskite-type catalysts have been prominent oxide catalysts for many years due to attributes such as flexibility in choosing cations, significant thermal stability, and the unique nature of lattice oxygen. Nearly 90% metallic elements of the Periodic Table can be stabilized in perovskite’s crystalline framework [1]. Moreover, by following the Goldschmidt rule [2], the A- and/or B-site elements can be partially substituted, making perovskites extremely flexible in catalyst design. One successful example is the commercialization of noble metal-incorporated perovskites (e.g., LaFe0.57Co0.38Pd0.05O3 for automotive emission control used by Daihatsu Motor Co. Ltd. [3]. Thus, growing interest in, and application of perovskites in the fields of material sciences, heterogeneous catalysis, and energy storage have prompted this Special Issue on perovskite catalysts. [...

Silica-supported (nBuCp)2ZrCl2: Effect of catalyst active center distribution on ethylene-1-hexene copolymerization

KAUST Repository

Atiqullah, Muhammad

2013-08-12

Metallocenes are a modern innovation in polyolefin catalysis research. Therefore, two supported metallocene catalysts-silica/MAO/(nBuCp)2ZrCl2 (Catalyst 1) and silica/nBuSnCl3/MAO/(nBuCp)2ZrCl2 (Catalyst 2), where MAO is methylaluminoxane-were synthesized, and subsequently used to prepare, without separate feeding of MAO, ethylene-1-hexene Copolymer 1 and Copolymer 2, respectively. Fouling-free copolymerization, catalyst kinetic stability and production of free-flowing polymer particles (replicating the catalyst particle size distribution) confirmed the occurrence of heterogeneous catalysis. The catalyst active center distribution was modeled by deconvoluting the measured molecular weight distribution and copolymer composition distribution. Five different active center types were predicted for each catalyst, which was corroborated by successive self-nucleation and annealing experiments, as well as by an extended X-ray absorption fine structure spectroscopy report published in the literature. Hence, metallocenes impregnated particularly on an MAO-pretreated support may be rightly envisioned to comprise an ensemble of isolated single sites that have varying coordination environments. This study shows how the active center distribution and the design of supported MAO anions affect copolymerization activity, polymerization mechanism and the resulting polymer microstructures. Catalyst 2 showed less copolymerization activity than Catalyst 1. Strong chain transfer and positive co-monomer effect-both by 1-hexene-were common. Each copolymer demonstrated vinyl, vinylidene and trans-vinylene end groups, and compositional heterogeneity. All these findings were explained, as appropriate, considering the modeled active center distribution, MAO cage structure repeat units, proposed catalyst surface chemistry, segregation effects and the literature that concerns and supports this study. While doing so, new insights were obtained. Additionally, future research, along the direction

Silica-supported (nBuCp)2ZrCl2: Effect of catalyst active center distribution on ethylene-1-hexene copolymerization

KAUST Repository

Atiqullah, Muhammad; Anantawaraskul, Siripon; Emwas, Abdul-Hamid M.; Al-Harthi, Mamdouh Ahmed; Hussain, Ikram; Ul-Hamid, Anwar; Hossaen, Anwar

2013-01-01

Metallocenes are a modern innovation in polyolefin catalysis research. Therefore, two supported metallocene catalysts-silica/MAO/(nBuCp)2ZrCl2 (Catalyst 1) and silica/nBuSnCl3/MAO/(nBuCp)2ZrCl2 (Catalyst 2), where MAO is methylaluminoxane-were synthesized, and subsequently used to prepare, without separate feeding of MAO, ethylene-1-hexene Copolymer 1 and Copolymer 2, respectively. Fouling-free copolymerization, catalyst kinetic stability and production of free-flowing polymer particles (replicating the catalyst particle size distribution) confirmed the occurrence of heterogeneous catalysis. The catalyst active center distribution was modeled by deconvoluting the measured molecular weight distribution and copolymer composition distribution. Five different active center types were predicted for each catalyst, which was corroborated by successive self-nucleation and annealing experiments, as well as by an extended X-ray absorption fine structure spectroscopy report published in the literature. Hence, metallocenes impregnated particularly on an MAO-pretreated support may be rightly envisioned to comprise an ensemble of isolated single sites that have varying coordination environments. This study shows how the active center distribution and the design of supported MAO anions affect copolymerization activity, polymerization mechanism and the resulting polymer microstructures. Catalyst 2 showed less copolymerization activity than Catalyst 1. Strong chain transfer and positive co-monomer effect-both by 1-hexene-were common. Each copolymer demonstrated vinyl, vinylidene and trans-vinylene end groups, and compositional heterogeneity. All these findings were explained, as appropriate, considering the modeled active center distribution, MAO cage structure repeat units, proposed catalyst surface chemistry, segregation effects and the literature that concerns and supports this study. While doing so, new insights were obtained. Additionally, future research, along the direction

Nanocrystalline Hierarchical ZSM-5: An Efficient Catalyst for the Alkylation of Phenol with Cyclohexene.

Science.gov (United States)

Radhika, N P; Selvin, Rosilda; Kakkar, Rita; Roselin, L Selva

2018-08-01

In this paper, authors report the synthesis of nanocrystalline hierarchical zeolite ZSM-5 and its application as a heterogeneous catalyst in the alkylation of phenol with cyclohexene. The catalyst was synthesized by vacuum-concentration coupled hydrothermal technique in the presence of two templates. This synthetic route could successfully introduce pores of higher hierarchy in the zeolite ZSM-5 structure. Hierarchical ZSM-5 could catalyse effectively the industrially important reaction of cyclohexene with phenol. We ascribe the high efficiency of the catalyst to its conducive structural features such as nanoscale size, high surface area, presence of hierarchy of pores and existence of Lewis sites along with Brønsted acid sites. The effect of various reaction parameters like duration, catalyst amount, reactant mole ratio and temperature were assessed. Under optimum reaction conditions, the catalyst showed up to 65% selectivity towards the major product, cyclohexyl phenyl ether. There was no discernible decline in percent conversion or selectivity even when the catalyst was re-used for up to four runs. Kinetic studies were done through regression analysis and a mechanistic route based on LHHW model was suggested.

XRLINE, a program to evaluate the crystallite size of supported metal catalysts by single X-ray profile Fourier analysis

International Nuclear Information System (INIS)

Aldea, N.; Indrea, E.

1990-01-01

The computer program presented is based on the Fourier analysis of a singel X-ray diffraction profile. An X-ray diffraction method is presented which is capable of determining the average particle size, microstrain, stacking fault probability as well as the particle size distribution function in crystalline materials. The main numerical methods used are: (i) Smoothing and interpolation by 3rd-order piecewise polynomial functions or by cubic splines with the least squares method; (ii) numerical integration by successive five points formulae and numerical derivative by cubic splines with the least squares method; (iii) estimation of parameters by the weighted least squares method. The results for supported platinum catalysts used in the H/D isotopic exchange reaction are illustrated. (orig.)

Hydroformylation of 1-Hexene over Rh/Nano-Oxide Catalysts

Directory of Open Access Journals (Sweden)

Sari Suvanto

2013-03-01

Full Text Available The effect of nanostructured supports on the activity of Rh catalysts was studied by comparing the catalytic performance of nano- and bulk-oxide supported Rh/ZnO, Rh/SiO2 and Rh/TiO2 systems in 1-hexene hydroformylation. The highest activity with 100% total conversion and 96% yield of aldehydes was obtained with the Rh/nano-ZnO catalyst. The Rh/nano-ZnO catalyst was found to be more stable and active than the corresponding rhodium catalyst supported on bulk ZnO. The favorable morphology of Rh/nano-ZnO particles led to an increased metal content and an increased number of weak acid sites compared to the bulk ZnO supported catalysts. Both these factors favored the improved catalytic performance. Improvements of catalytic properties were obtained also with the nano-SiO2 and nano-TiO2 supports in comparison with the bulk supports. All of the catalysts were characterized by scanning electron microscope (SEM, inductively coupled plasma mass spectrometry (ICP-MS, BET, powder X-ray diffraction (PXRD and NH3- temperature-programmed desorption (TPD.

Investigation of Au-Pt/C electro-catalysts for oxygen reduction reaction

International Nuclear Information System (INIS)

Lin Rui; Zhang Haiyan; Zhao Tiantian; Cao Chunhui; Yang Daijun; Ma Jianxin

2012-01-01

Highlights: ► Au-Pt core shell catalyst. ► Seed-mediated growth method. ► Au-Pt (2:4)/C best activity toward ORR. ► Four-electron pathway in acid solution. ► Single cell performance. - Abstract: Carbon-supported Au-Pt core shell nano-structured catalysts were synthesized by the seed-mediated growth method. The nano-structured catalysts were characterized by UV–vis spectroscopy, X-ray photoelectron spectra (XPS) and transmission electron microscopy (TEM) techniques. The oxygen reduction reaction (ORR) activity of the Au-Pt/C was tested by means of linear sweep voltammetry (LSV) by employing rotating disk electrode (RDE). It revealed that Au-Pt (2:4)/C (atomic ratio) catalyst exhibited the best catalytic activity toward ORR. Au-Pt (2:4)/C proceeded by an approximately four-electron pathway in acid solution, through which molecular oxygen was directly reduced to water. The stability of Au-Pt (2:4)/C is tested by cyclic voltammetry for 500 cycles. The performance of the membrane electrode assembly (MEA) prepared by Au-Pt (2:4)/C as the cathode catalyst in a single proton exchange membrane fuel cell (PEMFC) generated a maximum power density of 479 mW cm −2 at 0.431 V using H 2 and O 2 at 80 °C.

Graphitized Carbon: A Promising Stable Cathode Catalyst Support Material for Long Term PEMFC Applications.

Science.gov (United States)

Mohanta, Paritosh Kumar; Regnet, Fabian; Jörissen, Ludwig

2018-05-28

Stability of cathode catalyst support material is one of the big challenges of polymer electrolyte membrane fuel cells (PEMFC) for long term applications. Traditional carbon black (CB) supports are not stable enough to prevent oxidation to CO₂ under fuel cell operating conditions. The feasibility of a graphitized carbon (GC) as a cathode catalyst support for low temperature PEMFC is investigated herein. GC and CB supported Pt electrocatalysts were prepared via an already developed polyol process. The physical characterization of the prepared catalysts was performed using transmission electron microscope (TEM), X-ray Powder Diffraction (XRD) and inductively coupled plasma optical emission spectrometry (ICP-OES) analysis, and their electrochemical characterizations were conducted via cyclic voltammetry(CV), rotating disk electrode (RDE) and potential cycling, and eventually, the catalysts were processed using membrane electrode assemblies (MEA) for single cell performance tests. Electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SEM) have been used as MEA diagonostic tools. GC showed superior stability over CB in acid electrolyte under potential conditions. Single cell MEA performance of the GC-supported catalyst is comparable with the CB-supported catalyst. A correlation of MEA performance of the supported catalysts of different Brunauer⁻Emmett⁻Teller (BET) surface areas with the ionomer content was also established. GC was identified as a promising candidate for catalyst support in terms of both of the stability and the performance of fuel cell.

Catalyst deterioration over the lifetime of small utility engines.

Science.gov (United States)

Doll, Nicholas J; Reisel, John R

2007-10-01

In this paper, the deterioration of catalysts in small, four-stroke, spark-ignition engines is described. The laboratory testing performed followed a proven test method that mimics the lifetime of a small air-cooled utility engine operating under normal field conditions. The engines used were single-cylinder, 6.5-hp, side-valve engines. These engines have a nominal 125-hr lifetime. The effectiveness of the catalysts was determined by testing exhaust emissions before and after the catalyst to determine the catalyst's efficiency. This was done several times during the lifetime of the engines to determine the deterioration in the performance of the catalysts at lowering pollutant emissions. Additional testing was performed on the catalysts to determine wear patterns, contamination, and recoverable activity. The results indicate that considerable catalyst deterioration is occurring over the lifetime of the engine. The results reveal that soot buildup, poisons, and active surface loss appear to be the contributing factors to the deterioration. These results were determined after analyzing the exhaust emissions data, scanning electron microscope results analysis, and the impact of regeneration attempts. An ANOVA statistical analysis was performed, and it was determined that the emissions are also impacted, to some degree, by time and the engine itself.

Enhancement of Ag-Based Plasmonic Photocatalysis in Hydrogen Production from Ammonia Borane by the Assistance of Single-Site Ti-Oxide Moieties within a Silica Framework.

Science.gov (United States)

Verma, Priyanka; Kuwahara, Yasutaka; Mori, Kohsuke; Yamashita, Hiromi

2017-03-13

Ag nanoparticles (NPs) have gained great attention owing to their interesting plasmonic properties and efficient catalysis under visible-light irradiation. In this study, an Ag-based plasmonic catalyst supported on mesoporous silica with isolated and tetrahedrally coordinated single-site Ti-oxide moieties, namely, Ag/Ti-SBA-15, was designed with the purpose of utilizing the broad spectral range of solar energy. The Ti-SBA-15 support allows the deposition of small Ag NPs with a narrow size distribution. The chemical structure, morphology, and optical properties of the prepared catalyst were characterized by techniques such as UV/Vis, FT extended X-ray absorption fine structure, and X-ray photoelectron spectroscopy, field-emission SEM, TEM, and N 2 physisorption studies. The catalytic activity of Ag/Ti-SBA-15 in hydrogen production from ammonia borane by hydrolysis was significantly enhanced in comparison with Ag/SBA-15 without Ti-oxide moieties and Ag/TiO 2 /SBA-15 involving agglomerated TiO 2 , both in the dark and under light irradiation. Improved electron transfer under light irradiation caused by the creation of heterojunctions between Ag NPs and Ti-oxide moieties explains the results obtained in the present study. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrotreatment of heavy oil from coal liquefaction on Sulfide Ni - W Catalysts

International Nuclear Information System (INIS)

Zhi-ping Lei; Li-juan Gao; Heng-fu Shui; Shi-biao, Ren; Zhi-cai Wang; Kang-shi Gang

2011-01-01

Heavy oil (distillation temperature: 320-340 deg C) derived from the direct coal liquefaction process using Shengli coal were hydrotreated using sulfided Ni-Mo/Al 2 O 3 , Ni-W/Al 2 O 3 , and Ni-W/SiO 2 catalysts respectively. The sulfided catalysts were characterized by BET, XRD, H 2 -TPR and NH 3 -TPD respectively. The evaluations of the hydrodenitrogenation (HDN) and hydrodearomatization (HDA) properties of heavy oil on the three catalysts were carried out at 400 deg C and 5.0 MPa initial H2 pressure. The W-based catalysts displayed better performances than Mo-based catalysts for the HDN and HDA reactions. Al 2 O 3 supported catalysts were found to have higher catalytic activities than on SiO 2 supported ones. The activities of sulfided catalysts were associated mainly with the nature of active sites, acidity, metal sulfide crystallite size and the amount of the reducible sulfur species of metal sulfide. (author)

An Erbium-Based Bifuctional Heterogeneous Catalyst: A Cooperative Route Towards C-C Bond Formation

Directory of Open Access Journals (Sweden)

Manuela Oliverio

2014-07-01

Full Text Available Heterogeneous bifuctional catalysts are multifunctional synthetic catalysts enabling efficient organic transformations by exploiting two opposite functionalities without mutual destruction. In this paper we report the first Er(III-based metallorganic heterogeneous catalyst, synthesized by post-calcination MW-assisted grafting and modification of the natural aminoacid L-cysteine. The natural acid–base distance between sites was maintained to assure the cooperation. The applicability of this new bifunctional heterogeneous catalyst to C-C bond formation and the supposed mechanisms of action are discussed as well.

Elucidating the Origin of Hydrogen Evolution Reaction Activity in Mono- and Bimetallic Metal- and Nitrogen-Doped Carbon Catalysts (Me-N-C).

Science.gov (United States)

Shahraei, Ali; Moradabadi, Ashkan; Martinaiou, Ioanna; Lauterbach, Stefan; Klemenz, Sebastian; Dolique, Stephanie; Kleebe, Hans-Joachim; Kaghazchi, Payam; Kramm, Ulrike I

2017-08-02

In this work, we present a comprehensive study on the role of metal species in MOF-based Me-N-C (mono- and bimetallic) catalysts for the hydrogen evolution reaction (HER). The catalysts are investigated with respect to HER activity and stability in alkaline electrolyte. On the basis of the structural analysis by X-ray diffraction, X-ray-induced photoelectron spectroscopy, and transmission electron microscopy, it is concluded that MeN 4 sites seem to dominate the HER activity of these catalysts. There is a strong relation between the amount of MeN 4 sites that are formed and the energy of formation related to these sites integrated at the edge of a graphene layer, as obtained from density functional theory (DFT) calculations. Our results show, for the first time, that the combination of two metals (Co and Mo) in a bimetallic (Co,Mo)-N-C catalyst allows hydrogen production with a significantly improved overpotential in comparison to its monometallic counterparts and other Me-N-C catalysts. By the combination of experimental results with DFT calculations, we show that the origin of the enhanced performance of our (Co,Mo)-N-C catalyst seems to be provided by an improved hydrogen binding energy on one MeN 4 site because of the presence of a second MeN 4 site in its close vicinity, as investigated in detail for our most active (Co,Mo)-N-C catalyst. The outstanding stability and good activity make especially the bimetallic Me-N-C catalysts interesting candidates for solar fuel applications.

Mesoporous Zeolite Single Crystals for Catalytic Hydrocarbon Conversion

DEFF Research Database (Denmark)

Schmidt, I.; Christensen, Claus H.; Kustova, Marina

2005-01-01

Recently, mesoporous zeolite single crystals were discovered. They constitute a novel family of materials that features a combined micropore and mesopore architecture within each individual crystal. Here, we briefly summarize recent catalytic results from cracking and isomerization of alkalies......, alkylation of aromatics and present new results on isomerization of aromatics. Specifically, the shape-selective isomerization of meta-xylenc into para-xylene and ortho-xylene is studied. In all these reactions, rnesoporous zeolite single crystals prove to be unique catalysts since they provide easy...... transport to and from active sites and at the same time maintain the shape-selectivity required. Thus, all these results support the idea that the beneficial effect of the mesopores system in the mesoporous zeolite single crystals call be solely attributed to enhanced mass transport....

Report of liquefaction catalyst study meeting (March 1996); Ekika shokubai kentokai hokoku

Energy Technology Data Exchange (ETDEWEB)

NONE

1996-03-01

Studied in the research are four iron-based catalysts, which are natural pyrite, synthetic iron sulfide, synthetic iron hydroxide, and catalyst-attached carbon. Tanito Harum coal is treated in a 0.01t/d-capable continuous operation furnace (once-through) under conditions of 450 degrees C and 170kgf/cm{sup 2} with catalyst addition of 1.0, 3.0wt% (catalyst-attached carbon 0.6, 1.0wt%), and a liquid yield of 41.5-48.6wt%-daf coal is achieved. A higher yield results when more catalyst is added. The same yield as achieved by the addition of 3wt% natural pyrite is obtained by the addition of 1.9wt% synthetic iron sulfide, 1.5wt% of synthetic iron hydroxide, or 0.7wt% catalyst-attached coal. The catalyst cost for treating a ton of coal is 4-9 hundred yen, which is far more expensive than the cost set forth as the target. Catalysts whose production process embodiment is now under study are natural pyrite and synthetic iron sulfide, and studies for others are just preliminary. Provided that the practical application of the liquefaction technology realizes in about 2000, then the petroleum price is predicted to be 23 dollars per barrel. Coal liquefaction products will have to be produced at a cost which will enable competition with the said petroleum price. (NEDO)

Reduction of nanowire diameter beyond lithography limits by controlled catalyst dewetting

Science.gov (United States)

Calahorra, Yonatan; Kerlich, Alexander; Amram, Dor; Gavrilov, Arkady; Cohen, Shimon; Ritter, Dan

2016-04-01

Catalyst assisted vapour-liquid-solid is the most common method to realize bottom-up nanowire growth; establishing a parallel process for obtaining nanoscale catalysts at pre-defined locations is paramount for further advancement towards commercial nanowire applications. Herein, the effect of a selective area mask on the dewetting of metallic nanowire catalysts, deposited within lithography-defined mask pinholes, is reported. It was found that thin disc-like catalysts, with diameters of 120-450 nm, were transformed through dewetting into hemisphere-like catalysts, having diameters 2-3 fold smaller; the process was optimized to about 95% yield in preventing catalyst splitting, as would otherwise be expected due to their thickness-to-diameter ratio, which was as low as 1/60. The catalysts subsequently facilitated InP and InAs nanowire growth. We suggest that the mask edges prevent surface migration mediated spreading of the dewetted metal, and therefore induce its agglomeration into a single particle. This result presents a general strategy to diminish lithography-set dimensions for NW growth, and may answer a fundamental challenge faced by bottom-up nanowire technology.

Design of a surface alloy catalyst for steam reforming

DEFF Research Database (Denmark)

Besenbacher, F.; Chorkendorff, Ib; Clausen, B.S.

1998-01-01

Detailed studies of elementary chemical processes on well-characterized single crystal surfaces have contributed substantially to the understanding of heterogeneous catalysis. insight into the structure of surface alloys combined with an understanding of the relation between the surface compositi...... and reactivity is shown to lead directly to new ideas for catalyst design, The feasibility of such an approach is illustrated by the synthesis, characterization, and tests of a high-surface area gold-nickel catalyst for steam reforming....

Organic chemistry. A rhodium catalyst for single-step styrene production from benzene and ethylene.

Science.gov (United States)

Vaughan, Benjamin A; Webster-Gardiner, Michael S; Cundari, Thomas R; Gunnoe, T Brent

2015-04-24

Rising global demand for fossil resources has prompted a renewed interest in catalyst technologies that increase the efficiency of conversion of hydrocarbons from petroleum and natural gas to higher-value materials. Styrene is currently produced from benzene and ethylene through the intermediacy of ethylbenzene, which must be dehydrogenated in a separate step. The direct oxidative conversion of benzene and ethylene to styrene could provide a more efficient route, but achieving high selectivity and yield for this reaction has been challenging. Here, we report that the Rh catalyst ((Fl)DAB)Rh(TFA)(η(2)-C2H4) [(Fl)DAB is N,N'-bis(pentafluorophenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene; TFA is trifluoroacetate] converts benzene, ethylene, and Cu(II) acetate to styrene, Cu(I) acetate, and acetic acid with 100% selectivity and yields ≥95%. Turnover numbers >800 have been demonstrated, with catalyst stability up to 96 hours. Copyright © 2015, American Association for the Advancement of Science.

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

Science.gov (United States)

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

2018-06-01

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

Recent development of active nanoparticle catalysts for fuel cell reactions

Energy Technology Data Exchange (ETDEWEB)

Mazumder, Vismadeb; Lee, Youngmin; Sun, Shouheng [Department of Chemistry Brown University Providence, RI (United States)

2010-04-23

This review focuses on the recent advances in the synthesis of nanoparticle (NP) catalysts of Pt-, Pd- and Au-based NPs as well as composite NPs. First, new developments in the synthesis of single-component Pt, Pd and Au NPs are summarized. Then the chemistry used to make alloy and composite NP catalysts aiming to enhance their activity and durability for fuel cell reactions is outlined. The review next introduces the exciting new research push in developing CoN/C and FeN/C as non-Pt catalysts. Examples of size-, shape- and composition-dependent catalyses for oxygen reduction at cathode and formic acid oxidation at anode are highlighted to illustrate the potentials of the newly developed NP catalysts for fuel cell applications. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

Greater bottoms upgrading with Albemarle's e-bed catalysts

Energy Technology Data Exchange (ETDEWEB)

Toshima, H.; Sedlacek, Z.; Backhouse, D.; Mayo, S.; Plantenga, F. [Albemarle Catalysts, Houston, TX (United States)

2006-07-01

The E-bed process is a heavy oil upgrading technology that produces near isothermal reactor conditions at a constant catalytic activity. However, E-bed conversion optimization is limited by reactor and downstream fouling problems caused by asphaltene precipitation. While asphaltene precipitation can controlled by reducing hydrogenation, high hydrogenation activity is needed for the removal of sulfur and heavy metals. This presentation described an asphaltene molecule management concept to reduce the fouling of E-bed units. Sediment reduction and high hydrogenation catalysts were used in a modified E-bed process with a variety of feeds and operating conditions. It was observed that the KF1312 catalyst achieved much higher sediment-reduction capability along with satisfactory hydrogenation activity with the different kinds of crude oil sources tested. The catalyst hydrocracked the asphaltenes into smaller molecules, which created greater asphaltene solubility. The sediment reduction capacity of the catalyst-staging technology is now being optimized. It was concluded that the technology will help to reduce fouling in E-bed processes and lead to improved conversion rates for refineries. refs., tabs., figs.

Regeneration of Pt-catalysts deactivated in municipal waste flue gas with H2/N2 and the effect of regeneration step on the SCR catalyst

DEFF Research Database (Denmark)

Due-Hansen, Johannes; Rasmussen, Søren Birk; Kustov, Arkadii

Municipal waste flue gas was previously found to deactivate the Pt-based CO oxidation catalyst severely. In the specific case studied, siloxanes were found to cause the deactivation. An on-site method for complete regeneration of the catalyst activity was found without shutdown of the flue gas...... stream, i.e. by in situ treatment of the Pt-catalyst by reductive H2-gas. However, introduction of H2 gas in the gas stream could also affect other units in the tail pipe gas cleaning system. Of special interest here, is the effect of hydrogen gas on the performance of the deNOx + SCR catalytic process...

Constrained Geometry Organotitanium Catalysts Supported on Nanosized Silica for Ethylene (co)Polymerization.

Science.gov (United States)

Li, Kuo-Tseng; Wu, Ling-Huey

2017-05-05

Supported olefin polymerization catalysts can prevent reactor-fouling problems and produce uniform polymer particles. Constrained geometry complexes (CGCs) have less sterically hindered active sites than bis-cyclopentadienyl metallocene catalysts. In the literature, micrometer-sized silica particles were used for supporting CGC catalysts, which might have strong mass transfer limitations. This study aims to improve the activity of supported CGC catalysts by using nanometer-sized silica. Ti[(C₅Me₄)SiMe₂(N t Bu)]Cl₂, a "constrained-geometry" titanium catalyst, was supported on MAO-treated silicas (nano-sized and micro-sized) by an impregnation method. Ethylene homo-polymerization and co-polymerization with 1-octene were carried out in a temperature range of 80-120 °C using toluene as the solvent. Catalysts prepared and polymers produced were characterized. For both catalysts and for both reactions, the maximum activities occurred at 100 °C, which is significantly higher than that (60 °C) reported before for supported bis-cyclopentadienyl metallocene catalysts containing zirconium, and is lower than that (≥140 °C) used for unsupported Ti[(C₅Me₄)SiMe₂(N t Bu)]Me₂ catalyst. Activities of nano-sized catalyst were 2.6 and 1.6 times those of micro-sized catalyst for homopolymerization and copolymerization, respectively. The former produced polymers with higher crystallinity and melting point than the latter. In addition, copolymer produced with nanosized catalyst contained more 1-octene than that produced with microsized catalyst.

Single-site Lennard-Jones models via polynomial chaos surrogates of Monte Carlo molecular simulation

Energy Technology Data Exchange (ETDEWEB)

Kadoura, Ahmad, E-mail: ahmad.kadoura@kaust.edu.sa, E-mail: adil.siripatana@kaust.edu.sa, E-mail: shuyu.sun@kaust.edu.sa, E-mail: omar.knio@kaust.edu.sa; Sun, Shuyu, E-mail: ahmad.kadoura@kaust.edu.sa, E-mail: adil.siripatana@kaust.edu.sa, E-mail: shuyu.sun@kaust.edu.sa, E-mail: omar.knio@kaust.edu.sa [Computational Transport Phenomena Laboratory, The Earth Sciences and Engineering Department, The Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal 23955-6900 (Saudi Arabia); Siripatana, Adil, E-mail: ahmad.kadoura@kaust.edu.sa, E-mail: adil.siripatana@kaust.edu.sa, E-mail: shuyu.sun@kaust.edu.sa, E-mail: omar.knio@kaust.edu.sa; Hoteit, Ibrahim, E-mail: ibrahim.hoteit@kaust.edu.sa [Earth Fluid Modeling and Predicting Group, The Earth Sciences and Engineering Department, The Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal 23955-6900 (Saudi Arabia); Knio, Omar, E-mail: ahmad.kadoura@kaust.edu.sa, E-mail: adil.siripatana@kaust.edu.sa, E-mail: shuyu.sun@kaust.edu.sa, E-mail: omar.knio@kaust.edu.sa [Uncertainty Quantification Center, The Applied Mathematics and Computational Science Department, The Computer, Electrical and Mathematical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal 23955-6900 (Saudi Arabia)

2016-06-07

In this work, two Polynomial Chaos (PC) surrogates were generated to reproduce Monte Carlo (MC) molecular simulation results of the canonical (single-phase) and the NVT-Gibbs (two-phase) ensembles for a system of normalized structureless Lennard-Jones (LJ) particles. The main advantage of such surrogates, once generated, is the capability of accurately computing the needed thermodynamic quantities in a few seconds, thus efficiently replacing the computationally expensive MC molecular simulations. Benefiting from the tremendous computational time reduction, the PC surrogates were used to conduct large-scale optimization in order to propose single-site LJ models for several simple molecules. Experimental data, a set of supercritical isotherms, and part of the two-phase envelope, of several pure components were used for tuning the LJ parameters (ε, σ). Based on the conducted optimization, excellent fit was obtained for different noble gases (Ar, Kr, and Xe) and other small molecules (CH{sub 4}, N{sub 2}, and CO). On the other hand, due to the simplicity of the LJ model used, dramatic deviations between simulation and experimental data were observed, especially in the two-phase region, for more complex molecules such as CO{sub 2} and C{sub 2} H{sub 6}.

Methanol steam reforming over Pd/ZnO and Pd/CeO{sub 2} catalysts

Energy Technology Data Exchange (ETDEWEB)

Ranganathan, Easwar S.; Bej, Shyamal K.; Thompson, Levi T. [University of Michigan, Department of Chemical Engineering, 3026 H.H. Dow Building, 2300 Hayward Avenue, Ann Arbor, MI 48109-2136 (United States)

2005-08-10

The goal of work described in this paper was to better understand the methanol steam reforming (MSR) activity and selectivity patterns of ZnO and CeO{sub 2} supported Pd catalysts. This reaction is being used to produce H{sub 2}-rich gas for a number of applications including hydrogen fuel cells. The Pd/ZnO catalysts had lower MSR rates but were more selective for the production of CO{sub 2} than the Pd/CeO{sub 2} catalysts. The CH{sub 3}OH conversion rates were proportional to the H{sub 2} chemisorption uptake suggesting that the rate determining step was catalyzed by Pd. The corresponding turnover frequencies averaged 0.8+/-0.3s{sup -1} and 0.4+/-0.2s{sup -1} at 230{sup o}C for the Pd/ZnO and Pd/CeO{sub 2} catalysts, respectively. The selectivities are explained based on the reaction pathways, and characteristics of the support. The key surface intermediate appeared to be a formate. The ZnO supported catalysts had a higher density of acidic sites and favored pathways where the intermediate was converted to CO{sub 2} while the CeO{sub 2} supported catalysts had a higher density of basic sites and favored the production of CO.

Bimetallic Au-decorated Pd catalyst for the liquid phase hydrodechlorination of 2,4-dichlorophenol

International Nuclear Information System (INIS)

Zhou, Juan; Chen, Huan; Chen, Quanyuan; Huang, Zhaolu

2016-01-01

Graphical abstract: 2,4-Dichlorophenol can be converted to phenol via the catalytic HDC method over Pd-Au/CNTs and the catalytic activity first increased and then decreased with Au content. - Highlights: • Bimetallic catalysts had smaller metal particles and larger number of exposed active site than the monometallic catalysts. • The cationization of Pd particles increased with Au content in the bimetallic catalysts. • The bimetallic catalysts exhibited higher catalytic activities for HDC of 2,4-DCP than the monometallic counterparts. • The concerted pathway for HDC of 2,4-DCP was more predominant with increasing Au content in the bimetallic catalyst. - Abstract: Monometallic and bimetallic Pd-Au catalysts supported on multi-walled carbon nanotubes (CNTs) with varied Au cooperation amounts were prepared using the complexing-reduction method in the presence of tetrahydrofuran (THF). The liquid phase catalytic hydrodechlorination (HDC) of 2,4-dichlorophenol (2,4-DCP) was investigated over these bimetallic catalysts. The catalysts were characterized by N 2 adsorption-desorption isotherms, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and H 2 chemisorption. Characterization results showed that the co-reduction of Pd and Au mainly formed alloy-like structure. The bimetallic catalysts had smaller metal particles and larger numbers of exposed active site than that of monometallic catalysts. In addition, compared with Pd(1.7)/CNTs and Au(0.4)/CNTs, the binding energies of Pd 3d 5/2 shifted to higher positions while that of Au 4f 7/2 had negative shifts in the Pd-Au bimetallic catalysts, which can be ascribed to the electrons transferred from metal Pd to Au and the cationization of Pd particles was enhanced. Accordingly, the bimetallic Pd-Au particles with different Au contents in the catalysts exhibited varied synergistic effects for the catalytic HDC of 2,4-DCP, with Pd(1.8)Au(0.4)/CNTs having the highest catalytic activity

Study on supported binary sulfide catalysts for secondary hydrogenation of coal-derived liquids; Sekitan ekikayu niji suisoka shokubai no kenkyu

Energy Technology Data Exchange (ETDEWEB)

Shimada, H.; Matsubayashi, N.; Sato, T.; Imamura, M.; Yoshimura, Y.; Nishijima, A. [National Institute of Materials and Chemical Research, Tsukuba (Japan)

1995-07-28

To utilize the high performance of supported catalysts in coal liquefaction processes, one of the promising ways is to apply hydroprocessing sulfide catalysts to the secondary hydrogenation of coal-derived liquids which have undergone the solid separation unit. However, when the product yield from the first-stage liquefaction is maximized, the feed stocks in the secondary hydrogenation contain large amounts of residual fractions with preasphaltenes and metallic components. In this case, the development of a long-life catalyst is essential to establish the two-stage process as a practical one. From this viewpoint, the authors have investigated the deactivation causes of supported Ni-Mo sulfide catalysts through the analysis of the used catalysts in the secondary hydrogenation of coal-derived liquids for long periods. The major cause of the catalyst deactivation has been found to be metallic and carbonaceous deposition on the catalyst, which results thin layer which covers the catalyst particles. The catalysts located at the reactor inlet are more rapidly deactivated than those at the rector exit because of larger amounts of metallic foul ants and the above described shell-like layer. Hydrocracking active sites are much heavily deactivated compared with hydrogenation active sites. It is inferred that the basic or polar compounds contained in coal liquids are permanency adsorbed on the hydrocracking active sites. Spectroscopic analysis of the used catalysts clarified the destruction of the active phase of the binary sulfides, through the segregation and crystal growth. The structural changes of the catalysts are very likely caused by heteroatom compounds in the preasphaltenes. Thus, the primary cause of the catalyst deactivation is the preasphaltenes in the coal liquids. Hydroaromatic compounds in the coal liquids suppress the change of the deposited carbonaceous materials into inert coke which permanently deactivate the catalyst.

Sulphur poisoning of palladium catalysts used for methane combustion: Effect of the support

International Nuclear Information System (INIS)

Escandon, Lara S.; Ordonez, Salvador; Vega, Aurelio; Diez, Fernando V.

2008-01-01

Four different supported palladium catalysts (using alumina, silica, zirconia and titania as supports), prepared by incipient wetness impregnation, were tested as catalysts for methane oxidation in presence of sulphur dioxide. The catalyst supported on zirconia showed the best performance, whereas the silica-supported one showed the fastest deactivation. Temperature-programmed desorption experiments of the poisoned catalysts suggest that SO 2 adsorption capacity of the support plays a key role in the catalyst poisoning. In order to study the effect of promoters, expected to improve the thermal stability and thioresistance of the catalyst, commercial zirconia modified by yttrium and lantane was tested as supports. It was found that the presence of these promoters does not improve the performance of the zirconia-supported catalyst. A deactivation model - considering two different active sites (fresh and poisoning), pseudo-first order dependence on methane concentration and poisoning rate depending on sulphur concentration and fraction of non-poisoned palladium - was used for modelling the deactivation behaviour

Investigation of a Pt-Fe/C catalyst for oxygen reduction reaction in direct ethanol fuel cells

International Nuclear Information System (INIS)

Castro Luna, A. M.; Bonesi, A.; Triaca, W. E.; Blasi, A. Di; Stassi, A.; Baglio, V.; Antonucci, V.; Arico, A. S.

2010-01-01

Three cathode catalysts (60% Pt/C, 30% Pt/C and 60% Pt-Fe/C), with a particle size of about 2-3 nm, were prepared to investigate the effect of ethanol cross-over on cathode surfaces. All samples were studied in terms of structure and morphology by using X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses. Their electrocatalytic behavior in terms of oxygen reduction reaction (ORR) was investigated and compared using a rotating disk electrode (RDE). The tolerance of cathode catalysts in the presence of ethanol was evaluated. The Pt-Fe/C catalyst showed both higher ORR activity and tolerance to ethanol cross-over than Pt/C catalysts. Moreover, the more promising catalysts were tested in 5 cm 2 DEFC single cells at 60 and 80 o C. An improvement in single cell performance was observed in the presence of the Pt-Fe catalyst, due to an enhancement in the oxygen reduction kinetics. The maximum power density was 53 mW cm -2 at 2 bar rel. cathode pressure and 80 o C.

Catalytic cracking of iso-hexene over sapo-34 catalyst

International Nuclear Information System (INIS)

Nawaz, Z.; Shu, Q.

2009-01-01

The catalytic cracking of model feed compound, iso-hexene (2-methyl-1-pentene) was experimentally studied over 100% pure SAPO-34 zeolite catalyst. The critical focus was given to obtain maximum propylene selectivity. The product distributions were analyzed at temperature between 450-600 degree C. time-on-stream (TOS) from 1 to 5 min. and at WHSV = 7.9 h/sub -1/ The reaction behavior was quantified on both direct and indirect carbenium ion mechanisms owing to catalyst's small pore diameter with respect to 2-methyl-l-pentene kinetic diameter. The propylene yield and selectivity obtained was 41.2% and 43.1% respectively. with higher overall olefins selectivity 90.3%. The small pore size and week surface acid sites of 1000 percent pure SAPO-34 catalyst were found to be suitable for light olefins production and eliminate chances of bimolecular reactions. It was observed that both conversion and selectivity were strongly effected by TOS, as coke precursors become dominant and deactivate catalyst at higher TOS. (author)

Methanol Steam Reforming Promoted by Molten Salt-Modified Platinum on Alumina Catalysts

Science.gov (United States)

Kusche, Matthias; Agel, Friederike; Ní Bhriain, Nollaig; Kaftan, Andre; Laurin, Mathias; Libuda, Jörg; Wasserscheid, Peter

2014-01-01

We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the “solid catalyst with ionic liquid layer” (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass %. PMID:25124120

Hydrotreatment of heavy oil from coal liquefaction on Sulfide Ni - W Catalysts

Energy Technology Data Exchange (ETDEWEB)

Zhi-ping Lei; Li-juan Gao; Heng-fu Shui; Shi-biao, Ren; Zhi-cai Wang; Kang-shi Gang, E-mail: shhf@ahut.edu.c [Anhui University of Technology, Maanshan (China). School of Chemistry and Chemical Engineering. Anhui Key Lab. of Coal Clean Conversion and Utilization

2011-07-01

Heavy oil (distillation temperature: 320-340 deg C) derived from the direct coal liquefaction process using Shengli coal were hydrotreated using sulfided Ni-Mo/Al{sub 2}O{sub 3}, Ni-W/Al{sub 2}O{sub 3}, and Ni-W/SiO{sub 2} catalysts respectively. The sulfided catalysts were characterized by BET, XRD, H{sub 2}-TPR and NH{sub 3}-TPD respectively. The evaluations of the hydrodenitrogenation (HDN) and hydrodearomatization (HDA) properties of heavy oil on the three catalysts were carried out at 400 deg C and 5.0 MPa initial H2 pressure. The W-based catalysts displayed better performances than Mo-based catalysts for the HDN and HDA reactions. Al{sub 2}O{sub 3} supported catalysts were found to have higher catalytic activities than on SiO{sub 2} supported ones. The activities of sulfided catalysts were associated mainly with the nature of active sites, acidity, metal sulfide crystallite size and the amount of the reducible sulfur species of metal sulfide. (author)

Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework

Energy Technology Data Exchange (ETDEWEB)

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

2018-01-02

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

Cationic Zn-Porphyrin Polymer Coated onto CNTs as a Cooperative Catalyst for the Synthesis of Cyclic Carbonates.

Science.gov (United States)

Jayakumar, Sanjeevi; Li, He; Chen, Jian; Yang, Qihua

2018-01-24

The development of solid catalysts containing multiple active sites that work cooperatively is very attractive for biomimetic catalysis. Herein, we report the synthesis of bifunctional catalysts by supporting cationic porphyrin-based polymers on carbon nanotubes (CNTs) using the direct reaction of 5,10,15,20-tetrakis(4-pyridyl)porphyrin zinc(II), di(1H-imidazol-1-yl)methane, and 1,4-bis(bromomethyl)benzene in the presence of CNTs. The bifunctional catalysts could efficiently catalyze the cycloaddition reaction of epoxides and CO 2 under solvent-free conditions with porphyrin zinc(II) as the Lewis acid site and a bromine anion as a nucleophilic agent working in a cooperative way. Furthermore, a relative amount of porphyrin zinc(II) and quaternary ammonium bromide could be facilely adjusted for facilitating cooperative behavior. The bifunctional catalyst with a TOF up to 2602 h -1 is much more active than the corresponding homogeneous counterpart and is one of the most active heterogeneous catalysts ever reported under cocatalyst-free conditions. The high activity is mainly attributed to the enhanced cooperation effect of the bifunctional catalyst. With a wide substrate scope, the bifunctional catalyst could be stably recycled. This work demonstrates a new approach for the generation of a cooperative activation effect for solid catalysts.

Study and development of membrane electrode assemblies for Proton Exchange Membrane Fuel Cell (PEMFC) with palladium based catalysts

International Nuclear Information System (INIS)

Bonifacio, Rafael Nogueira

2013-01-01

PEMFC systems are capable of generating electricity with high efficiency and low or no emissions, but durability and cost issues prevent its large commercialization. In this work MEA with palladium based catalysts were developed, Pd/C, Pt/C and alloys PdPt/C catalysts with different ratios between metals and carbon were synthesized and characterized. A study of the ratio between catalyst and Nafion Ionomer for formation of high performance triple-phase reaction was carried out, a mathematical model to implement this adjustment to catalysts with different relations between metal and support taking into account the volumetric aspects of the catalyst layer was developed and then a study of the catalyst layer thickness was performed. X-ray diffraction, Transmission and Scanning Electron Microscopy, X-ray Energy Dispersive, Gas Pycnometry, Mercury Intrusion Porosimetry, Gas adsorption according to the BET and BJH equations, and Thermo Gravimetric Analysis techniques were used for characterization and particle size, specific surface areas and lattice parameters determinations were also carried out. All catalysts were used on MEAs preparation and evaluated in 5 cm 2 single cell from 25 to 100 °C at 1 atm and the best composition was also evaluated at 3 atm. In the study of metals for reactions, to reduce the platinum applied to the electrodes without performance losses, Pd/C and PdPt/C 1:1 were selected for anodes and cathodes, respectively. The developed MEA structure used 0,25 mgPt.cm -2 , showing power densities up to 550 mW.cm -2 and power of 2.2 kW net per gram of platinum. The estimated costs showed that there was a reduction of up to 64.5 %, compared to the MEA structures previously known. Depending on the temperature and operating pressure, values from US$ 1,475.30 to prepare MEAs for each installed kilowatt were obtained. Taking into account recent studies, it was concluded that the cost of the developed MEA is compatible with PEMFC stationary application

Aromatization of n-octane over Pd/C catalysts

KAUST Repository

Yin, Mengchen; Natelson, Robert H.; Campos, Andrew A.; Kolar, Praveen; Roberts, William L.

2013-01-01

Gas-phase aromatization of n-octane was investigated using Pd/C catalyst. The objectives were to: (1) determine the effects of temperature (400-600 °C), weight hourly space velocity (WHSV) (0.8-∞), and hydrogen to hydrocarbon molar ratio (MR) (0-6) on conversion, selectivity, and yield (2) compare the activity of Pd/C with Pt/C and Pt/KL catalysts and (3) test the suitability of Pd/C for aromatization of different alkanes including n-hexane, n-heptane, and n-octane. Pd/C exhibited the best aromatization performance, including 54.4% conversion and 31.5% aromatics yield at 500 °C, WHSV = 2 h-1, and a MR of 2. The Pd/C catalyst had higher selectivity towards the preferred aromatics including ethylbenzene and xylenes, whereas Pt/KL had higher selectivity towards benzene and toluene. The results were somewhat consistent with adsorbed n-octane cyclization proceeding mainly through the six-membered ring closure mechanism. In addition, Pd/C was also capable of catalyzing aromatization of n-hexane and n-heptane. © 2012 Elsevier Ltd. All rights reserved.

Production of Biodiesel by Esterification of Free Fatty Acid over Solid Catalyst from Biomass Waste

Science.gov (United States)

Mukti, N. I. F.; Sutrisno, B.; Hidayat, A.

2018-05-01

Recently, low cost feedstocks have been utilized to replace vegetable oils in order to improve the economic feasibility of biodiesel. The esterification of free fatty acid (FFA) on Palm Fatty Acid Distillate (PFAD) with methanol using solid catalyst generated from bagasse fly ash is a promising method to convert FFA into biodiesel. In this research, the esterification of FFA on PFAD using the sulfonated bagasse fly ash catalyst was studied. The performances of the catalysts were evaluated in terms of the reaction temperatures, the molar ratios of methanol to PFAD, and the catalyst loading. The effects of the mass ratio of catalyst to oil (1-10%), the molar ratio of methanol to oil (6:1-12:1), and the reaction temperature (40-60°C) were studied for the conversion of PFAD to optimize the reaction conditions. The results showed that the optimum conditions were methanol to PFAD molar ratio of 12:1, the amount of catalyst of 10%wt. of PFAD, and reaction temperature of 6°C. The reusability of the solid acid carbon catalysts was also studied in this work. The catalytic activity decreased up to 38% after third cycle. The significant decline in catalyst esterification activity was due to acid site leaching. The physico-characteristics and acid site densities were analyzed by Nitrogen gas adsorption, surface functional groups by Fourier transform infrared spectroscopy (FT-IR), elemental analysis using X-ray fluorescent (XRF), and acid-base back titration methods for determination of acid density.

Properties and application of noble metal catalysts for heterogeneous catalytic hydrogenations

Energy Technology Data Exchange (ETDEWEB)

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

1976-07-01

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

Nanocomposite catalyst with palladium nanoparticles encapsulated in a polymeric acid: A model for tandem environmental catalysis

KAUST Repository

Isimjan, Tayirjan T.

2013-04-01

The synthesis and characterization of a novel hybrid nanocomposite catalyst comprised of palladium nanoparticles embedded in polystyrene sulfonic acid (PSSH) and supported on metal oxides is reported. The catalysts are intended for application in green catalysis, and they are shown to be effective in the hydrolysisreduction sequence of tandem catalytic reactions required for conversion of 2-phenyl-1,3-dioxolane to toluene or of phenol to cyclohexane. The two distinct components in the catalyst, Pd nanoparticles and acidic PSSH, are capable of catalyzing sequential reactions in one pot under mild conditions. This work has demonstrated a powerful approach toward designing highperformance, multifunctional, scalable, and environmentally friendly nanostructured tandem catalysts. © 2013 American Chemical Society.

Production of liquid alkanes by controlling reactivity of sorbitol hydrogenation with a Ni/HZSM-5 catalyst in water

International Nuclear Information System (INIS)

Zhang, Qing; Wang, Tiejun; Xu, Ying; Zhang, Qi; Ma, Longlong

2014-01-01

Graphical abstract: MCM-41-modified Ni/HZSM-5 catalyst was developed by impregnation method with high catalytic performance for sorbitol hydrogenation in water. Appropriate amount of MCM-41 addition can distinctly promote the improvement in the surface structure and modulation of acidic sites of the catalyst. The scission of C–O bond in the sorbitol molecule into liquid alkanes was easily carried out on the catalyst containing more Lewis acidic sites. - Highlights: • Ni/HZSM-5 promoted with MCM-41 is active for sorbitol hydrogenation to liquid alkanes. • Lewis acidic sites of Ni/HZSM-5 can be modulated by pure silica MCM-41. • MCM-41 added can distinctly decrease carbon deposition on the catalyst surface. - Abstract: Liquid fuels derived from renewable biomass are of great importance on the potential substitution for diminishing fossil fuels. The conversion of sorbitol (a product of biomass-derived glucose hydrogenation) into liquid alkanes such as pentane and hexane over the Ni/HZSM-5 catalysts with or without MCM-41 addition was investigated in the presence of hydrogen in water medium. The production distribution of sorbitol hydrogenation can be controlled by adjusting the acidity of the catalyst. The scission of C–C bond in the sorbitol molecule into light C 1 –C 4 alkanes was mainly carried out over Ni/HZSM-5 containing strong Brønsted acid sites, while C–O bond scission into heavier alkanes was dominated over the catalysts added by MCM-41 containing weak Lewis acid sites. The sorbitol conversion and total liquid alkanes selectivity were found to be 67.1% and 98.7% over 2%Ni/HZSM-5 modified by 40 wt% of MCM-41, whereas the corresponding value was 40% and 35.6% over 2%Ni/HZSM-5 in the absence of MCM-41. The effect of MCM-41 on the structure, acidity, and reducibility of Ni/HZSM-5 was investigated by using XRD, Py-IR, IR, and H 2 -TPR. Meanwhile, the resistance of carbon deposition over the catalyst modified by MCM-41 was studied by using TG�

LaFePdO3 perovskite automotive catalyst having a self-regenerative function

International Nuclear Information System (INIS)

Tanaka, Hirohisa; Tan, Isao; Uenishi, Mari; Taniguchi, Masashi; Kimura, Mareo; Nishihata, Yasuo; Mizuki, Jun'ichiro

2006-01-01

An automotive gasoline engine is operated close to the stoichiometric air-to-fuel ratio to convert the pollutant emissions simultaneously, accompanying with redox (reduction and oxidation) fluctuations in exhaust-gas composition through adjusting the air-to-fuel ratio. An innovative LaFe 0.95 Pd 0.05 O 3 perovskite catalyst, named 'the intelligent catalyst', has been developed, and which has a new self-regenerative function of the precious metal in the inherent fluctuations of automotive exhaust-gas. The LaFe 0.95 Pd 0.05 O 3 perovskite catalyst, La located at the A-site, was prepared by the alkoxide method. Pd located at the B-site of the perovskite lattice in the oxidative atmosphere, and segregated out to form small metallic particles in the reductive atmosphere. The catalyst retained a predominantly perovskite structure throughout a redox cycle of the exhaust-gas, while the local structure around Pd could be changed in a completely reversible manner. The agglomeration and growth of Pd particles is suppressed, even under the severe environment, as a result of the movement between inside and outside the perovskite lattice. It is revealed that the self-regenerative function of Pd occurs even at 200 deg. C, unexpectedly low temperature, in the LaFe 0.95 Pd 0.05 O 3 catalyst. Since the high catalytic activity is maintained, the great reduction of Pd loading has been achieved. The intelligent catalyst is expected as a new application of the rare earth, and then the technology is expected in the same way in the global standard of the catalyst designing

Non-Precious Bimetallic Catalysts for Selective Dehydrogenation of an Organic Chemical Hydride System

KAUST Repository

Shaikh Ali, Anaam

2015-07-06

Methylcyclohexane (MCH)-Toluene (TOL) chemical hydride cycles as a hydrogen carrier system is successful with the selective dehydrogenation reaction of MCH to TOL, which has been achieved only using precious Pt-based catalysts. Herein, we report improved selectivity using non-precious metal nickel-based bimetallic catalysts, where the second metal occupies the unselective step sites.

Preparation of Monodispersed Fe-Mo Nanoparticles as the Catalyst for CVD Synthesis of Carbon Nanotubes

National Research Council Canada - National Science Library

Li, Yan; Liu, Jie; Wang, Yongqian; Wang, Zhong L

2001-01-01

...particles were systematically studied. The prepared nanoparticles were used as catalysts for single-walled carbon nanotube growth and the results indicate that there is an upper limit for the size of the catalyst particles to nucleate singlewalled carbon nanotubes.

Robotic Laparoendoscopic Single-site Retroperitioneal Renal Surgery: Initial Investigation of a Purpose-built Single-port Surgical System.

Science.gov (United States)

Maurice, Matthew J; Ramirez, Daniel; Kaouk, Jihad H

2017-04-01

Robotic single-site retroperitoneal renal surgery has the potential to minimize the morbidity of standard transperitoneal and multiport approaches. Traditionally, technological limitations of non-purpose-built robotic platforms have hindered the application of this approach. To assess the feasibility of retroperitoneal renal surgery using a new purpose-built robotic single-port surgical system. This was a preclinical study using three male cadavers to assess the feasibility of the da Vinci SP1098 surgical system for robotic laparoendoscopic single-site (R-LESS) retroperitoneal renal surgery. We used the SP1098 to perform retroperitoneal R-LESS radical nephrectomy (n=1) and bilateral partial nephrectomy (n=4) on the anterior and posterior surfaces of the kidney. Improvements unique to this system include enhanced optics and intelligent instrument arm control. Access was obtained 2cm anterior and inferior to the tip of the 12th rib using a novel 2.5-cm robotic single-port system that accommodates three double-jointed articulating robotic instruments, an articulating camera, and an assistant port. The primary outcome was the technical feasibility of the procedures, as measured by the need for conversion to standard techniques, intraoperative complications, and operative times. All cases were completed without the need for conversion. There were no intraoperative complications. The operative time was 100min for radical nephrectomy, and the mean operative time was 91.8±18.5min for partial nephrectomy. Limitations include the preclinical model, the small sample size, and the lack of a control group. Single-site retroperitoneal renal surgery is feasible using the latest-generation SP1098 robotic platform. While the potential of the SP1098 appears promising, further study is needed for clinical evaluation of this investigational technology. In an experimental model, we used a new robotic system to successfully perform major surgery on the kidney through a single small

Enhanced Carbon Dioxide Electroreduction to Carbon Monoxide over Defect-Rich Plasma-Activated Silver Catalysts.

Science.gov (United States)

Mistry, Hemma; Choi, Yong-Wook; Bagger, Alexander; Scholten, Fabian; Bonifacio, Cecile S; Sinev, Ilya; Divins, Nuria J; Zegkinoglou, Ioannis; Jeon, Hyo Sang; Kisslinger, Kim; Stach, Eric A; Yang, Judith C; Rossmeisl, Jan; Roldan Cuenya, Beatriz

2017-09-11

Efficient, stable catalysts with high selectivity for a single product are essential if electroreduction of CO 2 is to become a viable route to the synthesis of industrial feedstocks and fuels. A plasma oxidation pre-treatment of silver foil enhances the number of low-coordinated catalytically active sites, which dramatically lowers the overpotential and increases the activity of CO 2 electroreduction to CO. At -0.6 V versus RHE more than 90 % Faradaic efficiency towards CO was achieved on a pre-oxidized silver foil. While transmission electron microscopy (TEM) and operando X-ray absorption spectroscopy showed that oxygen species can survive in the bulk of the catalyst during the reaction, quasi in situ X-ray photoelectron spectroscopy showed that the surface is metallic under reaction conditions. DFT calculations reveal that the defect-rich surface of the plasma-oxidized silver foils in the presence of local electric fields drastically decrease the overpotential of CO 2 electroreduction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reduction of nanowire diameter beyond lithography limits by controlled catalyst dewetting

International Nuclear Information System (INIS)

Calahorra, Yonatan; Kerlich, Alexander; Gavrilov, Arkady; Cohen, Shimon; Ritter, Dan; Amram, Dor

2016-01-01

Catalyst assisted vapour-liquid–solid is the most common method to realize bottom-up nanowire growth; establishing a parallel process for obtaining nanoscale catalysts at pre-defined locations is paramount for further advancement towards commercial nanowire applications. Herein, the effect of a selective area mask on the dewetting of metallic nanowire catalysts, deposited within lithography-defined mask pinholes, is reported. It was found that thin disc-like catalysts, with diameters of 120–450 nm, were transformed through dewetting into hemisphere-like catalysts, having diameters 2–3 fold smaller; the process was optimized to about 95% yield in preventing catalyst splitting, as would otherwise be expected due to their thickness-to-diameter ratio, which was as low as 1/60. The catalysts subsequently facilitated InP and InAs nanowire growth. We suggest that the mask edges prevent surface migration mediated spreading of the dewetted metal, and therefore induce its agglomeration into a single particle. This result presents a general strategy to diminish lithography-set dimensions for NW growth, and may answer a fundamental challenge faced by bottom-up nanowire technology. (paper)

Alkali-Resistant Mechanism of a Hollandite DeNOx Catalyst.

Science.gov (United States)

Hu, Pingping; Huang, Zhiwei; Gu, Xiao; Xu, Fei; Gao, Jiayi; Wang, Yue; Chen, Yaxin; Tang, Xingfu

2015-06-02

A thorough understanding of the deactivation mechanism by alkalis is of great importance for rationally designing improved alkali-resistant deNOx catalysts, but a traditional ion-exchange mechanism cannot often accurately describe the nature of the deactivation, thus hampering the development of superior catalysts. Here, we establish a new exchange-coordination mechanism on the basis of the exhaustive study on the strong alkali resistance of a hollandite manganese oxide (HMO) catalyst. A combination of isothermal adsorption measurements of ammonia with X-ray absorption near-edge structure spectra and X-ray photoelectron spectra reveals that alkali metal ions first react with protons from Brønsted acid sites of HMO via the ion exchange. Synchrotron X-ray diffraction patterns and extended X-ray absorption fine structure spectra coupled with theoretical calculations demonstrate that the exchanged alkali metal ions are subsequently stabilized at size-suitable cavities in the HMO pores via a coordination model with an energy savings. This exchange-coordination mechanism not only gives a wholly convincing explanation for the intrinsic nature of the deactivation of the reported catalysts by alkalis but also provides a strategy for rationally designing improved alkali-resistant deNOx catalysts in general.

A tailored catalyst for the sustainable conversion of glycerol to acrolein: mechanistic aspect of sequential dehydration.

Science.gov (United States)

Yun, Danim; Kim, Tae Yong; Park, Dae Sung; Yun, Yang Sik; Han, Jeong Woo; Yi, Jongheop

2014-08-01

Developing a catalyst to resolve deactivation caused from coke is a primary challenge in the dehydration of glycerol to acrolein. An open-macropore-structured and Brønsted-acidic catalyst (Marigold-like silica functionalized with sulfonic acid groups, MS-FS) was synthesized for the stable and selective production of acrolein from glycerol. A high acrolein yield of 73% was achieved and maintained for 50 h in the presence of the MS-FS catalyst. The hierarchical structure of the catalyst with macropores was found to have an important effect on the stability of the catalyst because coke polymerization and pore blocking caused by coke deposition were inhibited. In addition, the behavior of 3-hydroxypropionaldehyde (3-HPA) during the sequential dehydration was studied using density functional theory (DFT) calculations because 3-HPA conversion is one of the main causes for coke formation. We found that the easily reproducible Brønsted acid sites in MS-FS permit the selective and stable production of acrolein. This is because the reactive intermediate (3-HPA) is readily adsorbed on the regenerated acid sites, which is essential for the selective production of acrolein during the sequential dehydration. The regeneration ability of the acid sites is related not only to the selective production of acrolein but also to the retardation of catalyst deactivation by suppressing the formation of coke precursors originating from 3-HPA degradation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Boehmite-An Efficient and Recyclable Acid-Base Bifunctional Catalyst for Aldol Condensation Reaction.

Science.gov (United States)

Reshma, P C Rajan; Vikneshvaran, Sekar; Velmathi, Sivan

2018-06-01

In this work boehmite was used as an acid-base bifunctional catalyst for aldol condensation reactions of aromatic aldehydes and ketones. The catalyst was prepared by simple sol-gel method using Al(NO3)3·9H2O and NH4OH as precursors. The catalyst has been characterized by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning Electron Microscopy (SEM), UV-visible spectroscopy (DRS), BET surface area analyses. Boehmite is successfully applied as catalyst for the condensation reaction between 4-nitrobenzaldehyde and acetone as a model substrate giving α, β-unsaturated ketones without any side product. The scope of the reaction is extended for various substituted aldehydes. A probable mechanism has been suggested to explain the cooperative behavior of the acidic and basic sites. The catalyst is environmentally friendly and easily recovered from the reaction mixture. Also the catalyst is reusable up to 3 catalytic cycles.

An introduction to catalyst

International Nuclear Information System (INIS)

Jeon, Hak Je

1988-11-01

This book explains basic conception of catalyst such as definition, velocity of chemical reaction and velocity of catalyst reaction, absorption with absorption energy and chemical absorption, pore structure with the role of pore and measurement of pore structure, catalyst activity on solid structure, electrical property on catalyst activity, choice and design of catalyst, catalytic reaction with reaction velocity and chemical equilibrium and reaction velocity model, measurement of reaction velocity and material analysis, catalyst for mixed compound, catalyst for solid acid and catalyst for supported metal.

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

Directory of Open Access Journals (Sweden)

Hermenegildo Garcia

2014-01-01

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

FMEF/experimental capabilities

International Nuclear Information System (INIS)

Burgess, C.A.; Dronen, V.R.

1981-01-01

The Fuels and Materials Examination Facility (FMEF), under construction at the Hanford site north of Richland, Washington, will be one of the most modern facilities offering irradiated fuels and materials examination capabilities and fuel fabrication development technologies. Scheduled for completion in 1984, the FMEF will provide examination capability for fuel assemblies, fuel pins and test pins irradiated in the FFTF. Various functions of the FMEF are described, with emphasis on experimental data-gathering capabilities in the facility's Nondestructive and Destructive examination cell complex

Synthesis of biodiesel from waste vegetable oil with large amounts of free fatty acids using a carbon-based solid acid catalyst

Energy Technology Data Exchange (ETDEWEB)

Shu, Qing; Gao, Jixian; Nawaz, Zeeshan; Liao, Yuhui; Wang, Dezheng; Wang, Jinfu [Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084 (China)

2010-08-15

A carbon-based solid acid catalyst was prepared by the sulfonation of carbonized vegetable oil asphalt. This catalyst was employed to simultaneously catalyze esterification and transesterification to synthesis biodiesel when a waste vegetable oil with large amounts of free fatty acids (FFAs) was used as feedstock. The physical and chemical properties of this catalyst were characterized by a variety of techniques. The maximum conversion of triglyceride and FFA reached 80.5 wt.% and 94.8 wt.% after 4.5 h at 220 C, when using a 16.8 M ratio of methanol to oil and 0.2 wt.% of catalyst to oil. The high catalytic activity and stability of this catalyst was related to its high acid site density (-OH, Broensted acid sites), hydrophobicity that prevented the hydration of -OH species, hydrophilic functional groups (-SO{sub 3}H) that gave improved accessibility of methanol to the triglyceride and FFAs, and large pores that provided more acid sites for the reactants. (author)

Catalysts for the reduction of SO{sub 2} to elemental sulfur

Energy Technology Data Exchange (ETDEWEB)

Jin, Y.; Yu, Q.Q.; Chang, S.G. [Lawrence Berkeley Lab., Berkeley, CA (United States)

1995-11-01

Catalysts have been prepared for the reduction of SO{sub 2} to elemental sulfur by synthesis gas. A catalyst allows to obtain more than 97% yield of elemental sulfur with a single-stage reactor at 540{degrees}C. A lifetime test has been successfully performed. The mass balance of sulfur and carbon has been checked. The effect of H{sub 2}S, COS, and H{sub 2}O has been studied.

Secondary promoters in alumina-supported nickel-molybdenum hydroprocessing catalysts

Energy Technology Data Exchange (ETDEWEB)

Lewis, J.M.

1992-01-01

Two secondary promoters, phosphorus and fluoride, have been investigated for their influences on the physicochemical properties of alumina-supported nickel-molybdenum hydroprocessing catalysts. Model compound reactions and infrared spectroscopy were used to probe the functionalities of the different catalysts, and the catalysts were tested in the hydroprocessing of a low-nitrogen and a high-nitrogen (quinoline-spiked) gas oil feed to assess the utility of the model compound reaction studies. Fluoride-promoted catalysts with high cumene hydrocracking activity and with comparable thiophene hydrodesulphurization (HDS) activity to Ni-Mo/Al[sub 2]O[sub 3] can be prepared by coimpregnation of the F, Ni and Mo additives. Fluoride promotes the hydrogenation (HYD) and HDS activity of Ni-Mo/Al[sub 2]O[sub 3] in the hydroprocessing (HYD) and HDS activity of Ni-Mo/Al[sub 2]O[sub 3] in the hydroprocessing of a low-nitrogen feed. Fluoride promotes the quinoline hydrodenitrogenation (HDN) activity of Ni-Mo/Al[sub 2]O[sub 3] catalysts. Impregnation of phosphorus prior to the metal additives results in catalysts which are more active in HDS. Phosphorus increases indirectly the Broensted acidity of the catalyst by increasing the activity of the MoS[sub 2]-associated acid sites. Phosphorus promotes the HDSW and HYD activities of Ni-Mo/Al[sub 2]O[sub 3] in the hydroprocessing of the low-N feed. A promotional effect of phosphorus is seen in quinoline HDN. P- and F-promoted Ni-MO/Al[sub 2]O[sub 3] catalysts are very active in quinoline HDN and maintain good activity in HDS and HYD of the high-N feed. Thiophene HDS was a good reaction for probing the activity of catalysts in the HDS of sterically-unhindered molecules, but an inaccurate probe for the HDS of hindered compounds.

Effect of Zn/ZSM-5 and FePO4 Catalysts on Cellulose Pyrolysis

Directory of Open Access Journals (Sweden)

Haian Xia

2015-01-01

Full Text Available A series of Zn/ZSM-5 catalysts with different Zn contents and FePO4 were used to pyrolyze cellulose to produce value added chemicals. The nature of these catalysts was characterized by ammonia-temperature programmed desorption (NH3-TPD, IR spectroscopy of pyridine adsorption, and X-ray diffraction (XRD techniques. Noncatalytic and catalytic pyrolytic behaviors of cellulose were studied by thermogravimetric (TG technique. The pyrolytic liquid products, that is, the biooils, were analyzed by gas chromatography-mass spectrometry (GC-MS. The major components of the biooils are anhydrosugars such as levoglucosan (LGA, 1,6-anhydro-β-D-glucofuranose (AGF, levoglucosenone (LGO, 1,6-anhydro-3,4-dideoxy-β-D-pyranosen-2-one, and 1,4:3,6-dianhydro-α-D-glucopyranose (DGP, as well as furan derivatives, alcohols, and so forth. Zn/ZSM-5 samples with Brønsted and Lewis acid sites and the FePO4 catalyst with Lewis acid sites were found to have a significant effect on the pyrolytic behaviors of cellulose and product distribution. These results show that Brønsted and Lewis acid sites modified remarkably components of the biooil, which could promote the production of furan compounds and LGO. On the basis of the findings, a model was proposed to describe the pyrolysis pathways of cellulose catalyzed by the solid acid catalysts.

ACTIVITY TEST AND REGENERATION OF NiMo/Z CATALYST FOR HYDROCRACKING OF WASTE PLASTIC FRACTION TO GASOLINE FRACTION

Directory of Open Access Journals (Sweden)

Rodiansono Rodiansono

2010-06-01

Full Text Available Activity test and regeneration of NiMo/active natural zeolite catalyst for hydrocracking of waste plastic fraction of polyprophylene (PP type have been carried out. The catalysts was prepared by loading Mo followed by Ni Metals onto the natural zeolite (Z sample, then calcined at 500oC, oxidized and reduced at 400oC under nitrogen, oxygen and hydrogen stream, respectively. The characterization of catalysts including spesific surface area, average pore radius, and total pore volume were performed by gas sorption analyzer, amount of total acid sites was determined by gas sorption method, and acid site strength was confirmed by IR spectroscopy. The hydrocracking process was carried out in a semi-flow reactor system at 360 oC and catalyst:feed ratio 0.5 under hydrogen stream (150 mL/hour. The feed was vaporized from the pyrolisis reactor into the hydrocracking reactor. A liquid product was collected and analyzed by gas chromatography (GC and gas chromatography-mass spectroscopy (GC-MS. The characterization results showed that spesific surface area, average pore radius, and total pore volume of the Z sample decreased after loading of the Ni and Mo metals. Amount of total acid sites of the NiMo/Z catalyst was higher than that of the Z sample. The activity of NiMo/Z catalyst decreased after several continously runs. Its regeneration produced the NiMo/Z reg catalyst with similar activity and selectivity to the fresh catalyst (NiMo/Z. The activity of catalysts at the optimum condition followed the order of NiMo/Z reg>NiMo/Z>Z (conversion of hydrocarbon C>12 and NiMo/Z reg>NiMo/Z>Z (total yield of gasoline fraction. The selectivity of catalysts for C7-C8 product followed the order of Z>NiMo/Z>NiMo/Z reg. Keywords: activity, polyprophylene, catalyst, gasoline fraction.

Learning curve for laparoendoscopic single-site surgery for an experienced laparoscopic surgeon

OpenAIRE

Pao-Ling Torng; Kuan-Hung Lin; Jing-Shiang Hwang; Hui-Shan Liu; I-Hui Chen; Chi-Ling Chen; Su-Cheng Huang

2013-01-01

Objectives: To assess the learning curve and safety of laparoendoscopic single-site (LESS) surgery of gynecological surgeries. Materials and methods: Sixty-three women who underwent LESS surgery by a single experienced laparoscopic surgeon from February 2011 to August 2011 were included. Commercialized single-incision laparoscopic surgery homemade ports were used, along with conventional straight instruments. The learning curve has been defined as the additional surgical time with respect ...

Used solid catalysts from chemical and petrochemical industries; Les catalyseurs solides uses de l`industrie chimique et du raffinage petrolier

Energy Technology Data Exchange (ETDEWEB)

NONE

1996-10-01

A comprehensive survey of the solid catalysts used in the chemical and petrochemical industries is presented; information on solid catalyst market demand prospective for 1998, the nature of solid catalysts used in the various industrial sectors and for the various chemical products production, the european catalysts manufacturers, solid catalyst poisons and inhibitors according to the various types of chemical reactions, mean compositions of used solid catalysts, an assessment of the volume of used solid catalysts generated by chemical and petrochemical industries, the various ways of solid catalyst regeneration and disposal, the potential for off-site regeneration of used catalysts, and French and European regulations, is presented

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

Bimetallic Au-decorated Pd catalyst for the liquid phase hydrodechlorination of 2,4-dichlorophenol

Energy Technology Data Exchange (ETDEWEB)

Zhou, Juan [School of the Environment, Donghua University, Shanghai 201620 (China); Chen, Huan, E-mail: hchen404@njust.edu.cn [Key Laboratory of Jiangsu Province for Chemical Pollution Control and Resources Reuse, School of Environmental & Biological Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Chen, Quanyuan; Huang, Zhaolu [School of the Environment, Donghua University, Shanghai 201620 (China)

2016-11-30

Graphical abstract: 2,4-Dichlorophenol can be converted to phenol via the catalytic HDC method over Pd-Au/CNTs and the catalytic activity first increased and then decreased with Au content. - Highlights: • Bimetallic catalysts had smaller metal particles and larger number of exposed active site than the monometallic catalysts. • The cationization of Pd particles increased with Au content in the bimetallic catalysts. • The bimetallic catalysts exhibited higher catalytic activities for HDC of 2,4-DCP than the monometallic counterparts. • The concerted pathway for HDC of 2,4-DCP was more predominant with increasing Au content in the bimetallic catalyst. - Abstract: Monometallic and bimetallic Pd-Au catalysts supported on multi-walled carbon nanotubes (CNTs) with varied Au cooperation amounts were prepared using the complexing-reduction method in the presence of tetrahydrofuran (THF). The liquid phase catalytic hydrodechlorination (HDC) of 2,4-dichlorophenol (2,4-DCP) was investigated over these bimetallic catalysts. The catalysts were characterized by N{sub 2} adsorption-desorption isotherms, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and H{sub 2} chemisorption. Characterization results showed that the co-reduction of Pd and Au mainly formed alloy-like structure. The bimetallic catalysts had smaller metal particles and larger numbers of exposed active site than that of monometallic catalysts. In addition, compared with Pd(1.7)/CNTs and Au(0.4)/CNTs, the binding energies of Pd 3d{sub 5/2} shifted to higher positions while that of Au 4f{sub 7/2} had negative shifts in the Pd-Au bimetallic catalysts, which can be ascribed to the electrons transferred from metal Pd to Au and the cationization of Pd particles was enhanced. Accordingly, the bimetallic Pd-Au particles with different Au contents in the catalysts exhibited varied synergistic effects for the catalytic HDC of 2,4-DCP, with Pd(1.8)Au(0.4)/CNTs having the highest

Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device.

Science.gov (United States)

Fremerey, Peter; Jess, Andreas; Moos, Ralf

2015-10-23

In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H₂S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nickel sulfide occurred. This conductivity increase by decades during sulfidation had not been expected since both nickel and nickel sulfides behave metallic. Only by assuming a percolation phenomenon that originates from a volume increase of the nickel contacts when reacting to nickel sulfides, this effect can be explained. This assumption was supported by sulfidation tests with differently nickel loaded catalysts and it was quantitatively estimated by a general effective media theory. The single pellet sensor device for in operando investigation of sulfidation can be considered as a valuable tool to get further insights into catalysts under reaction conditions.

Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device

Directory of Open Access Journals (Sweden)

Peter Fremerey

2015-10-01

Full Text Available In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H2S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nickel sulfide occurred. This conductivity increase by decades during sulfidation had not been expected since both nickel and nickel sulfides behave metallic. Only by assuming a percolation phenomenon that originates from a volume increase of the nickel contacts when reacting to nickel sulfides, this effect can be explained. This assumption was supported by sulfidation tests with differently nickel loaded catalysts and it was quantitatively estimated by a general effective media theory. The single pellet sensor device for in operando investigation of sulfidation can be considered as a valuable tool to get further insights into catalysts under reaction conditions.

Characterization of platinized and unplatinized cerium dioxide and other cerium containing catalyst supports

International Nuclear Information System (INIS)

Daniel, D.W.

1984-01-01

The adsorption of CO on platinized cerium dioxide has been investigated by FTIR (Fourier Transform Infrared Spectroscopy). Four active surface sites and two adsorption geometries were found for the oxidized catalyst. Although the metallic sites and both geometries, linear and bridged, were retained upon reduction the two cationic sites were not. During stepwise desorption, CO dissociates leaving behind adsorbed carbon inhibiting readsorption. At elevated temperatures CeO 2 oxidizes Pt. The large decrease in CO adsorption resulting from high temperature reduction was reversed by reoxidation. XPS (X-ray Photoelectron Spectroscopy) data provided no evidence of encapsulation and XRD (X-ray Diffraction) showed the retention of a constant particle size. The results were interpreted as electronic metal-support interaction. The addition of H 2 or D 2 to adsorbed CO at 25 0 C caused spillover of the CO onto the support and a decrease in CO band frequency. When O 2 was added to preadsorbed CO a new band associated with oxygen and CO coadsorbed on a single Pt atom appeared. Carbon dioxide dissociation at room temperature is proposed to occur via a Langmuir-Hinshelwood mechanism. CO adsorption on platinized titania, silica, ceria/titania, ceria/silica, and cerium titanate has also been studied by the same techniques. The adsorption/desorption behavior of the cerium/titania and the single oxide systems paralleled that of Pt/CeO 2

Growth of uniform thin-walled carbon nanotubes with spin-coated Fe catalyst and the correlation between the pre-growth catalyst size and the nanotube diameter

International Nuclear Information System (INIS)

Seah, Choon-Ming; Chai, Siang-Piao; Ichikawa, Satoshi; Mohamed, Abdul Rahman

2013-01-01

Single-walled carbon nanotubes (CNTs) and double-walled CNTs with a selectivity of 93 % were obtained by means of the novel homemade iron catalysts which were spin coated on silicon wafer. The average diameters of the iron particles prepared from the colloidal solutions containing 30, 40, 50, 60, and 70 mmol/L of iron nitrate were 8.2, 5.1, 20.8, 32.2, and 34.7 nm, respectively, and growing thin-walled CNTs with the average diameters of 4.1, 2.2, 9.2, 11.1, and 18.1 nm, respectively. The diameters of the CNTs were correlated with the geometric sizes of the pre-growth catalyst particles. Thin-walled CNTs were found to have a catalyst mean diameter-to-CNT average diameter ratio of 2.31. Iron carbide was formed after the growth of CNTs, and it is believed that during the growth of CNTs, carbon source decomposed and deposited on the surface of catalyst, followed by the diffusion of surface carbon into the iron catalyst particles, resulting in carbon supersaturation state before the growth of CNTs.

Biomass Conversion over Heteropoly Acid Catalysts

KAUST Repository

Zhang, Jizhe

2015-04-01

(Au/Cs2HPW12O40) that enabled the selective conversion of cellobiose to gluconic acid with a very high yield of 96.4% (Chapter II); we realized a direct oxidative conversion of cellulose to glycolic acid (yield of 49.3 %) in a water medium for the first time, by using a phosphomolybdic acid catalyst (chapter III); we found that a vanadium-substituted phosphomolybdic acid catalyst (H4PVMo11O40) is capable of converting various biomass-derived substrates to formic acid and acetic acid with high selectivity, and under optimized reaction conditions, high yield of formic acid (67.8%) can be obtained from cellulose (chapter IV); we discovered that the vanadium-substituted phosphomolybdic acids can also selectively oxidize glycerol, a low-cost by-product of biodiesel, to formic acid, and interestingly this conversion can be performed in highly concentration aqueous solution (glycerol: water = 50: 50), giving rise to exceptionally high conversion efficiency (chapter V). These results reveal that HPAs are useful and suitable catalysts for selective oxidation of biomass, and that the reaction pathway is largely determined by the type of addenda atom in the HPA catalyst. The optimization of the reaction conditions and processes in these systems are also discussed in this thesis.

Methods of ecological capability evaluation of forest

International Nuclear Information System (INIS)

Hosseini, M.; Makhdoum, M.F.; Akbarnia, M.; Saghebtalebi, Kh.

2000-01-01

In this research common methods of ecological capability evaluation of forests were reviewed and limitations for performance were analysed. Ecological capability of forests is an index that show site potential in several role of wood production, soil conservation, flood control, biodiversity, conservation and water supply. This index is related to ecological characteristics of land, such as soil, micro climate, elevation, slope and aspect that affect potential of sites. Suitable method of ecological capability evaluation must be chosen according to the objective of forestry. Common methods for ecological capability evaluation include plant and animal diversity, site index curve, soil and land form, inter branches, index plants, leave analyses, analyses regeneration and ecological mapping

Impeded solid state reactions and transformations in ceramic catalysts supports and catalysts

Directory of Open Access Journals (Sweden)

Ernő E. Kiss

2012-12-01

Full Text Available Impeded chemical reactions and impeded polymorphous transformation in materials are discussed, as desired effects, for stabilization of ceramic catalyst supports and ceramic based catalysts. This paper gives a short overview about the possibilities of slowing down the aging processes in ceramic catalyst supports and catalysts. Special attention is given to alumina and titania based catalysts.

Oxidation of mercury across selective catalytic reduction catalysts in coal-fired power plants

Energy Technology Data Exchange (ETDEWEB)

Constance L. Senior [Reaction Engineering International, Salt Lake City, UT (United States)

2006-01-15

A kinetic model for predicting the amount of mercury (Hg) oxidation across selective catalytic reduction (SCR) systems in coal-fired power plants was developed and tested. The model incorporated the effects of diffusion within the porous SCR catalyst and the competition between ammonia and Hg for active sites on the catalyst. Laboratory data on Hg oxidation in simulated flue gas and slipstream data on Hg oxidation in flue gas from power plants were modeled. The model provided good fits to the data for eight different catalysts, both plate and monolith, across a temperature range of 280-420{sup o}C, with space velocities varying from 1900 to 5000 hr{sup -1}. Space velocity, temperature, hydrochloric acid content of the flue gas, ratio of ammonia to nitric oxide, and catalyst design all affected Hg oxidation across the SCR catalyst. The model can be used to predict the impact of coal properties, catalyst design, and operating conditions on Hg oxidation across SCRs. 20 refs., 9 figs., 2 tabs.

Simulation of the Dynamics of Isothermal Growth of Single-Layer Graphene on a Copper Catalyst in the Process of Chemical Vapor Deposition of Hydrocarbons

Science.gov (United States)

Futko, S. I.; Shulitskii, B. G.; Labunov, V. A.; Ermolaeva, E. M.

2018-01-01

A new kinetic model of isothermal growth of single-layer graphene on a copper catalyst as a result of the chemical vapor deposition of hydrocarbons on it at a low pressure has been developed on the basis of in situ measurements of the growth of graphene in the process of its synthesis. This model defines the synthesis of graphene with regard for the chemisorption and catalytic decomposition of ethylene on the surface of a copper catalyst, the diffusion of carbon atoms in the radial direction to the nucleation centers within the thin melted near-surface copper layer, and the nucleation and autocatalytic growth of graphene domains. It is shown that the time dependence of the rate of growth of a graphene domain has a characteristic asymmetrical bell-like shape. The dependences of the surface area and size of a graphene domain and the rate of its growth on the time at different synthesis temperatures and ethylene concentrations have been obtained. Time characteristics of the growth of graphene domains depending on the parameters of their synthesis were calculated. The results obtained can be used for determining optimum regimes of synthesis of graphene in the process of chemical vapor deposition of hydrocarbons on different catalysts with a low solubility of carbon.

Co-Production of Ethanol and 1,2-Propanediol via Glycerol Hydrogenolysis Using Ni/Ce–Mg Catalysts: Effects of Catalyst Preparation and Reaction Conditions

Directory of Open Access Journals (Sweden)

Russel N. Menchavez

2017-09-01

Full Text Available Crude glycerol from biodiesel production is a biobased material capable of co-producing biofuels and chemicals. This study aimed to develop a line of Ni catalysts supported on cerium–magnesium (Ce–Mg to improve the process efficiency of glycerol hydrogenolysis for ethanol and 1,2-propanediol (1,2-PDO. Results showed that catalytic activity was greatly improved by changing the preparation method from impregnation to deposition precipitation (DP, and by adjusting calcination temperatures. Prepared via DP, the catalysts of 25 wt % Ni supported on Ce–Mg (9:1 mol/mol greatly improved the effectiveness in glycerol conversion while maintaining the selectivities to ethanol and 1,2-PDO. Calcination at 350 °C provided the catalysts better selectivities of 15.61% to ethanol and 67.93% to 1,2-PDO. Increases in reaction temperature and time improved the conversion of glycerol and the selectivity to ethanol, but reduced the selectivity to 1,2-PDO. A lower initial water content led to a higher conversion of glycerol, but lower selectivities to ethanol and 1,2-PDO. Higher hydrogen application affected the glycerol conversion rate positively, but the selectivities to ethanol and 1,2-PDO negatively. A comparison to the commercial Raney® Ni catalyst showed that the Ni/Ce–Mg catalyst developed in this study showed a better potential for the selective co-production of ethanol and 1,2-PDO from glycerol hydrogenolysis.

The kinetics and mechanism of methanol oxidation on Pt and PtRu catalysts in alkaline and acid media

Directory of Open Access Journals (Sweden)

JELENA LOVIC

2007-07-01

Full Text Available The kinetic of methanol electrochemical oxidation for a series of platinum and platinum–ruthenium catalysts was investigated. A correlation between the beginning of OHad adsorption and methanol oxidation was demonstarated on Pt single crystals and Pt nanocatalyst. The activity of the nano-structured Pt catalyst was compared with single crystal platinum electrodes assuming the Kinoshita model of nanoparticles. The ruthenium-containing catalysts shifted the onset of methanol oxidation to more negative potentials. The effect was more pronounced in acid than in alkaline media. Based on the established diagnostic criteria, the reaction between COad and OHad species according to the Langmuir–Hinshelwood mechanism was proposed as the rate determining step in alkaline and acid media on Pt and PtRu catalysts.

An Alumina-Supported Ni-La-Based Catalyst for Producing Synthetic Natural Gas

Directory of Open Access Journals (Sweden)

Daniel E. Rivero-Mendoza

2016-10-01

Full Text Available LaNi5, known for its hydrogen storage capability, was adapted to the form of a metal oxide-supported (γ-Al2O3 catalyst and its performance for the Sabatier reaction assessed. The 20 wt % La-Ni/γ-Al2O3 particles were prepared via solution combustion synthesis (SCS and exhibited good catalytic activity, achieving a CO2 conversion of 75% with a high CH4 selectivity (98% at 1 atm and 300 °C. Characteristics of the La-Ni/γ-Al2O3 catalyst were identified at various stages of the catalytic process (as-prepared, activated, and post-reaction and in-situ DRIFTS was used to probe the reaction mechanism. The as-prepared catalyst contained amorphous surface La–Ni spinels with particle sizes <6 nm. The reduction process altered the catalyst make-up where, despite the reducing conditions, Ni2+-based particles with diameters between 4 and 20 nm decorated with LaOx moieties were produced. However, the post-reaction catalyst had particle sizes of 4–9 nm and comprised metallic Ni, with the LaOx decoration reverting to a form akin to the as-prepared catalyst. DRIFTS analysis indicated that formates and adsorbed CO species were present on the catalyst surface during the reaction, implying the reaction proceeded via a H2-assisted and sequential CO2 dissociation to C and O. These were then rapidly hydrogenated into CH4 and H2O.

DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

Energy Technology Data Exchange (ETDEWEB)

Branko N. Popov

2009-02-20

The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst shows the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable

DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

Energy Technology Data Exchange (ETDEWEB)

Branko N. Popov

2009-03-03

The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst shows the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable

Fe3C-based oxygen reduction catalysts: synthesis, hollow spherical structures and applications in fuel cells

DEFF Research Database (Denmark)

Hu, Yang; Jensen, Jens Oluf; Zhang, Wei

2015-01-01

We present a detailed study of a novel Fe3C-based spherical catalyst with respect to synthetic parameters, nanostructure formation, ORR active sites and fuel cell demonstration. The catalyst is synthesized by high temperature autoclave pyrolysis using decomposing precursors. Below 500 °C, melamine...

Enhancement of kalman filter single loss detection capability

International Nuclear Information System (INIS)

Morrison, G.W.; Downing, D.J.; Pike, D.H.

1980-01-01

A new technique to significantly increase the sensitivity of the Kalman filter to detect one-time losses for nuclear marterial accountability and control has been developed. The technique uses the innovations sequence obtained from a Kalman filter analysis of a material balance area. The innovations are distributed as zero mean independent Gaussion random variables with known variance. This property enables an estimator to be formed with enhanced one time loss detection capabilities. Simulation studies of a material balance area indicate the new estimator greatly enhances the one time loss detection capability of the Kalman filter

Catalyst support structure, catalyst including the structure, reactor including a catalyst, and methods of forming same

Science.gov (United States)

Van Norman, Staci A.; Aston, Victoria J.; Weimer, Alan W.

2017-05-09

Structures, catalysts, and reactors suitable for use for a variety of applications, including gas-to-liquid and coal-to-liquid processes and methods of forming the structures, catalysts, and reactors are disclosed. The catalyst material can be deposited onto an inner wall of a microtubular reactor and/or onto porous tungsten support structures using atomic layer deposition techniques.

Micro-analysis of plaque fluid from single-site fasted plaque

International Nuclear Information System (INIS)

Vogel, G.L.; Carey, C.M.; Chow, L.C.; Tatevossian, A.

1990-01-01

Despite the site-specific nature of caries, nearly all data on the concentration of ions relevant to the level of saturation of plaque fluid with respect to calcium phosphate minerals or enamel are from studies that used pooled samples. A procedure is described for the collection and analysis of inorganic ions relevant to these saturation levels in plaque fluid samples collected from a single surface on a single tooth. Various methods for examining data obtained by this procedure are described, and a mathematical procedure employing potential plots is recommended

Stabilization of bacterially expressed erythropoietin by single site-specific introduction of short branched PEG chains at naturally occurring glycosylation sites.

Science.gov (United States)

Hoffmann, E; Streichert, K; Nischan, N; Seitz, C; Brunner, T; Schwagerus, S; Hackenberger, C P R; Rubini, M

2016-05-24

The covalent attachment of polyethylene glycol (PEG) to therapeutic proteins can improve their physicochemical properties. In this work we utilized the non-natural amino acid p-azidophenylalanine (pAzF) in combination with the chemoselective Staudinger-phosphite reaction to install branched PEG chains to recombinant unglycosylated erythropoietin (EPO) at each single naturally occurring glycosylation site. PEGylation with two short 750 or 2000 Da PEG units at positions 24, 38, or 83 significantly decreased unspecific aggregation and proteolytic degradation while biological activity in vitro was preserved or even increased in comparison to full-glycosylated EPO. This site-specific bioconjugation approach permits to analyse the impact of PEGylation at single positions. These results represent an important step towards the engineering of site-specifically modified EPO variants from bacterial expression with increased therapeutic efficacy.

The behavior of catalysts in hydrogasification of sub-bituminous coal in pressured fluidized bed