Microwave-assisted Extraction of Rare Earth Elements from Petroleum Refining Catalysts and Ambient Fine Aerosols Prior to Inductively Coupled Plasma - Mass Spectrometry

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Kulkarni, Pranav; Chellam, Shankar

2006-01-01

In the absence of a certified reference material, a robust microwave-assisted acid digestion procedure followed by inductively coupled plasma - mass spectrometry (ICP-MS) was developed to quantify rare earth elements (REEs) in fluidized-bed catalytic cracking (FCC) catalysts and atmospheric fine particulate matter (PM2.5). High temperature (200 C), high pressure (200 psig), acid digestion (HNO3, HF, and H3BO3) with 20 minute dwell time effectively solubilized REEs from six fresh catalysts, a spent catalyst, and PM2.5. This method was also employed to measure 27 non-REEs including Na, Mg, Al, Si, K, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Zr, Mo, Cd, Cs, Ba, Pb, and U. Complete extraction of several REEs (Y, La, Ce, Pr, Nd, Tb, Dy, and Er) required HF indicating that they were closely associated with the aluminosilicate structure of the zeolite FCC catalysts. Internal standardization using 115In quantitatively corrected non-spectral interferences in the catalyst digestate matrix. Inter-laboratory comparison using ICP-optical emission spectroscopy (ICP-OES) and instrumental neutron activation analysis (INAA) demonstrated the applicability of the newly developed analytical method for accurate analysis of REEs in FCC catalysts. The method developed for FCC catalysts was also successfully implemented to measure trace to ultra-trace concentrations of La, Ce, Pr, Nd, Sm, Gd, Eu, and Dy in ambient PM2.5 in an industrial area of Houston, TX.

Combined method for simultaneously dewatering and reconstituting finely divided carbonaceous material

DOEpatents

Wen, Wu-Wey; Deurbrouck, Albert W.

1990-01-01

A finely-divided carbonaceous material is dewatered and reconstituted in a combined process by adding a binding agent directly into slurry of finely divided material and dewatering the material to form a cake or consolidated piece which can be hardened by drying at ambient or elevated temperatures. Alternatively, the binder often in the form of a crusting agent is sprayed onto the surface of a moist cake prior to curing.

Pt-Ni and Pt-Co Catalyst Synthesis Route for Fuel Cell Applications

NASA Technical Reports Server (NTRS)

Firdosy, Samad A.; Ravi, Vilupanur A.; Valdez, Thomas I.; Kisor, Adam; Narayan, Sri R.

2013-01-01

Oxygen reduction reactions (ORRs) at the cathode are the rate-limiting step in fuel cell performance. The ORR is 100 times slower than the corresponding hydrogen oxidation at the anode. Speeding up the reaction at the cathode will improve fuel cell efficiency. The cathode material is generally Pt powder painted onto a substrate (e.g., graphite paper). Recent efforts in the fuel cell area have focused on replacing Pt with Pt-X alloys (where X = Co, Ni, Zr, etc.) in order to (a) reduce cost, and (b) increase ORR rates. One of these strategies is to increase ORR rates by reducing the powder size, which would result in an increase in the surface area, thereby facilitating faster reaction rates. In this work, a process has been developed that creates Pt-Ni or Pt-Co alloys that are finely divided (on the nano scale) and provide equivalent performance at lower Pt loadings. Lower Pt loadings will translate to lower cost. Precursor salts of the metals are dissolved in water and mixed. Next, the salt mixtures are dried on a hot plate. Finally, the dried salt mixture is heattreated in a furnace under flowing reducing gas. The catalyst powder is then used to fabricate a membrane electrode assembly (MEA) for electrochemical performance testing. The Pt- Co catalyst-based MEA showed comparable performance to an MEA fabri cated using a standard Pt black fuel cell catalyst. The main objective of this program has been to increase the overall efficiencies of fuel cell systems to support power for manned lunar bases. This work may also have an impact on terrestrial programs, possibly to support the effort to develop a carbon-free energy source. This catalyst can be used to fabricate high-efficiency fuel cell units that can be used in space as regenerative fuel cell systems, and terrestrially as primary fuel cells. Terrestrially, this technology will become increasingly important when transition to a hydrogen economy occurs.

Carbon fuel particles used in direct carbon conversion fuel cells

DOEpatents

Cooper, John F.; Cherepy, Nerine

2012-10-09

A system for preparing particulate carbon fuel and using the particulate carbon fuel in a fuel cell. Carbon particles are finely divided. The finely dividing carbon particles are introduced into the fuel cell. A gas containing oxygen is introduced into the fuel cell. The finely divided carbon particles are exposed to carbonate salts, or to molten NaOH or KOH or LiOH or mixtures of NaOH or KOH or LiOH, or to mixed hydroxides, or to alkali and alkaline earth nitrates.

Carbon Fuel Particles Used in Direct Carbon Conversion Fuel Cells

DOEpatents

Cooper, John F.; Cherepy, Nerine

2008-10-21

A system for preparing particulate carbon fuel and using the particulate carbon fuel in a fuel cell. Carbon particles are finely divided. The finely dividing carbon particles are introduced into the fuel cell. A gas containing oxygen is introduced into the fuel cell. The finely divided carbon particles are exposed to carbonate salts, or to molten NaOH or KOH or LiOH or mixtures of NaOH or KOH or LiOH, or to mixed hydroxides, or to alkali and alkaline earth nitrates.

Carbon fuel particles used in direct carbon conversion fuel cells

DOEpatents

Cooper, John F [Oakland, CA; Cherepy, Nerine [Oakland, CA

2011-08-16

A system for preparing particulate carbon fuel and using the particulate carbon fuel in a fuel cell. Carbon particles are finely divided. The finely dividing carbon particles are introduced into the fuel cell. A gas containing oxygen is introduced into the fuel cell. The finely divided carbon particles are exposed to carbonate salts, or to molten NaOH or KOH or LiOH or mixtures of NaOH or KOH or LiOH, or to mixed hydroxides, or to alkali and alkaline earth nitrates.

Carbon fuel particles used in direct carbon conversion fuel cells

DOEpatents

Cooper, John F [Oakland, CA; Cherepy, Nerine [Oakland, CA

2012-01-24

A system for preparing particulate carbon fuel and using the particulate carbon fuel in a fuel cell. Carbon particles are finely divided. The finely dividing carbon particles are introduced into the fuel cell. A gas containing oxygen is introduced into the fuel cell. The finely divided carbon particles are exposed to carbonate salts, or to molten NaOH or KOH or LiOH or mixtures of NaOH or KOH or LiOH, or to mixed hydroxides, or to alkali and alkaline earth nitrates.

Fine platinum nanoparticles supported on a porous ceramic membrane as efficient catalysts for the removal of benzene.

PubMed

Liu, Hui; Li, Chengyin; Ren, Xiaoyong; Liu, Kaiqi; Yang, Jun

2017-11-29

It would be desirable to remove volatile organic compounds (VOCs) while we eliminate the dusts using silicon carbide (SiC)-based porous ceramics from the hot gases. Aiming at functionalizing SiC-based porous ceramics with catalytic capability, we herein report a facile strategy to integrate high efficient catalysts into the porous SiC substrates for the VOC removal. We demonstrate an aqueous salt method for uniformly distributing fine platinum (Pt) particles on the alumina (Al 2 O 3 ) layers, which are pre-coated on the SiC substrates as supports for VOC catalysts. We confirm that at a Pt mass loading as low as 0.176% and a weight hourly space velocity of 6000 mL g -1 h -1 , the as-prepared Pt/SiC@Al 2 O 3 catalysts can convert 90% benzene at a temperature of ca. 215 °C. The results suggest a promising way to design ceramics-based bi-functional materials for simultaneously eliminating dusts and harmful VOCs from various hot gases.

Finely controlled multimetallic nanocluster catalysts for solvent-free aerobic oxidation of hydrocarbons

PubMed Central

Takahashi, Masaki; Koizumi, Hiromu; Chun, Wang-Jae; Kori, Makoto; Imaoka, Takane; Yamamoto, Kimihisa

2017-01-01

The catalytic activity of alloy nanoparticles depends on the particle size and composition ratio of different metals. Alloy nanoparticles composed of Pd, Pt, and Au are widely used as catalysts for oxidation reactions. The catalytic activities of Pt and Au nanoparticles in oxidation reactions are known to increase as the particle size decreases and to increase on the metal-metal interface of alloy nanoparticles. Therefore, multimetallic nanoclusters (MNCs) around 1 nm in diameter have potential as catalysts for oxidation reactions. However, there have been few reports describing the preparation of uniform alloy nanoclusters. We report the synthesis of finely controlled MNCs (around 1 nm) using a macromolecular template with coordination sites arranged in a gradient of basicity. We reveal that Cu-Pt-Au MNCs supported on graphitized mesoporous carbon show catalytic activity that is 24 times greater than that of a commercially available Pt catalyst for aerobic oxidation of hydrocarbons. In addition, solvent-free aerobic oxidation of hydrocarbons to ketones at room temperature, using small amounts of a radical initiator, was achieved as a heterogeneous catalytic reaction for the first time. PMID:28782020

Synthesis of iron based hydrocracking catalysts

DOEpatents

Farcasiu, Malvina; Eldredge, Patricia A.; Ladner, Edward P.

1993-01-01

A method of preparing a fine particle iron based hydrocracking catalyst and the catalyst prepared thereby. An iron (III) oxide powder and elemental sulfur are reacted with a liquid hydrogen donor having a hydroaromatic structure present in the range of from about 5 to about 50 times the weight of iron (III) oxide at a temperature in the range of from about 180.degree. C. to about 240.degree. C. for a time in the range of from about 0 to about 8 hours. Various specific hydrogen donors are disclosed. The catalysts are active at low temperature (<350.degree. C.) and low pressure.

Sulfur removal and comminution of carbonaceous material

DOEpatents

Narain, Nand K.; Ruether, John A.; Smith, Dennis N.

1988-01-01

Finely divided, clean coal or other carbonaceous material is provided by forming a slurry of coarse coal in aqueous alkali solution and heating the slurry under pressure to above the critical conditions of steam. The supercritical fluid penetrates and is trapped in the porosity of the coal as it swells in a thermoplastic condition at elevated temperature. By a sudden, explosive release of pressure the coal is fractured into finely divided particles with release of sulfur-containing gases and minerals. The finely divided coal is recovered from the minerals for use as a clean coal product.

A molecule-like PtAu24(SC6H13)18 nanocluster as an electrocatalyst for hydrogen production

PubMed Central

Kwak, Kyuju; Choi, Woojun; Tang, Qing; Kim, Minseok; Lee, Yongjin; Jiang, De-en; Lee, Dongil

2017-01-01

The theoretically predicted volcano plot for hydrogen production shows the best catalyst as the one that ensures that the hydrogen binding step is thermodynamically neutral. However, the experimental realization of this concept has suffered from the inherent surface heterogeneity of solid catalysts. It is even more challenging for molecular catalysts because of their complex chemical environment. Here, we report that the thermoneutral catalyst can be prepared by simple doping of a platinum atom into a molecule-like gold nanocluster. The catalytic activity of the resulting bimetallic nanocluster, PtAu24(SC6H13)18, for the hydrogen production is found to be significantly higher than reported catalysts. It is even better than the benchmarking platinum catalyst. The molecule-like bimetallic nanocluster represents a class of catalysts that bridge homogeneous and heterogeneous catalysis and may provide a platform for the discovery of finely optimized catalysts. PMID:28281526

Supported molten-metal catalysts

DOEpatents

Datta, Ravindra; Singh, Ajeet; Halasz, Istvan; Serban, Manuela

2001-01-01

An entirely new class of catalysts called supported molten-metal catalysts, SMMC, which can replace some of the existing precious metal catalysts used in the production of fuels, commodity chemicals, and fine chemicals, as well as in combating pollution. SMMC are based on supporting ultra-thin films or micro-droplets of the relatively low-melting (<600.degree. C.), inexpensive, and abundant metals and semimetals from groups 1, 12, 13, 14, 15 and 16, of the periodic table, or their alloys and intermetallic compounds, on porous refractory supports, much like supported microcrystallites of the traditional solid metal catalysts. It thus provides orders of magnitude higher surface area than is obtainable in conventional reactors containing molten metals in pool form and also avoids corrosion. These have so far been the chief stumbling blocks in the application of molten metal catalysts.

Probing solid catalysts under operating conditions: electrons or X-rays?

PubMed

Thomas, John Meurig; Hernandez-Garrido, Juan-Carlos

2009-01-01

Seeing is believing: In light of recent advances, the pros and cons of using electrons and X-rays for in situ studies of catalysts are analyzed: by using X-rays the structure of bound reactants at steady state are obtained from extended X-ray adsorption fine structure spectroscopy (EXAFS) data (see graph), thereby affording mechanistic insights.

Moving to Sustainable Metals. Multifunctional Ligands in Catalytic, Outer Sphere C-H, N-H and O-H Activation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crabtree, Robert

2015-03-03

Much of our work during this grant period has emphasized green chemistry and sustainability. For example, we were able to convert glycerine, a waste byproduct of biodiesel production, into lactic acid, a compound with numerous applications, notably in the food and cosmetics industry, as well as being a source material for a biodegradable plastic. This work required a catalyst, that ceases to work after a certain lapse of time. We were able to identify the way in which this deactivation occurs by identifying some of the metal catalyst deactivation products. These proved to be multimetallic clusters containing up to sixmore » metals and up to 14 hydrogen atoms. Both the catalytic reaction itself and the deactivation structures are novel and unexpected. We have previously proposed that nitrogen heterocycles could be good energy carriers in a low CO 2 future world. In another part of our study, we found catalysts for introduction of hydrogen, an energy carrier that is hard to store, into nitrogen heterocycles. The mechanism of this process proved to be unusual in that the catalyst transfers the H 2 to the heterocycle in the form of H + and H -, first transferring the H + and only then the H -. In a third area of study, some of our compounds, originally prepared for DOE catalysis purposes, also proved useful in hydrocarbon oxidation and in water oxidation. The latter is important in solar-to-fuel work, because, by analogy with natural photosynthesis, the goal of the Yale Solar Group of four PIs is to convert sunlight to hydrogen and oxygen, which requires water splitting catalysts. The catalysts that proved useful mediate the latter reaction: water oxidation to oxygen. In a more technical study, we developed methods for distinguishing the case where catalysis is mediated by a soluble catalyst from cases where catalysis arises from a deposit of finely divided solid. One particular application involved electrocatalysis, where catalysis is driven by application of a voltage to electrodes dipped in the reactant mixture. We measured the mass increase of an electrode as material is deposited, and were able to see how this process is affected by the voltage supplied to the electrode. Our work continues to be well cited and we often receive requests for information or samples from fellow researchers.« less

Titanium Dioxide as a Catalyst Support in Heterogeneous Catalysis

PubMed Central

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

Sulfur removal and comminution of carbonaceous material

DOEpatents

Narain, N.K.; Ruether, J.A.; Smith, D.N.

1987-10-07

Finely divided, clean coal or other carbonaceous material is provided by forming a slurry of coarse coal in aqueous alkali solution and heating the slurry under pressure to above the critical conditions of steam. The supercritical fluid penetrates and is trapped in the porosity of the coal as it swells in a thermoplastic condition at elevated temperature. By a sudden, explosive release of pressure the coal is fractured into finely divided particles with release of sulfur-containing gases and minerals. The finely divided coal is recovered from the minerals for use as a clean coal product. 2 figs.

Fluidized reduction of oxides on fine metal powders without sintering

NASA Technical Reports Server (NTRS)

Hayashi, T.

1985-01-01

In the process of reducing extremely fine metal particles (av. particle size or = 1000 angstroms) covered with an oxide layer, the metal particles are fluidized by a gas flow contg. H, heated, and reduced. The method uniformly and easily reduces surface oxide layers of the extremely fine metal particles without causing sintering. The metal particles are useful for magnetic recording materials, conductive paste, powder metallurgy materials, chem. reagents, and catalysts.

CO 2 hydrogenation over oxide-supported PtCo catalysts: The role of the oxide support in determining the product selectivity

DOE PAGES

Kattel, Shyam; Yu, Weiting; Yang, Xiaofang; ...

2016-05-09

By simply changing the oxide support, the selectivity of a metal–oxide catalysts can be tuned. For the CO 2 hydrogenation over PtCo bimetallic catalysts supported on different reducible oxides (CeO 2, ZrO 2, and TiO 2), replacing a TiO 2 support by CeO 2 or ZrO 2 selectively strengthens the binding of C,O-bound and O-bound species at the PtCo–oxide interface, leading to a different product selectivity. Lastly, these results reveal mechanistic insights into how the catalytic performance of metal–oxide catalysts can be fine-tuned.

Template Effect and Ligand Substitution Methods for the Synthesis of Iron Catalysts: A Two-Part Experiment for Inorganic Chemistry

ERIC Educational Resources Information Center

Sues, Peter E.; Cai, Kuihua; McIntosh, Douglas F.; Morris, Robert H.

2015-01-01

Asymmetric transfer hydrogenation is an important transformation for the production of fine chemicals. Traditionally, platinum group metals are used to catalyze this reaction, but recent pressure for greener practices has driven the development of base-metal catalysts. Due to the growing interest in this area of research, the underlying concepts…

Attrition Resistant Fischer-Tropsch Catalysts Based on FCC Supports

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adeyiga, Adeyinka

2010-02-05

Commercial spent fluid catalytic cracking (FCC) catalysts provided by Engelhard and Albemarle were used as supports for Fe-based catalysts with the goal of improving the attrition resistance of typical F-T catalysts. Catalysts with the Ruhrchemie composition (100 Fe/5 Cu/4.2 K/25 spent FCC on mass basis) were prepared by wet impregnation. XRD and XANES analysis showed the presence of Fe{sub 2}O{sub 3} in calcined catalysts. FeC{sub x} and Fe{sub 3}O{sub 4} were present in the activated catalysts. The metal composition of the catalysts was analyzed by ICP-MS. F-T activity of the catalysts activated in situ in CO at the same conditionsmore » as used prior to the attrition tests was measured using a fixed bed reactor at T = 573 K, P = 1.38 MPa and H{sub 2}:CO ratio of 0.67. Cu and K promoted Fe supported over Engelhard provided spent FCC catalyst shows relatively good attrition resistance (8.2 wt% fines lost), high CO conversion (81%) and C{sub 5}+ hydrocarbons selectivity (18.3%).« less

Hydrogenation of succinic acid to 1,4-butanediol over rhenium catalyst supported on copper-containing mesoporous carbon.

PubMed

Hong, Ung Gi; Park, Hai Woong; Lee, Joongwon; Hwang, Sunhwan; Kwak, Jimin; Yi, Jongheop; Song, In Kyu

2013-11-01

Copper-containing mesoporous carbon (Cu-MC) was prepared by a single-step surfactant-templating method. For comparison, copper-impregnated mesoporous carbon (Cu/MC) was also prepared by a surfactant-templating method and a subsequent impregnation method. Rhenium catalysts supported on copper-containing mesoporous carbon and copper-impregnated mesoporous carbon (Re/Cu-MC and Re/Cu/MC, respectively) were then prepared by an incipient wetness method, and they were applied to the liquid-phase hydrogenation of succinic acid to 1,4-butanediol (BDO). It was observed that copper in the Re/Cu-MC catalyst was well incorporated into carbon framework, resulting in higher surface area and larger pore volume than those of Re/Cu/MC catalyst. Therefore, Re/Cu-MC catalyst showed higher copper dispersion than Re/Cu/MC catalyst, although both catalysts retained the same amounts of copper and rhenium. In the liquid-phase hydrogenation of succinic acid to BDO, Re/Cu-MC catalyst showed a better catalytic activity than Re/Cu/MC catalyst. Fine dispersion of copper in the Re/Cu-MC catalyst was responsible for its enhanced catalytic activity.

Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy.

PubMed

Yang, Ke R; Matula, Adam J; Kwon, Gihan; Hong, Jiyun; Sheehan, Stafford W; Thomsen, Julianne M; Brudvig, Gary W; Crabtree, Robert H; Tiede, David M; Chen, Lin X; Batista, Victor S

2016-05-04

The solution structures of highly active Ir water-oxidation catalysts are elucidated by combining density functional theory, high-energy X-ray scattering (HEXS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. We find that the catalysts are Ir dimers with mono-μ-O cores and terminal anionic ligands, generated in situ through partial oxidation of a common catalyst precursor. The proposed structures are supported by (1)H and (17)O NMR, EPR, resonance Raman and UV-vis spectra, electrophoresis, etc. Our findings are particularly valuable to understand the mechanism of water oxidation by highly reactive Ir catalysts. Importantly, our DFT-EXAFS-HEXS methodology provides a new in situ technique for characterization of active species in catalytic systems.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Amitava Sarkar; James K. Neathery; Burtron H. Davis

A fundamental filtration study was started to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. Slurry-phase FTS in slurry bubble column reactor systems is the preferred mode of operation since the reaction is highly exothermic. Consequently, heavy wax products in one approach may be separated from catalyst particles before being removed from the reactor system. Achieving an efficient wax product separation from iron-based catalysts is one of the most challenging technical problems associated with slurry-phase iron-based FTS and is a key factor for optimizing operating costs. The separation problem is further compounded by attrition of ironmore » catalyst particles and the formation of ultra-fine particles.« less

Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition

NASA Astrophysics Data System (ADS)

Sun, Shuhui; Zhang, Gaixia; Gauquelin, Nicolas; Chen, Ning; Zhou, Jigang; Yang, Songlan; Chen, Weifeng; Meng, Xiangbo; Geng, Dongsheng; Banis, Mohammad N.; Li, Ruying; Ye, Siyu; Knights, Shanna; Botton, Gianluigi A.; Sham, Tsun-Kong; Sun, Xueliang

2013-05-01

Platinum-nanoparticle-based catalysts are widely used in many important chemical processes and automobile industries. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their use efficiency, however, very challenging. Here we report a practical synthesis for isolated single Pt atoms anchored to graphene nanosheet using the atomic layer deposition (ALD) technique. ALD offers the capability of precise control of catalyst size span from single atom, subnanometer cluster to nanoparticle. The single-atom catalysts exhibit significantly improved catalytic activity (up to 10 times) over that of the state-of-the-art commercial Pt/C catalyst. X-ray absorption fine structure (XAFS) analyses reveal that the low-coordination and partially unoccupied densities of states of 5d orbital of Pt atoms are responsible for the excellent performance. This work is anticipated to form the basis for the exploration of a next generation of highly efficient single-atom catalysts for various applications.

Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition

PubMed Central

Sun, Shuhui; Zhang, Gaixia; Gauquelin, Nicolas; Chen, Ning; Zhou, Jigang; Yang, Songlan; Chen, Weifeng; Meng, Xiangbo; Geng, Dongsheng; Banis, Mohammad N.; Li, Ruying; Ye, Siyu; Knights, Shanna; Botton, Gianluigi A.; Sham, Tsun-Kong; Sun, Xueliang

2013-01-01

Platinum-nanoparticle-based catalysts are widely used in many important chemical processes and automobile industries. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their use efficiency, however, very challenging. Here we report a practical synthesis for isolated single Pt atoms anchored to graphene nanosheet using the atomic layer deposition (ALD) technique. ALD offers the capability of precise control of catalyst size span from single atom, subnanometer cluster to nanoparticle. The single-atom catalysts exhibit significantly improved catalytic activity (up to 10 times) over that of the state-of-the-art commercial Pt/C catalyst. X-ray absorption fine structure (XAFS) analyses reveal that the low-coordination and partially unoccupied densities of states of 5d orbital of Pt atoms are responsible for the excellent performance. This work is anticipated to form the basis for the exploration of a next generation of highly efficient single-atom catalysts for various applications.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

The objective of the contract is to consolidate the advances made during the previous contract in the conversion of syngas to motor fuels using Molecular Sieve-containing catalysts and to demonstrate the practical utility and economic value of the new catalyst/process systems with appropriate laboratory runs. Work on the program is divided into the following six tasks: (1) preparation of a detailed work plan covering the entire performance of the contract; (2) preliminary techno-economic assessment of the UCC catalyst/process system; (3) optimization of the most promising catalysts developed under prior contract; (4) optimization of the UCC catalyst system in a mannermore » that will give it the longest possible service life; (5) optimization of a UCC process/catalyst system based upon a tubular reactor with a recycle loop; and (6) economic evaluation of the optimal performance found under Task 5 for the UCC process/catalyst system. Accomplishments are reported for Tasks 2 through 5.« less

Alloy formation and metal oxide segregation on Pt-Re/. gamma. -Al/sub 2/O/sub 3/ catalysts as investigated by temperature-programmed reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wagstaff, N.; Prins, R.

1979-10-15

Catalysts resembling reforming catalysts were prepared to contain finely dispersed 0.75% Pt, 0.7% Re, or 0.35% Pt plus 0.1-2% Re on chlorided ..gamma..-alumina. The catalysts were dried in an oxidizing atmosphere and studied by temperature-programed reduction. Up to a Re/Pt ratio of 0.6:1 the metals were completely reduced in hydrogen below 255/sup 0/C, i.e., the platinum catalyzed rhenium reduction. A small amount of added water (< 50 ppm) also promoted rhenium reduction. Segregation of the metals occurred in oxygen above 200/sup 0/C, but at 100/sup 0/C, the rate of segregation was slow. These results suggested that under reforming conditions, Pt-Remore » catalysts are completely reduced bimetallic clusters. The mechanisms of reduction, cluster formation, and oxidative segregation are discussed.« less

Hydrogen adsorption on two catalysts for the ortho- to parahydrogen conversion: Cr-doped silica and ferric oxide gel.

PubMed

Hartl, Monika; Gillis, Robert Chad; Daemen, Luke; Olds, Daniel P; Page, Katherine; Carlson, Stefan; Cheng, Yongqiang; Hügle, Thomas; Iverson, Erik B; Ramirez-Cuesta, A J; Lee, Yongjoong; Muhrer, Günter

2016-06-29

Molecular hydrogen exists in two spin-rotation coupled states: parahydrogen and orthohydrogen. Due to the variation of energy with rotational level, the occupation of ortho- and parahydrogen states is temperature dependent, with parahydrogen being the dominant species at low temperatures. The equilibrium at 20 K (99.8% parahydrogen) can be reached by natural conversion only after a lengthy process. With the use of a suitable catalyst, this process can be shortened significantly. Two types of commercial catalysts currently being used for ortho- to parahydrogen conversion are: iron(iii) oxide (Fe2O3, IONEX®), and chromium(ii) oxide doped silica catalyst (CrO·SiO2, OXISORB®). We investigate the interaction of ortho- and parahydrogen with the surfaces of these ortho-para conversion catalysts using neutron vibrational spectroscopy. The catalytic surfaces have been characterized using X-ray absorption fine structure (XAFS) and X-ray/neutron pair distribution function measurements.

Carbon nanocages: a new support material for Pt catalyst with remarkably high durability.

PubMed

Wang, Xiao Xia; Tan, Zhe Hua; Zeng, Min; Wang, Jian Nong

2014-03-24

Low durability is the major challenge hindering the large-scale implementation of proton exchange membrane fuel cell (PEMFC) technology, and corrosion of carbon support materials of current catalysts is the main cause. Here, we describe the finding of remarkably high durability with the use of a novel support material. This material is based on hollow carbon nanocages developed with a high degree of graphitization and concurrent nitrogen doping for oxidation resistance enhancement, uniform deposition of fine Pt particles, and strong Pt-support interaction. Accelerated degradation testing shows that such designed catalyst possesses a superior electrochemical activity and long-term stability for both hydrogen oxidation and oxygen reduction relative to industry benchmarks of current catalysts. Further testing under conditions of practical fuel cell operation reveals almost no degradation over long-term cycling. Such a catalyst of high activity, particularly, high durability, opens the door for the next-generation PEMFC for "real world" application.

Regeneration and reuse of iron catalyst for Fenton-like reactions.

PubMed

Cao, Guo-min; Sheng, Mei; Niu, Wen-feng; Fei, Yu-lei; Li, Dong

2009-12-30

Fenton and Fenton-like reactions employed for oxidative treatment of a typical industrial wastewater generate a large amount of ferric hydroxide sludge which has to be properly disposed at a high cost. This paper presents a simple and cost-effective method for recovering the iron catalyst from the iron hydroxide sludge for oxidative treatment of industrial wastewaters. The sludge was dewatered, dried and baked at 350-400 degrees C for 20-30 min; the residual solids were dissolved in sulfuric acid to form the reusable catalyst for Fenton and Fenton-like reactions. The recovered catalyst was highly effective for the oxidative pretreatment of a fine chemical wastewater to improve its biodegradability; the resulting COD removal and BOD(5)/COD ratio of the treated stream remained nearly unchanged during the time period when the regenerated catalyst was reused six times. The simple and effective catalyst regeneration method will make Fenton and Fenton-like oxidation a more cost-effective wastewater treatment alternative.

Controlling interfacial properties in supported metal oxide catalysts through metal–organic framework templating

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abney, Carter W.; Patterson, Jacob T.; Gilhula, James C.

Precise control over the chemical structure of hard-matter materials is a grand challenge of basic science and a prerequisite for the development of advanced catalyst systems. In this work we report the application of a sacrificial metal-organic framework (MOF) template for the synthesis of a porous supported metal oxide catalyst, demonstrating proof-of-concept for a highly generalizable approach to the preparation new catalyst materials. Application of 2,2’-bipyridine-5,5’-dicarboxylic acid as the organic strut in the Ce MOF precursor results in chelation of Cu 2+ and affords isolation of the metal oxide precursor. Following pyrolysis of the template, homogeneously dispersed CuO nanoparticles aremore » formed in the resulting porous CeO 2 support. By partially substituting non-chelating 1,1’-biphenyl-4,4’-dicarboxylic acid, the Cu 2+ loading and dispersion can be finely tuned, allowing precise control over the CuO/CeO 2 interface in the final catalyst system. Characterization by x-ray diffraction, x-ray absorption fine structure spectroscopy, and in situ IR spectroscopy/mass spectrometry confirm control over interface formation to be a function of template composition, constituting the first report of a MOF template being used to control interfacial properties in a supported metal oxide. Using CO oxidation as a model reaction, the system with the greatest number of interfaces possessed the lowest activation energy and better activity under differential conditions, but required higher temperature for catalytic onset and displayed inferior efficiency at 100 °C than systems with higher Cu-loading. This finding is attributable to greater CO adsorption in the more heavily-loaded systems, and indicates catalyst performance for these supported oxide systems to be a function of at least two parameters: size of adsorption site and extent of interface. In conclusion, optimization of catalyst materials thus requires precise control over synthesis parameters, such as is demonstrated by this MOF-templating method.« less

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

NASA Astrophysics Data System (ADS)

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.

Bifunctional Organic Polymeric Catalysts with a Tunable Acid-Base Distance and Framework Flexibility

PubMed Central

Chen, Huanhui; Wang, Yanan; Wang, Qunlong; Li, Junhui; Yang, Shiqi; Zhu, Zhirong

2014-01-01

Acid-base bifunctional organic polymeric catalysts were synthesized with tunable structures. we demonstrated two synthesis approaches for structural fine-tune. In the first case, the framework flexibility was tuned by changing the ratio of rigid blocks to flexible blocks within the polymer framework. In the second case, we precisely adjusted the acid-base distance by distributing basic monomers to be adjacent to acidic monomers, and by changing the chain length of acidic monomers. In a standard test reaction for the aldol condensation of 4-nitrobenzaldehyde with acetone, the catalysts showed good reusability upon recycling and maintained relatively high conversion percentage. PMID:25267260

Reactor for tracking catalyst nanoparticles in liquid at high temperature under a high-pressure gas phase with X-ray absorption spectroscopy.

PubMed

Nguyen, Luan; Tao, Franklin Feng

2018-02-01

Structure of catalyst nanoparticles dispersed in liquid phase at high temperature under gas phase of reactant(s) at higher pressure (≥5 bars) is important for fundamental understanding of catalytic reactions performed on these catalyst nanoparticles. Most structural characterizations of a catalyst performing catalysis in liquid at high temperature under gas phase at high pressure were performed in an ex situ condition in terms of characterizations before or after catalysis since, from technical point of view, access to the catalyst nanoparticles during catalysis in liquid phase at high temperature under high pressure reactant gas is challenging. Here we designed a reactor which allows us to perform structural characterization using X-ray absorption spectroscopy including X-ray absorption near edge structure spectroscopy and extended X-ray absorption fine structure spectroscopy to study catalyst nanoparticles under harsh catalysis conditions in terms of liquid up to 350 °C under gas phase with a pressure up to 50 bars. This reactor remains nanoparticles of a catalyst homogeneously dispersed in liquid during catalysis and X-ray absorption spectroscopy characterization.

Nature-driven photochemistry for catalytic solar hydrogen production: a Photosystem I-transition metal catalyst hybrid.

PubMed

Utschig, Lisa M; Silver, Sunshine C; Mulfort, Karen L; Tiede, David M

2011-10-19

Solar energy conversion of water into the environmentally clean fuel hydrogen offers one of the best long-term solutions for meeting future energy demands. Nature provides highly evolved, finely tuned molecular machinery for solar energy conversion that exquisitely manages photon capture and conversion processes to drive oxygenic water-splitting and carbon fixation. Herein, we use one of Nature's specialized energy-converters, the Photosystem I (PSI) protein, to drive hydrogen production from a synthetic molecular catalyst comprised of inexpensive, earth-abundant materials. PSI and a cobaloxime catalyst self-assemble, and the resultant complex rapidly produces hydrogen in aqueous solution upon exposure to visible light. This work establishes a strategy for enhancing photosynthetic efficiency for solar fuel production by augmenting natural photosynthetic systems with synthetically tunable abiotic catalysts.

Sources of fine organic aerosol. 2. Noncatalyst and catalyst-equipped automobiles and heavy-duty diesel trucks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rogge, W.F.; Hildemann, L.M.; Mazurek, M.A.

Gasoline- and diesel-powered vehicles are known to contribute appreciable amounts of inhalable fine particulate matter to the atmosphere in urban areas. Internal combustion engines burning gasoline and diesel fuel contribute more than 21% of the primary fine particulate organic carbon emitted to the Los Angeles atmosphere. In the present study, particulate (d[sub p] [le] 2 [mu]m) exhaust emissions from six noncatalyst automobiles, seven catalyst-equipped automobiles, and two heavy-duty diesel trucks are examined by gas chromatography/mass spectrometry. The purposes of this study are as follows: (a) to search for conservative marker compounds suitable for tracing the presence of vehicular particulate exhaustmore » emissions in the urban atmosphere, (b) to compile quantitative source profiles, and (c) to study the contributions of fine organic particulate vehicular exhaust to the Los Angeles atmosphere. More than 100 organic compounds are quantified, including n-alkanes, n-alkanoic acids, benzoic acids, benzaldehydes, PAH, oxy-PAH, steranes, pentacyclic triterpanes, azanaphthalenes, and others. Although fossil fuel markers such as steranes and pentacyclic triterpanes can be emitted from other sources, it can be shown that their ambient concentrations measured in the Los Angeles atmosphere are attributable mainly to vehicular exhaust emissions. 102 refs., 9 figs., 6 tabs.« less

Regenerative process and system for the simultaneous removal of particulates and the oxides of sulfur and nitrogen from a gas stream

DOEpatents

Cohen, M.R.; Gal, E.

1993-04-13

A process and system are described for simultaneously removing from a gaseous mixture, sulfur oxides by means of a solid sulfur oxide acceptor on a porous carrier, nitrogen oxides by means of ammonia gas and particulate matter by means of filtration and for the regeneration of loaded solid sulfur oxide acceptor. Finely-divided solid sulfur oxide acceptor is entrained in a gaseous mixture to deplete sulfur oxides from the gaseous mixture, the finely-divided solid sulfur oxide acceptor being dispersed on a porous carrier material having a particle size up to about 200 microns. In the process, the gaseous mixture is optionally pre-filtered to remove particulate matter and thereafter finely-divided solid sulfur oxide acceptor is injected into the gaseous mixture.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

The objective of the contract is to consolidate the advances made during the previous contract in the conversion of syngas to motor fuels using Molecular Sieve-containing catalysts and to demonstrate the practical utility and economic value of the new catalyst/process systems with appropriate laboratory runs. Work on the program is divided into the following six tasks: (1) preparation of a detailed work plan covering the entire performance of the contract; (2) preliminary techno-economic assessment of the UCC catalyst/process system; (3) optimization of the most promising catalyst developed under prior contract; (4) optimization of the UCC catalyst system in a mannermore » that will give it the longest possible service life; (5) optimization of a UCC process/catalyst system based upon a tubular reactor with a recycle loop containing the most promising catalyst developed under Tasks 3 and 4 studies; and (6) economic evaluation of the optimal performance found under Task 5 for the UCC process/catalyst system. Progress reports are presented for tasks 2 through 5. 232 figs., 19 tabs.« less

Systematic Identification of Promoters for Methane Oxidation Catalysts Using Size- and Composition-Controlled Pd-Based Bimetallic Nanocrystals.

PubMed

Willis, Joshua J; Goodman, Emmett D; Wu, Liheng; Riscoe, Andrew R; Martins, Pedro; Tassone, Christopher J; Cargnello, Matteo

2017-08-30

Promoters enhance the performance of catalytic active phases by increasing rates, stability, and/or selectivity. The process of identifying promoters is in most cases empirical and relies on testing a broad range of catalysts prepared with the random deposition of active and promoter phases, typically with no fine control over their localization. This issue is particularly relevant in supported bimetallic systems, where two metals are codeposited onto high-surface area materials. We here report the use of colloidal bimetallic nanocrystals to produce catalysts where the active and promoter phases are colocalized to a fine extent. This strategy enables a systematic approach to study the promotional effects of several transition metals on palladium catalysts for methane oxidation. In order to achieve these goals, we demonstrate a single synthetic protocol to obtain uniform palladium-based bimetallic nanocrystals (PdM, M = V, Mn, Fe, Co, Ni, Zn, Sn, and potentially extendable to other metal combinations) with a wide variety of compositions and sizes based on high-temperature thermal decomposition of readily available precursors. Once the nanocrystals are supported onto oxide materials, thermal treatments in air cause segregation of the base metal oxide phase in close proximity to the Pd phase. We demonstrate that some metals (Fe, Co, and Sn) inhibit the sintering of the active Pd metal phase, while others (Ni and Zn) increase its intrinsic activity compared to a monometallic Pd catalyst. This procedure can be generalized to systematically investigate the promotional effects of metal and metal oxide phases for a variety of active metal-promoter combinations and catalytic reactions.

DEVELOPMENT OF ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adeyinka A. Adeyiga

2003-12-01

Fischer-Tropsch (FT) synthesis to convert syngas (CO + H{sub 2}) derived from natural gas or coal to liquid fuels and wax is a well-established technology. For low H{sub 2} to CO ratio syngas produced from CO{sub 2} reforming of natural gas or from gasification of coal, the use of Fe catalysts is attractive because of their high water gas shift activity in addition to their high FT activity. Fe catalysts are also attractive due to their low cost and low methane selectivity. Because of the highly exothermic nature of the FT reaction, there has been a recent move away frommore » fixed-bed reactors toward the development of slurry bubble column reactors (SBCRs) that employ 30 to 90 {micro}m catalyst particles suspended in a waxy liquid for efficient heat removal. However, the use of Fe FT catalysts in an SBCR has been problematic due to severe catalyst attrition resulting in fines that plug the filter employed to separate the catalyst from the waxy product. Fe catalysts can undergo attrition in SBCRs not only due to vigorous movement and collisions but also due to phase changes that occur during activation and reaction. The objectives of this research were to develop a better understanding of the parameters affecting attrition of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. The catalysts were prepared by co-precipitation, followed by binder addition and spray drying at 250 C in a 1 m diameter, 2 m tall spray dryer. The binder silica content was varied from 0 to 20 wt %. The results show that use of small amounts of precipitated SiO{sub 2} alone in spray-dried Fe catalysts can result in good attrition resistance. All catalysts investigated with SiO{sub 2} wt% {le} 12 produced fines less than 10 wt% during the jet cup attrition test, making them suitable for long-term use in a slurry bubble column reactor. Thus, concentration rather than type of SiO{sub 2} incorporated into catalyst has a more critical impact on catalyst attrition resistance of spray-dried Fe catalysts. Lower amounts of SiO{sub 2} added to a catalyst give higher particle densities and therefore higher attrition resistances. In order to produce a suitable SBCR catalyst, however, the amount of SiO{sub 2} added has to be optimized to provide adequate surface area, particle density, and attrition resistance. Two of the catalysts with precipitated and binder silica were tested in Texas A&M University's CSTR (Autoclave Engineers). Spray-dried catalysts with compositions 100 Fe/5 Cu/4.2 K/11 (P) SiO{sub 2} and 100 Fe/5 Cu/4.2 K/1.1 (B) SiO{sub 2} have excellent selectivity characteristics (low methane and high C{sub 5}{sup +} yields), but their productivity and stability (deactivation rate) need to be improved. Mechanical integrity (attrition strength) of these two catalysts was markedly dependent upon their morphological features. The attrition strength of the catalyst made out of largely spherical particles (1.1 (B) SiO{sub 2}) was considerably higher than that of the catalyst consisting of irregularly shaped particles (11 (P) SiO{sub 2}).« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

The objective of the contract is to consolidate the advances made during the previous contract in the conversion of syngas to motor fuels using Molecular Sieve-containing catalysts and to demonstrate the practical utility and economic value of the new catalyst/process systems with appropriate laboratory runs. Work on the program is divided into the following six tasks: (1) preparation of a detailed work plan covering the entire performance of the contract; (2) techno-economic studies that will supplement those that are presently being carried out by MITRE; (3) optimization of the most promising catalysts developed under prior contract; (4) optimization of themore » UCC catalyst system in a manner that will give it the longest possible service life; (5) optimization of a UCC process/catalyst system based upon a tubular reactor with a recycle loop containing the most promising catalyst developed under Tasks 3 and 4 studies; and (6) economic evaluation of the optimal performance found under Task 5 for the UCC process/catalyst system. Progress reports are presented for Tasks 1, 3, 4, and 5.« less

Dispersed bubble reactor for enhanced gas-liquid-solids contact and mass transfer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vimalchand, Pannalal; Liu, Guohai; Peng, WanWang

An apparatus to promote gas-liquid contact and facilitate enhanced mass transfer. The dispersed bubble reactor (DBR) operates in the dispersed bubble flow regime to selectively absorb gas phase constituents into the liquid phase. The dispersion is achieved by shearing the large inlet gas bubbles into fine bubbles with circulating liquid and additional pumped liquid solvent when necessary. The DBR is capable of handling precipitates that may form during absorption or fine catalysts that may be necessary to promote liquid phase reactions. The DBR can be configured with multistage counter current flow sections by inserting concentric cylindrical sections into the risermore » to facilitate annular flow. While the DBR can absorb CO.sub.2 in liquid solvents that may lead to precipitates at high loadings, it is equally capable of handling many different types of chemical processes involving solids (precipitates/catalysts) along with gas and liquid phases.« less

Pt and Ru X-ray absorption spectroscopy of PtRu anode catalysts in operating direct methanol fuel cells.

PubMed

Stoupin, Stanislav; Chung, Eun-Hyuk; Chattopadhyay, Soma; Segre, Carlo U; Smotkin, Eugene S

2006-05-25

In situ X-ray absorption spectroscopy, ex situ X-ray fluorescence, and X-ray powder diffraction enabled detailed core analysis of phase segregated nanostructured PtRu anode catalysts in an operating direct methanol fuel cell (DMFC). No change in the core structures of the phase segregated catalyst was observed as the potential traversed the current onset potential of the DMFC. The methodology was exemplified using a Johnson Matthey unsupported PtRu (1:1) anode catalyst incorporated into a DMFC membrane electrode assembly. During DMFC operation the catalyst is essentially metallic with half of the Ru incorporated into a face-centered cubic (FCC) Pt alloy lattice and the remaining half in an amorphous phase. The extended X-ray absorption fine structure (EXAFS) analysis suggests that the FCC lattice is not fully disordered. The EXAFS indicates that the Ru-O bond lengths were significantly shorter than those reported for Ru-O of ruthenium oxides, suggesting that the phases in which the Ru resides in the catalysts are not similar to oxides.

Studies on KIT-6 Supported Cobalt Catalyst for Fischer–Tropsch Synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gnanamani, M.; Jacobs, G; Graham, U

2010-01-01

KIT-6 molecular sieve was used as a support to prepare cobalt catalyst for Fischer-Tropsch synthesis (FTS) using an incipient wetness impregnation method to produce cobalt loadings of 15 and 25 wt%. The catalysts were characterized by BET surface area, X-ray diffraction, scanning transmission election microscopy (STEM), extended X-ray absorption fine spectroscopy and X-ray absorption near edge spectroscopy. The catalytic properties for FTS were evaluated using a 1L CSTR reactor. XRD, pore size distribution, and STEM analysis indicate that the KIT-6 mesostructure remains stable during and after cobalt impregnation and tends to form smaller cobalt particles, probably located inside the mesopores.more » The mesoporous KIT-6 exhibited a slightly higher cobalt dispersion compared to amorphous SiO{sub 2} supported catalyst. With the higher Co loading (25 wt%) on KIT-6, partial structural collapse was observed after the FTS reaction. Compared to an amorphous SiO{sub 2} supported cobalt catalyst, KIT-6 supported cobalt catalyst displayed higher methane selectivity at a similar Co loading, likely due to diffusion effects.« less

Characterization of three-way automotive catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kenik, E.A.; More, K.L.; LaBarge, W.

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 improvedmore » 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.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Lidong; Zhou, Lu; Ould-Chikh, Samy

Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanningmore » transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. As a result, these catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Lidong; Zhou, Lu; Ould-Chikh, Samy

The surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. Moreover, the evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annularmore » dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. The catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.« less

Hydrodeoxygenation of water-insoluble bio-oil to alkanes using a highly dispersed Pd-Mo catalyst.

PubMed

Duan, Haohong; Dong, Juncai; Gu, Xianrui; Peng, Yung-Kang; Chen, Wenxing; Issariyakul, Titipong; Myers, William K; Li, Meng-Jung; Yi, Ni; Kilpatrick, Alexander F R; Wang, Yu; Zheng, Xusheng; Ji, Shufang; Wang, Qian; Feng, Junting; Chen, Dongliang; Li, Yadong; Buffet, Jean-Charles; Liu, Haichao; Tsang, Shik Chi Edman; O'Hare, Dermot

2017-09-19

Bio-oil, produced by the destructive distillation of cheap and renewable lignocellulosic biomass, contains high energy density oligomers in the water-insoluble fraction that can be utilized for diesel and valuable fine chemicals productions. Here, we show an efficient hydrodeoxygenation catalyst that combines highly dispersed palladium and ultrafine molybdenum phosphate nanoparticles on silica. Using phenol as a model substrate this catalyst is 100% effective and 97.5% selective for hydrodeoxygenation to cyclohexane under mild conditions in a batch reaction; this catalyst also demonstrates regeneration ability in long-term continuous flow tests. Detailed investigations into the nature of the catalyst show that it combines hydrogenation activity of Pd and high density of both Brønsted and Lewis acid sites; we believe these are key features for efficient catalytic hydrodeoxygenation behavior. Using a wood and bark-derived feedstock, this catalyst performs hydrodeoxygenation of lignin, cellulose, and hemicellulose-derived oligomers into liquid alkanes with high efficiency and yield.Bio-oil is a potential major source of renewable fuels and chemicals. Here, the authors report a palladium-molybdenum mixed catalyst for the selective hydrodeoxygenation of water-insoluble bio-oil to mixtures of alkanes with high carbon yield.

Alloy formation and metal oxide segregation in Pt-Re/. gamma. -Al/sub 2/O/sub 3/ catalysts as investigated by temperature-programmed reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wagstaff, N.; Prins, R.

1979-10-15

Temperature-programmed reduction has been used to characterize the finely dispersed metal compounds in a series of Pt-Re/..gamma..-Al/sub 2/O/sub 3/ catalysts. Strong evidence has been obtained that zerovalent Pt and Re atoms are in intimate contact with each other after catalyst reduction. The formation of bimetallic clusters supports the alloy explanation for the improved performance of this type of bimetallic reforming catalyst. Treatment of the reduced catalysts with oxygen above about 200/sup 0/C causes segregation of platinum and rhenium oxides. Adsorption of oxygen at temperatures up to 100/sup 0/C leaves the bimetallic clusters largely intact, but subsequent high-temperature treatment in themore » absence of extra oxygen leads to segregation of Pt and Re species. This suggests that in the presence of adsorbed oxygen the Pt-Re clusters are thermodynamically unstable, but that under mild conditions the rate of segregation is slow. 10 figures, 4 tables.« less

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

2016-11-01

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance.

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

PubMed Central

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

2016-01-01

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals. PMID:27574182

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manna, Kuntal; Ji, Pengfei; Lin, Zekai

2016-08-30

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

Carbon nanocages: A new support material for Pt catalyst with remarkably high durability

PubMed Central

Wang, Xiao Xia; Tan, Zhe Hua; Zeng, Min; Wang, Jian Nong

2014-01-01

Low durability is the major challenge hindering the large-scale implementation of proton exchange membrane fuel cell (PEMFC) technology, and corrosion of carbon support materials of current catalysts is the main cause. Here, we describe the finding of remarkably high durability with the use of a novel support material. This material is based on hollow carbon nanocages developed with a high degree of graphitization and concurrent nitrogen doping for oxidation resistance enhancement, uniform deposition of fine Pt particles, and strong Pt-support interaction. Accelerated degradation testing shows that such designed catalyst possesses a superior electrochemical activity and long-term stability for both hydrogen oxidation and oxygen reduction relative to industry benchmarks of current catalysts. Further testing under conditions of practical fuel cell operation reveals almost no degradation over long-term cycling. Such a catalyst of high activity, particularly, high durability, opens the door for the next-generation PEMFC for “real world” application. PMID:24658614

Ordered mesoporous porphyrinic carbons with very high electrocatalytic activity for the oxygen reduction reaction

PubMed Central

Cheon, Jae Yeong; Kim, Taeyoung; Choi, YongMan; Jeong, Hu Young; Kim, Min Gyu; Sa, Young Jin; Kim, Jaesik; Lee, Zonghoon; Yang, Tae-Hyun; Kwon, Kyungjung; Terasaki, Osamu; Park, Gu-Gon; Adzic, Radoslav R.; Joo, Sang Hoon

2013-01-01

The high cost of the platinum-based cathode catalysts for the oxygen reduction reaction (ORR) has impeded the widespread application of polymer electrolyte fuel cells. We report on a new family of non-precious metal catalysts based on ordered mesoporous porphyrinic carbons (M-OMPC; M = Fe, Co, or FeCo) with high surface areas and tunable pore structures, which were prepared by nanocasting mesoporous silica templates with metalloporphyrin precursors. The FeCo-OMPC catalyst exhibited an excellent ORR activity in an acidic medium, higher than other non-precious metal catalysts. It showed higher kinetic current at 0.9 V than Pt/C catalysts, as well as superior long-term durability and MeOH-tolerance. Density functional theory calculations in combination with extended X-ray absorption fine structure analysis revealed a weakening of the interaction between oxygen atom and FeCo-OMPC compared to Pt/C. This effect and high surface area of FeCo-OMPC appear responsible for its significantly high ORR activity. PMID:24056308

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

PubMed Central

Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

2016-01-01

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance. PMID:27901129

Controlled surface segregation leads to efficient coke-resistant nickel/platinum bimetallic catalysts for the dry reforming of methane

DOE PAGES

Li, Lidong; Zhou, Lu; Ould-Chikh, Samy; ...

2015-02-03

Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanningmore » transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. As a result, these catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.« less

Perspectives of Using Ultra-Fine Metals as Universal Safe BioStimulators to Get Cattle Breeding Quality Products

NASA Astrophysics Data System (ADS)

Polishchuk, S.

2015-11-01

We have conducted investigations of ultra-fine metals biological activity with lab non-pedigree white rats, rabbits breed “Soviet chinchilla” and cattle young stock of the black and white breed as the most widely spread in the central part of Russia. One can see the possibility of using microelements of ultra-fine iron, cobalt and copper as cheap, non-toxic and highly effective biological catalyst of biochemical processes in the organism that improve physiological state, morphological and biochemical blood parameters increasing activity of the experimental animals’ ferment systems and their productivity and meat biological value. We have proved the ultra-fine powders safety when adding them to the animals’ diet.

Method for preparing porous metal hydride compacts

DOEpatents

Ron, M.; Gruen, D.M.; Mendelsohn, M.H.; Sheft, I.

1980-01-21

A method for preparing porous metallic-matrix hydride compacts which can be repeatedly hydrided and dehydrided without disintegration. A mixture of a finely divided metal hydride and a finely divided matrix metal is contacted with a poison which prevents the metal hydride from dehydriding at room temperature and atmospheric pressure. The mixture of matrix metal and poisoned metal hydride is then compacted under pressure at room temperature to form porous metallic-matrix hydride compacts.

Method for preparing porous metal hydride compacts

DOEpatents

Ron, Moshe; Gruen, Dieter M.; Mendelsohn, Marshall H.; Sheft, Irving

1981-01-01

A method for preparing porous metallic-matrix hydride compacts which can be repeatedly hydrided and dehydrided without disintegration. A mixture of a finely divided metal hydride and a finely divided matrix metal is contacted with a poison which prevents the metal hydride from dehydriding at room temperature and atmospheric pressure. The mixture of matrix metal and poisoned metal hydride is then compacted under pressure at room temperature to form porous metallic-matrix hydride compacts.

Site-selective XAFS spectroscopy tuned to surface active sites of Cu/ZnO and Cr/SiO2 catalysts.

PubMed

Izumi, Y; Nagamori, H; Kiyotaki, F; Minato, T

2001-03-01

XAFS (X-ray absorption fine structure) spectra were measured by using the fluorescence spectrometer for the emitted X-ray from sample. The chemical shifts between Cu0 and Cu1 and between CrIII and CrVI were evaluated. Tuning the fluorescence spectrometer to each energy, the Cu0 and CuI site-selective XANES for Cu/ZnO catalyst were measured. The first one was similar to the XANES of Cu metal and the second one was the 5 : 5 average of XANES for CuI sites + Cu metal. The population ratio of copper site of the Cu/ZnO catalyst was found to be Cu metal: Cu2O : CuI atomically dispersed on surface = 70(+/-23) : 22(+/-14) : 8(+/-5). Site-selective XANES for CrIII site of Cr/SiO2 catalyst was also studied.

Rhodium(II) metallopeptide catalyst design enables fine control in selective functionalization of natural SH3 domains.

PubMed

Vohidov, Farrukh; Coughlin, Jane M; Ball, Zachary T

2015-04-07

Chemically modified proteins are increasingly important for use in fundamental biophysical studies, chemical biology, therapeutic protein development, and biomaterials. However, chemical methods typically produce heterogeneous labeling and cannot approach the exquisite selectivity of enzymatic reactions. While bioengineered methods are sometimes an option, selective reactions of natural proteins remain an unsolved problem. Here we show that rhodium(II) metallopeptides combine molecular recognition with promiscuous catalytic activity to allow covalent decoration of natural SH3 domains, depending on choice of catalyst but independent of the specific residue present. A metallopeptide catalyst succeeds in modifying a single SH3-containing kinase at endogenous concentrations in prostate cancer (PC-3) cell lysate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Palladium-bacterial cellulose membranes for fuel cells.

PubMed

Evans, Barbara R; O'Neill, Hugh M; Malyvanh, Valerie P; Lee, Ida; Woodward, Jonathan

2003-07-01

Bacterial cellulose is a versatile renewable biomaterial that can be used as a hydrophilic matrix for the incorporation of metals into thin, flexible, thermally stable membranes. In contrast to plant cellulose, we found it catalyzed the deposition of metals within its structure to generate a finely divided homogeneous catalyst layer. Experimental data suggested that bacterial cellulose possessed reducing groups capable of initiating the precipitation of palladium, gold, and silver from aqueous solution. Since the bacterial cellulose contained water equivalent to at least 200 times the dry weight of the cellulose, it was dried to a thin membranous structure suitable for the construction of membrane electrode assemblies (MEAs). Results of our study with palladium-cellulose showed that it was capable of catalyzing the generation of hydrogen when incubated with sodium dithionite and generated an electrical current from hydrogen in an MEA containing native cellulose as the polyelectrolyte membrane (PEM). Advantages of using native and metallized bacterial cellulose membranes in an MEA over other PEMs such as Nafion 117 include its higher thermal stability to 130 degrees C and lower gas crossover.

Catalytic upgrading of butyric acid towards fine chemicals and biofuels

PubMed Central

Matsakas, Leonidas; Christakopoulos, Paul; Rova, Ulrika

2016-01-01

Fermentation-based production of butyric acid is robust and efficient. Modern catalytic technologies make it possible to convert butyric acid to important fine chemicals and biofuels. Here, current chemocatalytic and biocatalytic conversion methods are reviewed with a focus on upgrading butyric acid to 1-butanol or butyl-butyrate. Supported Ruthenium- and Platinum-based catalyst and lipase exhibit important activities which can pave the way for more sustainable process concepts for the production of green fuels and chemicals. PMID:26994015

Catalytic upgrading of butyric acid towards fine chemicals and biofuels.

PubMed

Sjöblom, Magnus; Matsakas, Leonidas; Christakopoulos, Paul; Rova, Ulrika

2016-04-01

Fermentation-based production of butyric acid is robust and efficient. Modern catalytic technologies make it possible to convert butyric acid to important fine chemicals and biofuels. Here, current chemocatalytic and biocatalytic conversion methods are reviewed with a focus on upgrading butyric acid to 1-butanol or butyl-butyrate. Supported Ruthenium- and Platinum-based catalyst and lipase exhibit important activities which can pave the way for more sustainable process concepts for the production of green fuels and chemicals. © FEMS 2016.

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

PubMed Central

Pohl, Marga-Martina; Agapova, Anastasiya

2018-01-01

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 SiO2 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 H2 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. PMID:29888329

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

PubMed

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.

Physico-Chemical Characterization of Fine and Ultrafine Particles Emitted during Diesel Particulate Filter Active Regeneration of Euro5 Diesel Vehicles.

PubMed

R'Mili, Badr; Boréave, Antoinette; Meme, Aurelie; Vernoux, Philippe; Leblanc, Mickael; Noël, Ludovic; Raux, Stephane; D'Anna, Barbara

2018-03-06

Diesel particulate filters (DPFs) are commonly employed in modern passenger cars to comply with current particulate matter (PM) emission standards. DPFs requires periodic regeneration to remove the accumulated matter. During the process, high-concentration particles, in both nucleation and accumulation modes, are emitted. Here, we report new information on particle morphology and chemical composition of fine (FPs) and ultrafine particles (UFPs) measured downstream of the DPF during active regeneration of two Euro 5 passenger cars. The first vehicle was equipped with a close-coupled diesel oxidation catalyst (DOC) and noncatalyzed DPF combined with fuel borne catalyst and the second one with DOC and a catalyzed-diesel particle filter (CDPF). Differences in PM emission profiles of the two vehicles were related to different after treatment design, regeneration strategies, and vehicle characteristics and mileage. Particles in the nucleation mode consisted of ammonium bisulfate, sulfate and sulfuric acid, suggesting that the catalyst desulfation is the key process in the formation of UFPs. Larger particles and agglomerates, ranging from 90 to 600 nm, consisted of carbonaceous material (soot and soot aggregates) coated by condensable material including organics, ammonium bisulfate and sulfuric acid. Particle emission in the accumulation mode was due to the reduced filtration efficiency (soot cake oxidation) throughout the regeneration process.

Metal–Organic Frameworks Stabilize Solution-Inaccessible Cobalt Catalysts for Highly Efficient Broad-Scope Organic Transformations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Teng; Manna, Kuntal; Lin, Wenbin

New and active earth-abundant metal catalysts are critically needed to replace precious metal-based catalysts for sustainable production of commodity and fine chemicals. We report here the design of highly robust, active, and reusable cobalt-bipyridine- and cobalt-phenanthroline-based metal–organic framework (MOF) catalysts for alkene hydrogenation and hydroboration, aldehyde/ketone hydroboration, and arene C–H borylation. In alkene hydrogenation, the MOF catalysts tolerated a variety of functional groups and displayed unprecedentedly high turnover numbers of ~2.5 × 10 6 and turnover frequencies of ~1.1 × 10 5 h –1. Structural, computational, and spectroscopic studies show that site isolation of the highly reactive (bpy)Co(THF) 2 speciesmore » in the MOFs prevents intermolecular deactivation and stabilizes solution-inaccessible catalysts for broad-scope organic transformations. Computational, spectroscopic, and kinetic evidence further support a hitherto unknown (bpy•–)CoI(THF) 2 ground state that coordinates to alkene and dihydrogen and then undergoing σ-complex-assisted metathesis to form (bpy)Co(alkyl)(H). Reductive elimination of alkane followed by alkene binding completes the catalytic cycle. MOFs thus provide a novel platform for discovering new base-metal molecular catalysts and exhibit enormous potential in sustainable chemical catalysis.« less

Kinetic studies of the stability of Pt for No oxidation: effect of sulfur and long-term aging.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pazmino, J. H.; Miller, J. T.; Mulla, S. S.

2011-01-01

The stability of Pt catalysts for NO oxidation was analyzed by observing the effect of pre-adsorbed sulfur on the reaction kinetics using a series of Pt/SBA-15 catalysts with varying Pt particle sizes (ca 2-9 nm). Our results indicate that sulfur addition did not influence catalyst deactivation of any of the Pt catalysts, resulting in unchanged turnover rates (TOR) and reaction kinetics. The presence of sulfur on Pt was confirmed by X-ray absorption fine structure spectroscopy (EXAFS) under reducing environments. However, exposure of the catalyst to NO oxidation conditions displaced sulfur from the first coordination shell of Pt, yielding Pt-O bondsmore » instead. Re-reduction fully recovered the Pt-S backscattering, implying that sulfur remained near the Pt under oxidizing conditions. X-ray photoelectron spectroscopy (XPS) and chemisorption measurements confirmed the presence of sulfur near platinum. The invariance of the NO oxidation reaction to sulfur poisoning is explained by sulfur displacement to interfacial sites and/or sulfur binding on kinetically irrelevant sites. Formation of Pt oxides remains as the main source of catalyst deactivation as observed by kinetic and X-ray absorption spectroscopy (XAS) measurements.« less

Alkali-Resistant Mechanism of a Hollandite DeNOx Catalyst.

PubMed

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.

Synergistic Catalysis between Pd and Fe in Gas Phase Hydrodeoxygenation of m-Cresol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hong, Yongchun; Zhang, He; Sun, Junming

2014-10-31

In this work, a series of Pd/Fe2O3 catalysts were synthesized, characterized, and evaluated for the hydrodeoxygenation (HDO) of m-cresol. It was found that the addition of Pd remarkably promotes the catalytic activity of Fe while the product distributions resemble that of monometallic Fe catalyst, showing high selectivity towards the production of toluene (C-O cleavage without saturation of aromatic ring and C-C cleavage). Reduced catalysts featured with Pd patches on the top of reduced Fe nanoparticle surface, and the interaction between Pd and Fe was further confirmed using X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM) and X-ray absorption nearmore » edge fine structure (XANES). A possible mechanism, including Pd assisted H2 dissociation and Pd facilitated stabilization of metallic Fe surface as well as Pd enhanced product desorption, is proposed to be responsible for the high activity and HDO selectivity in Pd-Fe catalysts. The synergic catalysis derived from Pd-Fe interaction found in this work was proved to be applicable to other precious metal promoted Fe catalysts, providing a promising strategy for future design of highly active and selective HDO catalysts.« less

PROCESS FOR SEPARATING IODINE-132 FROM FISSION PRODUCTS

DOEpatents

Greene, M.W.; Tucker, W.D.; Samos, G.

1960-06-28

A process is given for isolating I/sup 132/ in substantially pure form. Te/sup 132/, which is the radioactive parent of I/sup 132/, is adsorbed on a finely divided mass of a chromatographic grade of refractory metal oxide. i.e., alumina, zirconia, titania, and ceria. After a period of time is allowed for the Te/sup 132/ to decay, a 0.001 to 0.01 molar solution of ammonium hydroxide is passed over the finely divided oxides and the I/sup 132/ values are eluted.

Unveiling N-protonation and anion-binding effects on Fe/N/C-catalysts for O2 reduction in PEM fuel cells

PubMed Central

Herranz, Juan; Jaouen, Frédéric; Lefèvre, Michel; Kramm, Ulrike I.; Proietti, Eric; Dodelet, Jean-Pol; Bogdanoff, Peter; Fiechter, Sebastian; Abs-Wurmbach, Irmgard; Bertrand, Patrick; Arruda, Thomas M.; Mukerjee, Sanjeev

2013-01-01

The high cost of proton-exchange-membrane fuel cells would be considerably reduced if platinumbased catalysts were replaced by iron-based substitutes, which have recently demonstrated comparable activity for oxygen reduction, but whose cause of activity decay in acidic medium has been elusive. Here, we reveal that the activity of Fe/N/C-catalysts prepared through a pyrolysis in NH3 is mostly imparted by acid-resistant FeN4-sites whose turnover frequency for the O2 reduction can be regulated by fine chemical changes of the catalyst surface. We show that surface N-groups protonate at pH 1 and subsequently bind anions. This results in decreased activity for the O2 reduction. The anions can be removed chemically or thermally, which restores the activity of acid-resistant FeN4-sites. These results are interpreted as an increased turnover frequency of FeN4-sites when specific surface N-groups protonate. These unprecedented findings provide new perspective for stabilizing the most active Fe/N/C-catalysts known to date. PMID:24179561

Unveiling N-protonation and anion-binding effects on Fe/N/C-catalysts for O2 reduction in PEM fuel cells.

PubMed

Herranz, Juan; Jaouen, Frédéric; Lefèvre, Michel; Kramm, Ulrike I; Proietti, Eric; Dodelet, Jean-Pol; Bogdanoff, Peter; Fiechter, Sebastian; Abs-Wurmbach, Irmgard; Bertrand, Patrick; Arruda, Thomas M; Mukerjee, Sanjeev

2011-11-18

The high cost of proton-exchange-membrane fuel cells would be considerably reduced if platinumbased catalysts were replaced by iron-based substitutes, which have recently demonstrated comparable activity for oxygen reduction, but whose cause of activity decay in acidic medium has been elusive. Here, we reveal that the activity of Fe/N/C-catalysts prepared through a pyrolysis in NH 3 is mostly imparted by acid-resistant FeN 4 -sites whose turnover frequency for the O 2 reduction can be regulated by fine chemical changes of the catalyst surface. We show that surface N-groups protonate at pH 1 and subsequently bind anions. This results in decreased activity for the O 2 reduction. The anions can be removed chemically or thermally, which restores the activity of acid-resistant FeN 4 -sites. These results are interpreted as an increased turnover frequency of FeN 4 -sites when specific surface N-groups protonate. These unprecedented findings provide new perspective for stabilizing the most active Fe/N/C-catalysts known to date.

DOE Office of Scientific and Technical Information (OSTI.GOV)

James K. Neathery; Gary Jacobs; Burtron H. Davis

In this reporting period, a fundamental filtration study was started to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. Slurry-phase FTS in slurry bubble column reactor systems is the preferred mode of production since the reaction is highly exothermic. Consequently, heavy wax products must be separated from catalyst particles before being removed from the reactor system. Achieving an efficient wax product separation from iron-based catalysts is one of the most challenging technical problems associated with slurry-phase FTS. The separation problem is further compounded by catalyst particle attrition and the formation of ultra-fine iron carbide and/or carbonmore » particles. Existing pilot-scale equipment was modified to include a filtration test apparatus. After undergoing an extensive plant shakedown period, filtration tests with cross-flow filter modules using simulant FTS wax slurry were conducted. The focus of these early tests was to find adequate mixtures of polyethylene wax to simulate FTS wax. Catalyst particle size analysis techniques were also developed. Initial analyses of the slurry and filter permeate particles will be used by the research team to design improved filter media and cleaning strategies.« less

Regenerative process and system for the simultaneous removal of particulates and the oxides of sulfur and nitrogen from a gas stream

DOEpatents

Cohen, Mitchell R.; Gal, Eli

1993-01-01

A process and system for simultaneously removing from a gaseous mixture, sulfur oxides by means of a solid sulfur oxide acceptor on a porous carrier, nitrogen oxides by means of ammonia gas and particulate matter by means of filtration and for the regeneration of loaded solid sulfur oxide acceptor. Finely-divided solid sulfur oxide acceptor is entrained in a gaseous mixture to deplete sulfur oxides from the gaseous mixture, the finely-divided solid sulfur oxide acceptor being dispersed on a porous carrier material having a particle size up to about 200 microns. In the process, the gaseous mixture is optionally pre-filtered to remove particulate matter and thereafter finely-divided solid sulfur oxide acceptor is injected into the gaseous The government of the United States of America has rights in this invention pursuant to Contract No. DE-AC21-88MC 23174 awarded by the U.S. Department of Energy.

Organo- and nano-catalyst in greener reaction medium: Microwave-assisted expedient synthesis of fine chemicals

EPA Science Inventory

The use of emerging microwave (MW) -assisted chemistry techniques is dramatically reducing chemical waste and reaction times in several organic syntheses and chemical transformations. A brief account of our experiences in developing MW-assisted organic transformations, which invo...

HYDROCARBON OXIDATION OVER VANADIUM PHOSPHORUS OXIDE CATALYST USING HYDROGEN PEROXIDE

EPA Science Inventory

Selective oxidation of hydrocarbons is one of the very important and challenging areas in industrial chemistry due to the wide ranging utility of the resulting oxygenates in fine chemical synthesis. Most of the existing processes for their oxidations employ toxic and often stoich...

Investigation of internal elements impaction on particles circulation in a fluidized bed reactor

NASA Astrophysics Data System (ADS)

Solovev, S. A.; Soloveva, O. V.; Antipin, A. V.; Shamsutdinov, E. V.

2018-01-01

A numerical study of the fluidized bed apparatus in the presence of various internal elements is carried out. A chemical reaction for temperature-dependent processes with heat absorption is considered. The task of incoming heated catalyst granules to the reactor is investigated. The main emphasis is focused on the circulation flows of the catalyst particles, heating of the reactor, and the efficiency of the chemical reaction. The analysis of the impact of various design elements on the efficiency of the reactor is carried out. The influence of feeding heated catalyst device design on the effectiveness of whole reactor heating is educed. The influence of the presence of fine particles on the efficiency of the reaction for different reactor design features is also educed.

Synthesis of finely divided molybdenum sulfide nanoparticles in propylene carbonate solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Afanasiev, Pavel, E-mail: pavel.afanasiev@ircelyon.univ-lyon1.fr

2014-05-01

Molybdenum sulfide nanoparticles have been prepared from the reflux solution reaction involving ammonium heptamolybdate and elemental sulfur in propylene carbonate. Addition to the reaction mixture of starch as a natural capping agent leads to lesser agglomeration and smaller size of the particles. Nanoparticles of MoS{sub x} (x≈4) of 10–30 nm size are highly divided and form stable colloidal suspensions in organic solvents. Mo K edge EXAFS of the amorphous materials shows rapid exchange of oxygen to sulfur in the molybdenum coordination sphere during the solution reaction. Thermal treatment of the amorphous sulfides MoS{sub x} under nitrogen or hydrogen flow atmore » 400 °C allows obtaining mesoporous MoS{sub 2} materials with very high pore volume and specific surface area, up to 0.45 cm{sup 3}/g and 190 m{sup 2}/g, respectively. The new materials show good potential for the application as unsupported hydrotreating catalysts. - Graphical abstract: Solution reaction in propylene carbonate allows preparing weakly agglomerated molybdenum sulfide with particle size 20 nm and advantageous catalytic properties. - Highlights: • Solution reaction in propylene carbonate yields MoS{sub x} particles near 20 nm size. • Addition of starch as capping agent reduces particles size and hinder agglomeration. • EXAFS at Mo K edge shows rapid oxygen to sulfur exchange in the solution. • Thermal treatment leads to MoS{sub 2} with very high porosity and surface area.« less

Enhancing the stability of copper chromite catalysts for the selective hydrogenation of furfural using ALD overcoating

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Hongbo; Lei, Yu; Kropf, A. Jeremy

2014-08-01

The stability of a gas-phase furfural hydrogenation catalyst (CuCr2O4 center dot CuO) was enhanced by depositing a thin Al2O3 layer using atomic layer deposition (ALD). Based on temperature-programed reduction (TPR) measurements, the reduction temperature of Cu was raised significantly, and the activation energy for furfural reduction was decreased following the ALD treatment. Thinner ALD layers yielded higher furfural hydrogenation activities. X-ray absorption fine structure (XAFS) spectroscopy studies indicated that Cu1+/Cu-0 are the active species for furfural reduction.

Improved catalysts by low-G processing

NASA Technical Reports Server (NTRS)

Grodzka, P. G.; Picklesimer, E. A.

1977-01-01

The advantages of space for manufacturing more perfect microcrystalline morphologies and structures will be investigated. Production of smaller silver and palladium crystals with enhanced catalytic properties is discussed. The elimination of convection accompanying electrodeposition of fine metallic powders at high overvoltages in a low gravity environment is outlined.

The degradation of wheat straw lignin

NASA Astrophysics Data System (ADS)

Liang, Jiaqi

2017-03-01

Lignin is a kind of formed by polymerization of aromatic alcohol, prices are lower and sources of renewable resources. Using lignin as raw material, through the push to resolve together preparation phenolic high value-added fine chemicals alkanes and aromatic hydrocarbons, such as the high grade biofuels, can partly replace fossil fuels as raw material to the production process, biomass resources is an important part of the comprehensive utilization of effective components. In lignin push solve clustering method, catalytic hydrogenolysis can directly to the lignin into liquid fuels, low oxygen content in the use of biofuels shows great potential. In this paper, through the optimization of the reaction time, reaction temperature, catalyst type and solvent type, dosage of catalyst, etc factors, determines the alcoholysis - hydrogen solution two-step degradation of lignin, the optimal process conditions: lignin alcoholysis under 50% methanol and NaOH catalyst in the solution, the lignin in methanol solution and 50% hydrogen solution under the Pd/C catalyst. In this process, the degradation of lignin yield can reach 42%.

A3-Coupling catalyzed by robust Au nanoparticles covalently bonded to HS-functionalized cellulose nanocrystalline films

PubMed Central

Huang, Jian-Lin

2013-01-01

Summary We decorated HS-functionalized cellulose nanocrystallite (CNC) films with monodisperse Au nanoparticles (AuNPs) to form a novel nanocomposite catalyst AuNPs@HS-CNC. The uniform, fine AuNPs were made by the reduction of HAuCl4 solution with thiol (HS-) group-functionalized CNC films. The AuNPs@HS-CNC nanocomposites were examined by X-ray photoelectron spectroscopy (XPS), TEM, ATR-IR and solid-state NMR. Characterizations suggested that the size of the AuNPs was about 2–3 nm and they were evenly distributed onto the surface of CNC films. Furthermore, the unique nanocomposite Au@HS-CNC catalyst displayed high catalytic efficiency in promoting three-component coupling of an aldehyde, an alkyne, and an amine (A3-coupling) either in water or without solvent. Most importantly, the catalyst could be used repetitively more than 11 times without significant deactivation. Our strategy also promotes the use of naturally renewable cellulose to prepare reusable nanocomposite catalysts for organic synthesis. PMID:23946833

Tandem catalysis by palladium nanoclusters encapsulated in metal–organic frameworks

DOE PAGES

Li, Xinle; Guo, Zhiyong; Xiao, Chaoxian; ...

2014-08-25

A bifunctional Zr-MOF catalyst containing palladium nanoclusters (NCs) has been developed. The formation of Pd NCs was confirmed by transmission electron microscopy (TEM) and extended X-ray absorption fine structure (EXAFS). Combining the oxidation activity of Pd NCs and the acetalization activity of the Lewis acid sites in UiO-66-NH 2, this catalyst (Pd@UiO-66-NH 2) exhibits excellent catalytic activity and selectivity in a one-pot tandem oxidation-acetalization reaction. This catalyst shows 99.9% selectivity to benzaldehyde ethylene acetal in the tandem reaction of benzyl alcohol and ethylene glycol at 99.9% conversion of benzyl alcohol. We also examined various substituted benzyl alcohols and found thatmore » alcohols with electron-donating groups showed better conversion and selectivity compared to those with electron-withdrawing groups. As a result, we further proved that there was no leaching of active catalytic species during the reaction and the catalyst can be recycled at least five times without significant deactivation.« less

Chemical Compositional Analysis of Catalytic Hydroconversion Products of Heishan Coal Liquefaction Residue

PubMed Central

Wu, Yajun; Zhang, Shuangquan; Yang, Xiaoqin; Wei, Xianyong

2017-01-01

Liquefaction residue of Heishan bituminous coal (HLR) was subject to two hydroconversion reactions under 5 MPa initial pressure of hydrogen at 300°C for 3 h, without catalyst and with acid supported catalyst (ASC), respectively. The reaction products were analyzed with gas chromatography/mass spectrometer (GC/MS). The results show that 222 organic compounds were detected totally in the products and they can be divided into alkanes, aromatic hydrocarbons (AHCs), phenols, ketones, ethers, and other species (OSs). The yield of hydroconversion over the ASC is much higher than that without catalyst. The most abundant products are aromatic hydrocarbons in the reaction products from both catalytic and noncatalytic reactions of HLR. The yield of aromatic hydrocarbons in the reaction product from hydroconversion with the ACS is considerably higher than that from hydroconversion without a catalyst. PMID:28250770

Thermal reactor for afterburning automotive internal combustion engine exhaust gases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Masaki, K.; Nagaishi, H.

1974-08-08

A thermal reactor for burning unburned components in exhaust gases of an internal combustion engine before emission to the atmosphere is described. An outer casing has an exhaust gas inlet connected to the exhaust ports, and an inner casing divides the reactor into an outer chamber and an inner chamber. The inner casing has an inlet from the outer chamber, an outlet to the atmosphere, and perforations opening to the outer chamber. An oxidation catalyst in the inner chamber promotes oxidation of the unburned components in the exhaust gases to generate oxidation reaction heat. A first secondary air injection nozzlemore » in the inner chamber between the oxidation catalyst and the outlet and a second secondary air injection nozzle in a portion upstream of the oxidation catalyst inject secondary air into oxidation catalyst.« less

Study on the water flooding in the cathode of direct methanol fuel cells.

PubMed

Im, Hun Suk; Kim, Sang-Kyung; Lim, Seongyop; Peck, Dong-Hyun; Jung, Doohwan; Hong, Won Hi

2011-07-01

Water flooding phenomena in the cathode of direct methanol fuel cells were analyzed by using electrochemical impedance spectroscopy. Two kinds of commercial gas diffusion layers with different PTFE contents of 5 wt% (GDL A5) and 20 wt% (GDL B20) were used to investigate the water flooding under various operating conditions. Water flooding was divided into two types: catalyst flooding and backing flooding. The cathode impedance spectra of each gas diffusion layer was obtained and compared under the same conditions. The diameter of the capacitive semicircle became larger with increasing current density for both, and this increase was greater for GDL B20 than GDL A5. Catalyst flooding is dominant and backing flooding is negligible when the air flow rate is high and current density is low. An equivalent model was suggested and fitted to the experimental data. Parameters for catalyst flooding and backing flooding were individually obtained. The capacitance of the catalyst layer decreases as the air flow rate decreases when the catalyst flooding is dominant.

The effects of divided attention at study and reporting procedure on regulation and monitoring for episodic recall.

PubMed

Sauer, James; Hope, Lorraine

2016-09-01

Eyewitnesses regulate the level of detail (grain size) reported to balance competing demands for informativeness and accuracy. However, research to date has predominantly examined metacognitive monitoring for semantic memory tasks, and used relatively artificial phased reporting procedures. Further, although the established role of confidence in this regulation process may affect the confidence-accuracy relation for volunteered responses in predictable ways, previous investigations of the confidence-accuracy relation for eyewitness recall have largely overlooked the regulation of response granularity. Using a non-phased paradigm, Experiment 1 compared reporting and monitoring following optimal and sub-optimal (divided attention) encoding conditions. Participants showed evidence of sacrificing accuracy for informativeness, even when memory quality was relatively weak. Participants in the divided (cf. full) attention condition showed reduced accuracy for fine- but not coarse-grained responses. However, indices of discrimination and confidence diagnosticity showed no effect of divided attention. Experiment 2 compared the effects of divided attention at encoding on reporting and monitoring using both non-phased and 2-phase procedures. Divided attention effects were consistent with Experiment 1. However, compared to those in the non-phased condition, participants in the 2-phase condition displayed a more conservative control strategy, and confidence ratings were less diagnostic of accuracy. When memory quality was reduced, although attempts to balance informativeness and accuracy increased the chance of fine-grained response errors, confidence provided an index of the likely accuracy of volunteered fine-grained responses for both condition. Copyright © 2016 Elsevier B.V. All rights reserved.

Fine-Grained Targets for Laser Synthesis of Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Smith, Michael W. (Inventor); Park, Cheol (Inventor)

2017-01-01

A mechanically robust, binder-free, inexpensive target for laser synthesis of carbon nanotubes and a method for making same, comprising the steps of mixing prismatic edge natural flake graphite with a metal powder catalyst and pressing the graphite and metal powder mixture into a mold having a desired target shape.

Fine-Grained Targets for Laser Synthesis of Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Smith, Michael W. (Inventor); Park, Cheol (Inventor)

2015-01-01

A mechanically robust, binder-free, inexpensive target for laser synthesis of carbon nanotubes and a method for making same, comprising the steps of mixing prismatic edge natural flake graphite with a metal powder catalyst and pressing the graphite and metal powder mixture into a mold having a desired target shape.

HYDROGENATION OF UNSATURATED CARBONYLS IN SCCO2 AS REACTION MEDIUM OVER NI-SUPPORTED CATALYSTS

EPA Science Inventory

Selective hydrogenation of a, a unsaturated carbonyls where molecules containing C=C and C=O double bonds has both practical importance for fine chemicals industry and theoretical significance. Various studies are reported to enhance the selective hydrogenation of C=O over group...

Metal-organic frameworks derived platinum-cobalt bimetallic nanoparticles in nitrogen-doped hollow porous carbon capsules as a highly active and durable catalyst for oxygen reduction reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ying, Jie; Li, Jing; Jiang, Gaopeng

Pt-based nanomaterials are regarded as the most efficient electrocatalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). However, widespread adoption of PEMFCs requires solutions to major challenges encountered with ORR catalysts, namely high cost, sluggish kinetics, and low durability. In this paper, a new efficient method utilizing Co-based metal-organic frameworks is developed to produce PtCo bimetallic nanoparticles embedded in unique nitrogen-doped hollow porous carbon capsules. The obtained catalyst demonstrates an outstanding ORR performance, with a mass activity that is 5.5 and 13.5 times greater than that of commercial Pt/C and Pt black, respectively. Most importantly,more » the product exhibits dramatically improved durability in terms of both electrochemically active surface area (ECAS) and mass activity compared to commercial Pt/C and Pt black catalysts. Finally, the remarkable ORR performance demonstrated here can be attributed to the structural features of the catalyst (its alloy structure, high dispersion and fine particle size) and the carbon support (its nitrogen dopant, large surface area and hollow porous structure).« less

Dry Reforming of Ethane and Butane with CO 2 over PtNi/CeO 2 Bimetallic Catalysts

DOE PAGES

Yan, Binhang; Yang, Xiaofang; Yao, Siyu; ...

2016-09-21

Dry reforming is a potential process to convert CO 2 and light alkanes into syngas (H 2 and CO), which can be subsequently transformed to chemicals and fuels. Here in this work, PtNi bimetallic catalysts have been investigated for dry reforming of ethane and butane using both model surfaces and supported powder catalysts. The PtNi bimetallic catalyst shows an improvement in both activity and stability as compared to the corresponding monometallic catalysts. The formation of PtNi alloy and the partial reduction of Ce 4+ to Ce 3+ under reaction conditions are demonstrated by in-situ Ambient Pressure X-ray Photoemission Spectroscopy (AP-XPS),more » X-ray Diffraction (XRD) and X-ray Absorption Fine Structure (XAFS) measurements. A Pt-rich bimetallic surface is revealed by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) following CO adsorption. Combined in-situ experimental results and Density Functional Theory (DFT) calculations suggest that the Pt-rich PtNi bimetallic surface structure would weaken the binding of surface oxygenates/carbon species and reduce the activation energy for C-C bond scission, leading to an enhanced dry reforming activity.« less

Dry Reforming of Ethane and Butane with CO 2 over PtNi/CeO 2 Bimetallic Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Binhang; Yang, Xiaofang; Yao, Siyu

Dry reforming is a potential process to convert CO 2 and light alkanes into syngas (H 2 and CO), which can be subsequently transformed to chemicals and fuels. Here in this work, PtNi bimetallic catalysts have been investigated for dry reforming of ethane and butane using both model surfaces and supported powder catalysts. The PtNi bimetallic catalyst shows an improvement in both activity and stability as compared to the corresponding monometallic catalysts. The formation of PtNi alloy and the partial reduction of Ce 4+ to Ce 3+ under reaction conditions are demonstrated by in-situ Ambient Pressure X-ray Photoemission Spectroscopy (AP-XPS),more » X-ray Diffraction (XRD) and X-ray Absorption Fine Structure (XAFS) measurements. A Pt-rich bimetallic surface is revealed by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) following CO adsorption. Combined in-situ experimental results and Density Functional Theory (DFT) calculations suggest that the Pt-rich PtNi bimetallic surface structure would weaken the binding of surface oxygenates/carbon species and reduce the activation energy for C-C bond scission, leading to an enhanced dry reforming activity.« less

Development and characterisation of novel heterogeneous palm oil mill boiler ash-based catalysts for biodiesel production.

PubMed

Ho, Wilson Wei Sheng; Ng, Hoon Kiat; Gan, Suyin

2012-12-01

Novel heterogeneous catalysts from calcium oxide (CaO)/calcined calcium carbonate (CaCO(3)) loaded onto different palm oil mill boiler ashes were synthesised and used in the transesterification of crude palm oil (CPO) with methanol to yield biodiesel. Catalyst preparation parameters including the type of ash support, the weight percentage of CaO and calcined CaCO(3) loadings, as well as the calcination temperature of CaCO(3) were optimised. The catalyst prepared by loading of 15 wt% calcined CaCO(3) at a fixed temperature of 800°C on fly ash exhibited a maximum oil conversion of 94.48%. Thermogravimetric analysis (TGA) revealed that the CaCO(3) was transformed into CaO at 770°C and interacted well with the ash support, whereas rich CaO, Al(2)O(3) and SiO(2) were identified in the composition using X-ray diffraction (XRD). The fine morphology size (<5 μm) and high surface area (1.719 m(2)/g) of the fly ash-based catalyst rendered it the highest catalytic activity. Copyright © 2012 Elsevier Ltd. All rights reserved.

Metal-organic frameworks derived platinum-cobalt bimetallic nanoparticles in nitrogen-doped hollow porous carbon capsules as a highly active and durable catalyst for oxygen reduction reaction

DOE PAGES

Ying, Jie; Li, Jing; Jiang, Gaopeng; ...

2017-11-29

Pt-based nanomaterials are regarded as the most efficient electrocatalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). However, widespread adoption of PEMFCs requires solutions to major challenges encountered with ORR catalysts, namely high cost, sluggish kinetics, and low durability. In this paper, a new efficient method utilizing Co-based metal-organic frameworks is developed to produce PtCo bimetallic nanoparticles embedded in unique nitrogen-doped hollow porous carbon capsules. The obtained catalyst demonstrates an outstanding ORR performance, with a mass activity that is 5.5 and 13.5 times greater than that of commercial Pt/C and Pt black, respectively. Most importantly,more » the product exhibits dramatically improved durability in terms of both electrochemically active surface area (ECAS) and mass activity compared to commercial Pt/C and Pt black catalysts. Finally, the remarkable ORR performance demonstrated here can be attributed to the structural features of the catalyst (its alloy structure, high dispersion and fine particle size) and the carbon support (its nitrogen dopant, large surface area and hollow porous structure).« less

Pyrolysis of triglyceride materials for the production of renewable fuels and chemicals.

PubMed

Maher, K D; Bressler, D C

2007-09-01

Conversion of vegetable oils and animal fats composed predominantly of triglycerides using pyrolysis type reactions represents a promising option for the production of renewable fuels and chemicals. The purpose of this article was to collect and review literature on the thermo-chemical conversion of triglyceride based materials. The literature was divided and discussed as (1) direct thermal cracking and (2) combination of thermal and catalytic cracking. Typically, four main catalyst types are used including transition metal catalysts, molecular sieve type catalysts, activated alumina, and sodium carbonate. Reaction products are heavily dependant on the catalyst type and reaction conditions and can range from diesel like fractions to gasoline like fractions. Research in this area is not as advanced as bio-oil and bio-diesel research and there is opportunity for further study in the areas of reaction optimization, detailed characterization of products and properties, and scale-up.

Rational approach to polymer-supported catalysts: synergy between catalytic reaction mechanism and polymer design.

PubMed

Madhavan, Nandita; Jones, Christopher W; Weck, Marcus

2008-09-01

Supported catalysis is emerging as a cornerstone of transition metal catalysis, as environmental awareness necessitates "green" methodologies and transition metal resources become scarcer and more expensive. Although these supported systems are quite useful, especially in their capacity for transition metal catalyst recycling and recovery, higher activity and selectivity have been elusive compared with nonsupported catalysts. This Account describes recent developments in polymer-supported metal-salen complexes, which often surpass nonsupported analogues in catalytic activity and selectivity, demonstrating the effectiveness of a systematic, logical approach to designing supported catalysts from a detailed understanding of the catalytic reaction mechanism. Over the past few decades, a large number of transition metal complex catalysts have been supported on a variety of materials ranging from polymers to mesoporous silica. In particular, soluble polymer supports are advantageous because of the development of controlled and living polymerization methods that are tolerant to a wide variety of functional groups, including controlled radical polymerizations and ring-opening metathesis polymerization. These methods allow for tuning the density and structure of the catalyst sites along the polymer chain, thereby enabling the development of structure-property relationships between a catalyst and its polymer support. The fine-tuning of the catalyst-support interface, in combination with a detailed understanding of catalytic reaction mechanisms, not only permits the generation of reusable and recyclable polymer-supported catalysts but also facilitates the design and realization of supported catalysts that are significantly more active and selective than their nonsupported counterparts. These superior supported catalysts are accessible through the optimization of four basic variables in their design: (i) polymer backbone rigidity, (ii) the nature of the linker, (iii) catalyst site density, and (iv) the nature of the catalyst attachment. Herein, we describe the design of polymer supports tuned to enhance the catalytic activity or decrease, or even eliminate, decomposition pathways of salen-based transition metal catalysts that follow either a monometallic or a bimetallic reaction mechanism. These findings result in the creation of some of the most active and selective salen catalysts in the literature.

Long-Term Mechanical Behavior of Nano Silica Sol Grouting

PubMed Central

Zhang, Nong; Zhang, Chenghao; Qian, Deyu; Han, Changliang; Yang, Sen

2018-01-01

The longevity of grouting has a significant effect on the safe and sustainable operation of many engineering projects. A 500-day experiment was carried out to study the long-term mechanical behavior of nano silica sol grouting. The nano silica sol was activated with different proportions of a NaCl catalyst and cured under fluctuating temperature and humidity conditions. The mechanical parameters of the grout samples were tested using an electrohydraulic uniaxial compression tester and an improved Vicat instrument. Scanning electron microscope, X-ray diffraction, and ultrasonic velocity tests were carried out to analyze the strength change micro-mechanism. Tests showed that as the catalyst dosage in the grout mix is decreased, the curves on the graphs showing changes in the weight and geometric parameters of the samples over time could be divided into three stages, a shrinkage stage, a stable stage, and a second shrinkage stage. The catalyst improved the stability of the samples and reduced moisture loss. Temperature rise was also a driving force for moisture loss. Uniaxial compressive stress-strain curves for all of the samples were elastoplastic. The curves for uniaxial compression strength and secant modulus plotted against time could be divided into three stages. Sample brittleness increased with time and the brittleness index increased with higher catalyst dosages in the latter part of the curing time. Plastic strength-time curves exhibit allometric scaling. Curing conditions mainly affect the compactness, and then affect the strength. PMID:29337897

Control system adds to precipitator efficiency

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gurrole, G.

1978-02-01

An electrostatic precipitator in use at Lion Oil Co., Martinez, Calif., in a fluid catalytic cracking and CO boiler application, was upgraded by mechanical sectionalization of the gas passage and a new electronic control system. The electrostatic precipitator is installed upstream of the CO boiler to handle gas flow up to 4.77 ft/sec, and pressure to 4.5 psi. The independent gas chambers in the electrostatic precipitator were divided by installing gas-tight partition walls to form a total of four electrostatic fields. The precipitator was also equipped with adjustable inlet gas flow-control baffles for even gas distribution. Rows of grounded collectingmore » electrodes are parallel with the flow of gas. The emitting electrode system, powered by separate high-energy transformers for each collecting field, uses silicon-controlled rectifiers and analog electronic networks for rapid response to changing gas and dust conditions. Regulatory requirements call for efficient collection of catalyst fines with no more than 40 lb/hr escaping through the boiler stack. Currently, stack losses average about 38 lb/hr. The installation of two additional control systems with transformers and rectifiers should reduce stack losses to 34 lb/hr.« less

Self-assembled nitrogen-doped fullerenes and their catalysis for fuel cell and rechargeable metal-air battery applications.

PubMed

Noh, Seung Hyo; Kwon, Choah; Hwang, Jeemin; Ohsaka, Takeo; Kim, Beom-Jun; Kim, Tae-Young; Yoon, Young-Gi; Chen, Zhongwei; Seo, Min Ho; Han, Byungchan

2017-06-08

In this study, we report self-assembled nitrogen-doped fullerenes (N-fullerene) as non-precious catalysts, which are active for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), and thus applicable for energy conversion and storage devices such as fuel cells and metal-air battery systems. We screen the best N-fullerene catalyst at the nitrogen doping level of 10 at%, not at the previously known doping level of 5 or 20 at% for graphene. We identify that the compressive surface strain induced by doped nitrogen plays a key role in the fine-tuning of catalytic activity.

Plasma vitrification of waste materials

DOEpatents

McLaughlin, David F.; Dighe, Shyam V.; Gass, William R.

1997-01-01

This invention provides a process wherein hazardous or radioactive wastes in the form of liquids, slurries, or finely divided solids are mixed with finely divided glassformers (silica, alumina, soda, etc.) and injected directly into the plume of a non-transferred arc plasma torch. The extremely high temperatures and heat transfer rates makes it possible to convert the waste-glassformer mixture into a fully vitrified molten glass product in a matter of milliseconds. The molten product may then be collected in a crucible for casting into final wasteform geometry, quenching in water, or further holding time to improve homogeneity and eliminate bubbles.

Method for producing and regenerating a synthetic CO.sub.2 acceptor

DOEpatents

Lancet, Michael S [Pittsburgh, PA; Curran, George P [Pittsburgh, PA; Gorin, Everett [San Rafael, CA

1982-01-01

A method for producing a synthetic CO.sub.2 acceptor by feeding a mixture of finely divided silica and at least one finely divided calcium compound selected from the group consisting of calcium oxide and calcium carbonate to a fluidized bed; operating the fluidized bed at suitable conditions to produce pellets of synthetic CO.sub.2 acceptor and recovering the pellets of synthetic CO.sub.2 acceptor from the fluidized bed. Optionally, spent synthetic CO.sub.2 acceptor can be charged to the fluidized bed to produce regenerated pellets of synthetic CO.sub.2 acceptor.

Method for producing and regenerating a synthetic CO[sub 2] acceptor

DOEpatents

Lancet, M. S.; Curran, G. P.; Gorin, E.

1982-05-18

A method is described for producing a synthetic CO[sub 2] acceptor by feeding a mixture of finely divided silica and at least one finely divided calcium compound selected from the group consisting of calcium oxide and calcium carbonate to a fluidized bed; operating the fluidized bed at suitable conditions to produce pellets of synthetic CO[sub 2] acceptor and recovering the pellets of synthetic CO[sub 2] acceptor from the fluidized bed. Optionally, spent synthetic CO[sub 2] acceptor can be charged to the fluidized bed to produce regenerated pellets of synthetic CO[sub 2] acceptor. 1 fig.

Plasma vitrification of waste materials

DOEpatents

McLaughlin, D.F.; Dighe, S.V.; Gass, W.R.

1997-06-10

This invention provides a process wherein hazardous or radioactive wastes in the form of liquids, slurries, or finely divided solids are mixed with finely divided glassformers (silica, alumina, soda, etc.) and injected directly into the plume of a non-transferred arc plasma torch. The extremely high temperatures and heat transfer rates makes it possible to convert the waste-glassformer mixture into a fully vitrified molten glass product in a matter of milliseconds. The molten product may then be collected in a crucible for casting into final wasteform geometry, quenching in water, or further holding time to improve homogeneity and eliminate bubbles. 4 figs.

Implementation of the use of higher micro-fines in concrete pavements final report.

DOT National Transportation Integrated Search

2009-12-01

The main purpose of this project was to implement previous research performed on concrete utilizing micro-fines : in a field test. The project can be divided into three main parts: First, predetermined materials that were local to : the field trial s...

Gasifiable carbon-graphite fibers

NASA Technical Reports Server (NTRS)

Humphrey, Marshall F. (Inventor); Ramohalli, Kumar N. R. (Inventor); Dowler, Warren L. (Inventor)

1982-01-01

Fine, carbon-graphite fibers do not combust during the combustion of a composite and are expelled into the air as fine conductive particles. Coating of the fibers with a salt of a metal having a work function below 4.2 eV such as an alkaline earth metal salt, e.g., calcium acetate, catalytically enhances combustion of the fibers at temperatures below 1000.degree. C. such that the fibers self-support combustion and burn to produce a non-conductive ash. Fire-polishing the fibers before application of the coating is desirable to remove sizing to expose the carbon surface to the catalyst.

General synthesis and definitive structural identification of MN 4C 4 single-atom catalysts with tunable electrocatalytic activities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fei, Huilong; Dong, Juncai; Feng, Yexin

Single-atom catalysts (SACs) have recently attracted broad research interest as they combine the merits of both homogeneous and heterogeneous catalysts. Rational design and synthesis of SACs are of immense significance but have so far been plagued by the lack of a definitive correlation between structure and catalytic properties. Here, we report a general approach to a series of monodispersed atomic transition metals (for example, Fe, Co, Ni) embedded in nitrogen-doped graphene with a common MNsub>4C 4 moiety, identified by systematic X-ray absorption fine structure analyses and direct transmission electron microscopy imaging. The unambiguous structure determination allows density functional theoretical predictionmore » of MNsub>4C 4 moieties as efficient oxygen evolution catalysts with activities following the trend Ni > Co > Fe, which is confirmed by electrochemical measurements. Determination of atomistic structure and its correlation with catalytic properties represents a critical step towards the rational design and synthesis of precious or nonprecious SACs with exceptional atom utilization efficiency and catalytic activities.« less

General synthesis and definitive structural identification of MN 4C 4 single-atom catalysts with tunable electrocatalytic activities

DOE PAGES

Fei, Huilong; Dong, Juncai; Feng, Yexin; ...

2018-01-08

Single-atom catalysts (SACs) have recently attracted broad research interest as they combine the merits of both homogeneous and heterogeneous catalysts. Rational design and synthesis of SACs are of immense significance but have so far been plagued by the lack of a definitive correlation between structure and catalytic properties. Here, we report a general approach to a series of monodispersed atomic transition metals (for example, Fe, Co, Ni) embedded in nitrogen-doped graphene with a common MNsub>4C 4 moiety, identified by systematic X-ray absorption fine structure analyses and direct transmission electron microscopy imaging. The unambiguous structure determination allows density functional theoretical predictionmore » of MNsub>4C 4 moieties as efficient oxygen evolution catalysts with activities following the trend Ni > Co > Fe, which is confirmed by electrochemical measurements. Determination of atomistic structure and its correlation with catalytic properties represents a critical step towards the rational design and synthesis of precious or nonprecious SACs with exceptional atom utilization efficiency and catalytic activities.« less

Reverse Micelle Synthesis and Characterization of Supported Pt/Ni Bimetallic Catalysts on gamma-Al2O3

DOE Office of Scientific and Technical Information (OSTI.GOV)

B Cheney; J Lauterbach; J Chen

2011-12-31

Reverse micelle synthesis was used to improve the nanoparticle size uniformity of bimetallic Pt/Ni nanoparticles supported on {gamma}-Al{sub 2}O{sub 3}. Two impregnation methods were investigated to optimize the use of the micelle method: (1) step-impregnation, where Ni nanoparticles were chemically reduced in microemulsion and then supported, followed by Pt deposition using incipient wetness impregnation, and (2) co-impregnation, where Ni and Pt were chemically reduced simultaneously in microemulsion and then supported. Transmission electron microscopy (TEM) was used to characterize the particle size distribution. Atomic absorption spectroscopy (AAS) was used to perform elemental analysis of bimetallic catalysts. Extended X-ray absorption fine structuremore » (EXAFS) measurements were utilized to confirm the formation of the Pt-Ni bimetallic bond in the step-impregnated catalyst. CO pulse chemisorption and Fourier transform infrared spectroscopy (FTIR) studies of 1,3-butadiene hydrogenation in a batch reactor were performed to determine the catalytic activity. Step-impregnated Pt/Ni catalyst demonstrated enhanced hydrogenation activity over the parent monometallic Pt and Ni catalysts due to bimetallic bond formation. The catalyst synthesized using co-impregnation showed no enhanced activity, behaving similarly to monometallic Ni. Overall, our results indicate that reverse micelle synthesis combined with incipient wetness impregnation produced small, uniform nanoparticles with bimetallic bonds that enhanced hydrogenation activity.« less

The epoxidation of limonene over the TS-1 and Ti-SBA-15 catalysts.

PubMed

Wróblewska, Agnieszka

2014-11-28

Limonene belongs to a group of very important intermediates used in the production of fine chemicals. This monoterpene compound can be obtained from peels of oranges or lemon which are a (biomass) waste from the orange juice industry. Thus, limonene is a renewable, easy available and a relatively cheap compound. This work presents preliminary studies on the process of limonene epoxidation over zeolite type catalysts such as: TS-1 and Ti-SBA-15. In these studies methanol was used as a solvent and as an oxidizing agent a 60 wt % hydrogen peroxide solution was applied. The activity of each catalyst was investigated for four chosen temperatures (0 °C, 40 °C, 80 °C and 120 °C). The reaction time was changed from 0.5 to 24 h. For each catalyst the most beneficial conditions (the appropriate temperature and the reaction time) have been established. The obtained results were compared and the most active catalyst was chosen. These studies have also shown different possible ways of limonene transformation, not only in the direction of 1,2-epoxylimonene and its corresponding diol, but also in direction of carveol, carvone and perillyl alcohol-compounds with a lot of applications. The possible mechanisms of formation of the allylic oxidation products were proposed.

REDUCING TITANIUM TETRACHLORIDE WITH HIGH-SURFACE SODIUM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fleck, D.C.; Wong, M.M.; Baker, D.H. Jr.

1960-01-01

A method of using sodium for reducing titanium tetrachloride, developed to improve the extractive metallurgy of titunium, is described. Finely divided titanium metal, titanium lower chlorides, or a mixture thereof was produced in a continuous operation at temperatures between 105 and 205 deg C by the reaction of molten sodium and vaporized titanium tetrachloride in an agitated bed of finely divided inert solids (powdered sodium chloride or the reaction products). Composition of the product was controlled by varying the relative quantities of sodium and titanium tetrachloride used. A description of the operations and analytical data of the reaction products aremore » given. (auth)« less

Immune Cells and Microbiota Response to Iron Starvation.

PubMed

Chieppa, Marcello; Giannelli, Gianluigi

2018-01-01

Metal ions are essential for life on Earth, mostly as crucial components of all living organisms; indeed, they are necessary for bioenergetics functions as crucial redox catalysts. Due to the essential role of iron in biological processes, body iron content is finely regulated and is the battlefield of a tug-of-war between the host and the microbiota.

Fine Arts and Humanities: Grade 7. Cluster III.

ERIC Educational Resources Information Center

Calhoun, Olivia H.

A curriculum guide for Grade 7, the document is devoted to the occupational cluster "Fine Arts and Humanities." It is divided into five units: drama and literature, music, dance, art, and crafts. Each unit is introduced by a statement of the topic, the unit's purpose, main ideas, quests, and a list of career opportunities…

FIB Secondary Etching Method for Fabrication of Fine CNT Forest Metamaterials

NASA Astrophysics Data System (ADS)

Pander, Adam; Hatta, Akimitsu; Furuta, Hiroshi

2017-10-01

Anisotropic materials, like carbon nanotubes (CNTs), are the perfect substitutes to overcome the limitations of conventional metamaterials; however, the successful fabrication of CNT forest metamaterial structures is still very challenging. In this study, a new method utilizing a focused ion beam (FIB) with additional secondary etching is presented, which can obtain uniform and fine patterning of CNT forest nanostructures for metamaterials and ranging in sizes from hundreds of nanometers to several micrometers. The influence of the FIB processing parameters on the morphology of the catalyst surface and the growth of the CNT forest was investigated, including the removal of redeposited material, decreasing the average surface roughness (from 0.45 to 0.15 nm), and a decrease in the thickness of the Fe catalyst. The results showed that the combination of FIB patterning and secondary etching enabled the growth of highly aligned, high-density CNT forest metamaterials. The improvement in the quality of single-walled CNTs (SWNTs), defined by the very high G/D peak ratio intensity of 10.47, demonstrated successful fine patterning of CNT forest for the first time. With a FIB patterning depth of 10 nm and a secondary etching of 0.5 nm, a minimum size of 150 nm of CNT forest metamaterials was achieved. The development of the FIB secondary etching method enabled for the first time, the fabrication of SWNT forest metamaterials for the optical and infrared regime, for future applications, e.g., in superlenses, antennas, or thermal metamaterials.

Structure-activity correlations in a nickel-borate oxygen evolution catalyst.

PubMed

Bediako, D Kwabena; Lassalle-Kaiser, Benedikt; Surendranath, Yogesh; Yano, Junko; Yachandra, Vittal K; Nocera, Daniel G

2012-04-18

An oxygen evolution catalyst that forms as a thin film from Ni(aq)(2+) solutions containing borate electrolyte (Ni-B(i)) has been studied by in situ X-ray absorption spectroscopy. A dramatic increase in catalytic rate, induced by anodic activation of the electrodeposited films, is accompanied by structure and oxidation state changes. Coulometric measurements correlated with X-ray absorption near-edge structure spectra of the active catalyst show that the nickel centers in activated films possess an average oxidation state of +3.6, indicating that a substantial proportion of nickel centers exist in a formal oxidation state of Ni(IV). In contrast, nickel centers in nonactivated films exist predominantly as Ni(III). Extended X-ray absorption fine structure reveals that activated catalyst films comprise bis-oxo/hydroxo-bridged nickel centers organized into sheets of edge-sharing NiO(6) octahedra. Diminished long-range ordering in catalyst films is due to their ostensibly amorphous nature. Nonactivated films display a similar oxidic nature but exhibit a distortion in the local coordination geometry about nickel centers, characteristic of Jahn-Teller distorted Ni(III) centers. Our findings indicate that the increase in catalytic activity of films is accompanied by changes in oxidation state and structure that are reminiscent of those observed for conversion of β-NiOOH to γ-NiOOH and consequently challenge the long-held notion that the β-NiOOH phase is a more efficient oxygen-evolving catalyst. © 2012 American Chemical Society

Oxygen-consuming chlor alkali cell configured to minimize peroxide formation

DOEpatents

Chlistunoff, Jerzy B [Los Alamos, NM; Lipp, Ludwig [Brookfield, CT; Gottesfeld, Shimshon [Niskayuna, NY

2006-08-01

Oxygen-consuming zero gap chlor-alkali cell was configured to minimize peroxide formation. The cell included an ion-exchange membrane that divided the cell into an anode chamber including an anode and a cathode chamber including an oxygen gas diffusion cathode. The cathode included a single-piece of electrically conducting graphitized carbon cloth. Catalyst and polytetrafluoroethylene were attached to only one side of the cloth. When the cathode was positioned against the cation exchange membrane with the catalyst side away from the membrane, electrolysis of sodium chloride to chlorine and caustic (sodium hydroxide) proceeded with minimal peroxide formation.

Reducing Problems in Fine Motor Development among Primary Children through the Use of Multi-Sensory Techniques.

ERIC Educational Resources Information Center

Wessel, Dorothy

A 10-week classroom intervention program was implemented to facilitate the fine-motor development of eight first-grade children assessed as being deficient in motor skills. The program was divided according to five deficits to be remediated: visual motor, visual discrimination, visual sequencing, visual figure-ground, and visual memory. Each area…

Thirty years through vanadium chemistry.

PubMed

Costa Pessoa, J

2015-06-01

The relevance of vanadium in biological systems is known for many years and vanadium-based catalysts have important industrial applications, however, till the beginning of the 80s research on vanadium chemistry and biochemistry did not receive much attention from the scientific community. The understanding of the broad bioinorganic implications resulting from the similarities between phosphate and vanadate(V) and the discovery of vanadium dependent enzymes gave rise to an enormous increase in interest in the chemistry and biological relevance of vanadium. Thereupon the last 30years corresponded to a period of enormous research effort in these fields, as well as in medicinal applications of vanadium and in the development of catalysts for use in fine-chemical synthesis, some of these inspired by enzymatic active sites. Since the 80s my group in collaboration with others made contributions, described throughout this text, namely in the understanding of the speciation of vanadium compounds in aqueous solution and in biological fluids, and to the transport of vanadium compounds in blood plasma and their uptake by cells. Several new types of vanadium compounds were also synthesized and characterized, with applications either as prospective therapeutic drugs or as homogeneous or heterogenized catalysts for the production of fine chemicals. The developments made are described also considering the international context of the evolution of the knowledge in the chemistry and bioinorganic chemistry of vanadium compounds during the last 30years. This article was compiled based on the Vanadis Award presentation at the 9th International Vanadium Symposium. Copyright © 2015 Elsevier Inc. All rights reserved.

Catalytic and electrocatalytic oxidation of ethanol over palladium-based nanoalloy catalysts.

PubMed

Yin, Jun; Shan, Shiyao; Ng, Mei Shan; Yang, Lefu; Mott, Derrick; Fang, Weiqin; Kang, Ning; Luo, Jin; Zhong, Chuan-Jian

2013-07-23

The control of the nanoscale composition and structure of alloy catalysts plays an important role in heterogeneous catalysis. This paper describes novel findings of an investigation for Pd-based nanoalloy catalysts (PdCo and PdCu) for ethanol oxidation reaction (EOR) in gas phase and alkaline electrolyte. Although the PdCo catalyst exhibits a mass activity similar to Pd, the PdCu catalyst is shown to display a much higher mass activity than Pd for the electrocatalytic EOR in alkaline electrolyte. This finding is consistent with the finding on the surface enrichment of Pd on the alloyed PdCu surface, in contrast to the surface enrichment of Co in the alloyed PdCo surface. The viability of C-C bond cleavage was also probed for the PdCu catalysts in both gas-phase and electrolyte-phase EOR. In the gas-phase reaction, although the catalytic conversion rate for CO2 product is higher over Pd than PdCu, the nanoalloy PdCu catalyst appears to suppress the formation of acetic acid, which is a significant portion of the product in the case of pure Pd catalyst. In the alkaline electrolyte, CO2 was detected from the gas phase above the electrolyte upon acid treatment following the electrolysis, along with traces of aldehyde and acetic acid. An analysis of the electrochemical properties indicates that the oxophilicity of the base metal alloyed with Pd, in addition to the surface enrichment of metals, may have played an important role in the observed difference of the catalytic and electrocatalytic activities. In comparison with Pd alloyed with Co, the results for Pd alloyed with Cu showed a more significant positive shift of the reduction potential of the oxygenated Pd species on the surface. These findings have important implications for further fine-tuning of the Pd nanoalloys in terms of base metal composition toward highly active and selective catalysts for EOR.

Carbon-Coated Core-Shell Fe-Cu Nanoparticles as Highly Active and Durable Electrocatalysts for a Zn-Air Battery.

PubMed

Nam, Gyutae; Park, Joohyuk; Choi, Min; Oh, Pilgun; Park, Suhyeon; Kim, Min Gyu; Park, Noejung; Cho, Jaephil; Lee, Jang-Soo

2015-06-23

Understanding the interaction between a catalyst and oxygen has been a key step in designing better electrocatalysts for the oxygen reduction reaction (ORR) as well as applying them in metal-air batteries and fuel cells. Alloying has been studied to finely tune the catalysts' electronic structures to afford proper binding affinities for oxygen. Herein, we synthesized a noble-metal-free and nanosized transition metal CuFe alloy encapsulated with a graphitic carbon shell as a highly efficient and durable electrocatalyst for the ORR in alkaline solution. Theoretical models and experimental results demonstrated that the CuFe alloy has a more moderate binding strength for oxygen molecules as well as the final product, OH(-), thus facilitating the oxygen reduction process. Furthermore, the nitrogen-doped graphitic carbon-coated layer, formed catalytically under the influence of iron, affords enhanced charge transfer during the oxygen reduction process and superior durability. These benefits were successfully confirmed by realizing the catalyst application in a mechanically rechargeable Zn-air battery.

Economy of Catalyst Synthesis-Convenient Access to Libraries of Di- and Tetranaphtho Azepinium Compounds.

PubMed

Tharamak, Sorachat; Knittl-Frank, Christian; Manaprasertsak, Auraya; Pengsook, Anchulee; Suchy, Lydia; Schuller, Philipp; Happl, Barbara; Roller, Alexander; Widhalm, Michael

2018-03-24

Efficient optimization procedures in chiral catalysis are usually linked to a straightforward strategy to access groups of structurally similar catalysts required for fine-tuning. The ease of building up such ligand libraries can be increased when the structure-modifying step (introduction of a substituent) is done at a later stage of the synthesis. This is demonstrated for the extended family of di- and tetranaphtho azepinium compounds, widely used as chiral phase transfer catalysts (PTC). Using 2,6-diiodo-4,5-dihydro-3 H -dinaphtho[2,1-c:1',2'-e]azepine and 4,8-diiodo-6,7-dihydro-5 H -dibenzo[c,e]azepine, respectively, as key intermediates, 18 spiro -azepinium compounds were synthesized in a total yield of 25-42% over 6-7 steps from 1,1'-binaphthyl-2,2'-dicarboxylic acid or diphenic acid, respectively. The replacement of iodo groups with aryl substituents was performed as the last or the penultimate step of the synthesis.

Atomic-Level Structural Dynamics of Polyoxoniobates during DMMP Decomposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Qi; Chapleski, Robert C.; Plonka, Anna M.

Ambient pressure in situ synchrotron-based spectroscopic techniques have been correlated to illuminate atomic-level details of bond breaking and formation during the hydrolysis of a chemical warfare nerve agent simulant over a polyoxometalate catalyst. Specifically, a Cs 8[Nb 6O 19] polyoxoniobate catalyst has been shown to react readily with dimethyl methylphosphonate (DMMP). The atomic-level transformations of all reactant moieties, the [Nb 6O 19] 8- polyanion, its Cs + counterions, and the DMMP substrate, were tracked under ambient conditions by a combination of X-ray absorption fine structure spectroscopy, Raman spectroscopy, and X-ray diffraction. Results reveal that the reaction mechanism follows general basemore » (in contrast to specific base) hydrolysis. Together with computational results, the work demonstrates that the ultimate fate of DMMP hydrolysis at the Cs 8[Nb 6O 19] catalyst is strong binding of the (methyl) methylphosphonic acid ((M)MPA) product to the polyanions, which ultimately inhibits catalytic turnover.« less

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

NASA Astrophysics Data System (ADS)

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.

Atomic-Level Structural Dynamics of Polyoxoniobates during DMMP Decomposition

DOE PAGES

Wang, Qi; Chapleski, Robert C.; Plonka, Anna M.; ...

2017-04-10

Ambient pressure in situ synchrotron-based spectroscopic techniques have been correlated to illuminate atomic-level details of bond breaking and formation during the hydrolysis of a chemical warfare nerve agent simulant over a polyoxometalate catalyst. Specifically, a Cs 8[Nb 6O 19] polyoxoniobate catalyst has been shown to react readily with dimethyl methylphosphonate (DMMP). The atomic-level transformations of all reactant moieties, the [Nb 6O 19] 8- polyanion, its Cs + counterions, and the DMMP substrate, were tracked under ambient conditions by a combination of X-ray absorption fine structure spectroscopy, Raman spectroscopy, and X-ray diffraction. Results reveal that the reaction mechanism follows general basemore » (in contrast to specific base) hydrolysis. Together with computational results, the work demonstrates that the ultimate fate of DMMP hydrolysis at the Cs 8[Nb 6O 19] catalyst is strong binding of the (methyl) methylphosphonic acid ((M)MPA) product to the polyanions, which ultimately inhibits catalytic turnover.« less

Catalyst and process development for synthesis gas conversion to isobutylene. Final report, September 1, 1990--January 31, 1994

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anthony, R.G.; Akgerman, A.

1994-05-06

Previous work on isosynthesis (conversion of synthesis gas to isobutane and isobutylene) was performed at very low conversions or extreme process conditions. The objectives of this research were (1) determine the optimum process conditions for isosynthesis; (2) determine the optimum catalyst preparation method and catalyst composition/properties for isosynthesis; (3) determine the kinetics for the best catalyst; (4) develop reactor models for trickle bed, slurry, and fixed bed reactors; and (5) simulate the performance of fixed bed trickle flow reactors, slurry flow reactors, and fixed bed gas phase reactors for isosynthesis. More improvement in catalyst activity and selectivity is needed beforemore » isosynthesis can become a commercially feasible (stand-alone) process. Catalysts prepared by the precipitation method show the most promise for future development as compared with those prepared hydrothermally, by calcining zirconyl nitrate, or by a modified sol-gel method. For current catalysts the high temperatures (>673 K) required for activity also cause the production of methane (because of thermodynamics). A catalyst with higher activity at lower temperatures would magnify the unique selectivity of zirconia for isobutylene. Perhaps with a more active catalyst and acidification, oxygenate production could be limited at lower temperatures. Pressures above 50 atm cause an undesirable shift in product distribution toward heavier hydrocarbons. A model was developed that can predict carbon monoxide conversion an product distribution. The rate equation for carbon monoxide conversion contains only a rate constant and an adsorption equilibrium constant. The product distribution was predicted using a simple ratio of the rate of CO conversion. This report is divided into Introduction, Experimental, and Results and Discussion sections.« less

A versatile in situ spectroscopic cell for fluorescence/transmission EXAFS and X-ray diffraction of heterogeneous catalysts in gas and liquid phase.

PubMed

Hannemann, Stefan; Casapu, Maria; Grunwaldt, Jan Dierk; Haider, Peter; Trüssel, Philippe; Baiker, Alfons; Welter, Edmund

2007-07-01

A new spectroscopic cell suitable for the analysis of heterogeneous catalysts by fluorescence EXAFS (extended X-ray absorption fine structure), transmission EXAFS and X-ray diffraction during in situ treatments and during catalysis is described. Both gas-phase and liquid-phase reactions can be investigated combined with on-line product analysis performed either by mass spectrometry or infrared spectroscopy. The set-up allows measurements from liquid-nitrogen temperature to 973 K. The catalysts are loaded preferentially as powders, but also as self-supporting wafers. The reaction cell was tested in various case studies demonstrating its flexibility and its wide applicability from model studies at liquid-nitrogen temperature to operando studies under realistic reaction conditions. Examples include structural studies during (i) the reduction of alumina-supported noble metal particles prepared by flame-spray pyrolysis and analysis of alloying in bimetallic noble metal particles (0.1%Pt-0.1%Pd/Al(2)O(3), 0.1%Pt-0.1%Ru/Al(2)O(3), 0.1%Pt-0.1%Rh/Al(2)O(3), 0.1%Au-0.1%Pd/Al(2)O(3)), (ii) reactivation of aged 0.8%Pt-16%BaO-CeO(2) NO(x) storage-reduction catalysts including the NO(x) storage/reduction cycle, and (iii) alcohol oxidation over gold catalysts (0.6%Au-20%CuO-CeO(2)).

Covalent heterogenization of discrete bis(8-quinolinolato)dioxomolybdenum(VI) and dioxotungsten(VI) complexes by a metal-template/metal-exchange method: Cyclooctene epoxidation catalysts with enhanced performances

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Ying; Chattopadhyay, Soma; Shibata, Tomohiro

A metal-template/metal-exchange method was used to imprint covalently attached bis(8- quinolinolato)dioxomolybdenum(VI) and dioxotungsten(VI) complexes onto large surface-area, mesoporous SBA-15 silica to obtain discrete MoO2 VIT and WO2 VIT catalysts bearing different metal loadings, respectively. Homogeneous counterparts, MoO2 VIN and WO2 VIN, as well as randomly ligandgrafted heterogeneous analogues, MoO2 VIG and WO2 VIG, were also prepared for comparison. X-ray absorption fine structure (XAFS), pair distribution function (PDF) and UV–vis data demonstrate that MoO2 VIT and WO2 VIT adopt a more solution-like bis(8-quinolinol) coordination environment than MoO2 VIG and WO2 VIG, respectively. Correspondingly, the templated MoVI and WVI catalysts show superiormore » performances to their randomly grafted counterparts and neat analogues in the epoxidation of cyclooctene. It is found that the representative MoO2 VIT-10% catalyst can be recycled up to five times without significant loss of reactivity, and heterogeneity test confirms the high stability of MoO2 VIT-10% catalyst against leaching of active species into solution. The homogeneity of the discrete bis(8-quinolinol) metal spheres templated on SBA-15 should be responsible for the superior performances.« less

Recent Advances in the Synthesis, Characterization and Application of Zn+-containing Heterogeneous Catalysts.

PubMed

Chen, Guangbo; Zhao, Yufei; Shang, Lu; Waterhouse, Geoffrey I N; Kang, Xiaofeng; Wu, Li-Zhu; Tung, Chen-Ho; Zhang, Tierui

2016-07-01

Monovalent Zn + (3d 10 4s 1 ) systems possess a special electronic structure that can be exploited in heterogeneous catalysis and photocatalysis, though it remains challenge to synthesize Zn + -containing materials. By careful design, Zn + -related species can be synthesized in zeolite and layered double hydroxide systems, which in turn exhibit excellent catalytic potential in methane, CO and CO 2 activation. Furthermore, by utilizing advanced characterization tools, including electron spin resonance, X-ray absorption fine structure and density functional theory calculations, the formation mechanism of the Zn + species and their structure-performance relationships can be understood. Such advanced characterization tools guide the rational design of high-performance Zn + -containing catalysts for efficient energy conversion.

Recent Advances in the Synthesis, Characterization and Application of Zn+‐containing Heterogeneous Catalysts

PubMed Central

Chen, Guangbo; Zhao, Yufei; Shang, Lu; Waterhouse, Geoffrey I. N.; Kang, Xiaofeng; Wu, Li‐Zhu; Tung, Chen‐Ho

2016-01-01

Monovalent Zn+ (3d104s1) systems possess a special electronic structure that can be exploited in heterogeneous catalysis and photocatalysis, though it remains challenge to synthesize Zn+‐containing materials. By careful design, Zn+‐related species can be synthesized in zeolite and layered double hydroxide systems, which in turn exhibit excellent catalytic potential in methane, CO and CO2 activation. Furthermore, by utilizing advanced characterization tools, including electron spin resonance, X‐ray absorption fine structure and density functional theory calculations, the formation mechanism of the Zn+ species and their structure‐performance relationships can be understood. Such advanced characterization tools guide the rational design of high‐performance Zn+‐containing catalysts for efficient energy conversion. PMID:27818902

Lipases as catalysts in synthesis of fine chemicals.

PubMed

Baldessari, Alicia

2012-01-01

The application of lipases as catalysts in the synthesis of an intermediate of alfuzosin and lapyrium chloride is described. In the first case, the one-pot procedure to obtain the intermediate involves the treatment of tetrahydrofuroic acid with ethanol in the presence of Candida antarctica lipase followed by the addition of N-methyl-1,3-diaminopropane. In the second part of the chapter, an efficient route for large-scale preparation of lapyrium chloride is developed from chloroacetic acid in four steps, three of them enzymatic. Due to the chemoselective behavior of the lipases, both products described in the present chapter were obtained in a high degree of purity and yield, applying mild reaction conditions, and following a low environmental impact methodology.

Finite Size Effects in Submonolayer Catalysts Investigated by CO Electrosorption on PtsML/Pd(100).

PubMed

Yuan, Qiuyi; Doan, Hieu A; Grabow, Lars C; Brankovic, Stanko R

2017-10-04

A combination of scanning tunneling microscopy, subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS), and density functional theory (DFT) is used to quantify the local strain in 2D Pt clusters on the 100 facet of Pd and its effect on CO chemisorption. Good agreement between SNIFTIRS experiments and DFT simulations provide strong evidence that, in the absence of coherent strain between Pt and Pd, finite size effects introduce local compressive strain, which alters the chemisorption properties of the surface. Though this effect has been widely neglected in prior studies, our results suggest that accurate control over cluster sizes in submonolayer catalyst systems can be an effective approach to fine-tune their catalytic properties.

Influence of Fine Motor Skill on Accuracy of Measurements Using a Handheld Sliding Caliper at Adolescents Group Aged 19-20

NASA Astrophysics Data System (ADS)

Brychta, Petr; Hojk, Vladimír; Hrubý, Jiří; Pilc, Jozef

2017-10-01

This innovate ve interdisciplinary study deals with influence of fine motor skill level (finger dexterity) of individual on his measurement results in metrology practice. The main objective of this study was determinate fine motor skill level of individuals using a motor test. Further determinate the potential effect of different fine motor skill levels on accuracy of measuring using a mechanical handheld sliding caliper. Fine motor skill test and metrological test were implemented. Pursuant the results of fine motor skill test were probands divided into 2 groups. The groups are significantly different on accuracy of measurement (p=0,006). Pearson coefficient shows a significant correlation r = - 0.66 between the Purdue Pegboard test and a measurement error. Results confirmed that the fine motor skill of the upper limbs (especially finger coordination) significantly influence accuracy of measurement using a mechanical handheld sliding caliper.

Water-medium and solvent-free organic reactions over a bifunctional catalyst with Au nanoparticles covalently bonded to HS/SO3H functionalized periodic mesoporous organosilica.

PubMed

Zhu, Feng-Xia; Wang, Wei; Li, He-Xing

2011-08-03

An operationally simple approach for the preparation of a new class of bifunctional Au nanoparticle-acid catalysts has been developed. In situ reduction of Au(3+) with HS-functionalized periodic mesoporous organosilicas (PMOs) creates robust, fine Au nanoparticles and concomitantly produces a sulfonic acid moiety strongly bonded to PMOs. Characterizations of the nanostructures reveal that Au nanoparticles are formed with uniformed, narrow size distribution around 1-2 nm, which is very critical for essential catalytic activities. Moreover, the Au nanoparticles are mainly attached onto the pore surface rather than onto the outer surface with ordered mesoporous channels, allowing for maximal exposure to reaction substrates while minimizing Au nanoparticle leaching. Their higher S(BET), V(P), and D(P) than either the Au-HS-PMO(Et) or the Au/SO(3)H-PMO(Et) render the catalyst with comparably even higher catalytic efficiency than its homogeneous counterparts. Furthermore, the unique amphiphilic compartment of the Au-HS/SO(3)H-PMO(Et) nanostructures enables organic reactions to proceed efficiently in a pure aqueous solution without using any organic solvents or even without water. As demonstrated experimentally, remarkably, the unique bifunctional Au-HS/SO(3)H-PMO(Et) catalyst displays higher efficiencies in promoting water-medium alkyne hydration, intramolecular hydroamination, styrene oxidation, and three-component coupling reactions and even the solvent-free alkyne hydration process than its homogeneous catalysts. The robust catalyst can be easily recycled and used repetitively at least 10 times without loss of catalytic efficiency. These features render the catalyst particularly attractive in the practice of organic synthesis in an environmentally friendly manner.

Tailoring Silica-alumina Supported Pt-Pd As Poison Tolerant Catalyst For Aromatics Hydrogenation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Yanzhe; Gutierrez, Oliver Y.; Haller, Gary L.

2013-08-01

The tailoring of the physicochemical and catalytic properties of mono- and bimetallic Pt-Pd catalysts supported on amorphous silica-alumina is studied. Electron energy loss spectroscopy and extended X-ray absorption fine structure analyses indicated that bimetallic Pt-Pd and relatively large monometallic Pd particles were formed, whereas the X-ray absorption near edge structure provided direct evidence for the electronic deficiency of the Pt atoms. The heterogeneous distribution of metal particles was also shown by high resolution transmission electron microscopy. The average structure of the bimetallic particles (Pt-rich core and Pd-rich shell) and the presence of Pd particles led to surface Pd enrichment, whichmore » was independently shown by IR spectra of adsorbed CO. The specific metal distribution, average size, and surface composition of the Pt-Pd particles depend to a large extent on the metal precursors. In the presence of NH3 ligands, Pt-Pd particles with a fairly homogeneous bulk and surface metal distribution were formed. Also high Lewis acid site concentration of the carrier leads to more homogeneous bimetallic particles. All catalysts were active for the hydrogenation of tetralin in the absence and presence of quinoline and dibenzothiophene (DBT). Monometallic Pt catalysts had the highest hydrogenation activity in poison-free and quinoline-containing feed. When DBT was present, bimetallic Pt-Pd catalysts with the most homogenous metal distribution showed the highest activity. The higher resistance of bimetallic catalysts towards sulfur poisoning compared to their monometallic Pt counterparts results from the weakened metal-sulfur bond on the electron deficient Pt atoms. Thus, increasing the fraction of electron deficient Pt on the surface of the bimetallic particles increases the efficiency of the catalyst in the presence of sulfur.« less

Preparation of metal/zeolite catalysts: Formation of palladium aquocomplexes in the precursor of palladium-mordenite catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1993-09-01

Previous research has revealed that the catalytic performance of metal/zeolite catalysts can be significantly modified by exposing the catalyst precursor to H[sub 2]O vapor during the period after calcination, but before reduction. For bimetallic PdCo/NaY catalysts used for CO hydrogenation, the selectivity was changed from predominant production of oxygenates to predominant production of higher hydrocarbons. For Pt/H-mordenite catalysts, this water treatment has been reported to improve the alkane isomerization activity. Although it is certain that Lewis sites are transformed to Bronsted sites by reaction with H[sub 2]O, the activity of the catalyst is affected most when the water is addedmore » after calcination, when the noble metal is present as ligand-free ions. This observation led to the hypothesis that complexation of transition metal ions with water might be instrumental for the observed effects. In zeolites containing cages, such as Y, the formation of metal-ligand complex ions appears to incite their migration from small to large cages. In cageless zeolites such as mordenite, however, it is not clear, a priori, whether hydration of transition metal ions will increase or decrease their reducibility and whether it will ultimately result in higher or lower metal dispersion. The authors have therefore undertaken research to clarify these issues. Palladium supported in H-mordenite (Pd/HMor) or Na-mordenite (Pd/Na-Mor) has been tested using methylcyclopentane as a probe reaction; temperature-programmed reduction (TPR), desorption (TPD), and extended X-ray absorption fine structure (EXAFS) spectroscopy have been used to characterize the effects of water treatment on the samples.« less

Professional Development Planning and Design. Issues in Science Education.

ERIC Educational Resources Information Center

Rhoton, Jack; Bowers, Patricia

This book focuses on the professional development of teachers and discusses issues related to the planning and design of professional development programs. The content of the book is divided into three parts. Part 1, Standards-Based Reform and Professional Development includes: (1) "National Science Education Standards as a Catalyst for…

Catalyst Complexed Carbon Slurry Fuel Development.

DTIC Science & Technology

1981-01-01

materials of fine particle size made by procedures denoted as furnace, channel , thermal, and lamp. Car- bon black materials are composed essentially of...far the largest group of commercially available materials, and are prepared by partial combustion of heavy hydrocarbon liquids. Channel blacks are...manufactured by impingement of natural gas flames on cold channel irons. Thermal blacks are produced by thermal decomposition of natural gas, while

Catalysts and process developments for two-stage liquefaction. Final technical report, October 1, 1989--September 30, 1992

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cronauer, D.C.; Swanson, A.J.; Sajkowski, D.J.

1992-12-31

Research in this project centered upon developing and evaluating catalysts and process improvements for coal liquefaction in the two-stage, close-coupled catalytic process. The major results are summarized here and they are described in more detail under each Task. In tasks for coal pretreatment and beneficiation, it was shown for coal handling that drying of both lignite or subbituminous coals using warm air, vacuum oven or exposing to air for long time was detrimental to subsequent liquefaction. Both laboratory and bench-scale beneficiations indicated that in order to achieve increased liquefaction yield for Illinois No. 6 bituminous coal, size separation with inmore » sink-float technique should be used. For subbituminous coal, the best beneficiation was aqueous SO{sub 2} treatment, which reduced mineral matter. In the case of lignite, the fines should be rejected prior to aqueous SO{sub 2} treatment and sink-float gravity separation. In liquefying coals with supported catalysts in both first and second stages, coal conversion was highest (93%) with Illinois No. 6 coal, which also had the highest total liquid yield of 80%, however, the product contained unacceptably high level of resid (30%). Both low rank coals gave lower conversion (85--87%) and liquid yields (57--59%), but lighter products (no resid). The analysis of spent first stage catalysts indicated significant sodium and calcium deposits causing severe deactivation. The second stage catalysts were in better condition showing high surface areas and low coke and metal deposits. The use of dispersed catalyst in the first stage would combat the severe deactivation.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shan, Junjun; Zhang, Shiran; Choksi, Tej

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 weremore » 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.« less

Production of zinc pellets

DOEpatents

Cooper, J.F.

1996-11-26

Uniform zinc pellets are formed for use in batteries having a stationary or moving slurry zinc particle electrode. The process involves the cathodic deposition of zinc in a finely divided morphology from battery reaction product onto a non-adhering electrode substrate. The mossy zinc is removed from the electrode substrate by the action of gravity, entrainment in a flowing electrolyte, or by mechanical action. The finely divided zinc particles are collected and pressed into pellets by a mechanical device such as an extruder, a roller and chopper, or a punch and die. The pure zinc pellets are returned to the zinc battery in a pumped slurry and have uniform size, density and reactivity. Applications include zinc-air fuel batteries, zinc-ferricyanide storage batteries, and zinc-nickel-oxide secondary batteries. 6 figs.

Production of zinc pellets

DOEpatents

Cooper, John F.

1996-01-01

Uniform zinc pellets are formed for use in batteries having a stationary or moving slurry zinc particle electrode. The process involves the cathodic deposition of zinc in a finely divided morphology from battery reaction product onto a non-adhering electrode substrate. The mossy zinc is removed from the electrode substrate by the action of gravity, entrainment in a flowing electrolyte, or by mechanical action. The finely divided zinc particles are collected and pressed into pellets by a mechanical device such as an extruder, a roller and chopper, or a punch and die. The pure zinc pellets are returned to the zinc battery in a pumped slurry and have uniform size, density and reactivity. Applications include zinc-air fuel batteries, zinc-ferricyanide storage batteries, and zinc-nickel-oxide secondary batteries.

DEVELOPMENT OF ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adeyinka A. Adeyiga

2001-09-01

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. The use of iron-based catalysts is attractive not only due to their low cost and ready availability, but also due to their high water-gas shift activity which makes it possible to use these catalysts with low H{sub 2}/CO ratios. However, a serious problem with use ofmore » Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, makes the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. Recently, fundamental understanding of physical attrition is being addressed by incorporating suitable binders into the catalyst recipe. This has resulted in the preparation of a spray dried Fe-based catalyst having aps of 70 mm with high attrition resistance. This Fe-based attrition resistant, active and selective catalyst gave 95% CO conversion through 125 hours of testing in a fixed-bed at 270 C, 1.48 MPa, H{sub 2}/CO=0.67 and 2.0 NL/g-cat/h with C{sub 5}{sup +} selectivity of >78% and methane selectivity of <5%. However, further development of the catalyst is needed to address the chemical attrition due to phase changes that any Fe-catalyst goes through potentially causing internal stresses within the particle and resulting in weakening, spalling or cracking. The objective of this research is to develop robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry bubble column reactor. Specifically we aim to develop to: (i) improve the performance and preparation procedure of the high activity, high attrition resistant, high alpha iron-based catalysts synthesized at Hampton University, (ii) seek improvements in the catalyst performance through variations in process conditions, pretreatment procedures and/or modifications in catalyst preparation steps and (iii) investigate the performance in a slurry reactor. The effort during the reporting period has been devoted to attrition study of the iron-based catalysts. Precipitated silica appeared to decrease attrition resistance of spray-dried iron FT catalysts. It was found that the catalyst with precipitated silica content at around 12wt% showed the lowest attrition resistance. The results of net change in volume moment and catalyst morphology showed supporting evidences to the attrition results. Catalysts with low attrition resistance generated more fines loss, had higher net change in volume moment and showed more breakage of particles. BET surface area and pore volume of this catalyst series fluctuated; therefore no conclusion can be drawn from the data obtained. However, catalyst with no precipitated silica showed the lowest in BET surface area and pore volume, as expected. Addition of precipitated silica to the catalysts had no effect to the phase changes of iron that could have significant influence to catalyst attrition. The presence of precipitated silica is needed for enhancing catalyst surface area; however, the amount of silica added should be compromising with attrition resistance of catalysts.« less

Reducing Iridium Loading in Oxygen Evolution Reaction Electrocatalysts Using Core–Shell Particles with Nitride Cores

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tackett, Brian M.; Sheng, Wenchao; Kattel, Shyam

Here, the oxygen evolution reaction (OER) has broad applications in electrochemical devices, but it often requires expensive and scarce Ir-based catalysts in acid electrolyte. Presented here is a framework to reduce Ir loading by combining core–shell iridium/metal nitride morphologies using in situ experiments and density functional theory (DFT) calculations. Several group VIII transition metal (Fe, Co, and Ni) nitrides are studied as core materials, with Ir/Fe 4N core–shell particles showing enhancement in both OER activity and stability. In situ X-ray absorption fine structure measurements are used to determine the structure and stability of the core–shell catalysts under OER conditions. DFTmore » calculations are used to demonstrate adsorbate binding energies as descriptors of the observed activity trends.« less

Evaluation parameters for the alkaline fuel cell oxygen electrode

NASA Technical Reports Server (NTRS)

Singer, J.; Srinivasan, V.

1985-01-01

Studies were made of Pt- and Au-catalyzed porous electrodes, designed for the cathode of the alkaline H2/O2 fuel cell, employing cyclic voltammetry and the floating half-cell method. The purpose was to obtain parameters from the cyclic voltammograms which could predict performance in the fuel cell. It was found that a satisfactory relationship between these two types of measurement could not be established; however, useful observations were made of relative performance of several types of carbon used as supports for noble metal catalysts and of some Au catalysts. The best half-cell performance with H2/O2 in a 35 percent KOH electrolyte at 80 C was given by unsupported fine particle Au on Teflon; this electrode is used in the Orbiter fuel cell.

Reducing Iridium Loading in Oxygen Evolution Reaction Electrocatalysts Using Core–Shell Particles with Nitride Cores

DOE PAGES

Tackett, Brian M.; Sheng, Wenchao; Kattel, Shyam; ...

2018-02-16

Here, the oxygen evolution reaction (OER) has broad applications in electrochemical devices, but it often requires expensive and scarce Ir-based catalysts in acid electrolyte. Presented here is a framework to reduce Ir loading by combining core–shell iridium/metal nitride morphologies using in situ experiments and density functional theory (DFT) calculations. Several group VIII transition metal (Fe, Co, and Ni) nitrides are studied as core materials, with Ir/Fe 4N core–shell particles showing enhancement in both OER activity and stability. In situ X-ray absorption fine structure measurements are used to determine the structure and stability of the core–shell catalysts under OER conditions. DFTmore » calculations are used to demonstrate adsorbate binding energies as descriptors of the observed activity trends.« less

Iridium clusters in KLTL zeolite: Structure and catalytic selectivity for n-hexane aromatization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Triantafillou, N.D.; Miller, J.T.; Gates, B.C.

Catalysts consisting of Ir clusters in zeolite KLTL were prepared by reduction of [Ir(NH{sub 3}){sub 5}Cl]Cl{sub 2} in the zeolite with H{sub 2} at temperatures 300 or 500{degrees}C. The catalysts were tested for reactions of n-hexane and H{sub 2} at 400, 440 and 480{degrees}C and were characterized by temperature-programmed reduction, hydrogen chemisorption, transmission electron microscopy, infrared spectroscopy of adsorbed CO, and extended X-ray absorption fine structure spectroscopy. The clusters consist of 4 to 6 Ir atoms on average and are sufficiently small to reside within the pores of the zeolite. The infrared spectra characteristic of terminal CO suggest that themore » support environment is slightly basic and that the Ir clusters are electron rich relative to the bulk metal. Notwithstanding the small cluster size, the support basicity, and the confining geometry of the LTL zeolite pore structure, the catalytic performance is similar to those of other Ir catalysts, with a poor selectivity for aromatization and a high selectivity for hydrogenolysis. These results are consistent with the inference that the principal requirements for selective naphtha aromatization catalysts are both a nonacidic support and a metal with a low hydrogenolsis activity, i.e., Pt. 47 refs., 6 figs., 3 tabs.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

James K. Neathery; Gary Jacobs; Amitava Sarkar

In the previous reporting period, modifications were completed for integrating a continuous wax filtration system for a 4 liter slurry bubble column reactor. During the current reporting period, a shakedown of the system was completed. Several problems were encountered with the progressive cavity pump used to circulate the wax/catalyst slurry though the cross-flow filter element and reactor. During the activation of the catalyst with elevated temperature (> 270 C) the elastomer pump stator released sulfur thereby totally deactivating the iron-based catalyst. Difficulties in maintaining an acceptable leak rate from the pump seal and stator housing were also encountered. Consequently, themore » system leak rate exceeded the expected production rate of wax; therefore, no online filtration could be accomplished. Work continued regarding the characterization of ultra-fine catalyst structures. The effect of carbidation on the morphology of iron hydroxide oxide particles was the focus of the study during this reporting period. Oxidation of Fe (II) sulfate results in predominantly {gamma}-FeOOH particles which have a rod-shaped (nano-needles) crystalline structure. Carbidation of the prepared {gamma}-FeOOH with CO at atmospheric pressure produced iron carbides with spherical layered structure. HRTEM and EDS analysis revealed that carbidation of {gamma}-FeOOH particles changes the initial nano-needles morphology and generates ultrafine carbide particles with irregular spherical shape.« less

Enantioselective syntheses of aeruginosin 298-A and its analogues using a catalytic asymmetric phase-transfer reaction and epoxidation.

PubMed

Ohshima, Takashi; Gnanadesikan, Vijay; Shibuguchi, Tomoyuki; Fukuta, Yuhei; Nemoto, Tetsuhiro; Shibasaki, Masakatsu

2003-09-17

We developed a versatile synthetic process for aeruginosin 298-A as well as several attractive analogues, in which all stereocenters were controlled by a catalytic asymmetric phase-transfer reaction and epoxidation. Furthermore, drastic counteranion effects in phase-transfer catalysis were observed for the first time, making it possible to three-dimensionally fine-tune the catalyst (ketal part, aromatic part, and counteranion).

"...If We Were Cavemen We'd Be Fine": Facebook as a Catalyst for Critical Literacy Learning by Dyslexic Sixth-Form Students

ERIC Educational Resources Information Center

Barden, Owen

2012-01-01

This article is derived from a study of the use of Facebook as an educational resource by five dyslexic students at a sixth form college in north-west England. Through a project in which teacher-researcher and student-participants co-constructed a group Facebook page about the students' scaffolded research into dyslexia, the study examined the…

Self-Supported Copper Oxide Electrocatalyst for Water Oxidation at Low Overpotential and Confirmation of Its Robustness by Cu K-edge X-ray Absorption Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Xiang; Cui, Shengsheng; Sun, Zijun

Developing efficient water oxidation catalysts made of earth-abundant elements is a demanding challenge that should be met to fulfill the promise of water splitting for clean energy. Herein we report an annealing approach to synthesize binder-free, self-supported heterogeneous copper oxide (CuO) on conductive electrodes for oxygen evolution reaction (OER), producing electrodes with excellent electrocatalytic properties such as high efficiency, low overpotential, and good stability. The catalysts were grown in situ on fluorine-doped tin oxide (FTO) by electrodeposition from a simple Cu(II) salt solution, followed by annealing at a high temperature. Under optimal conditions, the CuO-based OER catalyst shows an onsetmore » potential of <0.58 V (vs Ag/AgCl) in 1.0 M KOH at pH 13.6. From the Tafel plot, the required overpotentials for current densities of 0.1 and 1.0 mA/cm2 are only 360 and 430 mV, respectively. The structure and the presence of a CuO motif in the catalyst have been identified by high-energy X-ray diffraction (HE-XRD), Cu K-edge X-ray absorption (XAS) spectra including X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS). To the best of our knowledge, this represents the best catalytic activity for CuO-based OER catalysts to date.« less

Synthesis and characterization of nickel and zinc ferrite nanocatalysts for decomposition of CO2 greenhouse effect gas.

PubMed

Lin, Kuen-Song; Adhikari, Abhijit Krishna; Wang, Chi-Yu; Hsu, Pei-Ju; Chan, Ho-Yang

2013-04-01

The decomposition of CO2 over oxygen deficient nickel ferrite nanoparticles (NFNs) and zinc ferrite nanoparticles (ZFNs) at 573 K was studied. The oxidation states with fine structure of Fe/Ni or Fe/Zn species were also measured in NFNs and ZFNs catalysts, respectively. Oxygen deficiency of catalysts was obtained by reduction in hydrogen. Decomposition of CO2 into carbon and oxygen has been carried out within few minutes when it comes into contact with oxygen deficient catalysts through incorporation of oxygen into ferrite nanoparticles. Oxygen and carbon rather than CO were produced in the decomposition process. The complete decomposition of CO2 was possible because of higher degree of oxygen deficiency andsurface-to-volume ratio of the catalysts. The pre-edge XANES spectra of Fe species in both catalysts exhibit an absorbance feature at 7114 eV for the 1s to 3d transition which is forbidden by the selection rule in case of perfect octahedral symmetry. The EXAFS data showed that the NFNs had two central Fe atoms coordinated by primarily Fe-O and Fe-Fe with bond distances of 1.871 and 3.051 angstroms, respectively. In case of ZFNs these values are 1.889 and 3.062 A, respectively. Methane gas was produced during the reactivation of NFNs by flowing hydrogen gas. Decomposition of CO2, moreover, recovery of valuable methane using heat energy of offgas produced from power generation plant or steel industry is an appealing alternative for energy recovery.

Morphology controlled synthesis of 2-D Ni-Ni3S2 and Ni3S2 nanostructures on Ni foam towards oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Chaudhari, Nitin Kaduba; Oh, Aram; Sa, Young Jin; Jin, Haneul; Baik, Hionsuck; Kim, Sang Gu; Lee, Suk Joong; Joo, Sang Hoon; Lee, Kwangyeol

2017-03-01

Catalysts for oxygen evolution reactions (OER) are at the heart of key renewable energy technologies, and development of non-precious metal catalysts with high activity and stability remain a great challenge in this field. Among various material candidates, metal sulfides are receiving increasing attention. While morphology-dependent catalytic performances are well established in noble metal-based catalysts, relatively little is known for the morphology‒catalytic performance relationship in metal sulfide catalysts. In this study, uniform spider web-like Ni nanosheets-Ni3S2 and honeycomb-like Ni3S2 structures are deposited on nickel foam (Ni3S2/NF) by a facile one-step hydrothermal synthetic route. When used as an oxygen evolution electrode, the spider web-like Ni-Ni3S2/NF with the large exposed surface area shown excellent catalytic activity and stability with an overpotential of 310 mV to achieve at 10 mA/cm2 and a Tafel slope of 63 mV/dec in alkaline media, which is superior to the honeycomb-like structure without Ni nanosheet. The low Tafel slope of the spider web-like Ni-Ni3S2/NF represents one of the best OER kinetics among nickel sulfide-based OER catalysts. The results point to the fact that performance of the metal sulfide electrocatalysts might be fine-tuned and optimized with morphological controls.

Superior performance of Ni–W–Ce mixed-metal oxide catalysts for ethanol steam reforming: Synergistic effects of W- and Ni-dopants

DOE PAGES

Liu, Zongyuan; Xu, Wenqian; Yao, Siyu; ...

2014-11-26

In this study, the ethanol steam reforming (ESR) reaction was examined over a series of Ni-W-Ce oxide catalysts. The structures of the catalysts were characterized using in-situ techniques including X-ray diffraction, Pair Distribution Function, X-ray absorption fine structure and transmission electron microscopy; while possible surface intermediates for the ESR reaction were investigated by Diffuse Reflectance Infrared Fourier Transform Spectroscopy. In these materials, all the W and part of the Ni were incorporated into the CeO₂ lattice, with the remaining Ni forming highly dispersed nano NiO (< 2 nm) outside the Ni-W-Ce oxide structure. The nano NiO was reduced to Nimore » under ESR conditions. The Ni-W-Ce systeme exhibited a much larger lattice strain than those seen for Ni-Ce and W-Ce. Synergistic effects between Ni and W inside ceria produced a substantial amount of defects and O vacancies that led to high catalytic activity, selectivity and stability (i.e. resistance to coke formation) during ethanol steam reforming.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mihaela Grigore; Richard Sakurovs; David French

Gasification of coke contributes to its degradation in the blast furnace. In this study, the effect of gasification on the inherent catalytic minerals in cokes and their reciprocal influence on gasification are investigated. The catalytic mineral phases identified in the cokes used in this study were metallic iron, iron sulfides, and iron oxides. Metallic iron and pyrrhotite were rapidly oxidized during gasification to iron oxide. The catalysts had a strong influence on the apparent rates at the initial stages of reaction. As gasification proceeds, their effect on the reaction rate diminishes as a result of reducing the surface contact betweenmore » catalyst and carbon matrix because of carbon consumption around the catalyst particles; with extended burnout the reactivity of the coke becomes increasingly dependent on surface area. The reaction rate in the initial stages was also influenced by the particle size of the catalytic minerals; for a given catalytic iron level, the cokes whose catalytic minerals were more finely dispersed had a higher apparent reaction rate than cokes containing larger catalytic particles. Iron, sodium, and potassium in the amorphous phase did not appear to affect the reaction rate. 40 refs., 16 figs., 6 tabs.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei

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 catalysismore » 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.« less

Rational Design of Single Molybdenum Atoms Anchored on N-Doped Carbon for Effective Hydrogen Evolution Reaction.

PubMed

Chen, Wenxing; Pei, Jiajing; He, Chun-Ting; Wan, Jiawei; Ren, Hanlin; Zhu, Youqi; Wang, Yu; Dong, Juncai; Tian, Shubo; Cheong, Weng-Chon; Lu, Siqi; Zheng, Lirong; Zheng, Xusheng; Yan, Wensheng; Zhuang, Zhongbin; Chen, Chen; Peng, Qing; Wang, Dingsheng; Li, Yadong

2017-12-11

The highly efficient electrochemical hydrogen evolution reaction (HER) provides a promising pathway to resolve energy and environment problems. An electrocatalyst was designed with single Mo atoms (Mo-SAs) supported on N-doped carbon having outstanding HER performance. The structure of the catalyst was probed by aberration-corrected scanning transmission electron microscopy (AC-STEM) and X-ray absorption fine structure (XAFS) spectroscopy, indicating the formation of Mo-SAs anchored with one nitrogen atom and two carbon atoms (Mo 1 N 1 C 2 ). Importantly, the Mo 1 N 1 C 2 catalyst displayed much more excellent activity compared with Mo 2 C and MoN, and better stability than commercial Pt/C. Density functional theory (DFT) calculation revealed that the unique structure of Mo 1 N 1 C 2 moiety played a crucial effect to improve the HER performance. This work opens up new opportunities for the preparation and application of highly active and stable Mo-based HER catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tuning the Selectivity of Catalytic Carbon Dioxide Hydrogenation over Iridium/Cerium Oxide Catalysts with a Strong Metal-Support Interaction.

PubMed

Li, Siwei; Xu, Yao; Chen, Yifu; Li, Weizhen; Lin, Lili; Li, Mengzhu; Deng, Yuchen; Wang, Xiaoping; Ge, Binghui; Yang, Ce; Yao, Siyu; Xie, Jinglin; Li, Yongwang; Liu, Xi; Ma, Ding

2017-08-28

A one-step ligand-free method based on an adsorption-precipitation process was developed to fabricate iridium/cerium oxide (Ir/CeO 2 ) nanocatalysts. Ir species demonstrated a strong metal-support interaction (SMSI) with the CeO 2 substrate. The chemical state of Ir could be finely tuned by altering the loading of the metal. In the carbon dioxide (CO 2 ) hydrogenation reaction it was shown that the chemical state of Ir species-induced by a SMSI-has a major impact on the reaction selectivity. Direct evidence is provided indicating that a single-site catalyst is not a prerequisite for inhibition of methanation and sole production of carbon monoxide (CO) in CO 2 hydrogenation. Instead, modulation of the chemical state of metal species by a strong metal-support interaction is more important for regulation of the observed selectivity (metallic Ir particles select for methane while partially oxidized Ir species select for CO production). The study provides insight into heterogeneous catalysts at nano, sub-nano, and atomic scales. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Commercial-scale demonstration of the Liquid Phase Methanol (LPMEOH{trademark}) process. Technical progress report number 9, July 1--September 30, 1996

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

The Liquid Phase Methanol (LPMEOH{trademark}) Demonstration Project at Kingsport, Tennessee, is a $213.7 million cooperative agreement between the US Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership). The LPMEOH{trademark} Process Demonstration Unit is being built at a site located at the Eastman Chemical Company (Eastman) complex in Kingsport. The project involves the construction of an 80,000 gallons per day (260 tons per day (TPD)) methanol unit utilizing coal-derived synthesis gas from Eastman`s integrated coal gasification facility. The new equipment consists of synthesis gas feed preparation and compression facilities, the liquid phase reactor and auxiliaries,more » product distillation facilities, and utilities. This liquid phase process suspends fine catalyst particles in an inert liquid, forming a slurry. The slurry dissipates the heat of the chemical reaction away from the catalyst surface, protecting the catalyst and allowing the methanol synthesis reaction to proceed at higher rates. At the Eastman complex, the technology is being integrated with existing coal-gasifiers.« less

Chemicals from ethanol: the acetone synthesis from ethanol employing Ce0.75Zr0.25O2, ZrO2 and Cu/ZnO/Al2O3.

PubMed

Rodrigues, Clarissa Perdomo; Zonetti, Priscila da Costa; Appel, Lucia Gorenstin

2017-04-04

Acetone is an important solvent and widely used in the synthesis of drugs and polymers. Currently, acetone is mainly generated by the Cumene Process, which employs benzene and propylene as fossil raw materials. Phenol is a co-product of this synthesis. However, this ketone can be generated from ethanol (a renewable feedstock) in one-step. The aim of this work is to describe the influence of physical-chemical properties of three different catalysts on each step of this reaction. Furthermore, contribute to improve the description of the mechanism of this synthesis. The acetone synthesis from ethanol was studied employing Cu/ZnO/Al 2 O 3 , Ce 0.75 Zr 0.25 O 2 and ZrO 2 . It was verified that the acidity of the catalysts needs fine-tuning in order to promote the oxygenate species adsorption and avoid the dehydration of ethanol. The higher the reducibility and the H 2 O dissociation activity of the catalysts are, the higher the selectivity to acetone is. In relation to the oxides, these properties are associated with the presence of O vacancies. The H 2 generation, which occurs during the TPSR, indicates the redox character of this synthesis. The main steps of the acetone synthesis from ethanol are the generation of acetaldehyde, the oxidation of this aldehyde to acetate species (which reduces the catalyst), the H 2 O dissociation, the oxidation of the catalyst producing H 2 , and, finally, the ketonization reaction. These pieces of information will support the development of active catalysts for not only the acetone synthesis from ethanol, but also the isobutene and propylene syntheses in which this ketone is an intermediate. Graphical abstract Acetone from ethanol.

Electrocatalytic performance of fuel cell reactions at low catalyst loading and high mass transport.

PubMed

Zalitis, Christopher M; Kramer, Denis; Kucernak, Anthony R

2013-03-28

An alternative approach to the rotating disk electrode (RDE) for characterising fuel cell electrocatalysts is presented. The approach combines high mass transport with a flat, uniform, and homogeneous catalyst deposition process, well suited for studying intrinsic catalyst properties at realistic operating conditions of a polymer electrolyte fuel cell (PEFC). Uniform catalyst layers were produced with loadings as low as 0.16 μgPt cm(-2) and thicknesses as low as 200 nm. Such ultra thin catalyst layers are considered advantageous to minimize internal resistances and mass transport limitations. Geometric current densities as high as 5.7 A cm(-2)Geo were experimentally achieved at a loading of 10.15 μgPt cm(-2) for the hydrogen oxidation reaction (HOR) at room temperature, which is three orders of magnitude higher than current densities achievable with the RDE. Modelling of the associated diffusion field suggests that such high performance is enabled by fast lateral diffusion within the electrode. The electrodes operate over a wide potential range with insignificant mass transport losses, allowing the study of the ORR at high overpotentials. Electrodes produced a specific current density of 31 ± 9 mA cm(-2)Spec at a potential of 0.65 V vs. RHE for the oxygen reduction reaction (ORR) and 600 ± 60 mA cm(-2)Spec for the peak potential of the HOR. The mass activity of a commercial 60 wt% Pt/C catalyst towards the ORR was found to exceed a range of literature PEFC mass activities across the entire potential range. The HOR also revealed fine structure in the limiting current range and an asymptotic current decay for potentials above 0.36 V. These characteristics are not visible with techniques limited by mass transport in aqueous media such as the RDE.

An XAS experimental approach to study low Pt content electrocatalysts operating in PEM fuel cells.

PubMed

Principi, Emiliano; Witkowska, Agnieszka; Dsoke, Sonia; Marassi, Roberto; Di Cicco, Andrea

2009-11-21

We present an X-ray absorption spectroscopy (XAS) study of a low Pt content catalyst layer (Pt loading 0.1 mg cm(-2)) operating at the cathode of a proton exchange membrane fuel cell (PEMFC). This catalyst is based on the use of a mesoporous inorganic matrix as a support for the catalyst Pt nanoparticles. Due to the high Pt dilution, in situ measurements of its structural properties by XAS are challenging and suitable experimental strategies must be devised for this purpose. In particular, we show that accurate XAS in situ fluorescence measurements can be obtained using an optimized fuel cell, suitable protocols for alignment of a focused X-ray beam and an appropriate filter for the background signal of the other atomic species contained in the electrodes. Details, advantages and limitations of the XAS technique for in situ measurements are discussed. Analysis of the near-edge XAS and EXAFS (extended X-ray absorption fine structure) data, corroborated by a HRTEM (high-resolution transmission electron microscopy) study, shows that the Pt particles have a local structure compatible with that of bulk Pt (fcc) and coordination numbers match those expected for particles with typical sizes in the 1.5-2.0 nm range. Substantial changes in the oxidation state and in local atomic arrangement of the Pt particles are found for different applied potentials. The catalyst support, containing W atoms, exhibits a partial reduction upon PEMFC activation, thus mimicking the catalyst behavior. This indicates a possible role of the mesoporous matrix in favouring the oxygen reduction reaction (ORR) and stimulates further research on active catalyst supports.

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

NASA Astrophysics Data System (ADS)

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.

Enantioselective and regiodivergent copper-catalyzed conjugate addition of trialkylaluminium reagents to extended nitro-Michael acceptors.

PubMed

Tissot, Matthieu; Müller, Daniel; Belot, Sébastien; Alexakis, Alexandre

2010-06-18

The first highly enantioselective and regiodivergent conjugate addition of trialkylaluminium reagents to nitrodienes and nitroenynes is described. By a design of the substrate and a fine-tuning of the reaction conditions, it is possible to selectively form the 1,4- or 1,6-adduct. The same combination of catalyst, copper source, and a ferrocene-based phosphine ligand afforded enantioselectivities up to 95% and 91%, respectively.

Intensification of biodiesel production from soybean oil and waste cooking oil in the presence of heterogeneous catalyst using high speed homogenizer.

PubMed

Joshi, Saurabh; Gogate, Parag R; Moreira, Paulo F; Giudici, Reinaldo

2017-11-01

In the present work, high speed homogenizer has been used for the intensification of biodiesel synthesis from soybean oil and waste cooking oil (WCO) used as a sustainable feedstock. High acid value waste cooking oil (27mg of KOH/g of oil) was first esterified with methanol using sulphuric acid as catalyst in two stages to bring the acid value to desired value of 1.5mg of KOH/g of oil. Transesterification of soybean oil (directly due to lower acid value) and esterified waste cooking oil was performed in the presence of heterogeneous catalyst (CaO) for the production of biodiesel. Various experiments were performed for understanding the effect of operating parameters viz. molar ratio, catalyst loading, reaction temperature and speed of rotation of the homogenizer. For soybean oil, the maximum biodiesel yield as 84% was obtained with catalyst loading of 3wt% and molar ratio of oil to methanol of 1:10 at 50°C with 12,000rpm as the speed of rotation in 30min. Similarly biodiesel yield of 88% was obtained from waste cooking oil under identical operating conditions except for the catalyst loading which was 1wt%. Significant increase in the rate of biodiesel production with yields from soybean oil as 84% (in 30min) and from WCO as 88% (30min) was established due to the use of high speed homogenizer as compared to the conventional stirring method (requiring 2-3h for obtaining similar biodiesel yield). The observed intensification was attributed to the turbulence caused at microscale and generation of fine emulsions due to the cavitational effects. Overall it can be concluded from this study that high speed homogenizer can be used as an alternate cavitating device to efficiently produce biodiesel in the presence of heterogeneous catalysts. Copyright © 2017 Elsevier B.V. All rights reserved.

Apparatus for photon excited catalysis

NASA Technical Reports Server (NTRS)

Saffren, M. M. (Inventor)

1977-01-01

An apparatus is described for increasing the yield of photonically excited gas phase reactions by extracting excess energy from unstable, excited species by contacting the species with the surface of a finely divided solid.

Interfaces in Heterogeneous Catalysts: Advancing Mechanistic Understanding through Atomic-Scale Measurements.

PubMed

Gao, Wenpei; Hood, Zachary D; Chi, Miaofang

2017-04-18

Developing novel catalysts with high efficiency and selectivity is critical for enabling future clean energy conversion technologies. Interfaces in catalyst systems have long been considered the most critical factor in controlling catalytic reaction mechanisms. Interfaces include not only the catalyst surface but also interfaces within catalyst particles and those formed by constructing heterogeneous catalysts. The atomic and electronic structures of catalytic surfaces govern the kinetics of binding and release of reactant molecules from surface atoms. Interfaces within catalysts are introduced to enhance the intrinsic activity and stability of the catalyst by tuning the surface atomic and chemical structures. Examples include interfaces between the core and shell, twin or domain boundaries, or phase boundaries within single catalyst particles. In supported catalyst nanoparticles (NPs), the interface between the metallic NP and support serves as a critical tuning factor for enhancing catalytic activity. Surface electronic structure can be indirectly tuned and catalytically active sites can be increased through the use of supporting oxides. Tuning interfaces in catalyst systems has been identified as an important strategy in the design of novel catalysts. However, the governing principle of how interfaces contribute to catalyst behavior, especially in terms of interactions with intermediates and their stability during electrochemical operation, are largely unknown. This is mainly due to the evolving nature of such interfaces. Small changes in the structural and chemical configuration of these interfaces may result in altering the catalytic performance. These interfacial arrangements evolve continuously during synthesis, processing, use, and even static operation. A technique that can probe the local atomic and electronic interfacial structures with high precision while monitoring the dynamic interfacial behavior in situ is essential for elucidating the role of interfaces and providing deeper insight for fine-tuning and optimizing catalyst properties. Scanning transmission electron microscopy (STEM) has long been a primary characterization technique used for studying nanomaterials because of its exceptional imaging resolution and simultaneous chemical analysis. Over the past decade, advances in STEM, that is, the commercialization of both aberration correctors and monochromators, have significantly improved the spatial and energy resolution. Imaging atomic structures with subangstrom resolution and identifying chemical species with single-atom sensitivity are now routine for STEM. These advancements have greatly benefitted catalytic research. For example, the roles of lattice strain and surface elemental distribution and their effect on catalytic stability and reactivity have been well documented in bimetallic catalysts. In addition, three-dimensional atomic structures revealed by STEM tomography have been integrated in theoretical modeling for predictive catalyst NP design. Recent developments in stable electronic and mechanical devices have opened opportunities to monitor the evolution of catalysts in operando under synthesis and reaction conditions; high-speed direct electron detectors have achieved sub-millisecond time resolutions and allow for rapid structural and chemical changes to be captured. Investigations of catalysts using these latest microscopy techniques have provided new insights into atomic-level catalytic mechanisms. Further integration of new microscopy methods is expected to provide multidimensional descriptions of interfaces under relevant synthesis and reaction conditions. In this Account, we discuss recent insights on understanding catalyst activity, selectivity, and stability using advanced STEM techniques, with an emphasis on how critical interfaces dictate the performance of precious metal-based heterogeneous catalysts. The role of extended interfacial structures, including those between core and shell, between separate phases and twinned grains, between the catalyst surface and gas, and between metal and support are discussed. We also provide an outlook on how emerging electron microscopy techniques, such as vibrational spectroscopy and electron ptychography, will impact future catalysis research.

Liquid phase methanol LaPorte process development unit: Modification, operation, and support studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

The objectives of the present work can be divided into three parts. The first objective was to develop a best-fit model for the older methanol synthesis catalyst (BASF S3-85) data base. At the time that this work commenced (June 1989), the BASF S3-85 data base contained many rate measurements accumulated over a few years. The newer catalyst (BASF S3-86) data base, at that time, contained only a few observations and did not include a broad range of conditions. Thus, a second objective of this work was to expand the BASF S3-86 data base to include more rate observations over amore » broader range of conditions. Finally, after expansion of the BASF S3-86 data base, the third objective was to develop a rate expression to describe this data base. This would include the application of rate expressions developed for the BASF S3-85 catalyst, as well as new models. (VC)« less

A hierarchical flower-like hollow alumina supported bimetallic AuPd nanoparticle catalyst for enhanced solvent-free ethylbenzene oxidation.

PubMed

Dong, Huijuan; Xie, Renfeng; Yang, Lan; Li, Feng

2018-06-12

Currently, oxidation of alkylaromatics is considered as one of the most crucial chemical technologies to produce high added-value alcohols, ketones and carboxylic acids, due to its significant importance both in fine synthetic chemistry and in the academic field. In this work, a novel hierarchical marigold-like hollow alumina supported bimetallic AuPd nanoparticle catalyst was successfully fabricated and employed for highly efficient solvent-free ethylbenzene oxidation to produce acetophenone with the coexistence of both molecular oxygen and tert-butyl hydroperoxide as the oxidant and the initiator. The as-fabricated bimetallic AuPd nanocatalyst conferred a superior catalytic performance to the corresponding monometallic counterparts and commercial Al2O3 or solid Al2O3 microsphere supported AuPd ones, along with a high acetophenone selectivity of 88.2% at a conversion of 50.9% under mild reaction conditions (120 °C and oxygen pressure of 1.0 MPa), as well as an unprecedentedly high turnover frequency value of 46 768 h-1. Such exceptional efficiency of the catalyst was related to both the significant synergy between the Au-Pd atoms and strong metal-support interactions, and the unique hierarchical micro/nanostructure of the support being beneficial to the close contact of reactants with surface adsorption and reaction sites and easy product diffusion. Moreover, the present bimetallic AuPd catalyst was recyclable and stable. The developed approach is expected to offer exciting opportunities for designing other supported monometallic or bimetallic catalysts with various active components applied in heterogeneous catalysis.

Importance of Low Dimensional CeO x Nanostructures in Pt/CeO x –TiO 2 Catalysts for the Water–Gas Shift Reaction

DOE PAGES

Luo, Si; Barrio, Laura; Nguyen-Phan, Thuy-Duong; ...

2017-03-15

CO 2 and H 2 production from the water–gas shift (WGS) reaction was studied over Pt/CeO x–TiO 2 catalysts with incremental loadings of CeO x, which adopts variations in the local morphology. The lowest loading of CeO x (1 wt % to 0.5 at. %) that is configured in its smallest dimensions exhibited the best WGS activity over larger dimensional structures. We attribute this to several factors including the ultrafine dispersed one-dimensional nanocluster geometry, a large concentration of Ce 3+ and enhanced reducibility of the low loadings. We utilized several in situ experiments to monitor the active state of themore » catalyst during the WGS reaction. X-ray diffraction (XRD) results showed lattice expansion that indicated reduced ceria was prevalent during the WGS reaction. On the surface, Ce 3+ related hydroxyl groups were identified by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The enhanced reducibility of the catalyst with the introduction of ceria was further revealed by H 2-temperature programed reduction (H 2-TPR) and good thermal stability was confirmed by in situ environmental transmission electron microscopy (ETEM). Finally, we also investigated the formation of the low dimensional structures during catalyst preparation, through a two-stage crystal growth of ceria crystallite on TiO 2 nanoparticle: fine crystallites ~1D formed at ~250 °C, followed by crystal growth into 2D chain and 3D particle from 250–400 °C.« less

Structure and function of real catalysts

NASA Astrophysics Data System (ADS)

Klier, K.

1984-11-01

This paper addresses issues such as the relation between the physical and chemical nature of active centers, activation of reactant molecules, mechanisms of catalytic reactions and distribution of promoters in real catalysts which are invariably multicomponent multiphase systems. Interactions among the catalyst components and phases often result in the formation of compounds and defects that do not exist in the separate components. Although such interactions give rise to a great variety of morphologic, chemical, and electronic properties of the real catalysts, they can be controlled, mostly by careful preparation and doping procedures, to the degree that the catalyst displays reproducible activity and selectivity. Most of the examples given in this paper are based on the results from the author's laboratory concerning the activity and selectivity of copper-based catalysts for the hydrogenation of carbon monoxide and carbon dioxide, the water gas shift reaction, and some reactions of amines. Evidence is presented for the interactions between the copper and zinc oxide then analyzed in terms of defect equilibria using models and constants partially known from the literature and adapted for the present system. It is shown on the basis of boundary layer theory for small particles that charge transfer between copper metal particles, also present in the system, and the zinc oxide phase is insignificant. On the other hand, electron equilibria between the solute copper species and the zinc oxide matrix are dictated primarily by intrinsic ionization Cu 0 → Cu + + e - and oxygen vacancy formation. Optical absorption spectroscopy strongly corroborates the theoretical contention that a significant portion of the copper is in electron deficient state, and there is some evidence based on Auger spectroscopy for the presence of Cu + species on the catalyst surface. It is reiterated, as has been proposed before in our earlier work, that these copper species activate substrates such as carbon monoxide or unsaturated hydrocarbons through back-bonding of the copper d-orbitals into the π ∗ orbitals of the substrates. In a paper by D.L. Roberts and G.L. Griffin at this Symposium, additional evidence is presented that the same finely dispersed Cu species are the chemisorption and activation sites for hydrogen. Some significant mechanistic features of carbon monoxide hydrogenation are demonstrated by the enhancement of methanol synthesis rates and carbon-carbon bond formation in the presence of alkali promoters. The nature and concentration of the alkali ions on the catalyst surface determine the outcome of the carbon monoxide hydrogenations in the following way: (i) of all the alkali and alkaline earth promoters, cesium displays the most pronounced effects; (ii) at high temperatures and low hydrogen-to-carbon monoxide ratios, maximum amount of n-propanol and 2-methyl-propanol is observed in the product over the Cs/Cu/ZnO catalysts, consistent with the function of the alkali as base catalysts in aldol condensation of aldehydic or enolic surface intermediates; (iii) at low temperatures and high hydrogen-to-carbon monoxide ratios, cesium enhances methanol synthesis as well as water gas shift rates in water- and CO 2-free synthesis gas, retards the methanol synthesis rate in synthesis gas containing intermediate amounts of water, primarily due to loss of surface area upon cesium doping, and again accelerates the synthesis in water-rich synthesis gas. These latter effects point to a mechanism in which the rate of formation of surface formate is enhanced by cesium in water-free synthesis gas and a rapid removal of surface hydroxyls free sites that activate hydrogen in water-rich synthesis gas. The role of Group VIII metals as promoters of the Cu/ZnO catalysts for low alcohol and hydrocarbon synthesis is represented by the effects of small additions of iron. Product composition is intermediate between that in methanol and Fischer-Tropsch syntheses, with significant amount of low alcohols formed. Characterization of the 1%Fe/Cu/ZnO catalyst by analytical electron microscopy reveals two forms of iron, a fine dispersion in the Cu/ZnO catalyst and metallic particles, suggesting that the alcohol and hydrocarbon products are formed over two different parts of the catalyst. In the concluding remarks it is contended that in many systems the catalytic activity and selectivity is primarily controlled by chemical entities, defects with respect to the pure components, that are induced and stabilized by solid state reactions involving a significant part of the bulk of the catalyst particles. As the various spectroscopic techniques as well as the tools of high resolution and analytical electron microscopy are used in an increasingly refined way for the analysis of real catalysts, it seems inevitable that the traditional art of catalyst preparation will take advantage of the new understanding of catalyst structure and will become a branch of materials science firmly footed in solid state chemistry and physics.

Amine-Functionalized Sugarcane Bagasse: A Renewable Catalyst for Efficient Continuous Flow Knoevenagel Condensation Reaction at Room Temperature.

PubMed

Qiao, Yanhui; Teng, Junjiang; Wang, Shuangfei; Ma, Hao

2017-12-24

A biomass-based catalyst with amine groups (-NH₂), viz., amine-functionalized sugarcane bagasse (SCB-NH₂), was prepared through the amination of sugarcane bagasse (SCB) in a two-step process. The physicochemical properties of the catalyst were characterized through FT-IR, elemental analysis, XRD, TG, and SEM-EDX techniques, which confirmed the -NH₂ group was grafted onto SCB successfully. The catalytic performance of SCB-NH₂ in Knoevenagel condensation reaction was tested in the batch and continuous flow reactions. Significantly, it was found that the catalytic performance of SCB-NH₂ is better in flow system than that in batch system. Moreover, the SCB-NH₂ presented an excellent catalytic activity and stability at the high flow rate. When the flow rate is at the 1.5 mL/min, no obvious deactivation was observed and the product yield and selectivity are more than 97% and 99% after 80 h of continuous reaction time, respectively. After the recovery of solvent from the resulting solution, a white solid was obtained as a target product. As a result, the SCB-NH₂ is a promising catalyst for the synthesis of fine chemicals by Knoevenagel condensation reaction in large scale, and the modification of the renewable SCB with -NH₂ group is a potential avenue for the preparation of amine-functionalized catalytic materials in industry.

Ir/KLTL zeolites: Structural characterization and catalysis on n-hexane reforming

DOE Office of Scientific and Technical Information (OSTI.GOV)

Triantafillou, N.D.; Gates, B.C.

Ir/KLTL zeolite catalysts were prepared by incipient wetness impregnation of LTL zeolites with [Ir(NH{sub 3}){sub 5}Cl]Cl{sub 2}. The catalysts were characterized by extended X-ray absorption fine structure (EX-AFS) spectroscopy, infrared spectroscopy, and H{sub 2} chemisorption. EXAFS data show that the average Ir cluster size (after treatment at 300{degrees}C in H{sub 2}) increased from about 7 to 20 {Angstrom} as the zeolite K:Al atomic ratio increased from 0.34 to 1.56. Infrared spectra of adsorbed CO show that the electron donation to the Ir increased as the K:Al ratio increased. In contrast to the performance reported for Pt/KLTL zeolites with metal clustersmore » as small as those observed in the present experiments, the Ir/KLTL catalyst has a low selectivity for dehydrocyclization of n-hexane at 440-480{degrees}C and 1 atm with a H{sub 2}: n-hexane feed molar ratio of 6. Instead, the catalysts are selective for hydrogenolysis. The selectivity is insensitive to the K:Al ratio, but the activity for dehydrocyclization is a maximum at a K:Al atomic ratio of about 1. The results show that even the smallest Ir clusters to which electron donation is significant still behave essentially like metallic Ir in the catalytic reactions. 49 refs., 4 figs., 7 tabs.« less

[Development ideas of fine pharmaceutical materials of traditional Chinese medicine preparations based on active cluster theory].

PubMed

Ke, Zhong-Cheng; Hou, Xue-Feng; Jia, Xiao-Bin

2016-07-01

The pharmaceutical materials are divided into coarse and fine types in the development of traditional Chinese medicine preparations. Fine materials with clear composition, stable content and high quality control conform to the international development trend of traditional Chinese medicine preparations. In this paper, the status of fine materials was analyzed, and the development ideas were tentatively put forward. On the one hand, the study on simple methods and efficient equipment shall be strengthened for the simultaneous separation of multiple components of traditional Chinese medicine; on the other hand, the knowledge for traditional Chinese medicine shall be broadened to further develop the scientific compatibility of monomers under the guidance of the theory of traditional Chinese medicine. Copyright© by the Chinese Pharmaceutical Association.

Crystal Structural Effect of AuCu Alloy Nanoparticles on Catalytic CO Oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhan, Wangcheng; Wang, Jinglin; Wang, Haifeng

2017-06-07

Controlling the physical and chemical properties of alloy nanoparticles (NPs) is an important approach to optimize NP catalysis. Unlike other tuning knobs, such as size, shape, and composition, crystal structure has received limited attention and not been well understood for its role in catalysis. This deficiency is mainly due to the difficulty in synthesis and fine-tuning of the NPs’ crystal structure. Here, Exemplifying by AuCu alloy NPs with face centered cubic (fcc) and face centered tetragonal (fct) structure, we demonstrate a remarkable difference in phase segregation and catalytic performance depending on the crystal structure. During the thermal treatment in air,more » the Cu component in fcc-AuCu alloy NPs segregates more easily onto the alloy surface as compared to that in fct-AuCu alloy NPs. As a result, after annealing at 250 °C in air for 1 h, the fcc- and fct-AuCu alloy NPs are phase transferred into Au/CuO and AuCu/CuO core/shell structures, respectively. More importantly, this variation in heterostructures introduces a significant difference in CO adsorption on two catalysts, leading to a largely enhanced catalytic activity of AuCu/CuO NP catalyst for CO oxidation. Furthermore, the same concept can be extended to other alloy NPs, making it possible to fine-tune NP catalysis for many different chemical reactions.« less

Preparation of titanium diboride powder

DOEpatents

Brynestad, Jorulf; Bamberger, Carlos E.

1985-01-01

Finely-divided titanium diboride or zirconium diboride powders are formed by reacting gaseous boron trichloride with a material selected from the group consisting of titanium powder, zirconium powder, titanium dichloride powder, titanium trichloride powder, and gaseous titanium trichloride.

Biocatalysis and biomimetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burrington, J.D.; Clark, D.S.

1989-01-01

The proceedings are divided into three parts: Bioscience and biotechnology; Structure-function relationships; and Biomimetics. Topics include: the chemistry of biotechnology, biomimetics, and biocatalysts; crystallography and mutagenesis; computerized simulation of biocatalysis and biomimetic processes; enzymatic reactions in micellar systems; hydroxylation of hydrocarbons; oxidation of lignin; zeolite catalysts as enzyme mimics; and immobilization of proteins and enzymes. Some papers have been processed separately for inclusion on the data base.

From Forty-to-One to One-to-One: Eliminating the Digital Divide and Making Equity Actionable

ERIC Educational Resources Information Center

Mucetti, Rosanna

2017-01-01

This article shows how the adoption of technology may serve as a catalyst for deeper, systemic reforms. This article shares a local case of organizational learning in which a midsize California urban school district faithfully acted on a technology goal nested in its strategic plan. Through this experience, the school district demonstrated various…

Process for preparing fine grain silicon carbide powder

DOEpatents

Wei, G.C.

Finely divided silicon carbide powder is obtained by mixing colloidal silica and unreacted phenolic resin in either acetone or methanol, evaporating solvent from the obtained solution to form a gel, drying and calcining the gel to polymerize the phenolic resin therein, pyrolyzing the dried and calcined gel at a temperature in the range of 500 to 1000/sup 0/C, and reacting silicon and carbon in the pyrolyzed gel at a temperature in the range of 1550 to 1700/sup 0/C to form the powder.

Process for preparing fine grain titanium carbide powder

DOEpatents

Janney, M.A.

1985-03-12

A method for preparing finely divided titanium carbide powder in which an organotitanate is reacted with a carbon precursor polymer to provide an admixture of the titanium and the polymer at a molecular level due to a crosslinking reaction between the organotitanate and the polymer. The resulting gel is dried, pyrolyzed to drive off volatile components and provide carbon. The resulting solids are then heated at an elevated temperature to convert the titanium and carbon to high-purity titanium carbide powder in a submicron size range.

Process for preparing fine grain titanium carbide powder

DOEpatents

Janey, Mark A.

1986-01-01

A method for preparing finely divided titanium carbide powder in which an organotitanate is reacted with a carbon precursor polymer to provide an admixture of the titanium and the polymer at a molecular-level due to a crosslinking reaction between the organotitanate and the polymer. The resulting gel is dried, pyrolyzed to drive off volatile components and provide carbon. The resulting solids are then heated at an elevated temperature to convert the titanium and carbon to high-purity titanium carbide powder in a submicron size range.

Silicon drift detectors as a tool for time-resolved fluorescence XAFS on low-concentrated samples in catalysis.

PubMed

Kappen, Peter; Tröger, Larc; Materlik, Gerhard; Reckleben, Christian; Hansen, Karsten; Grunwaldt, Jan-Dierk; Clausen, Bjerne S

2002-07-01

A silicon drift detector (SDD) was used for ex situ and time-resolved in situ fluorescence X-ray absorption fine structure (XAFS) on low-concentrated catalyst samples. For a single-element and a seven-element SDD the energy resolution and the peak-to-background ratio were verified at high count rates, sufficient for fluorescence XAFS. An experimental set-up including the seven-element SDD without any cooling and an in situ cell with gas supply and on-line gas analysis was developed. With this set-up the reduction and oxidation of a zeolite supported catalyst containing 0.3 wt% platinum was followed by fluorescence near-edge scans with a time resolution of 10 min each. From ex situ experiments on low-concentrated platinum- and gold-based catalysts fluorescence XAFS scans could be obtained with sufficient statistical quality for a quantitative analysis. Structural information on the gold and platinum particles could be extracted by both the Fourier transforms and the near-edge region of the XAFS spectra. Moreover, it was found that with the seven-element SDD concentrations of the element of interest as low as 100 ppm can be examined by fluorescence XAFS.

In situ X-ray absorption fine structure analysis of redox reactions of nickel species with variable particle sizes supported on silica

NASA Astrophysics Data System (ADS)

Yamamoto, Yusaku; Suzuki, Atsushi; Tsutsumi, Naoki; Katagiri, Masaki; Yamashita, Shohei; Niwa, Yasuhiro; Katayama, Misaki; Inada, Yasuhiro

2018-02-01

The chemical states of Ni species were systematically investigated using an in situ XAFS technique for a series of SiO2-supported Ni catalysts with different Ni particle sizes. The Ni particles were refined by varying the Ni loading in the range between 0.10 and 5 wt% and by adding citric acid into the precursor solution. An in situ observation cell for fluorescence-yield XAFS measurements was developed for the dilute Ni catalysts. The chemical state of the supported Ni species converted between Ni(0) and NiO, and no other stable species were formed during the temperature-programmed oxidation and reduction processes. Refinement of the Ni particles resulted in decreasing the oxidation temperature and increasing the reduction temperature. These shifts were explained by the affinity of NiO to SiO2, and more effective stabilization was thus anticipated for flattened small NiO particles with an increased contact area. In addition, the inhomogeneous distribution of small Ni particles observed for dilute catalysts was explained in terms of the precursor solution volume when nuclei of the precursor compound precipitated on SiO2 during the drying process.

Catalysis, nanostructure and macroscopic property triangle in bioactive calcium-containing ceramic systems.

PubMed

Meiszterics, Anikó; Havancsák, Károly; Sinkó, Katalin

2013-04-01

Calcium silicate ceramics are intended for application as long-term implant materials. In the present work, attention was paid to understand the correlations between the nanostructure (aggregate size, crystallinity, porosity) and the macroscopic properties (solubility in water and simulated body fluids, SBF; hardness) varying the chemical composition. Varying the catalyst (from a base to various acids) during the chemical synthesis was shown to significantly impact on the pore size, crystallinity and mechanical properties. The basic catalyst yields the ceramics with the highest mechanical strength. Ammonia used in 1.0 or 10.0 molar ratio results in bulk ceramics with parameters required for a biomedical application, good hardness (180-200 HV) and low solubility (1-3%) in water and in SBF. The fine porosity (~50 nm) and homogeneous amorphous structure induce good mechanical character. Copyright © 2012 Elsevier B.V. All rights reserved.

Catalysis by metal-organic frameworks: fundamentals and opportunities.

PubMed

Ranocchiari, Marco; van Bokhoven, Jeroen Anton

2011-04-14

Crystalline porous materials are extremely important for developing catalytic systems with high scientific and industrial impact. Metal-organic frameworks (MOFs) show unique potential that still has to be fully exploited. This perspective summarizes the properties of MOFs with the aim to understand what are possible approaches to catalysis with these materials. We categorize three classes of MOF catalysts: (1) those with active site on the framework, (2) those with encapsulated active species, and (3) those with active sites attached through post-synthetic modification. We identify the tunable porosity, the ability to fine tune the structure of the active site and its environment, the presence of multiple active sites, and the opportunity to synthesize structures in which key-lock bonding of substrates occurs as the characteristics that distinguish MOFs from other materials. We experience a unique opportunity to imagine and design heterogeneous catalysts, which might catalyze reactions previously thought impossible.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Dong; Xu, Pinghong; Browning, Nigel D.

The initial steps of rhodium cluster formation from zeolite-supported mononuclear Rh(C2H4)2 complexes in H2 at 373 K and 1 bar were investigated by infrared and extended X-ray absorption fine structure spectroscopies and scanning transmission electron microscopy (STEM). The data show that ethylene ligands on the rhodium react with H2 to give supported rhodium hydrides and trigger the formation of rhodium clusters. STEM provided the first images of the smallest rhodium clusters (Rh2) and their further conversion into larger clusters. The samples were investigated in a plug-flow reactor as catalysts for the conversion of ethylene + H2 in a molar ratiomore » of 4:1 at 1 bar and 298 K, with the results showing how the changes in catalyst structure affect the activity and selectivity; the rhodium clusters are more active for hydrogenation of ethylene than the single-site complexes, which are more selective for dimerization of ethylene to give butenes« less

Highly selective hydrogenation of arenes using nanostructured ruthenium catalysts modified with a carbon–nitrogen matrix

PubMed Central

Cui, Xinjiang; Surkus, Annette-Enrica; Junge, Kathrin; Topf, Christoph; Radnik, Jörg; Kreyenschulte, Carsten; Beller, Matthias

2016-01-01

Selective hydrogenations of (hetero)arenes represent essential processes in the chemical industry, especially for the production of polymer intermediates and a multitude of fine chemicals. Herein, we describe a new type of well-dispersed Ru nanoparticles supported on a nitrogen-doped carbon material obtained from ruthenium chloride and dicyanamide in a facile and scalable method. These novel catalysts are stable and display both excellent activity and selectivity in the hydrogenation of aromatic ethers, phenols as well as other functionalized substrates to the corresponding alicyclic reaction products. Furthermore, reduction of the aromatic core is preferred over hydrogenolysis of the C–O bond in the case of ether substrates. The selective hydrogenation of biomass-derived arenes, such as lignin building blocks, plays a pivotal role in the exploitation of novel sustainable feedstocks for chemical production and represents a notoriously difficult transformation up to now. PMID:27113087

One-pot low-temperature green synthesis of magnetic graphene nanocomposite for the selective reduction of nitrobenzene

NASA Astrophysics Data System (ADS)

Haridas, Vijayasree; Sugunan, Sankaran; Narayanan, Binitha N.

2018-06-01

In the present study, a green one-pot low-temperature method is adopted for the synthesis of a novel magnetic graphene nanocomposite catalyst. Graphene preparation is performed without employing any oxidizing agents or corrosive chemicals, under mild sonication in isopropyl alcohol - water mixture. Monolayered nanoplatelets of graphene are obtained in the green solvent mixture and the composite material is found to be ferromagnetic in nature, obvious from the vibrating sample magnetometric measurements. Fe in the nanocomposite exists in two different forms i.e., α-Fe2O3 and α-FeOOH, as evident from the material characterization results. The graphene nanocomposite is found to be highly efficient in the selective reduction of nitrobenzene to aniline under solvent free reaction conditions and magnetic separation of this fine nanomaterial from the reaction mixture is successfully carried out. The catalyst is efficiently reusable till five repeated cycles.

Influence of support morphology on the bonding of molecules to nanoparticles

PubMed Central

Yim, Chi Ming; Pang, Chi L.; Hermoso, Diego R.; Dover, Coinneach M.; Muryn, Christopher A.; Maccherozzi, Francesco; Dhesi, Sarnjeet S.; Pérez, Rubén; Thornton, Geoff

2015-01-01

Supported metal nanoparticles form the basis of heterogeneous catalysts. Above a certain nanoparticle size, it is generally assumed that adsorbates bond in an identical fashion as on a semiinfinite crystal. This assumption has allowed the database on metal single crystals accumulated over the past 40 years to be used to model heterogeneous catalysts. Using a surface science approach to CO adsorption on supported Pd nanoparticles, we show that this assumption may be flawed. Near-edge X-ray absorption fine structure measurements, isolated to one nanoparticle, show that CO bonds upright on the nanoparticle top facets as expected from single-crystal data. However, the CO lateral registry differs from the single crystal. Our calculations indicate that this is caused by the strain on the nanoparticle, induced by carpet growth across the substrate step edges. This strain also weakens the CO–metal bond, which will reduce the energy barrier for catalytic reactions, including CO oxidation. PMID:26080433

Uric acid-derived Fe3C-containing mesoporous Fe/N/C composite with high activity for oxygen reduction reaction in alkaline medium

NASA Astrophysics Data System (ADS)

Ma, Jun; Xiao, Dejian; Chen, Chang Li; Luo, Qiaomei; Yu, Yue; Zhou, Junhao; Guo, Changding; Li, Kai; Ma, Jie; Zheng, Lirong; Zuo, Xia

2018-02-01

In this work, a category of Fe3C-containing Fe/N/C mesoporous material has been fabricated by carbonizing the mixture of uric acid, Iron (Ⅲ) chloride anhydrous and carbon support (XC-72) under different pyrolysis temperature. Of all these samples, pyrolysis temperature (800 °C) becomes the most crucial factor in forming Fe3C active sites which synergizes with high content of graphitic N to catalyze oxygen reduction reaction (ORR). X-ray absorption fine structure spectroscopy (XAFS) is used to exhibit that the space structure around Fe atoms in the catalyst. This kind of catalyst possesses comparable ORR properties with commercial 20% Pt/C (onset potential is 0 V vs. Ag/AgCl in 0.1 M KOH), the average transfer electron number is 3.84 reflecting the 4-electron process. Moreover, superior stability and methanol tolerance deserve to be mentioned.

Preparation of metal diboride powders

DOEpatents

Brynestad, J.; Bamberger, C.E.

Finely-divided titanium diboride or zirconium diboride powders are formed by reacting gaseous boron trichloride with a material selected from the group of consisting of titanium powder, zirconium powder, titanium dichloride powder, titanium trichloride powder, and gaseous titanium trichloride.

Determination of Structural Parameters from EXAFS (Extended X-Ray Absorption Fine Structure): Application to Solutions and Catalysts.

DTIC Science & Technology

1984-05-23

the disorder was accurately known. Inverse Transform To isolate the EAFS contribution due to a single feature in the Fourier transform, the inverse ...is associated with setting the "fold" components to 27 zero in r-space. An inverse transform (real part) of the major feature of the Fig. 4 Fourier...phase of the resulting inverse transform represents only any differences between the material being studied and the reference. This residual is

Interfacial Cu + promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts

DOE PAGES

Senanayake, S. D.; Pappoe, N. A.; Nguyen-Phan, T. -D.; ...

2016-10-01

We have studied the catalytic carbon monoxide (CO) oxidation (CO+0.5O2 → CO2) reaction using a powder catalyst composed of both copper (5wt% loading) and titania (CuOx-TiO2). Our study was focused on revealing the role of Cu, and the interaction between Cu and TiO2, by systematic comparison between two nanocatalysts, CuOx-TiO2 and pure CuOx. We interrogated these catalysts under in situ conditions using X-ray Diffraction (XRD), X-ray Absorption Fine Structure (XAFS) and Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) to probe the structure and electronic properties of the catalyst at all stages of the reaction and simultaneously probe the surface statesmore » or intermediates of this reaction. With the aid of several ex situ characterization techniques including Transmission Electron Microscopy (TEM), the local catalyst morphology and structure was also studied. Our results show that a CuOx-TiO2 system is more active than bulk CuOx for the CO oxidation reaction due to its lower onset temperature and better stability at higher temperatures. Our results also suggests that a surface Cu+ species observed in the CuOx-TiO2 interface are likely to be a key player in the CO oxidation mechanism, while implicating that the stabilization of this species is probably associated with the oxide-oxide interface. Both in situ DRIFTS and XAFS measurements reveal that there is likely to be a Cu(Ti)-O mixed oxide at this interface. We discuss the nature of this Cu(Ti)-O interface and interpret its role on the CO oxidation reaction.« less

Synthesis and Characterization of CO-and H2S-Tolerant Electrocatalysts for PEM Fuel Cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shamsuddin Ilias

2005-12-22

The present state-of-art Proton Exchange Membrane Fuel Cell (PEMFC) technology is based on platinum (Pt) as a catalyst for both the fuel (anode) and air (cathode) electrodes. This catalyst is highly active but susceptible to poisoning by CO, which may be present in the H{sub 2}-fuel used or may be introduced during the fuel processing. Presence of trace amount of CO and H{sub 2}S in the H{sub 2}-fuel poisons the anode irreversibly and decreases the performance of the PEMFCs. In an effort to reduce the Pt-loading and improve the PEMFC performance, we propose to synthesize a number of Pt-based binary,more » ternary, and quaternary electrocatalysts using Ru, Mo, Ir, Ni, and Co as a substitute for Pt. By fine-tuning the metal loadings and compositions of candidate electrocatalysts, we plan to minimize the cost and optimize the catalyst activity and performance in PEMFC. The feasibility of the novel electrocatalysts will be demonstrated in the proposed effort with gas phase CO and H{sub 2}S concentrations typical of those found in reformed fuel gas with coal/natural gas/methanol feedstocks. During this reporting period we synthesized four Pt-based electrocatalysts catalysts (Pt/Ru/Mo/Se, Pt/Ru/Mo/Ir, Pt/Ru/Mo/W, Ptr/Ru/Mo/Co) on Vulcan XG72 Carbon support by both conventional and ultra-sonication method. From current-voltage performance study, the catalytic activity was found in the increasing order of Pt/Ru/Mo/Ir > Pt/Ru/Mo/W > Pt/Ru/Mo/Co > Pt/Ru/MO/Se. Sonication method appears to provide better dispersion of catalysts on carbon support.« less

Catalyzing the oxidation of sulfamethoxazole by permanganate using molecular sieves supported ruthenium nanoparticles.

PubMed

Zhang, Jing; Sun, Bo; Huang, Yuying; Guan, Xiaohong

2015-12-01

This study developed a heterogeneous catalytic permanganate oxidation system with three molecular sieves, i.e., nanosized ZSM-5 (ZSM-5A), microsized ZSM-5 (ZSM-5B) and MCM-41, supported ruthenium nanoparticles as catalyst, denoted as Ru/ZSM-5A, Ru/ZSM-5B and Ru/MCM-41, respectively. The presence of 0.5gL(-1) Ru/ZSM-5A, Ru/ZSM-5B and Ru/MCM-41 increased the oxidation rate of sulfamethoxazole (SMX) by permanganate at pH 7.0 by 27-1144 times. The catalytic performance of Ru catalysts toward SMX oxidation by permanganate was strongly dependent on Ru loading on the catalysts. The X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses confirmed that Ru catalyst acted as an electron shuttle in catalytic permanganate oxidation process. Ru(III) deposited on the surface of catalysts was oxidized by permanganate to its higher oxidation state Ru(VII), which could work as a co-oxidant with permanganate to decompose SMX and was then reduced to its initial tri-valence. During the successive runs, Ru/ZSM-5A could not maintain its catalytic activity due to the deposition of MnO2, which was the reductive product of permanganate, onto the surface of Ru/ZSM-5A. Thus, the regeneration of partially deactivated Ru catalysts by reductant NH2OH⋅HCl or ascorbic acid was proposed. Ru/ZSM-5A regenerated by NH2OH⋅HCl displayed comparable catalytic ability to its virgin counterpart, while ascorbic acid could not completely remove the deposited MnO2. A trace amount of leaching of Ru into the reaction solution was also observed, which would be ameliorated by improving the preparation conditions in the future study. Copyright © 2015 Elsevier Ltd. All rights reserved.

Catalyst surfaces for the chromous/chromic redox couple

NASA Technical Reports Server (NTRS)

Giner, J. D.; Cahill, K. J. (Inventor)

1981-01-01

An electricity producing cell of the reduction-oxidation (REDOX) type divided into two compartments by a membrane is disclosed. A ferrous/ferric couple in a chloride solution serves as a cathode fluid to produce a positive electric potential. A chromic/chromous couple in a chloride solution serves as an anode fluid to produce a negative potential. The electrode is an electrically conductive, inert material plated with copper, silver or gold. A thin layer of lead plates onto the copper, silver or gold layer when the cell is being charged, the lead ions being available from lead chloride which has been added to the anode fluid. If the REDOX cell is then discharged, the lead deplates from the negative electrode and the metal coating on the electrode acts as a catalyst to increase current density.

Metrology for Fuel Cell Manufacturing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stocker, Michael; Stanfield, Eric

2015-02-04

The project was divided into three subprojects. The first subproject is Fuel Cell Manufacturing Variability and Its Impact on Performance. The objective was to determine if flow field channel dimensional variability has an impact on fuel cell performance. The second subproject is Non-contact Sensor Evaluation for Bipolar Plate Manufacturing Process Control and Smart Assembly of Fuel Cell Stacks. The objective was to enable cost reduction in the manufacture of fuel cell plates by providing a rapid non-contact measurement system for in-line process control. The third subproject is Optical Scatterfield Metrology for Online Catalyst Coating Inspection of PEM Soft Goods. Themore » objective was to evaluate the suitability of Optical Scatterfield Microscopy as a viable measurement tool for in situ process control of catalyst coatings.« less

Small-sized and contacting Pt-WC nanostructures on graphene as highly efficient anode catalysts for direct methanol fuel cells.

PubMed

Wang, Ruihong; Xie, Ying; Shi, Keying; Wang, Jianqiang; Tian, Chungui; Shen, Peikang; Fu, Honggang

2012-06-11

The synergistic effect between Pt and WC is beneficial for methanol electro-oxidation, and makes Pt-WC catalyst a promising anode candidate for the direct methanol fuel cell. This paper reports on the design and synthesis of small-sized and contacting Pt-WC nanostructures on graphene that bring the synergistic effect into full play. Firstly, DFT calculations show the existence of a strong covalent interaction between WC and graphene, which suggests great potential for anchoring WC on graphene with formation of small-sized, well-dispersed WC particles. The calculations also reveal that, when Pt attaches to the pre-existing WC/graphene hybrid, Pt particles preferentially grow on WC rather than graphene. Our experiments confirmed that highly disperse WC nanoparticles (ca. 5 nm) can indeed be anchored on graphene. Also, Pt particles 2-3 nm in size are well dispersed on WC/graphene hybrid and preferentially grow on WC grains, forming contacting Pt-WC nanostructures. These results are consistent with the theoretical findings. X-ray absorption fine structure spectroscopy further confirms the intimate contact between Pt and WC, and demonstrates that the presence of WC can facilitate the crystallinity of Pt particles. This new Pt-WC/graphene catalyst exhibits a high catalytic efficiency toward methanol oxidation, with a mass activity 1.98 and 4.52 times those of commercial PtRu/C and Pt/C catalysts, respectively. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ/operando studies for the production of hydrogen through the water-gas shift on metal oxide catalysts.

PubMed

Rodriguez, José A; Hanson, Jonathan C; Stacchiola, Dario; Senanayake, Sanjaya D

2013-08-07

In this perspective article, we show how a series of in situ techniques {X-ray diffraction (XRD), pair-distribution-function analysis (PDF), X-ray absorption fine structure (XAFS), environmental transmission electron microscopy (ETEM), infrared spectroscopy (IR), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS)} can be combined to perform detailed studies of the structural, electronic and chemical properties of metal oxide catalysts used for the production of hydrogen through the water-gas shift reaction (WGS, CO + H2O → H2 + CO2). Under reaction conditions most WGS catalysts undergo chemical transformations that drastically modify their composition with respect to that obtained during the synthesis process. Experiments of time-resolved in situ XRD, XAFS, and PDF indicate that the active phase of catalysts which combine Cu, Au or Pt with oxides such as ZnO, CeO2, TiO2, CeOx/TiO2 and Fe2O3 essentially involves nanoparticles of the reduced noble metals. The oxide support undergoes partial reduction and is not a simple spectator, facilitating the dissociation of water and in some cases modifying the chemical properties of the supported metal. Therefore, to optimize the performance of these catalysts one must take into consideration the properties of the metal and oxide phases. IR and AP-XPS have been used to study the reaction mechanism for the WGS on metal oxide catalysts. Data of IR spectroscopy indicate that formate species are not necessarily involved in the main reaction path for the water-gas shift on Cu-, Au- and Pt-based catalysts. Thus, a pure redox mechanism or associative mechanisms that involve either carbonate-like (CO3, HCO3) or carboxyl (HOCO) species should be considered. In the last two decades, there have been tremendous advances in our ability to study catalytic materials under reaction conditions and we are moving towards the major goal of fully understanding how the active sites for the production of hydrogen through the WGS actually work.

Reducing carbon dioxide to products

DOEpatents

Cole, Emily Barton; Sivasankar, Narayanappa; Parajuli, Rishi; Keets, Kate A

2014-09-30

A method reducing carbon dioxide to one or more products may include steps (A) to (C). Step (A) may bubble said carbon dioxide into a solution of an electrolyte and a catalyst in a divided electrochemical cell. The divided electrochemical cell may include an anode in a first cell compartment and a cathode in a second cell compartment. The cathode may reduce said carbon dioxide into said products. Step (B) may adjust one or more of (a) a cathode material, (b) a surface morphology of said cathode, (c) said electrolyte, (d) a manner in which said carbon dioxide is bubbled, (e), a pH level of said solution, and (f) an electrical potential of said divided electrochemical cell, to vary at least one of (i) which of said products is produced and (ii) a faradaic yield of said products. Step (C) may separate said products from said solution.

Anodization process produces opaque, reflective coatings on aluminum

NASA Technical Reports Server (NTRS)

1965-01-01

Opaque, reflective coatings are produced on aluminum articles by an anodizing process wherein the anodizing bath contains an aqueous dispersion of finely divided insoluble inorganic compounds. These particles appear as uniformly distributed occlusions in the anodic deposit on the aluminum.

PARTICULATE EMISSION CONTROL

EPA Science Inventory

Particle or particulate matter is defined as any finely divided solid or liquid material, other than uncombined water, emitted to the ambient air as measured by applicable reference methods, or an equivalent or alternative method, or by a test method specified in 40CFR50.

BIO-OIL FROM GUAYULE BAGASSE

USDA-ARS?s Scientific Manuscript database

Guayule, Parthenium argentatum, has recently been commercialized as a domestic source of rubber, primarily sold as latex for circum-allergenic medical applications. Latex extraction leaves ~90% of the crop biomass as a finely-divided, free flowing feedstock suitable for conversion to biofuels. Fast ...

Occupations, U. S. A.

ERIC Educational Resources Information Center

Geneva Area City Schools, OH.

The booklet divides job titles, selected from the Dictionary of Occupational Titles, into 15 career clusters: agribusiness and natural resources, business and office education, communication and media, construction, consumer and home economics, fine arts and humanities, health occupations, hospitality and recreation, manufacturing, marine science,…

Fast coarse-fine locating method for φ-OTDR.

PubMed

Mei, Xuanwei; Pang, Fufei; Liu, Huanhuan; Yu, Guoqin; Shao, Yuying; Qian, Tianyu; Mou, Chengbo; Lv, Longbao; Wang, Tingyun

2018-02-05

We proposed and demonstrated a coarse-fine method to achieve fast locating of external vibration for the phase-sensitive optical time-domain reflectometer (φ-OTDR) sensing system. Firstly, the acquired backscattered traces from heterodyne coherent φ-OTDR systems are spatially divided into a few segments along a sensing fiber for coarse locating, and most of the acquired data can be excluded by comparing the phase difference between the endpoints in adjacent segments. Secondly, the amplitude-based locating is implemented within the target segments for fine locating. By using the proposed coarse-fine locating method, we have numerically and experimentally investigated a distributed vibration sensor based on the heterodyne coherent φ-OTDR system with a 50-km-long sensing fiber. We find that the computation cost of signal processing for locating is significantly reduced in the long-haul sensing fiber, showing a potential application in real-time locating of external vibration.

Nano-Engineered Catalysts for Direct Methanol Fuel Cells

NASA Technical Reports Server (NTRS)

Myung, Nosang; Narayanan, Sekharipuram; Wiberg, Dean

2008-01-01

Nano-engineered catalysts, and a method of fabricating them, have been developed in a continuing effort to improve the performances of direct methanol fuel cells as candidate power sources to supplant primary and secondary batteries in a variety of portable electronic products. In order to realize the potential for high energy densities (as much as 1.5 W h/g) of direct methanol fuel cells, it will be necessary to optimize the chemical compositions and geometric configurations of catalyst layers and electrode structures. High performance can be achieved when catalyst particles and electrode structures have the necessary small feature sizes (typically of the order of nanometers), large surface areas, optimal metal compositions, high porosity, and hydrophobicity. The present method involves electrodeposition of one or more catalytic metal(s) or a catalytic-metal/polytetrafluoroethylene nanocomposite on an alumina nanotemplate. The alumina nanotemplate is then dissolved, leaving the desired metal or metal/polytetrafluoroethylene-composite catalyst layer. Unlike some prior methods of making fine metal catalysts, this method does not involve processing at elevated temperature; all processing can be done at room temperature. In addition, this method involves fewer steps and is more amenable to scaling up for mass production. Alumina nanotemplates are porous alumina membranes that have been fabricated, variously, by anodizing either pure aluminum or aluminum that has been deposited on silicon by electronbeam evaporation. The diameters of the pores (7 to 300 nm), areal densities of pores (as much as 7 x 10(exp 10)sq cm), and lengths of pores (up to about 100 nm) can be tailored by selection of fabrication conditions. In a given case, the catalytic metal, catalytic metal alloy, or catalytic metal/ polytetrafluoroethylene composite is electrodeposited in the pores of the alumina nanotemplate. The dimensions of the pores, together with the electrodeposition conditions, determine the sizes and surface areas of the catalytic particles. Hence, the small features and large surface areas of the porosity translate to the desired small particle size and large surface area of the catalyst (see figure). When polytetrafluoroethylene is included, it is for the purpose of imparting hydrophobicity in order to prevent water from impeding the desired diffusion of gases through the catalyst layer. To incorporate polytetrafluoroethylene into a catalytic-metal/polytetrafluoroethylene nanocomposite, one suspends polytetrafluoroethylene nanoparticles in the electrodeposition solution. The polytetrafluoroethylene content can be varied to obtain the desired degree of hydrophobicity and permeability by gas.

Improvement of Electrochemical Water Oxidation by Fine-Tuning the Structure of Tetradentate N4 Ligands of Molecular Copper Catalysts.

PubMed

Shen, Junyu; Wang, Mei; Gao, Jinsuo; Han, Hongxian; Liu, Hong; Sun, Licheng

2017-11-23

Two copper complexes, [(L1)Cu(OH 2 )](BF 4 ) 2 [1; L1=N,N'-dimethyl-N,N'-bis(pyridin-2-ylmethyl)-1,2-diaminoethane] and [(L2)Cu(OH 2 )](BF 4 ) 2 [2, L2=2,7-bis(2-pyridyl)-3,6-diaza-2,6-octadiene], were prepared as molecular water oxidation catalysts. Complex 1 displayed an overpotential (η) of 1.07 V at 1 mA cm -2 and an observed rate constant (k obs ) of 13.5 s -1 at η 1.0 V in pH 9.0 phosphate buffer solution, whereas 2 exhibited a significantly smaller η (0.70 V) to reach 1 mA cm -2 and a higher k obs (50.4 s -1 ) than 1 under identical test conditions. Additionally, 2 displayed better stability than 1 in controlled potential electrolysis experiments with a faradaic efficiency of 94 % for O 2 evolution at 1.58 V, when a casing tube was used for the Pt cathode. A possible mechanism for 1- and 2-catalyzed O 2 evolution reactions is discussed based on the experimental evidence. These comparative results indicate that fine-tuning the structures of tetradentate N 4 ligands can bring about significant change in the performance of copper complexes for electrochemical water oxidation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Zheng; Li, Zhilin; Institute of Carbon Fibers and Composites, Beijing University of Chemical Technology, Beijing 100029

Graphical abstract: The MWCNT/Ni-B catalyst has been successfully prepared by an electroless deposition process. The Ni-B nanoparticles on the supporter are amorphous and are well-distributed. The catalytic conversion towards hydrogenation of styrene shows excellent catalytic activity of the obtained materials. Highlights: Black-Right-Pointing-Pointer A two-step treatment of MWCNTs enabled the homogeneous growth of Ni-B nanoparticles. Black-Right-Pointing-Pointer Ni-B nanoparticles were amorphous with an average size of 60 nm. Black-Right-Pointing-Pointer There were electron transfer between Ni and B. Black-Right-Pointing-Pointer The catalyst had excellent catalytic activity towards hydrogenation of styrene. -- Abstract: Nickel-boron (Ni-B) nanoparticles supported on multi-walled carbon nanotubes (MWCNTs) were successfully synthesizedmore » through an electroless deposition process using the plating bath with sodium borohydride as a reducing agent. The structural and morphological analyses using field-emission scanning electron microscopy, X-ray diffractometry and high-resolution transmission electron microscopy have shown that the Ni-B nanoparticles deposited on the sidewalls of MWCNTs are fine spheres comprised of amorphous structure with the morphologically unique fine-structure like flowers, and homogenously dispersed with a narrow particle size distribution centered at around 60 nm diameter. The catalytic activity of MWCNT/Ni-B nanoparticles was evaluated with respect to hydrogenation of styrene. The hydrogenation catalyzed by MWCNT-supported Ni-B nanoparticles has been found to make styrene selectively converted into ethylbenzene. The highest conversion reaches 99.8% under proper reaction conditions, which demonstrates the high catalytic activity of MWCNT/Ni-B nanoparticles.« less

SEPARATION OF TECHNETIUM FROM AQUEOUS SOLUTIONS BY COPRECIPITATION WITH MAGNETITE

DOEpatents

Rimshaw, S.J.

1961-10-24

A method of separating technetium in the 4+ oxidation state from an aqueous basic solution containing products of uranium fission is described. The method consists of contacting the solution with finely divided magnetite and recovering a technetium-bearing precipitate. (AEC)

Impact of micro-porous layer on liquid water distribution at the catalyst layer interface and cell performance in a polymer electrolyte membrane fuel cell

NASA Astrophysics Data System (ADS)

Tabe, Yutaka; Aoyama, Yusuke; Kadowaki, Kazumasa; Suzuki, Kengo; Chikahisa, Takemi

2015-08-01

In polymer electrolyte membrane fuel cells, a gas diffusion layer (GDL) with a micro-porous layer (MPL) gives better anti-flooding performance than GDLs without an MPL. To investigate the function and mechanism of the MPL to suppress water flooding, the liquid water distribution at the cathode catalyst layer (CL) surface are observed by a freezing method; in the method liquid water is immobilized in ice form by rapid freezing, followed by disassembling the cell for observations. The ice covered area is quantified by image processing and cells with and without an MPL are compared. The results show that the MPL suppresses water accumulation at the interface due to smaller pore size and finer contact with the CL, and this results in less water flooding. Investigation of ice formed after -10 °C cold start shutdowns and the temporary performance deterioration at ordinary temperatures also indicates a significant influence of the liquid water accumulating at the interface. The importance of the fine contact between CL and MPL, the relative absence of gaps, is demonstrated by a gas diffusion electrode (GDE) which is directly coated with catalyst ink on the surface of the MPL achieving finer contact of the layers.

Multimodal Study of the Speciations and Activities of Supported Pd Catalysts During the Hydrogenation of Ethylene

DOE PAGES

Zhao, Shen; Li, Yuanyuan; Liu, Deyu; ...

2017-08-07

In this paper we describe a multimodal exploration of the atomic structure and chemical state of silica-supported palladium nanocluster catalysts during the hydrogenation of ethylene in operando conditions that variously transform the metallic phases between hydride and carbide speciations. The work exploits a microreactor that allows combined multiprobe investigations by high-resolution transmission electron microscopy (HR-TEM), X-ray absorption fine structure (XAFS), and microbeam IR (μ-IR) analyses on the catalyst under operando conditions. The work specifically explores the reaction processes that mediate the interconversion of hydride and carbide phases of the Pd clusters in consequence to changes made in the composition ofmore » the gas-phase reactant feeds, their stability against coarsening, the reversibility of structural/compositional transformations, and the role that oligomeric/waxy byproducts (here forming under hydrogen-limited reactant compositions) might play in modifying activity. The results provide new insights into structural features of the chemistry/mechanisms of Pd catalysis during the selective hydrogenation of acetylene in ethylene—a process simplified here in the use of binary ethylene/hydrogen mixtures. Finally, these explorations, performed in operando conditions, provide new understandings of structure–activity relationships for Pd catalysis in regimes that actively transmute important attributes of electronic and atomic structures.« less

Single-Atom Catalysts of Precious Metals for Electrochemical Reactions.

PubMed

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.

Energy Level Engineering of MoS2 by Transition-Metal Doping for Accelerating Hydrogen Evolution Reaction.

PubMed

Shi, Yi; Zhou, Yue; Yang, Dong-Rui; Xu, Wei-Xuan; Wang, Chen; Wang, Feng-Bin; Xu, Jing-Juan; Xia, Xing-Hua; Chen, Hong-Yuan

2017-11-01

Water-splitting devices for hydrogen generation through electrolysis (hydrogen evolution reaction, HER) hold great promise for clean energy. However, their practical application relies on the development of inexpensive and efficient catalysts to replace precious platinum catalysts. We previously reported that HER can be largely enhanced through finely tuning the energy level of molybdenum sulfide (MoS 2 ) by hot electron injection from plasmonic gold nanoparticles. Under this inspiration, herein, we propose a strategy to improve the HER performance of MoS 2 by engineering its energy level via direct transition-metal doping. We find that zinc-doped MoS 2 (Zn-MoS 2 ) exhibits superior electrochemical activity toward HER as evidenced by the positively shifted onset potential to -0.13 V vs RHE. A turnover of 15.44 s -1 at 300 mV overpotential is achieved, which by far exceeds the activity of MoS 2 catalysts reported. The large enhancement can be attributed to the synergistic effect of electronic effect (energy level matching) and morphological effect (rich active sites) via thermodynamic and kinetic acceleration, respectively. This design opens up further opportunities for improving electrocatalysts by incorporating promoters, which broadens the understanding toward the optimization of electrocatalytic activity of these unique materials.

Effects of cobalt precursor on pyrolyzed carbon-supported cobalt-polypyrrole as electrocatalyst toward oxygen reduction reaction

PubMed Central

2013-01-01

A series of non-precious metal electrocatalysts, namely pyrolyzed carbon-supported cobalt-polypyrrole, Co-PPy-TsOH/C, are synthesized with various cobalt precursors, including cobalt acetate, cobalt nitrate, cobalt oxalate, and cobalt chloride. The catalytic performance towards oxygen reduction reaction (ORR) is comparatively investigated with electrochemical techniques of cyclic voltammogram, rotating disk electrode and rotating ring-disk electrode. The results are analyzed and discussed employing physiochemical techniques of X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma, elemental analysis, and extended X-ray absorption fine structure. It shows that the cobalt precursor plays an essential role on the synthesis process as well as microstructure and performance of the Co-PPy-TsOH/C catalysts towards ORR. Among the studied Co-PPy-TsOH/C catalysts, that prepared with cobalt acetate exhibits the best ORR performance. The crystallite/particle size of cobalt and its distribution as well as the graphitization degree of carbon in the catalyst greatly affects the catalytic performance of Co-PPy-TsOH/C towards ORR. Metallic cobalt is the main component in the active site in Co-PPy-TsOH/C for catalyzing ORR, but some other elements such as nitrogen are probably involved, too. PMID:24229351

Multimodal Study of the Speciations and Activities of Supported Pd Catalysts During the Hydrogenation of Ethylene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Shen; Li, Yuanyuan; Liu, Deyu

In this paper we describe a multimodal exploration of the atomic structure and chemical state of silica-supported palladium nanocluster catalysts during the hydrogenation of ethylene in operando conditions that variously transform the metallic phases between hydride and carbide speciations. The work exploits a microreactor that allows combined multiprobe investigations by high-resolution transmission electron microscopy (HR-TEM), X-ray absorption fine structure (XAFS), and microbeam IR (μ-IR) analyses on the catalyst under operando conditions. The work specifically explores the reaction processes that mediate the interconversion of hydride and carbide phases of the Pd clusters in consequence to changes made in the composition ofmore » the gas-phase reactant feeds, their stability against coarsening, the reversibility of structural/compositional transformations, and the role that oligomeric/waxy byproducts (here forming under hydrogen-limited reactant compositions) might play in modifying activity. The results provide new insights into structural features of the chemistry/mechanisms of Pd catalysis during the selective hydrogenation of acetylene in ethylene—a process simplified here in the use of binary ethylene/hydrogen mixtures. Finally, these explorations, performed in operando conditions, provide new understandings of structure–activity relationships for Pd catalysis in regimes that actively transmute important attributes of electronic and atomic structures.« less

Catalytic Ethanol Dehydration to Ethylene over Nanocrystalline χ- and γ-Al2O3 Catalysts.

PubMed

Janlamool, Jakrapan; Jongsomjit, Bunjerd

2017-01-01

The study is aimed to investigate the combination of nanocrystalline γ- and χ- alumina that displays the attractive chemical and physical properties for the catalytic dehydration of ethanol. The correlation between the acid density and ethanol conversion was observed. The high acid density apparently results in high catalytic activity, especially for the equally mixed γ- and χ- phase alumina (G50C50). In order to obtain a better understanding on how different catalysts would affect the ethylene yield, one of the most powerful techniques such as X-ray photoelectron spectroscopy (XPS) was performed. Hence, the different O 1s surface atoms can be identified and divided into three types including lattice oxygen (O, 530.7 eV), surface hydroxyl (OH, 532.1 eV) and lattice water (H 2 O, 532.9 eV). It was remarkably found that the large amount of O 1s surface atoms in lattice water can result in increased ethylene yield. In summary, the appearance of metastable χ-alumina structure exhibited better catalytic activity and ethylene yield than γ- alumina. Thus, the introduction of metastable χ- alumina structure into γ- alumina enhanced catalytic activity and ethylene yield. As the result, it was found that the G50C50 catalyst exhibits the ethylene yield (80%) at the lowest reaction temperature ca. 250°C among other catalysts.

Analysis of soybean tissue culture protein dynamics using difference gel electrophoresis

USDA-ARS?s Scientific Manuscript database

Excised hypocotyls from developing soybean (Glycine max (L.) merr. cv. Jack) were cultivated on agar-solidified medium until callus formed. The calli were then propagated in liquid medium until stable, relatively uniform, finely-divided suspension cultures were obtained. Cells were typically transfe...

Attrition Resistant Iron-Based Catalysts For F-T SBCRs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adeyinka A. Adeyiga

2006-01-31

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+ H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. The use of iron-(FE) based catalysts is attractive not only due to their low cost and ready availability, but also due to their high water-gas shift activity which makes it possible to use these catalysts with low H{sub 2}/CO ratios. However, a serious problem withmore » the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment; makes the separation of catalyst from the oil/wax product very difficult, if not impossible; and results in a steady loss of catalyst from the reactor. Under a previous Department of Energy (DOE)/University Research Grant (UCR) grant, Hampton University reported, for the first time, the development of demonstrably attrition-resistant Fe F-T synthesis catalysts having good activity, selectivity, and attrition resistance. These catalysts were prepared by spray drying Fe catalysts with potassium (K), copper (Cu), and silica (SiO{sub 2}) as promoters. SiO{sub 2} was also used as a binder for spray drying. These catalysts were tested for activity and selectivity in a laboratory-scale fixed-bed reactor. Fundamental understanding of attrition is being addressed by incorporating suitable binders into the catalyst recipe. This has resulted in the preparation of a spray dried HPR-43 catalyst having average particle size (aps) of 70 {micro}m with high attrition resistance. This HPR-43 attrition resistant, active and selective catalyst gave 95% CO conversion through 125 hours of testing in a fixed-bed at 270 C, 1.48 MPa, H{sub 2}/CO=0.67 and 2.0 NL/g-cat/h with C{sub 5+} selectivity of >78% and methane selectivity of less than 5% at an {alpha} of 0.9. Research is proposed to enable further development and optimization of these catalysts by (1) better understanding the role and interrelationship of various catalyst composition and preparation parameters on attrition resistance, activity, and selectivity of these catalysts, (2) the presence of sulfide ions on a precipitated iron catalyst, and (3) the effect of water on sulfided iron F-T catalysts for its activity, selectivity, and attrition. Catalyst preparations will be based on spray drying. The research employed, among other measurements, attrition testing and F-T synthesis at high pressure. Catalyst activity and selectivity is evaluated using a small fixed-bed reactor and a continuous stirred tank reactor (CSTR). The catalysts were prepared by co-precipitation, followed by binder addition and spray drying at 250 C in a 1-m-diameter, 2-m-tall spray dryer. The binder silica content was varied from 0 to 20 wt%. The results show that the use of small amounts of precipitated SiO{sub 2} alone in spray-dried Fe catalysts can result in good attrition resistance. All catalysts investigated with SiO2 wt% {le} 12 produced fines less than 10 wt% during the jet cup attrition test, making them suitable for long-term use in a slurry bubble column reactor. Thus, concentration rather than the type of SiO{sub 2} incorporated into catalyst has a more critical impact on catalyst attrition resistance of spray-dried Fe catalysts. Lower amounts of SiO{sub 2} added to a catalyst give higher particle densities and therefore higher attrition resistances. In order to produce a suitable SBCR catalyst, however, the amount of SiO{sub 2} added has to be optimized to provide adequate surface area, particle density, and attrition resistance. Two of the catalysts with precipitated and binder silica were tested in Texas A&M University's CSTR (Autoclave Engineers). The two catalysts were also tested at The Center for Applied Energy Research in Lexington, Kentucky of the University of Kentucky. Spray-dried catalysts with compositions 100 Fe/5 Cu/4.2 K/11 (P) SiO{sub 2} and 100 Fe/5 Cu/4.2 K/1.1 (B) SiO{sub 2} have excellent selectivity characteristics (low methane and high C{sub 5+} yields), but their productivity and stability (deactivation rate) need to be improved. Mechanical integrity (attrition strength) of these two catalysts was markedly dependent upon their morphological features. The attrition strength of the catalyst made out of largely spherical particles (1.1 (B) SiO{sub 2}) was considerably higher than that of the catalyst consisting of irregularly shaped particles (11 (P) SiO{sub 2}).« less

Radial/axial power divider/combiner

NASA Technical Reports Server (NTRS)

Vaddiparty, Yerriah P. (Inventor)

1987-01-01

An electromagnetic power divider/combiner comprises N radial outputs (31) having equal powers and preferably equal phases, and a single axial output (20). A divider structure (1) and a preferably identical combiner structure (2) are broadside coupled across a dielectric substrate (30) containing on one side the network of N radial outputs (31) and on its other side a set of N equispaced stubs (42) which are capacitively coupled through the dielectric substrate (30) to the N radial outputs (31). The divider structure (1) and the combiner structure (2) each comprise a dielectric disk (12, 22, respectively) on which is mounted a set of N radial impedance transformers (14, 24, respectively). Gross axial coupling is determined by the thickness of the dielectric layer (30). Rotating the disks (12, 22) with respect to each other effectuates fine adjustment in the degree of axial coupling.

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

PubMed

Serna, Pedro; Gates, Bruce C

2014-08-19

Recent advances in the synthesis and characterization of small, essentially molecular metal complexes and metal clusters on support surfaces have brought new insights to catalysis and point the way to systematic catalyst design. We summarize recent work unraveling effects of key design variables of site-isolated catalysts: the metal, metal nuclearity, support, and other ligands on the metals, also considering catalysts with separate, complementary functions on supports. The catalysts were synthesized with the goal of structural simplicity and uniformity to facilitate incisive characterization. Thus, they are essentially molecular species bonded to porous supports chosen for their high degree of uniformity; the supports are crystalline aluminosilicates (zeolites) and MgO. The catalytic species are synthesized in reactions of organometallic precursors with the support surfaces; the precursors include M(L)2(acetylacetonate)1-2, with M = Ru, Rh, Ir, or Au and the ligands L = C2H4, CO, or CH3. Os3(CO)12 and Ir4(CO)12 are used as precursors of supported metal clusters, and some such catalysts are made by ship-in-a-bottle syntheses to trap the clusters in zeolite cages. The simplicity and uniformity of the supported catalysts facilitate precise structure determinations, even in reactive atmospheres and during catalysis. The methods of characterizing catalysts in reactive atmospheres include infrared (IR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and nuclear magnetic resonance (NMR) spectroscopies, and complementary methods include density functional theory and atomic-resolution aberration-corrected scanning transmission electron microscopy for imaging of individual metal atoms. IR, NMR, XANES, and microscopy data demonstrate the high degrees of uniformity of well-prepared supported species. The characterizations determine the compositions of surface metal complexes and clusters, including the ligands and the metal-support bonding and structure, which identify the supports as ligands with electron-donor properties that influence reactivity and catalysis. Each of the catalyst design variables has been varied independently, illustrated by mononuclear and tetranuclear iridium on zeolite HY and on MgO and by isostructural rhodium and iridium (diethylene or dicarbonyl) complexes on these supports. The data provide examples resolving the roles of the catalyst design variables and place the catalysis science on a firm foundation of organometallic chemistry linked with surface science. Supported molecular catalysts offer the advantages of characterization in the absence of solvents and with surface-science methods that do not require ultrahigh vacuum. Families of supported metal complexes have been made by replacement of ligands with others from the gas phase. Spectroscopically identified catalytic reaction intermediates help to elucidate catalyst performance and guide design. The methods are illustrated for supported complexes and clusters of rhodium, iridium, osmium, and gold used to catalyze reactions of small molecules that facilitate identification of the ligands present during catalysis: alkene dimerization and hydrogenation, H-D exchange in the reaction of H2 with D2, and CO oxidation. The approach is illustrated with the discovery of a highly active and selective MgO-supported rhodium carbonyl dimer catalyst for hydrogenation of 1,3-butadiene to give butenes.

Synthesis and characterization of a novel porous titanium silicate/g-C{sub 3}N{sub 4} hybrid nanocomposite catalyst for environmental applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adepu, Ajay Kumar; Narayanan, Venkatathri, E-mail: venkatathrin@yahoo.com, E-mail: ajay.kumar553@gmail.com

2016-04-13

Herein we developed a novel porous Titanium silicate/g-C{sub 3}N{sub 4} (TSCN) hybrid composite with a inorganic-organic heterojunction. The synthesized porous TSCN were well characterized by various analytical techniques for structural and chemical properties evaluation. FESEM results shows the growth of finely distributed porous titanium silicate on the surface of the g-C{sub 3}N{sub 4}. Porous TSCN hybrid nanocomposite has a great influence on the electronic and optical properties.

Sugar Blowing-Induced Porous Cobalt Phosphide/Nitrogen-Doped Carbon Nanostructures with Enhanced Electrochemical Oxidation Performance toward Water and Other Small Molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Chengzhou; Fu, Shaofang; Xu, Bo Z.

Finely controlled synthesis of high active and robust nonprecious metal catalysts with excellent catalytic efficiency in oxygen evolution reaction (OER) is extremely vital for making the water splitting process more energy-efficient and economical. Among these noble metal-free catalysts, transition-metal-based nanomaterials are considered as one of the most promising OER catalysts due to their relatively low-cost intrinsic activities, high abundance and diversity in terms of structure and morphology. In this work, we reported a facile sugar-blowing technique and low-temperature phosphorization to generate 3D self-supported metal involved carbon nanostructures, which termed as Co2P@Co/nitrogen-doped carbon (Co2P@Co/N-C). By capitalizing on the 3D porous nanostructuresmore » with high surface area, generously dispersed active sites, the intimate interaction between active sites and 3D N-doped carbon, the resultant Co2P@Co/N-C exhibited satisfying OER performance superior to CoO@Co/N-C, delivering 10 mA cm-2 at overpotential of 0.32 V. It is noting that in contrast to the substantial current density loss of RuO2, Co2P@Co/N-C showed much enhanced catalytic activity during the stability test and the 1.8-fold increase in current density was observed after stability test. Furthermore, the obtained Co2P@Co/N-C can also be served as an excellent nonprecious metal catalyst for methanol and glucose electrooxidation in alkaline media, further extending their potential applications.« less

Facile Fabrication of Composition-Tuned Ru-Ni Bimetallics in Ordered Mesoporous Carbon for Levulinic Acid Hydrogenation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Ying; Gao, Guang; Zhang, Xin

Bimetallic catalysts are of great importance due to their unique catalytic properties. However, their conventional synthesis requires tedious multistep procedures and prolonged synthetic time, and the resulting bimetallics usually disperse unevenly and show poor stability. It is challenging to develop a facile and step-economic synthetic methodology for highly efficient bimetallic catalysts. In this study, we report an elegant metal complex-involved multicomponent assembly route to highly efficient Ru–Ni bimetallics in ordered mesoporous carbons (OMC). The fabrication of composition-tuned Ru–Ni bimetallics in OMC (Ru xNi 1–x–OMC, x = 0.5–0.9) was facilely realized via in situ construction of CTAB-directed cubic Ia3d chitosan-ruthenium–nickel–silica mesophasemore » before pyrolysis and silica removal. The resulting Ru xNi 1–x–OMC materials are in-depth characterized with X-ray diffraction, N 2 adsorption–desorption, transmission electron microscopy, infrared spectrum, and X-ray absorption fine structure. This facile fabrication method renders homogeneously dispersed Ru–Ni bimetallics embedded in the mesoporous carbonaceous framework and creates a highly active and stable Ru 0.9Ni 0.1–OMC catalyst for the hydrogenation of levulinic acid (LA) to prepare γ-valerolactone (GVL), a biomass-derived platform molecule with wide application in the preparation of renewable chemicals and liquid transportation fuels. A high TOF (>2000 h –1) was obtained, and the Ru 0.9Ni 0.1–OMC catalyst could be used at least 15 times without obvious loss of its catalytic performance.« less

Valorization of unauthorized sea disposal dredged sediments as a road foundation material.

PubMed

Achour, Raouf; Abriak, Nor-Edine; Zentar, Rachid; Rivard, Patrice; Gregoire, Pascal

2014-08-01

The main objective of this study is to show the ability of fine dredged material (mainly silty material) to be used in road construction project. This paper is divided into three parts. In the first part, the physical, the mineralogical and the mechanical characteristics of the used fine dredged sediments, as well as their chemical composition and environmental impacts are presented. In the second part, the methodology developed to design the road made from dredged fine sediment is developed. The third part of the paper focuses on the presentation of the road construction and the interpretation of analyses made on cores drilled samples from the road and measurements of the deflection of the road. The environmental assessment, based on leaching tests, is also performed at different issues.

Self-Assembled Fe-N-Doped Carbon Nanotube Aerogels with Single-Atom Catalyst Feature as High-Efficiency Oxygen Reduction Electrocatalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Chengzhou; Fu, Shaofang; Song, Junhua

Finely controlled synthesis of high active and robust non-precious metal catalysts with excellent electrocatalytic efficiency towards oxygen reduction reaction is extremely vital for successful implementation of fuel cells and metal batteries. Unprecedented oxygen reduction reaction electrocatalytic performances and the diversified synthetic procedure in term of favorable structure/morphology characteristics make transition metals-derived M–N–C (M=Fe, Co) structures the most promising nanocatalysts. Herein, using the nitrogen-containing small molecular and inorganic salt as precursors and ultrathin tellurium nanowires as templates, we successfully synthesized a series of well-defined M-N-doped hollow carbon nanowire aerogels through one step hydrothermal route and subsequent facile annealing treatment. Taking advantagemore » of the porous nanostructures, one-dimensional building block as well as homogeneity of active sites, the resultant Fe-N-doped carbon hollow nanowire aerogels exhibited excellent ORR electrocatalytic performance even better than commercial Pt/C in alkaline solution, holding great potential in fuel cell applications.« less

Metallic tin quantum sheets confined in graphene toward high-efficiency carbon dioxide electroreduction

NASA Astrophysics Data System (ADS)

Lei, Fengcai; Liu, Wei; Sun, Yongfu; Xu, Jiaqi; Liu, Katong; Liang, Liang; Yao, Tao; Pan, Bicai; Wei, Shiqiang; Xie, Yi

2016-09-01

Ultrathin metal layers can be highly active carbon dioxide electroreduction catalysts, but may also be prone to oxidation. Here we construct a model of graphene confined ultrathin layers of highly reactive metals, taking the synthetic highly reactive tin quantum sheets confined in graphene as an example. The higher electrochemical active area ensures 9 times larger carbon dioxide adsorption capacity relative to bulk tin, while the highly-conductive graphene favours rate-determining electron transfer from carbon dioxide to its radical anion. The lowered tin-tin coordination numbers, revealed by X-ray absorption fine structure spectroscopy, enable tin quantum sheets confined in graphene to efficiently stabilize the carbon dioxide radical anion, verified by 0.13 volts lowered potential of hydroxyl ion adsorption compared with bulk tin. Hence, the tin quantum sheets confined in graphene show enhanced electrocatalytic activity and stability. This work may provide a promising lead for designing efficient and robust catalysts for electrolytic fuel synthesis.

XAS Investigations of PEM Fuel Cells

NASA Astrophysics Data System (ADS)

Roth, Christina; Ramaker, David E.

Polymer-electrolyte membrane (PEM) fuel cells are still far from an area-wide market launch due in part to long-term stability, reliability and cost issues. A more detailed knowledge of the underlying reaction mechanisms is expected to further their application, as it would allow for the design of tailor-made catalysts. However, this will only be possible by complementing traditional in situ studies on single-crystals in electrochemical cells with more sophisticated metal/electrolyte interfacial studies by novel spectroscopic methodologies, which can provide complementary insights into the behaviour of commercial catalysts under real fuel cell operating conditions. This review will focus on the advances of Xray absorption spectroscopy (XAS) in applied fuel cell research utilizing several examples. XAS enables both the nanoparticle morphology and the adsorbate coverage and binding site to be investigated with just one technique. The latter is possible when complementing the conventional extended X-ray absorption fine structure (EXAFS) analysis with the more novel Δμ XANES approach.

Composite catalyst surfaces: Effect of inert and active heterogeneities on pattern formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baer, M.; Bangia, A.K.; Kevrekidis, I.G.

1996-12-05

Spatiotemporal dynamics in reaction-diffusion systems can be altered through the properties (reactivity, diffusivity) of the medium in which they occur. We construct active heterogeneous media (composite catalytic surfaces with inert as well as active illusions) using microelectronics fabrication techniques and study the spatiotemporal dynamics of heterogeneous catalytic reactions on these catalysts. In parallel, we perform simulations as well as numerical stability and bifurcation analysis of these patterns using mechanistic models. At the limit of large heterogeneity `grain size` (compared to the wavelength of spontaneously arising structures) the interaction patterns with inert or active boundaries dominates (e.g., pinning, transmission, and boundarymore » breakup of spirals, interaction of pulses with corners, `pacemaker` effects). At the opposite limit of very small or very finely distributed heterogeneity, effective behavior is observed (slight modulation of pulses, nearly uniform oscillations, effective spirals). Some representative studies of transitions between the two limits are presented. 48 refs., 11 figs.« less

Epoxy Grout With Silica Thickener

NASA Technical Reports Server (NTRS)

Mcclung, C. E.

1984-01-01

Grout cures quickly, even in presence of hydraulic oil. Grout is mixture of aggregate particles, finely-divided silica, epoxy resin, and triethylenetetramine curing agent, with mixture containing about 85 percent silica and aggregate particle sand 15 percent resin and curing agent. Silica is thickening agent and keeps grout from sagging.

Dispersion-strengthened chromium alloy

NASA Technical Reports Server (NTRS)

Blocker, J. M., Jr.; Veigel, N. D.

1972-01-01

Finely divided powder mixture produced by vapor deposition of CR on small ThO2 particles was hot pressed or pressure bonded. Resulting alloy has lower ductile-to-brittle transition temperature than pure chromium, and high strength and oxidation resistance at elevated temperatures, both in as-rolled condition and after annealing.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vorogushin, M.F.

Principle and experimental analysis of RF power feed system, based on 3 db directional couplers, for undesirable modes eliminating, divided power coupling with the RFQ accelerating structure, endotron type RF power source matching, are presented. The structure fine tuning and the system adjustment results and high-speed RF autocontrol system design are considered also.

Influence of H 2O and H 2S on the composition, activity, and stability of sulfided Mo, CoMo, and NiMo supported on MgAl 2O 4 for hydrodeoxygenation of ethylene glycol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dabros, Trine Marie Hartmann; Gaur, Abhijeet; Pintos, Delfina Garcia

Here in this work, density functional theory (DFT), catalytic activity tests, and in-situ X-ray absorption spectroscopy (XAS) was performed to gain detailed insights into the activity and stability of MoS 2, Ni-MoS 2, and Co-MoS 2 catalysts used for hydrodeoxygenation (HDO) of ethylene glycol upon variation of the partial pressures of H 2O and H 2S. The results show high water tolerance of the catalysts and highlight the importance of promotion and H 2S level during HDO. DFT calculations unraveled that the active edge of MoS 2 could be stabilized against SO exchanges by increasing the partial pressure of Hmore » 2S or by promotion with either Ni or Co. The Mo, NiMo, and CoMo catalysts of the present study were all active and fairly selective for ethylene glycol HDO at 400 °C, 27 bar H 2, and 550–2200 ppm H 2S, and conversions of ≈50–100%. The unpromoted Mo/MgAl 2O 4 catalyst had a lower stability and activity per gram catalyst than the promoted analogues. The NiMo and CoMo catalysts produced ethane, ethylene, and C1 cracking products with a C 2/C 1 ratio of 1.5–2.0 at 550 ppm H 2S. This ratio of HDO to cracking could be increased to ≈2 at 2200 ppm H 2S which also stabilized the activity. Removing H 2S from the feed caused severe catalyst deactivation. Both DFT and catalytic activity tests indicated that increasing the H 2S concentration increased the concentration of SH groups on the catalyst, which correspondingly activated and stabilized the catalytic HDO performance. In-situ XAS further supported that the catalysts were tolerant towards water when exposed to increasing water concentration with H2O/H2S ratios up to 300 at 400–450 °C. Raman spectroscopy and XAS showed that MoS2 was present in the prepared catalysts as small and highly dispersed particles, probably owing to a strong interaction with the support. Linear combination fitting (LCF) analysis of the X-ray absorption near edge structure (XANES) spectra obtained during in-situ sulfidation showed that Ni was sulfided faster than Mo and CoMo, and that Mo was sulfided faster when promoted with Ni. Extended X-ray absorption fine structure (EXAFS) results showed the presence of MoS 2 in all sulfided catalysts. Lastly, sulfided CoMo was present as a mixture of CoMoS and Co 9S 8, whereas sulfided NiMo was present as NiMoS.« less

Influence of H 2O and H 2S on the composition, activity, and stability of sulfided Mo, CoMo, and NiMo supported on MgAl 2O 4 for hydrodeoxygenation of ethylene glycol

DOE PAGES

Dabros, Trine Marie Hartmann; Gaur, Abhijeet; Pintos, Delfina Garcia; ...

2017-12-10

Here in this work, density functional theory (DFT), catalytic activity tests, and in-situ X-ray absorption spectroscopy (XAS) was performed to gain detailed insights into the activity and stability of MoS 2, Ni-MoS 2, and Co-MoS 2 catalysts used for hydrodeoxygenation (HDO) of ethylene glycol upon variation of the partial pressures of H 2O and H 2S. The results show high water tolerance of the catalysts and highlight the importance of promotion and H 2S level during HDO. DFT calculations unraveled that the active edge of MoS 2 could be stabilized against SO exchanges by increasing the partial pressure of Hmore » 2S or by promotion with either Ni or Co. The Mo, NiMo, and CoMo catalysts of the present study were all active and fairly selective for ethylene glycol HDO at 400 °C, 27 bar H 2, and 550–2200 ppm H 2S, and conversions of ≈50–100%. The unpromoted Mo/MgAl 2O 4 catalyst had a lower stability and activity per gram catalyst than the promoted analogues. The NiMo and CoMo catalysts produced ethane, ethylene, and C1 cracking products with a C 2/C 1 ratio of 1.5–2.0 at 550 ppm H 2S. This ratio of HDO to cracking could be increased to ≈2 at 2200 ppm H 2S which also stabilized the activity. Removing H 2S from the feed caused severe catalyst deactivation. Both DFT and catalytic activity tests indicated that increasing the H 2S concentration increased the concentration of SH groups on the catalyst, which correspondingly activated and stabilized the catalytic HDO performance. In-situ XAS further supported that the catalysts were tolerant towards water when exposed to increasing water concentration with H2O/H2S ratios up to 300 at 400–450 °C. Raman spectroscopy and XAS showed that MoS2 was present in the prepared catalysts as small and highly dispersed particles, probably owing to a strong interaction with the support. Linear combination fitting (LCF) analysis of the X-ray absorption near edge structure (XANES) spectra obtained during in-situ sulfidation showed that Ni was sulfided faster than Mo and CoMo, and that Mo was sulfided faster when promoted with Ni. Extended X-ray absorption fine structure (EXAFS) results showed the presence of MoS 2 in all sulfided catalysts. Lastly, sulfided CoMo was present as a mixture of CoMoS and Co 9S 8, whereas sulfided NiMo was present as NiMoS.« less

HIGH STRENGTH CONTROL RODS FOR NEUTRONIC REACTORS

DOEpatents

Lustman, B.; Losco, E.F.; Cohen, I.

1961-07-11

Nuclear reactor control rods comprised of highly compressed and sintered finely divided metal alloy panticles and fine metal oxide panticles substantially uniformly distributed theretbrough are described. The metal alloy consists essentially of silver, indium, cadmium, tin, and aluminum, the amount of each being present in centain percentages by weight. The oxide particles are metal oxides of the metal alloy composition, the amount of oxygen being present in certain percentages by weight and all the oxygen present being substantially in the form of metal oxide. This control rod is characterized by its high strength and resistance to creep at elevated temperatures.

Electronic states of carbon alloy catalysts and nitrogen substituent effects on catalytic activity

NASA Astrophysics Data System (ADS)

Hata, Tomoyuki; Ushiyama, Hiroshi; Yamashita, Koichi

2013-03-01

In recent years, Carbon Alloy Catalysts (CACs) are attracting attention as a candidate for non-platinum-based cathode catalysts in fuel cells. Oxygen reduction reactions at the cathode are divided into two elementary processes, electron transfer and oxygen adsorption. The electron transfer reaction is the rate-determining, and by comparison of energy levels, catalytic activity can be evaluated quantitatively. On the other hand, to begin with, adsorption mechanism is obscure. The purpose of this study is to understand the effect of nitrogen substitution and oxygen adsorption mechanism, by first-principle electronic structure calculations for nitrogen substituted models. To reproduce the elementary processes of oxygen adsorption, we assumed that the initial structures are formed based on the Pauling model, a CACs model and nitrogen substituted CACs models in which various points are replaced with nitrogen. When we try to focus only on the DOS peaks of oxygen, in some substituted model that has high adsorption activity, a characteristic partial occupancy state was found. We conclude that this state will affect the adsorption activity, and discuss on why partially occupied states appear with simplification by using an orbital correlation diagram.

Efficient ammonia synthesis over a Ru/La0.5Ce0.5O1.75 catalyst pre-reduced at high temperature† †Electronic supplementary information (ESI) available: Detailed procedures for each method, catalytic performance, STEM-EDX images, and detailed characterizations. See DOI: 10.1039/c7sc05343f

PubMed Central

Ogura, Yuta; Sato, Katsutoshi; Miyahara, Shin-ichiro; Kawano, Yukiko; Toriyama, Takaaki; Yamamoto, Tomokazu; Matsumura, Syo; Hosokawa, Saburo

2018-01-01

Ammonia is an important feedstock for producing fertiliser and is also a potential energy carrier. However, the process currently used for ammonia synthesis, the Haber–Bosch process, consumes a huge amount of energy; therefore the development of new catalysts for synthesising ammonia at a high rate under mild conditions (low temperature and low pressure) is necessary. Here, we show that Ru/La0.5Ce0.5O1.75 pre-reduced at an unusually high temperature (650 °C) catalysed ammonia synthesis at extremely high rates under mild conditions; specifically, at a reaction temperature of 350 °C, the rates were 13.4, 31.3, and 44.4 mmol g–1 h–1 at 0.1, 1.0, and 3.0 MPa, respectively. Kinetic analysis revealed that this catalyst is free of hydrogen poisoning under the conditions tested. Electron energy loss spectroscopy combined with O2 absorption capacity measurements revealed that the reduced catalyst consisted of fine Ru particles (mean diameter < 2.0 nm) that were partially covered with partially reduced La0.5Ce0.5O1.75 and were dispersed on a thermostable support. Furthermore, Fourier transform infrared spectra measured after N2 addition to the catalyst revealed that N2 adsorption on Ru atoms that interacted directly with the reduced La0.5Ce0.5O1.75 weakened the N 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 N bond and thus promoted its cleavage, which is the rate-determining step for ammonia synthesis. Our results indicate that high-temperature pre-reduction of this catalyst, which consists of Ru supported on a thermostable composite oxide with a cubic fluorite structure and containing reducible cerium, resulted in the formation of many sites that were highly active for N2 reduction by hydrogen. PMID:29719696

Pt/Al{sub 2}O{sub 3} catalysts and Pt-Sn/Al{sub 2}O{sub 3} catalysts prepared by two different methods: Hydrogen pressure effects in the reactions of n-hexane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paal, Z.; Gyory, A.; Uszkurat, I.

Pt-Sn/Al{sub 2}O{sub 3} catalysts were prepared using two different methods, namely, by {open_quotes}traditional{close_quotes} coimpregnation with H{sub 2}PtCl{sub 6} and SnCl{sub 4} and by a {open_quotes}new{close_quotes} method in which the bimetallic complex precursor [Pt(NH{sub 3}){sub 4}] [SnCl{sub 6}] is prepared on the support. Their catalytic activity and selectivity in n-hexane reactions were studied as a function of the hydrogen pressure (60-480 Torr) and compared with those of monometallic Pt/Al{sub 2}O{sub 3} catalysts using H{sub 2}PtCl{sub 6} or [Pt(NH{sub 3}){sub 4}]Cl{sub 2} as Pt precursors. Pt/Al{sub 2}O{sub 3} ex [Pt(NH{sub 3}){sub 4}]Cl{sub 2} showed very low dispersion and exhibited high selectivity inmore » reactions attributed to multiatomic ensembles. The results with bimetallic catalysts can be rationalized in terms of two phases being present, a PtSn alloy phase plus Pt in fine distribution. The {open_quotes}new{close_quotes} Pt-Sn/Al{sub 2}O{sub 3} from the bimetallic precursor contains the two metals in a better dispersion, resulting in a larger number of atomically dispersed surface Pt active sites. This catalyst gave more isomers (and methylcyclopentane) and fewer fragments and less benzene than the {open_quotes}traditional{close_quotes} sample. The {open_quotes}new{close_quotes} Pt-Sn/Al{sub 2}O{sub 3} sample possessed good long-term stability. The {open_quotes}traditional{close_quotes} sample lost some of its activity and its high hydrogenolysis selectivity during long use; i.e., it approached the catalytic properties of the {open_quotes}new{close_quotes} sample. Both samples are potential candidates as catalysts with high isomerizing and low aromatic selectivities (up to 75% isohexanes plus methylcyclopentane as opposed to a maximum of 20%, benzene). The results could be explained sufficiently with a geometric model, electronic interactions playing a less important role in the catalytic phenomena observed. 59 refs., 9 figs., 5 tabs.« less

Native American Biographies. Multicultural Biographies Collection.

ERIC Educational Resources Information Center

Seeley, Virginia, Ed.; And Others

This book, appropriate for secondary students, includes brief biographies of 21 Native Americans of the 20th century. The biographies focus on childhood experiences, cultural heritage, and career goals. The book is divided into four units that feature Native Americans with successful careers in the fields of literature and drama; fine arts and…

7 CFR 330.100 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-01-01

..., DEPARTMENT OF AGRICULTURE FEDERAL PLANT PEST REGULATIONS; GENERAL; PLANT PESTS; SOIL, STONE, AND QUARRY... composing part of the surface of the globe, in distinction from the firm rock, and including the soil and subsoil, as well as finely divided rock and other soil formation materials down to the rock layer. Garbage...

7 CFR 330.100 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-01-01

..., DEPARTMENT OF AGRICULTURE FEDERAL PLANT PEST REGULATIONS; GENERAL; PLANT PESTS; SOIL, STONE, AND QUARRY... composing part of the surface of the globe, in distinction from the firm rock, and including the soil and subsoil, as well as finely divided rock and other soil formation materials down to the rock layer. Garbage...

7 CFR 330.100 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-01-01

..., DEPARTMENT OF AGRICULTURE FEDERAL PLANT PEST REGULATIONS; GENERAL; PLANT PESTS; SOIL, STONE, AND QUARRY... composing part of the surface of the globe, in distinction from the firm rock, and including the soil and subsoil, as well as finely divided rock and other soil formation materials down to the rock layer. Garbage...

7 CFR 330.100 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-01-01

..., DEPARTMENT OF AGRICULTURE FEDERAL PLANT PEST REGULATIONS; GENERAL; PLANT PESTS; SOIL, STONE, AND QUARRY... composing part of the surface of the globe, in distinction from the firm rock, and including the soil and subsoil, as well as finely divided rock and other soil formation materials down to the rock layer. Garbage...

7 CFR 330.100 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-01-01

..., DEPARTMENT OF AGRICULTURE FEDERAL PLANT PEST REGULATIONS; GENERAL; PLANT PESTS; SOIL, STONE, AND QUARRY... composing part of the surface of the globe, in distinction from the firm rock, and including the soil and subsoil, as well as finely divided rock and other soil formation materials down to the rock layer. Garbage...

Special Course on Advances in Cryogenic Wind Tunnel Technology

DTIC Science & Technology

1989-06-09

shatter. However, in the finely divided form of fibres, powders, films, foams and expanded granules they are widely used for thermal and electrical...it is inevitable that the lecture will also have something of the flavour of a research report. 2. Remurements (i) Aerodynamic An important requirement

PRODUCTION OF URANIUM TETRAFLUORIDE

DOEpatents

Shaw, W.E.; Spenceley, R.M.; Teetzel, F.M.

1959-08-01

A method is presented for producing uranium tetrafluoride from the gaseous hexafluoride by feeding the hexafluoride into a high temperature zone obtained by the recombination of molecularly dissociated hydrogen. The molal ratio of hydrogen to uranium hexnfluoride is preferably about 3 to 1. Uranium tetrafluoride is obtained in a finely divided, anhydrous state.

7 CFR 319.37-1 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-01-01

... including the soil and subsoil, as well as finely divided rock and other soil formation materials down to the rock layer. Europe. The continent of Europe, the British Isles, Iceland, the Azores, and the... authority to act in his/her stead has been or may hereafter be delegated. Soil. The loose surface material...

7 CFR 319.37-1 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-01-01

... the globe, in distinction from the firm rock, and including the soil and subsoil, as well as finely divided rock and other soil formation materials down to the rock layer. Europe. The continent of Europe... stead has been or may hereafter be delegated. Soil. The loose surface material of the earth in which...

7 CFR 319.37-1 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-01-01

... including the soil and subsoil, as well as finely divided rock and other soil formation materials down to the rock layer. Europe. The continent of Europe, the British Isles, Iceland, the Azores, and the... authority to act in his/her stead has been or may hereafter be delegated. Soil. The loose surface material...

21 CFR 156.145 - Tomato juice.

Code of Federal Regulations, 2014 CFR

2014-04-01

... be applied by any method which does not add water thereto. Such juice is strained free from peel, seeds, and other coarse or hard substances, but contains finely divided insoluble solids from the flesh... have been concentrated and later reconstituted with water and/or tomato juice to a tomato soluble...

Method for producing UO$sub 2$ loaded refractory metals

DOEpatents

Baker, R.D.; Hayter, S.W.; Lewis, H.D.

1973-12-11

A finely divided dispersion of UO/sub 2/ in tungsten or molybdenum is prepared by co-precipitating the metals from mixed aqueous solution with oxine. The co-precipitate thus formed is separated from the solution, dried, calcined, and finally reduced to UO/sub 2/ and refractory metal. (Official Gazette)

Transport equations in an enzymatic glucose fuel cell

NASA Astrophysics Data System (ADS)

Jariwala, Soham; Krishnamurthy, Balaji

2018-01-01

A mathematical model is developed to study the effects of convective flux and operating temperature on the performance of an enzymatic glucose fuel cell with a membrane. The model assumes isothermal operating conditions and constant feed rate of glucose. The glucose fuel cell domain is divided into five sections, with governing equations describing transport characteristics in each region, namely - anode diffusion layer, anode catalyst layer (enzyme layer), membrane, cathode catalyst layer and cathode diffusion layer. The mass transport is assumed to be one-dimensional and the governing equations are solved numerically. The effects flow rate of glucose feed on the performance of the fuel cell are studied as it contributes significantly to the convective flux. The effects of operating temperature on the performance of a glucose fuel cell are also modeled. The cell performances are compared using cell polarization curves, which were found compliant with experimental observations.

Apparatuses and methods for deoxygenating biomass-derived pyrolysis oil

DOEpatents

Kalnes, Tom N.

2015-12-29

Apparatuses and methods for deoxygenating a biomass-derived pyrolysis oil are provided herein. In one example, the method comprises of dividing a feedstock stream into first and second feedstock portions. The feedstock stream comprises the biomass-derived pyrolysis oil and has a temperature of about 60.degree. C. or less. The first feedstock portion is combined with a heated organic liquid stream to form a first heated diluted pyoil feed stream. The first heated diluted pyoil feed stream is contacted with a first deoxygenating catalyst in the presence of hydrogen to form an intermediate low-oxygen pyoil effluent. The second feedstock portion is combined with the intermediate low-oxygen pyoil effluent to form a second heated diluted pyoil feed stream. The second heated diluted pyoil feed stream is contacted with a second deoxygenating catalyst in the presence of hydrogen to form additional low-oxygen pyoil effluent.

Iridium Ziegler-Type Hydrogenation Catalysts Made from [(1,5-COD)Ir( -O2C8H15)]2 and AlEt3: Spectroscopic and Kinetic Evidence for the Irn Species Present and for Nanoparticles as the Fastest Catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alley, W.; Hamdemir, I; Wang, Q

2010-01-01

Ziegler-type hydrogenation catalysts, those made from a group 8-10 transition metal precatalyst and an AlR{sub 3} cocatalyst, are often used for large scale industrial polymer hydrogenation; note that Ziegler-type hydrogenation catalysts are not the same as Ziegler-Natta polymerization catalysts. A review of prior studies of Ziegler-type hydrogenation catalysts (Alley et al. J. Mol. Catal. A: Chem. 2010, 315, 1-27) reveals that a {approx}50 year old problem is identifying the metal species present before, during, and after Ziegler-type hydrogenation catalysis, and which species are the kinetically best, fastest catalysts-that is, which species are the true hydrogenation catalysts. Also of significant interestmore » is whether what we have termed 'Ziegler nanoclusters' are present and what their relative catalytic activity is. Reported herein is the characterization of an Ir Ziegler-type hydrogenation catalyst, a valuable model (vide infra) for the Co-based industrial Ziegler-type hydrogenation catalyst, made from the crystallographically characterized [(1,5-COD)Ir({mu}-O{sub 2}C{sub 8}H{sub 15})]{sub 2} precatalyst plus AlEt{sub 3}. Characterization of this Ir model system is accomplished before and after catalysis using a battery of physical methods including Z-contrast scanning transmission electron microscopy (STEM), high resolution (HR)TEM, and X-ray absorption fine structure (XAFS) spectroscopy. Kinetic studies plus Hg(0) poisoning experiments are then employed to probe which species are the fastest catalysts. The main findings herein are that (i) a combination of the catalyst precursors [(1,5-COD)Ir({mu}-O{sub 2}C{sub 8}H{sub 15})]{sub 2} and AlEt{sub 3} gives catalytically active solutions containing a broad distribution of Ir{sub n} species ranging from monometallic Ir complexes to nanometer scale, noncrystalline Ir{sub n} nanoclusters (up to Ir{sub {approx}100} by Z-contrast STEM) with the estimated mean Ir species being 0.5-0.7 nm, Ir{sub {approx}4-15} clusters considering the similar, but not identical results from the different analytical methods; furthermore, (ii) the mean Ir{sub n} species are practically the same regardless of the Al/Ir ratio employed, suggesting that the observed changes in catalytic activity at different Al/Ir ratios are primarily the result of changes in the form or function of the Al-derived component (and not due to significant AlEt{sub 3}-induced changes in initial Ir{sub n} nuclearity). However (iii), during hydrogenation, a shift in the population of Ir species toward roughly 1.0-1.6 nm, fcc Ir(0){sub {approx}40-150}, Ziegler nanoclusters occurs with, significantly, (iv) a concomitant increase in catalytic activity. Importantly, and although catalysis by discrete subnanometer Ir species is not ruled out by this study, (v) the increases in activity with increased nanocluster size, plus Hg(0) poisoning studies, provide the best evidence to date that the approximately 1.0-1.6 nm, fcc Ir(0){sub {approx}40-150}, heterogeneous Ziegler nanoclusters are the fastest catalysts in this industrially related catalytic hydrogenation system (and in the simplest, Ockham's Razor interpretation of the data). In addition, (vi) Ziegler nanoclusters are confirmed to be an unusual, hydrocarbon-soluble, highly coordinatively unsaturated, Lewis-acid containing, and highly catalytically active type of nanocluster for use in other catalytic applications and other areas.« less

Fe Isolated Single Atoms on S, N Codoped Carbon by Copolymer Pyrolysis Strategy for Highly Efficient Oxygen Reduction Reaction.

PubMed

Li, Qiheng; Chen, Wenxing; Xiao, Hai; Gong, Yue; Li, Zhi; Zheng, Lirong; Zheng, Xusheng; Yan, Wensheng; Cheong, Weng-Chon; Shen, Rongan; Fu, Ninghua; Gu, Lin; Zhuang, Zhongbin; Chen, Chen; Wang, Dingsheng; Peng, Qing; Li, Jun; Li, Yadong

2018-06-01

Heteroatom-doped Fe-NC catalyst has emerged as one of the most promising candidates to replace noble metal-based catalysts for highly efficient oxygen reduction reaction (ORR). However, delicate controls over their structure parameters to optimize the catalytic efficiency and molecular-level understandings of the catalytic mechanism are still challenging. Herein, a novel pyrrole-thiophene copolymer pyrolysis strategy to synthesize Fe-isolated single atoms on sulfur and nitrogen-codoped carbon (Fe-ISA/SNC) with controllable S, N doping is rationally designed. The catalytic efficiency of Fe-ISA/SNC shows a volcano-type curve with the increase of sulfur doping. The optimized Fe-ISA/SNC exhibits a half-wave potential of 0.896 V (vs reversible hydrogen electrode (RHE)), which is more positive than those of Fe-isolated single atoms on nitrogen codoped carbon (Fe-ISA/NC, 0.839 V), commercial Pt/C (0.841 V), and most reported nonprecious metal catalysts. Fe-ISA/SNC is methanol tolerable and shows negligible activity decay in alkaline condition during 15 000 voltage cycles. X-ray absorption fine structure analysis and density functional theory calculations reveal that the incorporated sulfur engineers the charges on N atoms surrounding the Fe reactive center. The enriched charge facilitates the rate-limiting reductive release of OH* and therefore improved the overall ORR efficiency. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solar fuels generation and molecular systems: is it homogeneous or heterogeneous catalysis?

PubMed

Artero, Vincent; Fontecave, Marc

2013-03-21

Catalysis is a key enabling technology for solar fuel generation. A number of catalytic systems, either molecular/homogeneous or solid/heterogeneous, have been developed during the last few decades for both the reductive and oxidative multi-electron reactions required for fuel production from water or CO(2) as renewable raw materials. While allowing for a fine tuning of the catalytic properties through ligand design, molecular approaches are frequently criticized because of the inherent fragility of the resulting catalysts, when exposed to extreme redox potentials. In a number of cases, it has been clearly established that the true catalytic species is heterogeneous in nature, arising from the transformation of the initial molecular species, which should rather be considered as a pre-catalyst. Whether such a situation is general or not is a matter of debate in the community. In this review, covering water oxidation and reduction catalysts, involving noble and non-noble metal ions, we limit our discussion to the cases in which this issue has been directly and properly addressed as well as those requiring more confirmation. The methodologies proposed for discriminating homogeneous and heterogeneous catalysis are inspired in part by those previously discussed by Finke in the case of homogeneous hydrogenation reaction in organometallic chemistry [J. A. Widegren and R. G. Finke, J. Mol. Catal. A, 2003, 198, 317-341].

Selective Hydrodeoxygenation of Alkyl Lactates to Alkyl Propionates with Fe-based Bimetallic Supported Catalysts.

PubMed

Khokarale, Santosh Govind; He, Jian; Schill, Leonhard; Yang, Song; Riisager, Anders; Saravanamurugan, Shunmugavel

2018-02-22

Hydrodeoxygenation (HDO) of methyl lactate (ML) to methyl propionate (MP) was performed with various base-metal supported catalysts. A high yield of 77 % MP was obtained with bimetallic Fe-Ni/ZrO 2 in methanol at 220 °C and 50 bar H 2 . A synergistic effect of Ni increased the yield of MP significantly when using Fe-Ni/ZrO 2 instead of Fe/ZrO 2 alone. Moreover, the ZrO 2 support contributed to improve the yield as a phase transition of ZrO 2 from tetragonal to monoclinic occurred after metal doping giving rise to fine dispersion of the Fe and Ni on the ZrO 2 , resulting in a higher catalytic activity of the material. Interestingly, it was observed that Fe-Ni/ZrO 2 also effectively catalyzed methanol reforming to produce H 2 in situ, followed by HDO of ML, yielding 60 % MP at 220 °C with 50 bar N 2 instead of H 2 . Fe-Ni/ZrO 2 also catalyzed HDO of other short-chain alkyl lactates to the corresponding alkyl propionates in high yields around 70 %. No loss of activity of Fe-Ni/ZrO 2 occurred in five consecutive reaction runs demonstrating the high durability of the catalyst system. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalysts for selective hydrogenation of furfural derived from the double complex salt [Pd(NH 3 ) 4 ](ReO 4 ) 2 on γ-Al 2 O 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, Simon T.; Lamb, H. Henry

The double complex salt [Pd(NH3)4](ReO4)2 was employed as precursor of supported bimetallic catalysts for selective hydrogenation of furfural. Direct reduction of [Pd(NH3)4](ReO4)2 on γ-Al2O3 in flowing H2 at 400 °C yields bimetallic nanoparticles 1–2 nm in size that exhibit significant interaction between the metals, as evidenced by temperature-programmed hydride decomposition (complete suppression of β-PdHx formation), extended X-ray absorption fine structure spectroscopy at the Pd K and Re LIII edges (PdRe distance = 2.72 Å), and scanning transmission electron microscopy with energy dispersive X-ray analysis. In contrast, calcination of [Pd(NH3)4](ReO4)2 on γ-Al2O3 at 350 °C in air and subsequent reduction inmore » H2 at 400 °C results in metal segregation and formation of large (>50 nm) supported Pd particles; Re species cover the Pd particles and γ-Al2O3 support. A PdRe 1:2 catalyst prepared by sequential impregnation and calcination using HReO4 and [Pd(NH3)4](NO3)2 has a similar morphology. The catalyst derived by direct reduction of [Pd(NH3)4](ReO4)2 on γ-Al2O3 exhibits remarkably high activity for selective hydrogenation of furfural to furfuryl alcohol (FAL) at 150 °C and 1 atm. Suppression of H2 chemisorption via elimination of Pd threefold sites, as evidenced by CO diffuse-reflectance infrared Fourier transform spectroscopy, correlates with increased FAL selectivity.« less

Cobalt Ferrite Bearing Nitrogen-Doped Reduced Graphene Oxide Layers Spatially Separated with Microporous Carbon as Efficient Oxygen Reduction Electrocatalyst.

PubMed

Kashyap, Varchaswal; Singh, Santosh K; Kurungot, Sreekumar

2016-08-17

The present work discloses how high-quality dispersion of fine particles of cobalt ferrite (CF) could be attained on nitrogen-doped reduced graphene oxide (CF/N-rGO) and how this material in association with a microporous carbon phase could deliver significantly enhanced activity toward electrochemical oxygen reduction reaction (ORR). Our study indicates that the microporous carbon phase plays a critical role in spatially separating the layers of CF/N-rGO and in creating a favorable atmosphere to ensure the seamless distribution of the reactants to the active sites located on CF/N-rGO. In terms of the ORR current density, the heat-treated hybrid catalyst at 150 °C (CF/N-rGO-150) is found to be clearly outperforming (7.4 ± 0.5 mA/cm(2)) the state-of-the-art 20 wt % Pt-supported carbon catalyst (PtC) (5.4 ± 0.5 mA/cm(2)). The mass activity and stability of CF-N-rGO-150 are distinctly superior to PtC even after 5000 electrochemical cycles. As a realistic system level exploration of the catalyst, testing of a primary zinc-air battery could be demonstrated using CF/N-rGO-150 as the cathode catalyst. The battery is giving a galvanostatic discharge time of 15 h at a discharge current density of 20 mA/cm(2) and a specific capacity of ∼630 mAh g(-1) in 6 M KOH by using a Zn foil as the anode. Distinctly, the battery performance of this system is found to be superior to that of PtC in less concentrated KOH solution as the electrolyte.

Cobalt-Iron-Manganese Catalysts for the Conversion of End-of-Life-Tire-Derived Syngas into Light Terminal Olefins.

PubMed

Falkenhagen, Jan P; Maisonneuve, Lise; Paalanen, Pasi P; Coste, Nathalie; Malicki, Nicolas; Weckhuysen, Bert M

2018-03-26

Co-Fe-Mn/γ-Al 2 O 3 Fischer-Tropsch synthesis (FTS) catalysts were synthesized, characterized and tested for CO hydrogenation, mimicking end-of-life-tire (ELT)-derived syngas. It was found that an increase of C 2 -C 4 olefin selectivities to 49 % could be reached for 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn/γ-Al 2 O 3 with Na at ambient pressure. Furthermore, by using a 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ-Al 2 O 3 catalyst the selectivity towards the fractions of C 5+ and CH 4 could be reduced, whereas the selectivity towards the fraction of C 4 olefins could be improved to 12.6 % at 10 bar. Moreover, the Na/S ratio influences the ratio of terminal to internal olefins observed as products, that is, a high Na loading prevents the isomerization of primary olefins, which is unwanted if 1,3-butadiene is the target product. Thus, by fine-tuning the addition of promoter elements the volume of waste streams that need to be recycled, treated or upgraded during ELT syngas processing could be reduced. The most promising catalyst (5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ-Al 2 O 3 ) has been investigated using operando transmission X-ray microscopy (TXM) and X-ray diffraction (XRD). It was found that a cobalt-iron alloy was formed, whereas manganese remained in its oxidic phase. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of visible-light-activated metal complexes and their use in photoredox/nickel dual catalysis.

PubMed

Kelly, Christopher B; Patel, Niki R; Primer, David N; Jouffroy, Matthieu; Tellis, John C; Molander, Gary A

2017-03-01

Visible-light-activated photoredox catalysts provide synthetic chemists with the unprecedented capability to harness reactive radicals through discrete, single-electron transfer (SET) events. This protocol describes the synthesis of two transition metal complexes, [Ir{dF(CF 3 ) 2 ppy} 2 (bpy)]PF 6 (1a) and [Ru(bpy) 3 ](PF 6 ) 2 (2a), that are activated by visible light. These photoredox catalysts are SET agents that can be used to facilitate transformations ranging from proton-coupled electron-transfer-mediated cyclizations to C-C bond constructions, dehalogenations, and H-atom abstractions. These photocatalysts have been used in the synthesis of medicinally relevant compounds for drug discovery, as well as the degradation of biological polymers to access fine chemicals. These catalysts are prepared from IrCl 3 and RuCl 3 , respectively, in three chemical steps. These steps can be described as a series of two ligand modifications followed by an anion metathesis. Using the cost-effective, scalable procedures described here, the ruthenium-based photocatalyst 2a can be synthesized in a 78% overall yield (∼8.1 g), and the iridium-based photocatalyst 1a can be prepared in a 56% overall yield (∼4.4 g). The total time necessary for the complete protocols ranges from ∼2 d for 2a to 5-7 d for 1a. Procedures for applying each catalyst in representative photoredox/Ni cross-coupling to form C sp 3-C sp 2 bonds using the appropriate radical precursor-organotrifluoroborates with 1a and bis(catecholato)alkylsilicates with 2a-are described. In addition, more traditional photoredox-mediated transformations are included as diagnostic tests for catalytic activity.

CuI/Pd0 cooperative dual catalysis: tunable stereoselective construction of tetra-substituted alkenes.

PubMed

Vercruysse, Sébastien; Cornelissen, Loïc; Nahra, Fady; Collard, Laurent; Riant, Olivier

2014-02-10

This paper describes a tunable and stereoselective dual catalytic system that uses copper and palladium reagents. This cooperative silylcupration and palladium-catalyzed allylation readily affords trisubstituted alkenylsilanes. Fine-tuning the reaction conditions allows selective access to one stereoisomer over the other. This new methodology tolerates different substituents on both coupling partners with high levels of stereoselectivity. The one-pot reaction involving a Cu(I)/Pd(0) cooperative dual catalyst directly addresses the need to develop more time-efficient and less-wasteful synthetic pathways. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient adsorption and photocatalytic degradation of organic pollutants diluted in water using fluoride-modified hydrophobic mesoporous silica

NASA Astrophysics Data System (ADS)

Yamashita, Hiromi; Maekawa, Kazuhiro; Nakao, Hidetoshi; Anpo, Masakazu

2004-10-01

Using a mixture of tetraethylammonium fluoride and dodecylamine as templates, hydrophobic mesoporous silica supports were prepared. The fine anatase TiO 2 photocatalysts were prepared on the fluoride-modified hydrophobic mesoporous silica and the adsorption properties and the photocatalytic degradation of an aqueous 2-propanol or 2-hexanol solution into CO 2 and H 2O have been studied. The amount of adsorption and the photocatalytic reactivities increased with increasing the content of fluoride ions on these photocatalysts. 2-Hexanol diluted in water was adsorbed on the hydrophobic catalysts more efficiently than 2-propanol.

Fine-Scale Population Estimation by 3D Reconstruction of Urban Residential Buildings

PubMed Central

Wang, Shixin; Tian, Ye; Zhou, Yi; Liu, Wenliang; Lin, Chenxi

2016-01-01

Fine-scale population estimation is essential in emergency response and epidemiological applications as well as urban planning and management. However, representing populations in heterogeneous urban regions with a finer resolution is a challenge. This study aims to obtain fine-scale population distribution based on 3D reconstruction of urban residential buildings with morphological operations using optical high-resolution (HR) images from the Chinese No. 3 Resources Satellite (ZY-3). Specifically, the research area was first divided into three categories when dasymetric mapping was taken into consideration. The results demonstrate that the morphological building index (MBI) yielded better results than built-up presence index (PanTex) in building detection, and the morphological shadow index (MSI) outperformed color invariant indices (CIIT) in shadow extraction and height retrieval. Building extraction and height retrieval were then combined to reconstruct 3D models and to estimate population. Final results show that this approach is effective in fine-scale population estimation, with a mean relative error of 16.46% and an overall Relative Total Absolute Error (RATE) of 0.158. This study gives significant insights into fine-scale population estimation in complicated urban landscapes, when detailed 3D information of buildings is unavailable. PMID:27775670

Method for preparing actinide nitrides

DOEpatents

Bryan, G.H.; Cleveland, J.M.; Heiple, C.R.

1975-12-01

Actinide nitrides, and particularly plutonium and uranium nitrides, are prepared by reacting an ammonia solution of an actinide compound with an ammonia solution of a reactant or reductant metal, to form finely divided actinide nitride precipitate which may then be appropriately separated from the solution. The actinide nitride precipitate is particularly suitable for forming nuclear fuels.

High-resolution solution-state NMR of unfractionated plant cell walls

Treesearch

John Ralph; Fachuang Lu; Hoon Kim; Dino Ress; Daniel J. Yelle; Kenneth E. Hammel; Sally A. Ralph; Bernadette Nanayakkara; Armin Wagner; Takuya Akiyama; Paul F. Schatz; Shawn D. Mansfield; Noritsugu Terashima; Wout Boerjan; Bjorn Sundberg; Mattias Hedenstrom

2009-01-01

Detailed structural studies on the plant cell wall have traditionally been difficult. NMR is one of the preeminent structural tools, but obtaining high-resolution solution-state spectra has typically required fractionation and isolation of components of interest. With recent methods for dissolution of, admittedly, finely divided plant cell wall material, the wall can...

Variable porosity in siliceous skeletons: Determination and importance

USGS Publications Warehouse

Hurd, D.C.; Wenkam, C.; Pankratz, H.S.; Fugate, J.

1979-01-01

Gas adsorption data were used to obtain the specific surface area and specific pore volume for a variety of biogenically precipitated silica semples. The results suggest that this material is finely divided and porous. This interp tation was corroborated by the use of transmission electron microscopy at magnifications up to 180,000. Copyright ?? 1979 AAAS.

DISPERSION HARDENING OF URANIUM METAL

DOEpatents

Arbiter, W.

1963-01-15

A method of hardening U metal involves the forming of a fine dispersion of UO/sub 2/. This method consists of first hydriding the U to form a finely divided powder and then exposing the powder to a very dilute O gas in an inert atmosphere under such pressure and temperature conditions as to cause a thin oxide film to coat each particle of the U hydride, The oxide skin prevents agglomeration of the particles as the remaining H is removed, thus preserving the small particle size. The oxide skin coatings remain as an oxide dispersion. The resulting product may be workhardened to improve its physical characteristics. (AEC)

[The study of ultra-fine diamond powder used in magnetic head polishing slurry].

PubMed

Jin, Hong-Yun; Hou, Shu-En; Pan, Yong; Xiao, Hong-Yan

2008-05-01

In the present paper, atomic absorption spectrometry(AAS), inductively-coupled plasma mass spectrometry (ICP-MS), transmission electron microscopy (TEM), X-ray diffraction (XRD) and laser Raman spectroscopy (RM) were employed to study the commercial ultra-fine diamond powders prepared by the static pressure-catalyst method and used in magnetic head polishing slurry. The results of AAS and ICP-MS indicated that there were silicon oxide, Fe, Ni, Al and some other metal elements in the ultra-fine powders. XRD patterns showed the peaks of SiO2 at 2theta = 35.6 degrees, 39.4 degrees and 59.7 degrees and diamond sharp peaks in agreement with the results above. Diamond sharp peaks implied perfect crystal and high-hardness beneficial to high-efficiency in polishing. The broader Raman band of graphite at 1 592 cm(-1) observed by Raman analysis proved graphite existing in the diamond powders. In the TEM images, the size of ultra-fine powders was estimated between 0.1 and 0.5 microm distributed in a wide scope, however, sharp edges of the powder particles was useful to polish. The ultra-fine diamond powders have many advantages, for example, high-hardness, well abrasion performance, high-polishing efficiency and being useful in magnetic head polishing slurry. But, the impurities influence the polishing efficiency, shortening its service life and the wide distribution reduces the polishing precision. Consequently, before use the powders must be purified and classified. The purity demands is 99.9% and trace silicon oxide under 0.01% should be reached. The classification demands that the particle distribution should be in a narrower scope, with the mean size of 100 nm and the percentage of particles lager than 200 nm not over 2%.

Nano Catalysts for Diesel Engine Emission Remediation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Narula, Chaitanya Kumar; Yang, Xiaofan; Debusk, Melanie Moses

2012-06-01

The objective of this project was to develop durable zeolite nanocatalysts with broader operating temperature windows to treat diesel engine emissions to enable diesel engine based equipment and vehicles to meet future regulatory requirements. A second objective was to improve hydrothermal durability of zeolite catalysts to at least 675 C. The results presented in this report show that we have successfully achieved both objectives. Since it is accepted that the first step in NO{sub x} conversion under SCR (selective catalytic reduction) conditions involves NO oxidation to NO{sub 2}, we reasoned that catalyst modification that can enhance NO oxidation at low-temperaturesmore » should facilitate NO{sub x} reduction at low temperatures. Considering that Cu-ZSM-5 is a more efficient catalyst than Fe-ZSM-5 at low-temperature, we chose to modify Cu-ZSM-5. It is important to point out that the poor low-temperature efficiency of Fe-ZSM-5 has been shown to be due to selective absorption of NH{sub 3} at low-temperatures rather than poor NO oxidation activity. In view of this, we also reasoned that an increased electron density on copper in Cu-ZSM-5 would inhibit any bonding with NH{sub 3} at low-temperatures. In addition to modified Cu-ZSM-5, we synthesized a series of new heterobimetallic zeolites, by incorporating a secondary metal cation M (Sc{sup 3+}, Fe{sup 3+}, In{sup 3+}, and La{sup 3+}) in Cu exchanged ZSM-5, zeolite-beta, and SSZ-13 zeolites under carefully controlled experimental conditions. Characterization by diffuse-reflectance ultra-violet-visible spectroscopy (UV-Vis), X-ray powder diffraction (XRD), extended X-ray absorption fine structure spectroscopy (EXAFS) and electron paramagnetic resonance spectroscopy (EPR) does not permit conclusive structural determination but supports the proposal that M{sup 3+} has been incorporated in the vicinity of Cu(II). The protocols for degreening catalysts, testing under various operating conditions, and accelerated aging conditions were provided by our collaborators at John Deere Power Systems. Among various zeolites reported here, CuFe-SSZ-13 offers the best NO{sub x} conversion activity in 150-650 C range and is hydrothermally stable when tested under accelerated aging conditions. It is important to note that Cu-SSZ-13 is now a commercial catalyst for NO{sub x} treatment on diesel passenger vehicles. Thus, our catalyst performs better than the commercial catalyst under fast SCR conditions. We initially focused on fast SCR tests to enable us to screen catalysts rapidly. Only the catalysts that exhibit high NO{sub x} conversion at low temperatures are selected for screening under varying NO{sub 2}:NO{sub x} ratio. The detailed tests of CuFe-SSZ-13 show that CuFe-SSZ-13 is more effective than commercial Cu-SSZ-13 even at NO{sub 2}:NO{sub x} ratio of 0.1. The mechanistic studies, employing stop-flow diffuse reflectance FTIR spectroscopy (DRIFTS), suggest that high concentration of NO{sup +}, generated by heterobimetallic zeolites, is probably responsible for their superior low temperature NO{sub x} activity. The results described in this report clearly show that we have successfully completed the first step in a new emission treatment catalyst which is synthesis and laboratory testing employing simulated exhaust. The next step in the catalyst development is engine testing. Efforts are in progress to obtain follow-on funding to carry out scale-up and engine testing to facilitate commercialization of this technology.« less

Randomized controlled study of the safety and efficacy of nitrous oxide-sedated endoscopic ultrasound-guided fine needle aspiration for digestive tract diseases.

PubMed

Wang, Cai-Xia; Wang, Jian; Chen, Yuan-Yuan; Wang, Jia-Ni; Yu, Xin; Yang, Feng; Sun, Si-Yu

2016-12-14

To evaluate the efficacy and safety of nitrous oxide-sedated endoscopic ultrasound-guided fine needle aspiration. Enrolled patients were divided randomly into an experimental group (inhalation of nitrous oxide) and a control group (inhalation of pure oxygen) and heart rate, blood oxygen saturation, blood pressure, electrocardiogram (ECG) changes, and the occurrence of complications were monitored and recorded. All patients and physicians completed satisfaction questionnaires about the examination and scored the process using a visual analog scale. There was no significant difference in heart rate, blood oxygen saturation, blood pressure, ECG changes, or complication rate between the two groups of patients ( P > 0.05). However, patient and physician satisfaction were both significantly higher in the nitrous oxide compared with the control group ( P < 0.05). Nitrous oxide-sedation is a safe and effective option for patients undergoing endoscopic ultrasound-guided fine needle aspiration.

The role of water management on the oxygen transport resistance in polymer electrolyte fuel cell with ultra-low precious metal loading

NASA Astrophysics Data System (ADS)

Srouji, A. K.; Zheng, L. J.; Dross, R.; Aaron, D.; Mench, M. M.

2017-10-01

Limiting current measurements are used to evaluate oxygen transport resistance in the catalyst layer of a polymer electrolyte fuel cell (PEFC). The pressure independent oxygen transport resistance in the electrode is quantified for two cell architectures and two cathode Pt loadings (0.4 and 0.07 mgPt.cm-2). The compounded effect of the flow field and Pt loading is used to shed light on the nature of the observed transport resistance, especially its response to fundamentally different flow fields, which is shown to directly or indirectly scale with Pt loading in the open literature. By varying gas pressure and using low oxygen concentrations, the total oxygen transport resistance is divided into intermolecular gas diffusion (a pressure-dependent component) and a pressure independent component, which can be attributed to Knudsen diffusion or dissolution film resistance. The pressure-independent oxygen transport resistance in the catalyst layer varies between 13.3 and 34.4 s/m. It is shown that the pressure independent oxygen transport resistance increases with reduced Pt loading, but that effect is greatly exacerbated by using conventional channel/lands. The results indicate that open metallic element architecture improves the oxygen transport resistance in ultra-low Pt loading electrodes, likely due to enhanced water management at the catalyst layer.

Activating and optimizing MoS 2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies

DOE PAGES

Li, Hong; Tsai, Charlie; Koh, Ai Leen; ...

2015-11-09

As a promising non-precious catalyst for the hydrogen evolution reaction, molybdenum disulphide (MoS 2) is known to contain active edge sites and an inert basal plane. Activating the MoS 2 basal plane could further enhance its HER activity but is not often a strategy for doing so. Herein, we report the first activation and optimization of the basal plane of monolayer 2H-MoS 2 for HER by introducing sulphur (S) vacancies and strain. Our theoretical and experimental results show that the S-vacancies are new catalytic sites in the basal plane, where gap states around the Fermi level allow hydrogen to bindmore » directly to exposed Mo atoms. The hydrogen adsorption free energy (ΔG H) can be further manipulated by straining the surface with S-vacancies, which fine-tunes the catalytic activity. Furthermore, proper combinations of S-vacancy and strain yield the optimal ΔG H = 0 eV, which allows us to achieve the highest intrinsic HER activity among molybdenum-sulphide-based catalysts.« less

Chiral Nickel(II) Complex Catalyzed Enantioselective Doyle-Kirmse Reaction of α-Diazo Pyrazoleamides.

PubMed

Lin, Xiaobin; Tang, Yu; Yang, Wei; Tan, Fei; Lin, Lili; Liu, Xiaohua; Feng, Xiaoming

2018-03-07

Although high enantioselectivity of [2,3]-sigmatropic rearrangement of sulfonium ylides (Doyle-Kirmse reaction) has proven surprisingly elusive using classic chiral Rh(II) and Cu(I) catalysts, in principle it is due to the difficulty in fine discrimination of the heterotopic lone pairs of sulfur and chirality inversion at sulfur of sulfonium ylides. Here, we show that the synergistic merger of new α-diazo pyrazoleamides and a chiral N, N'-dioxide-nickel(II) complex catalyst enables a highly enantioselective Doyle-Kirmse reaction. The pyrazoleamide substituent serves as both an activating and a directing group for the ready formation of a metal-carbene- and Lewis-acid-bonded ylide intermediate in the assistance of a dual-tasking nickel(II) complex. An alternative chiral Lewis-acid-bonded ylide pathway greatly improves the product enantiopurity even for the reaction of a symmetric diallylsulfane. The majority of transformations over a series of aryl- or vinyl-substituted α-diazo pyrazoleamindes and sulfides proceed rapidly (within 5-20 min in most cases) with excellent results (up to 99% yield and 96% ee), providing a breakthrough in enantioselective Doyle-Kirmse reaction.

Graphene-Immobilized fac-Re(bipy)(CO)3Cl for Syngas Generation from Carbon Dioxide.

PubMed

Zhou, Xin; Micheroni, Daniel; Lin, Zekai; Poon, Christopher; Li, Zhong; Lin, Wenbin

2016-02-17

We report the synthesis of fac-M(4-amino-bipy)(CO)3X (M = Mn and X = Br or M = Re and X = Cl, with bipy = 2,2'-bipyridine), their immobilization on graphene oxide (GrO) via diazonium grafting, and the use of Re-functionalized GrO for electrocatalytic syngas production. Infrared (IR) spectroscopy, X-ray absorption fine structure (XAFS) spectroscopy, and electrocatalysis indicated successful grafting of the Re catalyst onto GrO. Re-functionalized GrO was then deposited onto a glassy carbon electrode (GCE) for CO2 reduction. Investigation of the Re-functionalized GCE for syngas production was performed in a CO2-saturated acetonitrile solution with 3.1 M H2O as the proton source and 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF6) as the supporting electrolyte. Cyclic voltammetry (CV), controlled potential electrolysis (CPE), and gas chromatography (GC) were employed to determine its CO2-to-CO conversion performance. The Re catalyst shows a turnover frequency (TOF) for generating CO up to 4.44 s(-1) with a CO/H2 ratio of 7:5.

Sintering of catalytic nanoparticles: particle migration or Ostwald ripening?

PubMed

Hansen, Thomas W; Delariva, Andrew T; Challa, Sivakumar R; Datye, Abhaya K

2013-08-20

Metal nanoparticles contain the active sites in heterogeneous catalysts, which are important for many industrial applications including the production of clean fuels, chemicals 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. This is especially true for high temperature catalytic processes, such as steam reforming, automotive exhaust treatment, or catalytic combustion. With dwindling supplies of precious metals and increasing demand, fundamental understanding of catalyst sintering is very important for achieving clean energy and a clean environment, and for efficient chemical conversion processes with atom selectivity. Scientists have proposed two mechanisms for sintering of nanoparticles: particle migration and coalescence (PMC) and Ostwald ripening (OR). PMC involves the mobility of particles in a Brownian-like motion on the support surface, with subsequent coalescence leading to nanoparticle growth. In contrast, OR involves the migration of adatoms or mobile molecular species, driven by differences in free energy and local adatom concentrations on the support surface. In this Account, we divide the process of sintering into three phases. Phase I involves rapid loss in catalyst activity (or surface area), phase II is where sintering slows down, and phase III is where the catalyst may reach a stable performance. Much of the previous work is based on inferences from catalysts that were observed before and after long term treatments. While the general phenomena can be captured correctly, the mechanisms cannot be determined. Advancements in the techniques of in situ TEM allow us to observe catalysts at elevated temperatures under working conditions. We review recent evidence obtained via in situ methods to determine the relative importance of PMC and OR in each of these phases of catalyst sintering. The evidence suggests that, in phase I, OR is responsible for the rapid loss of activity that occurs when particles are very small. Surprisingly, very little PMC is observed in this phase. Instead, the rapid loss of activity is caused by the disappearance of the smallest particles. These findings are in good agreement with representative atomistic simulations of sintering. In phase II, sintering slows down since the smallest particles have disappeared. We now see a combination of PMC and OR, but do not fully understand the relative contribution of each of these processes to the overall rates of sintering. In phase III, the particles have grown large and other parasitic phenomena, such as support restructuring, can become important, especially at high temperatures. Examining the evolution of particle size and surface area with time, we do not see a stable or equilibrium state, especially for catalysts operating at elevated temperatures. In conclusion, the recent literature, especially on in situ studies, shows that OR is the dominant process causing the growth of nanoparticle size. Consequently, this leads to the loss of surface area and activity. While particle migration could be controlled through suitable structuring of catalyst supports, it is more difficult to control the mobility of atomically dispersed species. These insights into the mechanisms of sintering could help to develop sinter-resistant catalysts, with the ultimate goal of designing catalysts that are self-healing.

Educational Reports That Scale across Users and Data

ERIC Educational Resources Information Center

Rolleston, Rob; Howe, Richard; Sprague, Mary Ann

2015-01-01

The field of education is undergoing fundamental change with the growing use of data. Fine-scale data collection at the item-response level is now possible. Xerox has developed a system that bridges the paper-to-digital divide by providing the well-established and easy-to-use paper interface to students, but digitizes the responses for scoring,…

Calcium silicate insulation structure

DOEpatents

Kollie, Thomas G.; Lauf, Robert J.

1995-01-01

An insulative structure including a powder-filled evacuated casing utilizes a quantity of finely divided synthetic calcium silicate having a relatively high surface area. The resultant structure-provides superior thermal insulating characteristics over a broad temperature range and is particularly well-suited as a panel for a refrigerator or freezer or the insulative barrier for a cooler or a insulated bottle.

MOOCs: A Differentiation by Pedagogy, Content and Assessment

ERIC Educational Resources Information Center

Mohamed, Misrah Hamisah; Hammond, Michael

2018-01-01

Purpose: Massive open online courses (MOOCs) have often been divided between connectivist MOOCs and extended MOOCs (xMOOCs). Each form of MOOC proposes a distinctive view about knowledge acquisition. However, the breakdown between the two MOOCs is too broad in practice, and a more fine-grained approach is needed. Thus, the purpose of this paper is…

Aerosol processing: a wind of innovation in the field of advanced heterogeneous catalysts.

PubMed

Debecker, Damien P; Le Bras, Solène; Boissière, Cédric; Chaumonnot, Alexandra; Sanchez, Clément

2018-06-05

Aerosol processing is long known and implemented industrially to obtain various types of divided materials and nanomaterials. The atomisation of a liquid solution or suspension produces a mist of aerosol droplets which can then be transformed via a diversity of processes including spray-drying, spray pyrolysis, flame spray pyrolysis, thermal decomposition, micronisation, gas atomisation, etc. The attractive technical features of these aerosol processes make them highly interesting for the continuous, large scale, and tailored production of heterogeneous catalysts. Indeed, during aerosol processing, each liquid droplet undergoes well-controlled physical and chemical transformations, allowing for example to dry and aggregate pre-existing solid particles or to synthesise new micro- or nanoparticles from mixtures of molecular or colloidal precursors. In the last two decades, more advanced reactive aerosol processes have emerged as innovative means to synthesise tailored-made nanomaterials with tunable surface properties, textures, compositions, etc. In particular, the "aerosol-assisted sol-gel" process (AASG) has demonstrated tremendous potential for the preparation of high-performance heterogeneous catalysts. The method is mainly based on the low-cost, scalable, and environmentally benign sol-gel chemistry process, often coupled with the evaporation-induced self-assembly (EISA) concept. It allows producing micronic or submicronic, inorganic or hybrid organic-inorganic particles bearing tuneable and calibrated porous structures at different scales. In addition, pre-formed nanoparticles can be easily incorporated or formed in a "one-pot" bottom-up approach within the porous inorganic or hybrid spheres produced by such spray drying method. Thus, multifunctional catalysts with tailored catalytic activities can be prepared in a relatively simple way. This account is an overview of aerosol processed heterogeneous catalysts which demonstrated interesting performance in various relevant chemical reactions like isomerisation, hydrogenation, olefin metathesis, pollutant total oxidation, selective oxidation, CO2 methanation, etc. A short survey of patents and industrial applications is also presented. Our objective is to demonstrate the tremendous possibilities offered by the coupling between bottom up synthesis routes and these aerosol processing technologies which will most probably represent a major route of innovation in the mushrooming field of catalyst preparation research.

Electrochemical trapping of metastable Mn3+ ions for activation of MnO2 oxygen evolution catalysts.

PubMed

Morgan Chan, Zamyla; Kitchaev, Daniil A; Nelson Weker, Johanna; Schnedermann, Christoph; Lim, Kipil; Ceder, Gerbrand; Tumas, William; Toney, Michael F; Nocera, Daniel G

2018-06-05

Electrodeposited manganese oxide films are promising catalysts for promoting the oxygen evolution reaction (OER), especially in acidic solutions. The activity of these catalysts is known to be enhanced by the introduction of Mn 3+ We present in situ electrochemical and X-ray absorption spectroscopic studies, which reveal that Mn 3+ may be introduced into MnO 2 by an electrochemically induced comproportionation reaction with Mn 2+ and that Mn 3+ persists in OER active films. Extended X-ray absorption fine structure (EXAFS) spectra of the Mn 3+ -activated films indicate a decrease in the Mn-O coordination number, and Raman microspectroscopy reveals the presence of distorted Mn-O environments. Computational studies show that Mn 3+ is kinetically trapped in tetrahedral sites and in a fully oxidized structure, consistent with the reduction of coordination number observed in EXAFS. Although in a reduced state, computation shows that Mn 3+ states are stabilized relative to those of oxygen and that the highest occupied molecular orbital (HOMO) is thus dominated by oxygen states. Furthermore, the Mn 3+ (T d ) induces local strain on the oxide sublattice as observed in Raman spectra and results in a reduced gap between the HOMO and the lowest unoccupied molecular orbital (LUMO). The confluence of a reduced HOMO-LUMO gap and oxygen-based HOMO results in the facilitation of OER on the application of anodic potentials to the δ-MnO 2 polymorph incorporating Mn 3+ ions.

Electrochemical Trapping of Metastable Mn3+ Ions for Activation of MnO2 Oxygen Evolution Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tumas, William; Chan, Zamyla Morgan; Kitchaev, Daniil A.

Electrodeposited manganese oxide films are promising catalysts for promoting the oxygen evolution reaction (OER), especially in acidic solutions. The activity of these catalysts is known to be enhanced by the introduction of Mn3+. We present in situ electrochemical and X-ray absorption spectroscopic studies, which reveal that Mn3+ may be introduced into MnO2 by an electrochemically induced comproportionation reaction with Mn2+ and that Mn3+ persists in OER active films. Extended X-ray absorption fine structure (EXAFS) spectra of the Mn3+-activated films indicate a decrease in the Mn-O coordination number, and Raman microspectroscopy reveals the presence of distorted Mn-O environments. Computational studies showmore » that Mn3+ is kinetically trapped in tetrahedral sites and in a fully oxidized structure, consistent with the reduction of coordination number observed in EXAFS. Although in a reduced state, computation shows that Mn3+ states are stabilized relative to those of oxygen and that the highest occupied molecular orbital (HOMO) is thus dominated by oxygen states. Furthermore, the Mn3+(Td) induces local strain on the oxide sublattice as observed in Raman spectra and results in a reduced gap between the HOMO and the lowest unoccupied molecular orbital (LUMO). The confluence of a reduced HOMO-LUMO gap and oxygen-based HOMO results in the facilitation of OER on the application of anodic potentials to the d-MnO2 polymorph incorporating Mn3+ ions.« less

Advance concepts for conversion of syngas to liquids. Quarterly progress report No. 4, July 30, 1995--October 29, 1995

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pei-Shing Eugene Dai; Petty, R.H.; Ingram, C.

Substitution of transition metals for either aluminum and/or phosphorus in the AlPO{sub 4}-11 framework is found to afford novel heterogeneous catalysts for liquid phase hydroxylation of phenol with hydrogen peroxide. AlPO{sub 4}-11 is more active than SAPO-11 and MgAPO-11 for phenol conversion to hydroquinone. The Bronsted acid sites of SAPO-11 and MgAPO-11 may promote the decomposition of hydrogen peroxide to water and oxygen, thus leading to lower phenol conversions. Substitution of divalent and trivalent metal cations, such as Fe, Co and Mn appears to significantly improve the conversion of phenol. The activity follows the order of FeAPO-11>FeMnAPO-11>CoAPO-11>MnAPO-11{much_gt}ALPO{sub 4}-11. FeAPO-11, FeMnAPO-11more » and AlPO{sub 4}-11 give similar product selectivities of about 1:1 hydroquitione (HQ) to catechol (CT). MnAPO-11 and CoAPO-11 favor the production of catechol, particularly at low conversions. FeAPO-11 and TS-1 (titanium silicate with MFI topology) are comparable for the phenol conversions with TS-1 giving higher selectivities toward hydroquinone. The external surfaces of the catalysts plays a significant role in these oxidation reactions. MeAPO molecular sieves may be complementary to the metal silicalite catalysts for the catalytic oxidations in the manufacture of fine chemicals.« less

Determination of the dominant catalyst derived from the classic [RhCp*Cl₂]₂ precatalyst system: Is it single-metal Rh₁Cp*-based, subnanometer Rh₄ cluster-based, or Rh(0) n nanoparticle-based cyclohexene hydrogenation catalysis at room temperature and mild pressures?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bayram, Ercan; Linehan, John C.; Fulton, John L.

Determining the kinetically dominant catalyst in a given catalytic system is a forefront topic in catalysis. The [RhCp*Cl₂]₂ (Cp* =[η⁵-C₅(CH₃)₅]) system pioneered by Maitlis and co-workers is a classic precatalyst system from which homogeneous mononuclear Rh₁, subnanometer Rh₄ cluster, and heterogeneous polymetallic Rh(0) n nanoparticle have all arisen as viable candidates for the true hydrogenation catalyst, depending on the precise substrate, H₂ pressure, temperature, and catalyst concentration conditions. Addressed herein is the question of whether the prior assignment of homogeneous, mononuclear Rh₁Cp*-based catalysis is correct, or are trace Rh₄ subnanometer clusters or possibly Rh(0) n nanoparticles the dominant, actualmore » cyclohexene hydrogenation catalyst at 22 °C and 2.7 atm initial H₂ pressure? The observation herein of Rh₄ species by in operando-X-ray absorption fine structure (XAFS) spectroscopy, at the only slightly more vigorous conditions of 26 °C and 8.3 atm H₂ pressure, and the confirmation of Rh₄ clusters by ex situ mass spectroscopy raises the question of the dominant, room temperature, and mild pressure cyclohexene hydrogenation catalyst derived from the classic [RhCp*Cl₂]₂ precatalyst pioneered by Maitlis and co-workers. Ten lines of evidence are provided herein to address the nature of the true room temperature and mild pressure cyclohexene hydrogenation catalyst derived from [RhCp*Cl₂]₂. Especially significant among those experiments are quantitative catalyst poisoning experiments, in the present case using 1,10-phenanthroline. Those poisoning studies allow one to distinguish mononuclear Rh₁, subnanometer Rh₄ cluster, and Rh(0) n nanoparticle catalysis hypotheses. The evidence obtained provides a compelling case for a mononuclear, Rh₁Cp*-based cyclohexene hydrogenation catalyst at 22 °C and 2.7 atm H₂ pressure. The resultant methodology, especially the quantitative catalyst poisoning experiments in combination with in operando spectroscopy, is expected to be more broadly applicable to the study of other systems and the “what is the true catalyst?” question. The authors would like to thank Finke Group members and Prof. Saim Ö zkar for their valuable input as this work was proceeding. This work was supported at Colorado State University by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences, vial DOE Grant SE-FG402-03ER15453. The work at PNNL was also supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geo-sciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for the DOE by Battelle. XSD/PNC facilities at the Advanced Photon Source and research at these facilities are supported by the U.S. Department of Energy, Basic Energy Sciences; a Major Resources Support Grant from NSERC; the University of Washington; the Canadian Light Source; and the Advanced Photon Source. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy Office of Science by Argonne National Laboratory was supported by the U.S. DOE under Contract No. DE-AC02- 06CH11357.« less

Method of preparing thin porous sheets of ceramic material

DOEpatents

Swarr, Thomas E.; Nickols, Richard C.; Krasij, Myron

1987-03-24

A method of forming thin porous sheets of ceramic material for use as electrodes or other components in a molten carbonate fuel cell is disclosed. The method involves spray drying a slurry of fine ceramic particles in liquid carrier to produce generally spherical agglomerates of high porosity and a rough surface texture. The ceramic particles may include the electrode catalyst and the agglomerates can be calcined to improve mechanical strength. After slurrying with suitable volatile material and binder tape casting is used to form sheets that are sufficiently strong for further processing and handling in the assembly of a high temperature fuel cell.

Method of preparing thin porous sheets of ceramic material

DOEpatents

Swarr, T.E.; Nickols, R.C.; Krasij, M.

1984-05-23

A method of forming thin porous sheets of ceramic material for use as electrodes or other components in a molten carbonate fuel cell is disclosed. The method involves spray drying a slurry of fine ceramic particles in liquid carrier to produce generally spherical agglomerates of high porosity and a rough surface texture. The ceramic particles may include the electrode catalyst and the agglomerates can be calcined to improve mechanical strength. After slurrying with suitable volatile material and binder tape casting is used to form sheets that are sufficiently strong for further processing and handling in the assembly of a high temperature fuel cell.

Catalyst surfaces for the chromous/chromic redox couple

NASA Technical Reports Server (NTRS)

Giner, J. D.; Cahill, K. J. (Inventor)

1980-01-01

An electricity producing cell of the reduction-oxidation (REDOX) type is described. The cell is divided into two compartments by a membrane, each compartment containing a solid inert electrode. A ferrous/ferric couple in a chloride solution serves as a cathode fluid which is circulated through one of the compartments to produce a positive electric potential disposed therein. A chromic/chromous couple in a chloride solution serves as an anode fluid which is circulated through the second compartment to produce a negative potential on an electrode disposed therein. The electrode is an electrically conductive, inert material plated with copper, silver or gold. A thin layer of lead plates onto the copper, silver or gold layer when the cell is being charged, the lead ions being available from lead chloride which was added to the anode fluid. If the REDOX cell is then discharged, the current flows between the electrodes causing the lead to deplate from the negative electrode and the metal coating on the electrode will act as a catalyst to cause increased current density.

O–O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O–O radical coupling

DOE PAGES

Shaffer, David W.; Xie, Yan; Concepcion, Javier J.

2017-09-01

In this review we discuss at the mechanistic level the different steps involved in water oxidation catalysis with ruthenium-based molecular catalysts. We have chosen to focus on ruthenium-based catalysts to provide a more coherent discussion and because of the availability of detailed mechanistic studies for these systems but many of the aspects presented in this review are applicable to other systems as well. The water oxidation cycle has been divided in four major steps: water oxidative activation, O–O bond formation, oxidative activation of peroxide intermediates, and O 2 evolution. A significant portion of the review is dedicated to the O–Omore » bond formation step as the key step in water oxidation catalysis. As a result, the two main pathways to accomplish this step, single-site water nucleophilic attack and O–O radical coupling, are discussed in detail and compared in terms of their potential use in photoelectrochemical cells for solar fuels generation.« less

O–O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O–O radical coupling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shaffer, David W.; Xie, Yan; Concepcion, Javier J.

In this review we discuss at the mechanistic level the different steps involved in water oxidation catalysis with ruthenium-based molecular catalysts. We have chosen to focus on ruthenium-based catalysts to provide a more coherent discussion and because of the availability of detailed mechanistic studies for these systems but many of the aspects presented in this review are applicable to other systems as well. The water oxidation cycle has been divided in four major steps: water oxidative activation, O–O bond formation, oxidative activation of peroxide intermediates, and O 2 evolution. A significant portion of the review is dedicated to the O–Omore » bond formation step as the key step in water oxidation catalysis. As a result, the two main pathways to accomplish this step, single-site water nucleophilic attack and O–O radical coupling, are discussed in detail and compared in terms of their potential use in photoelectrochemical cells for solar fuels generation.« less

O-O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O-O radical coupling.

PubMed

Shaffer, David W; Xie, Yan; Concepcion, Javier J

2017-10-16

In this review we discuss at the mechanistic level the different steps involved in water oxidation catalysis with ruthenium-based molecular catalysts. We have chosen to focus on ruthenium-based catalysts to provide a more coherent discussion and because of the availability of detailed mechanistic studies for these systems but many of the aspects presented in this review are applicable to other systems as well. The water oxidation cycle has been divided in four major steps: water oxidative activation, O-O bond formation, oxidative activation of peroxide intermediates, and O 2 evolution. A significant portion of the review is dedicated to the O-O bond formation step as the key step in water oxidation catalysis. The two main pathways to accomplish this step, single-site water nucleophilic attack and O-O radical coupling, are discussed in detail and compared in terms of their potential use in photoelectrochemical cells for solar fuels generation.

Advantages of MgAlOx over gamma-Al2O3 as a support material for potassium-based high temperature lean NOx traps

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Jinyong; Gao, Feng; Karim, Ayman M.

MgAlOx mixed oxides were employed as supports for potassium-based lean NOx traps (LNTs) targeted for high temperature applications. Effects of support compositions, K/Pt loadings, thermal aging and catalyst regeneration on NOx storage capacity were systematically investigated. The catalysts were characterized by XRD, NOx-TPD, TEM, STEM-HAADF and in-situ XAFS. The results indicate that MgAlOx mixed oxides have significant advantages over conventional gamma-Al2O3-supports for LNT catalysts, in terms of high temperature NOx trapping capacity and thermal stability. First, as a basic support, MgAlOx stabilizes stored nitrates (in the form of KNO3) to much higher temperatures than mildly acidic gamma-Al2O3. Second, MgAlOx minimizesmore » Pt sintering during thermal aging, which is not possible for gamma-Al2O3 supports. Notably, combined XRD, in-situ XAFS and STEM-HAADF results indicate that Pt species in the thermally aged Pt/MgAlOx samples are finely dispersed in the oxide matrix as isolated atoms. This strong metal-support interaction stabilizes Pt and minimizes the extent of sintering. However, such strong interactions result in Pt oxidation via coordination with the support so that NO oxidation activity can be adversely affected after aging which, in turn, decreases NOx trapping ability for these catalysts. Interestingly, a high-temperature reduction treatment regenerates essentially full NOx trapping performance. In fact, regenerated Pt/K/MgAlOx catalyst exhibits much better NOx trapping performance than fresh Pt/K/Al2O3 LNTs over the entire temperature range investigated here. In addition to thermal aging, Pt/K loading effects were systemically studied over the fresh samples. The results indicate that NOx trapping is kinetically limited at low temperatures, while thermodynamically limited at high temperatures. A simple conceptual model was developed to explain the Pt and K loading effects on NOx storage. An optimized K loading, which allows balancing between the stability of nitrates and exposed Pt surface, gives the best NOx trapping capability.« less

Green diesel production via catalytic hydrogenation/decarboxylation of triglycerides and fatty acids of vegetable oil and brown grease

NASA Astrophysics Data System (ADS)

Sari, Elvan

Increase in the petroleum prices, projected increases in the world's energy demand and environmental awareness have shifted the research interest to the alternative fuel technologies. In particular, green diesel, vegetable oil/animal fat/waste oil and grease derived hydrocarbons in diesel boiling range, has become an attractive alternative to biodiesel---a mixture of fatty acid methyl esters, particularly due to its superior fuel properties that are similar to petroleum diesel. Hence, green diesel can be used as a drop-in fuel in the current diesel engines. The current technology for production of green diesel-hydrodeoxygenation of triglycerides and fatty acids over conventional hydrotreating catalysts suffers from fast catalyst deactivation in the absence of hydrogen combined with high temperatures and high fatty acid content in the feedstock. Additionally, excess hydrogen requirement for hydrodeoxygenation technique leads to high production costs. This thesis proposes a new technology-selective decarboxylation of brown grease, which is a mixture of fats and oils collected from waste water trap and rich in fatty acids, over a supported noble metal catalyst that overcomes the green diesel production challenges. In contrast to other feedstocks used for liquid biofuel production, brown grease is inexpensive and non-food competing feedstock, therefore the process finds solution to waste management issues, reduces the renewable fuel production cost and does not add to the global food shortage problems. Special catalyst formulations were developed to have a high activity and stability in the absence of hydrogen in the fatty acid decarboxylation process. The study shows how catalyst innovations can lead to a new technology that overcomes the process challenges. First, the effect of reaction parameters on the activity and the selectivity of brown grease decarboxylation with minimum hydrogen consumption over an activated carbon supported palladium catalyst were investigated. A 90% conversion of brown grease in a semi-batch mode was obtained in 7 hours. In contrast, in a batch reaction the conversion was roughly 40% in the same reaction time. However, by pre-treating the "as received" brown grease with H 2, the conversion in a batch reactor was increased 1.4--fold; and when the H2 to BG ratio was increased to 3/1 (mol/mol), the conversion was further improved. Therefore, such a two-step processing with selective hydrogenation prior to the decarboxylation of BG improves the product selectivity. The commercial 5% Pd/C catalyst was highly active for the decarboxylation of brown grease to green diesel at 300 °C and 1.5 MPa. Second, a class of Pd catalyst supported on a silica-activated carbon nanocomposite for free fatty acid decarboxylation was developed, and displayed excellent activity and operation stability selectively for the green diesel hydrocarbons formation in the absence of hydrogen under mild reaction conditions. The decarboxylation activities of different amount of silica containing catalysts were investigated in a batch reactor under inert gas. Among them, the formulation with the fewer oxygen surface groups (Pd/Si--C--4) was the most active catalyst for the decarboxylation of an unsaturated fatty acid. The high activity of the Pd/Si--C--4 catalyst is attributed to its accessible and well-distributed metallic Pd nanoparticles inside hybrid mesopores as well as to its low acidity, weak surface interactions and inertness. Thus, Pd supported on carbon modified with silica may be regarded as a prospective decarboxylation catalyst for the removal of oxygen from vegetable oil/animal fat without the need of additional hydrogen. Third, in order to design a suitable catalyst for conversion of brown grease to green diesel, a systematic study of the model compounds--oleic acid was conducted on various catalysts in super-critical water to understand the reaction pathways in the absence of hydrogen. A Si--C support was more effective than activated carbon itself for both decarboxylation of oleic acid and hydrogenation of alkenes. In an additional effort to reduce Pd amount in the catalyst, Pd2Co/C catalysts with various Pd content were prepared and the catalytic activity study showed that 0.5 wt% Pd2Co/C catalyst performs even better than a 5 wt% Pd/C catalyst. Pd and Co alloys were very well dispersed and formed fine clusters, which led to a higher active metal surface area and hence favored the decarboxylation of oleic acid. This study showed that an alloy of Pd on carbon with a significantly low Pd content is much more active and selective to diesel hydrocarbons production from an unsaturated fatty acid in super-critical water and may be regarded as a prospective feasible decarboxylation catalyst for the removal of oxygen from vegetable oil/animal fat without the need of additional hydrogen.

[Fine root dynamics and its relationship with soil fertility in tropical rainforests of Chocó].

PubMed

Quinto, Harley; Caicedo, Haylin; Thelis Perez, May; Moreno, Flavio

2016-12-01

The fine roots play an important role in the acquisition of water and minerals from the soil, the global carbon balance and mitigation of climate change. The dynamics (productivity and turnover) of fine roots is essential for nutrient cycling and carbon balance of forest ecosystems. The availability of soil water and nutrients has significantly determined the productivity and turnover of fine roots. It has been hypothesized that fine roots dynamics increases with the availability of soil resources in tropical forest ecosystems. To test this hypothesis in tropical rainforests of Chocó (ecosystems with the highest rainfall in the world), five one-ha permanent plots were established in the localities of Opogodó and Pacurita, where the productivity and turnover of fine roots were measured at 0-10 cm and 10-20 cm depth. The measurement of the fine root production was realized by the Ingrowth core method. The fine root turnover was measured like fine roots production divided mean annual biomass. In addition, soil fertility parameters (pH, nutrients, and texture) were measured and their association with productivity and turnover of fine roots was evaluated. It was found that the sites had nutrient-poor soils. The localities also differ in soil; Opogodó has sandy soils and flat topography, and Pacurita has clay soils, rich in aluminum and mountainous topography. In Opogodó fine root production was 6.50 ± 2.62 t/ha.yr (mean ± SD). In Pacurita, fine root production was 3.61 ± 0.88 t/ha.yr. Also in Opogodó, the fine root turnover was higher than in Pacurita (1.17 /y and 0.62 /y, respectively). Fine root turnover and production in the upper soil layers (10 cm upper soil) was considerably higher. Productivity and turnover of fine roots showed positive correlation with pH and contents of organic matter, total N, K, Mg, and sand; whereas correlations were negative with ECEC and contents of Al, silt, and clay. The percentage of sand was the parameter that best explained the variations of fine root production. The fine root turnover was negatively explained by soil Al availability. Results suggested the increase of fine root dynamics with soil fertility at a local scale, which also indicates that under the oligotrophic conditions of soils in tropical rainforests, fine roots tend to proliferate rapidly in small patches of soil rich in sand and nutrients.

Aquatic Plants Aid Sewage Filter

NASA Technical Reports Server (NTRS)

Wolverton, B. C.

1985-01-01

Method of wastewater treatment combines micro-organisms and aquatic plant roots in filter bed. Treatment occurs as liquid flows up through system. Micro-organisms, attached themselves to rocky base material of filter, act in several steps to decompose organic matter in wastewater. Vascular aquatic plants (typically, reeds, rushes, cattails, or water hyacinths) absorb nitrogen, phosphorus, other nutrients, and heavy metals from water through finely divided roots.

Fibers and fabrics with insulating, water-proofing, and flame-resistant properties

DOEpatents

Hrubesh, Lawrence W.; Poco, John F.; Coronado, Paul R.

2004-04-20

Fibers, and fabrics produced from the fibers, are made water repellent, fire-retardant and/or thermally insulating by filling void spaces in the fibers and/or fabrics with a powdered material. When the powder is sufficiently finely divided, it clings tenaciously to the fabric's fibers and to itself, resisting the tendency to be removed from the fabric.

Proceedings of the Annual Conference on Academic Computing Applications (6th, Indiana University Northwest, Bloomington, Indiana, April 6, 1979).

ERIC Educational Resources Information Center

Stentz, Michael, Ed.; Motsinger, Linda, Ed.

Topics which range from the more popular computing applications in accounting, statistics, and administration to the less ordinary applications of the computer to the fields of fine arts, medicine, and linguistics, are discussed in this collection of 22 conference papers. The papers are divided into four tracks: the first deals with statistical…

Fire extinguishant materials

NASA Technical Reports Server (NTRS)

Altman, R. L.; Mayer, L. A.; Ling, A. C. (Inventor)

1983-01-01

Fire extinguishant composition comprising a mixture of a finely divided aluminum compound and alkali metal, stannous or plumbous halide is provided. Aluminum compound may be aluminum hydroxide, alumina or boehmite but preferably it is an alkali metal dawsonite. The metal halide may be an alkali metal, e.g. potassium iodide, bromide or chloride or stannous or plumbous iodide, bromide or chloride. Potassium iodide is preferred.

Wood flour

Treesearch

Craig M. Clemons; Daniel F. Caufield

2005-01-01

The term “wood flour” is somewhat ambiguous. Reineke states that the term wood flour “is applied somewhat loosely to wood reduced to finely divided particles approximating those of cereal flours in size, appearance, and texture”. Though its definition is imprecise, the term wood flour is in common use. Practically speaking, wood flour usually refers to wood particles...

Certificate Revocation Using Fine Grained Certificate Space Partitioning

NASA Astrophysics Data System (ADS)

Goyal, Vipul

A new certificate revocation system is presented. The basic idea is to divide the certificate space into several partitions, the number of partitions being dependent on the PKI environment. Each partition contains the status of a set of certificates. A partition may either expire or be renewed at the end of a time slot. This is done efficiently using hash chains.

Wood flour

Treesearch

Craig M. Clemons

2010-01-01

The term “wood flour” is somewhat ambiguous. Reineke states that the term wood flour “is applied somewhat loosely to wood reduced to finely divided particles approximating those of cereal flours in size, appearance, and texture.” Though its definition is imprecise, the term wood flour is in common use. Practically speaking, wood flour usually refers to wood particles...

PROCESS FOR CONTINUOUSLY SEPARATING IRRADIATION PRODUCTS OF THORIUM

DOEpatents

Hatch, L.P.; Miles, F.T.; Sheehan, T.V.; Wiswall, R.H.; Heus, R.J.

1959-07-01

A method is presented for separating uranium-233 and protactinium from thorium-232 containing compositions which comprises irradiating finely divided particles of said thorium with a neutron flux to form uranium-233 and protactinium, heating the neutron-irradiated composition in a fluorine and hydrogen atmosphere to form volatile fluorides of uranium and protactinium and thereafter separating said volatile fluorides from the thorium.

Transport of fine sediment over a coarse, immobile riverbed

USGS Publications Warehouse

Grams, Paul E.; Wilcock, Peter R.

2014-01-01

Sediment transport in cobble-boulder rivers consists mostly of fine sediment moving over a coarse, immobile bed. Transport rate depends on several interrelated factors: boundary shear stress, the grain size and volume of fine sediment, and the configuration of fine sediment into interstitial deposits and bed forms. Existing models do not incorporate all of these factors. Approaches that partition stress face a daunting challenge because most of the boundary shear is exerted on immobile grains. We present an alternative approach that divides the bed into sand patches and interstitial deposits and is well constrained by two clear end-member cases: full sand cover and absence of sand. Entrainment from sand patches is a function of their aerial coverage. Entrainment from interstices among immobile grains is a function of sand elevation relative to the size of the immobile grains. The bed-sand coverage function is used to predict the ratio of the rate of entrainment from a partially covered bed to the rate of entrainment from a completely sand-covered bed, which is determined using a standard sand transport model. We implement the bed-sand coverage function in a morphodynamic routing model and test it against observations of sand bed elevation and suspended sand concentration for conditions of nonuniform fine sediment transport in a large flume with steady uniform flow over immobile hemispheres. The results suggest that this approach may provide a simple and robust method for predicting the transport and migration of fine sediment through rivers with coarse, immobile beds.

Randomized controlled study of the safety and efficacy of nitrous oxide-sedated endoscopic ultrasound-guided fine needle aspiration for digestive tract diseases

PubMed Central

Wang, Cai-Xia; Wang, Jian; Chen, Yuan-Yuan; Wang, Jia-Ni; Yu, Xin; Yang, Feng; Sun, Si-Yu

2016-01-01

AIM To evaluate the efficacy and safety of nitrous oxide-sedated endoscopic ultrasound-guided fine needle aspiration. METHODS Enrolled patients were divided randomly into an experimental group (inhalation of nitrous oxide) and a control group (inhalation of pure oxygen) and heart rate, blood oxygen saturation, blood pressure, electrocardiogram (ECG) changes, and the occurrence of complications were monitored and recorded. All patients and physicians completed satisfaction questionnaires about the examination and scored the process using a visual analog scale. RESULTS There was no significant difference in heart rate, blood oxygen saturation, blood pressure, ECG changes, or complication rate between the two groups of patients (P > 0.05). However, patient and physician satisfaction were both significantly higher in the nitrous oxide compared with the control group (P < 0.05). CONCLUSION Nitrous oxide-sedation is a safe and effective option for patients undergoing endoscopic ultrasound-guided fine needle aspiration. PMID:28028373

In-situ X-Ray Absorption Spectroscopy (XAS) Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction

PubMed Central

Benck, Jesse D.; Gul, Sheraz; Webb, Samuel M.; Yachandra, Vittal K.; Yano, Junko; Jaramillo, Thomas F.

2013-01-01

In-situ x-ray absorption spectroscopy (XAS) is a powerful technique that can be applied to electrochemical systems, with the ability to elucidate the chemical nature of electrocatalysts under reaction conditions. In this study, we perform in-situ XAS measurements on a bifunctional manganese oxide (MnOx) catalyst with high electrochemical activity for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Using x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS), we find that exposure to an ORR-relevant potential of 0.7 V vs. RHE produces a disordered Mn3II,III,IIIO4 phase with negligible contributions from other phases. After the potential is increased to a highly anodic value of 1.8 V vs. RHE, relevant to the OER, we observe an oxidation of approximately 80% of the catalytic thin film to form a mixed MnIII,IV oxide, while the remaining 20% of the film consists of a less oxidized phase, likely corresponding to unchanged Mn3II,III,IIIO4. XAS and electrochemical characterization of two thin film catalysts with different MnOx thicknesses reveals no significant influence of thickness on the measured oxidation states, at either ORR or OER potentials, but demonstrates that the OER activity scales with film thickness. This result suggests that the films have porous structure, which does not restrict electrocatalysis to the top geometric layer of the film. As the portion of the catalyst film that is most likely to be oxidized at the high potentials necessary for the OER is that which is closest to the electrolyte interface, we hypothesize that the MnIII,IV oxide, rather than Mn3II,III,IIIO4, is the phase pertinent to the observed OER activity. PMID:23758050

Enhanced photo-catalytic activity of Sr and Ag co-doped TiO2 nanoparticles for the degradation of Direct Green-6 and Reactive Blue-160 under UV & visible light.

PubMed

Naraginti, Saraschandra; Thejaswini, T V L; Prabhakaran, D; Sivakumar, A; Satyanarayana, V S V; Arun Prasad, A S

2015-10-05

This work is focused on sol-gel synthesis of silver and strontium co-doped TiO2 nanoparticles and their utilization as photo-catalysts in degradation of two textile dyes. Effect of pH, intensity of light, amount of photo-catalyst, concentration of dye, sensitizers, etc., were studied to optimize conditions for obtaining enhanced photo-catalytic activity of synthesized nanoparticles. XRD, BET, HR-TEM, EDAX and UV-Vis (diffused reflectance mode) techniques were used to characterize the nanoparticles. Interestingly, band gap of Sr and Ag co-doped TiO2 nanoparticles showed considerable narrowing (2.6 eV) when compared to Ag doped TiO2 (2.7 eV) and undoped TiO2 (3.17 eV) nanoparticles. Incorporation of Ag and Sr in the lattice of TiO2 could bring isolated energy levels near conduction and valence bands thus narrowing band gap. The XRD analysis shows that both Ag and Sr nanoparticles are finely dispersed on the surface of titania framework, without disturbing its crystalline structure. TEM images indicate that representative grain sizes of Ag-doped TiO2 & Sr and Ag co-doped TiO2 nanoparticles are in the range of 8-20 nm and 11-25 nm, respectively. Effective degradation of Direct Green-6 (DG-6) and Reactive Blue-160 (RB-160) under UV and visible light has been achieved using the photo-catalysts. Sr and Ag co-doped TiO2 photo-catalysts showed higher catalytic activity during degradation process in visible region when compared to Ag-doped and undoped TiO2 nanoparticles which could be attributed to the interactive effect caused by band gap narrowing and enhancement in charge separation. For confirming degradation of the dyes, total organic carbon (TOC) content was monitored periodically. Copyright © 2015 Elsevier B.V. All rights reserved.

Platinum-mordenite catalysts for n-Hexane isomerization: Characterization by X-ray absorption spectroscopy and chemical probes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Otten, M.M.; Clayton, M.J.; Lamb, H.H.

Platinum-mordenite (Pt-MOR) catalysts were prepared from NH{sub 4}-MOR by ion exchange with (Pt{sup II}(NH{sub 3}){sub 4})(OH){sub 2}, calcination in O{sub 2} at 350{degrees}C, and reduction in H{sub 2} at 350{degrees}C. The resultant Pt-H-MOR was active for n-hexane isomerization and hydrocracking via bifunctional catalysis at 240-300{degrees}C and 1 atm. The observed activation energies for C{sub 6} branched-isomer formation are unusually low, suggesting that the isomerization rates were controlled by pore diffusion. A Pt-KH-MOR catalyst was prepared by ion exchange with aqueous KNO{sub 3} and re-reduction at 350{degrees}C; elemental analysis evidenced 90% exchange of protons for K{sup +} ions. The product distributionmore » and observed activation energies for C{sub 6} branched-isomer formation over Pt-KH-MOR are consistent with n-hexane isomerization via bifunctional catalysis. Hydrocracking was strongly suppressed, and light hydrocarbons were formed primarily by Pt-catalyzed hydrogenolysis. From in-situ extended X-ray absorption fine structure spectroscopy and H{sub 2} temperature-programmed desorption, we conclude that the Pt-MOR catalysts consist of small Pt clusters hosted within the mordenite crystals. The PtL{sub III}X-ray absorption near-edge structure (XANES) spectra of Pt-H-MOR and Pt-KH-MOR are closely similar, suggesting that the electronic structure of the Pt clusters is unaffected by mordenite acid-base chemistry. The infrared spectrum of CO adsorbed on Pt-H-MOR contains an intense band at 2084 cm{sup -1}, which is assigned to linear CO moieties on Pt clusters. The infrared spectrum of CO adsorbed on Pt-KH-MOR evidences a red shift of the linear CO band, which the authors suggest is due to electrostatic interactions between carbonyl O atoms and nearby K{sup +} ions. 45 refs., 9 figs., 6 tabs.« less

Synthesis and Characterization of CO- and H2S-Tolerant Electrocatalysts for PEM Fuel Cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shamsuddin Ilias

2006-05-18

The present state-of-art Proton Exchange Membrane Fuel Cell (PEMFC) technology is based on platinum (Pt) as a catalyst for both the fuel (anode) and air (cathode) electrodes. This catalyst is highly active but susceptible to poisoning by CO, which may be present in the H{sub 2}-fuel used or may be introduced during the fuel processing. Presence of trace amount of CO and H{sub 2}S in the H{sub 2}-fuel poisons the anode irreversibly and decreases the performance of the PEMFCs. In an effort to reduce the Pt-loading and improve the PEMFC performance, we propose to synthesize a number of Pt-based binary,more » ternary, and quaternary electrocatalysts using Ru, Mo, Ir, Ni, and Co as a substitute for Pt. By fine-tuning the metal loadings and compositions of candidate electrocatalysts, we plan to minimize the cost and optimize the catalyst activity and performance in PEMFC. The feasibility of the novel electrocatalysts will be demonstrated in the proposed effort with gas phase CO and H{sub 2}S concentrations typical of those found in reformed fuel gas with coal/natural gas/methanol feedstocks. During this reporting period we used four Pt-based electrocatalysts (Pt/Ru/Mo/Se, Pt/Ru/Mo/Ir, Pt/Ru/Mo/W, Ptr/Ru/Mo/Co) in MEAs and these were evaluated for CO-tolerance with 20 and 100 ppm CO concentration in H{sub 2}-fuel. From current-voltage performance study, the catalytic activity was found in the increasing order of Pt/Ru/Mo/Ir > Pt/Ru/Mo/W > Pt/Ru/Mo/Co > Pt/Ru/MO/Se. From preliminary cost analysis it appears that could of the catalyst metal loading can reduced by 40% to 60% depending on the selection of metal combinations without compromising the fuel cell performance.« less

Process for reproducibly preparing titanium subhydride

DOEpatents

Carlson, Richard S.

1982-01-01

Titanium subhydride is produced in a reactor by heating a selected amount of finely divided titanium compound at a selected temperature for a selected period of time under dynamic vacuum conditions. Hydrogen is removed substantially uniformly from each powder grain and there is produced a subhydride of substantially uniform titanium-hydrogen composition. Selection of the amount, temperature and time produces a subhydride of selected titanium-hydrogen composition.

Use of silicon in liquid sintered silicon nitrides and sialons

DOEpatents

Raj, Rishi; Baik, Sunggi

1984-12-11

This invention relates to the production of improved high density nitrogen based ceramics by liquid-phase densification of silicon nitride or a compound of silicon-nitrogen-oxygen-metal, e.g. a sialon. In the process and compositions of the invention minor amounts of finely divided silicon are employed together with the conventional liquid phase producing additives to enhance the densification of the resultant ceramic.

MOLDS FOR CASTING PLUTONIUM

DOEpatents

Anderson, J.W.; Miley, F.; Pritchard, W.C.

1962-02-27

A coated mold for casting plutonium comprises a mold base portion of a material which remains solid and stable at temperatures as high as the pouring temperature of the metal to be cast and having a thin coating of the order of 0.005 inch thick on the interior thereof. The coating is composed of finely divided calcium fluoride having a particle size of about 149 microns. (AEC)

Spectroscopic investigation of nitrogen-functionalized carbon materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wood, Kevin N.; Christensen, Steven T.; Nordlund, Dennis

2016-04-07

Carbon materials are used in a diverse set of applications ranging from pharmaceuticals to catalysis. Nitrogen modification of carbon powders has shown to be an effective method for enhancing both surface and bulk properties of as-received material for a number of applications. Unfortunately, control of the nitrogen modification process is challenging and can limit the effectiveness and reproducibility of N-doped materials. Additionally, the assignment of functional groups to specific moieties on the surface of nitrogen-modified carbon materials is not straightforward. Herein, we complete an in-depth analysis of functional groups present at the surface of ion-implanted Vulcan and Graphitic Vulcan throughmore » the use of X-ray photoelectron spectroscopy (XPS) and near edge X-ray adsorption fine structure spectroscopy (NEXAFS). Our results show that regardless of the initial starting materials used, nitrogen ion implantation conditions can be tuned to increase the amount of nitrogen incorporation and to obtain both similar and reproducible final distributions of nitrogen functional groups. The development of a well-controlled/reproducible nitrogen implantation pathway opens the door for carbon supported catalyst architectures to have improved numbers of nucleation sites, decreased particle size, and enhanced catalyst-support interactions.« less

Heterogeneous activation of H2O2 by defect-engineered TiO(2-x) single crystals for refractory pollutants degradation: A Fenton-like mechanism.

PubMed

Zhang, Ai-Yong; Lin, Tan; He, Yuan-Yi; Mou, Yu-Xuan

2016-07-05

The heterogeneous catalyst plays a key role in Fenton-like reaction for advanced oxidation of refractory pollutants in water treatment. Titanium dioxide (TiO2) is a typical semiconductor with high industrial importance due to its earth abundance, low cost and no toxicity. In this work, it is found that TiO2 can heterogeneously activate hydrogen peroxide (H2O2, E°=1.78 eV), a common chemical oxidant, to efficiently generate highly-powerful hydroxyl radical, OH (E(0)=2.80 eV), for advanced water treatment, when its crystal shape, exposed facet and oxygen-stoichiometry are finely tuned. The defect-engineered TiO2 single crystals exposed by high-energy {001} facets exhibited an excellent Fenton-like activity and stability for degrading typical refractory organic pollutants such as methyl orange and p-nitrophenol. Its defect-centered Fenton-like superiority is mainly attributed to the crystal oxygen-vacancy, single-crystalline structure and exposed polar {001} facet. Our findings could provide new chance to utilize TiO2 for Fenton-like technology, and develop novel heterogeneous catalyst for advanced water treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

Reverse micelle synthesis of nanoscale metal containing catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Darab, J.G.; Fulton, J.L.; Linehan, J.C.

1993-03-01

The need for morphological control during the synthesis of catalyst precursor powders is generally accepted to be important. In the liquefaction of coal, for example, iron-bearing catalyst precursor particles containing individual crystallites with diameters in the 1-100 nanometer range are believed to achieve good dispersion through out the coal-solvent slurry during liquefaction 2 runs and to undergo chemical transformations to catalytically active iron sulfide phases. The production of the nanoscale powders described here employs the confining spherical microdomains comprising the aqueous phase of a modified reverse micelle (MRM) microemulsion system as nanoscale reaction vessels in which polymerization, electrochemical reduction andmore » precipitation of solvated salts can occur. The goal is to take advantage of the confining nature of micelles to kinetically hinder transformation processes which readily occur in bulk aqueous solution in order to control the morphology and phase of the resulting powder. We have prepared a variety of metal, alloy, and metal- and mixed metal-oxide nanoscale powders from appropriate MRM systems. Examples of nanoscale powders produced include Co, Mo-Co, Ni{sub 3}Fe, Ni, and various oxides and oxyhydroxides of iron. Here, we discuss the preparation and characterization of nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide MRM nanoscale powders. We have used extended x-ray absorption fine structure (EXAFS) spectroscopy to study the chemical polymerization process in situ, x-ray diffraction (XRD), scanning and transmission electron microcroscopies (SEM and TEM), elemental analysis and structural modelling to characterize the nanoscale powders produced. The catalytic activity of these powders is currently being studied.« less

Commercial-scale demonstration of the Liquid Phase Methanol process. Technical progress report number 8, April 1--June 30, 1996

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1996-12-31

The project involves the construction of an 80,000 gallon per day (260 tons per day (TPD)) methanol unit utilizing coal-derived synthesis gas from Eastman`s integrated coal gasification facility. The new equipment consists of synthesis gas feed preparation and compression facilities, the liquid phase reactor and auxiliaries, product distillation facilities, and utilities. The technology to be demonstrated is the product of a cooperative development effort by Air Products and DOE in a program that started in 1981. Developed to enhance electric power generation using integrated gasification combined cycle (IGCC) technology, the LPMEOH{trademark} process is ideally suited for directly processing gases producedmore » by modern-day coal gasifiers. Originally tested at a small (10 TPD), DOE-owned experimental unit in LaPorte, Texas, the technology provides several improvements essential for the economic coproduction of methanol and electricity directly from gasified coal. This liquid phase process suspends fine catalyst particles in an inert liquid, forming a slurry. The slurry dissipates the heat of the chemical reaction away from the catalyst surface, protecting the catalyst and allowing the methanol synthesis reaction to proceed at higher rates. At the Eastman complex, the technology is being integrated with existing coal-gasifiers. A carefully developed test plan will allow operations at Eastman to simulate electricity demand load-following in coal-based IGCC facilities. The operations will also demonstrate the enhanced stability and heat dissipation of the conversion process, its reliable on/off operation, and its ability to produce methanol as a clean liquid fuel without additional upgrading.« less

Effects of Potassium loading and thermal aging on K/Pt/Al2O3 high-temperature lean NOx trap catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Jinyong; Gao, Feng; Kim, Do Heui

2014-03-31

The effects of K loading and thermal aging on the structural properties and high temperature performance of Pt/K/Al2O3 lean NOx trap (LNT) catalysts were investigated using in situ X-ray diffraction (XRD), temperature-programmed decomposition/desorption of NOx (NOx-TPD), transmission electron microscopy (TEM), NO oxidation and NOx storage tests. In situ XRD results demonstrate that KNO3 becomes extremely mobile on the Al2O3 surface, and experiences complex transformations between orthorhombic and rhombohedral structures, accompanied by sintering, melting and thermal decomposition upon heating. NOx storage results show an optimum K loading around 10% for the best performance at high temperatures. At lower K loadings wheremore » the majority of KNO3 stays as a surface layer, the strong interaction between KNO3 and Al2O3 promotes KNO3 decomposition and deteriorates high-temperature performance. At K loadings higher than 10%, the performance drop is not caused by NOx diffusion limitations as for the case of barium-based LNTs, but rather from the blocking of Pt sites by K species, which adversely affects NO oxidation. Thermal aging at 800 ºC severely deactivates the Pt/K/Al2O3 catalysts due to Pt sintering. However, in the presence of potassium, some Pt remains in a dispersed and oxidized form. These Pt species interact strongly with K and, therefore, do not sinter. After a reduction treatment, these Pt species remain finely dispersed, contributing to a partial recovery of NOx storage performance.« less

Hydrogenation of carboxylic acids with a homogeneous cobalt catalyst.

PubMed

Korstanje, Ties J; van der Vlugt, Jarl Ivar; Elsevier, Cornelis J; de Bruin, Bas

2015-10-16

The reduction of esters and carboxylic acids to alcohols is a highly relevant conversion for the pharmaceutical and fine-chemical industries and for biomass conversion. It is commonly performed using stoichiometric reagents, and the catalytic hydrogenation of the acids previously required precious metals. Here we report the homogeneously catalyzed hydrogenation of carboxylic acids to alcohols using earth-abundant cobalt. This system, which pairs Co(BF4)2·6H2O with a tridentate phosphine ligand, can reduce a wide range of esters and carboxylic acids under relatively mild conditions (100°C, 80 bar H2) and reaches turnover numbers of up to 8000. Copyright © 2015, American Association for the Advancement of Science.

Use of silicon in liquid sintered silicon nitrides and sialons

DOEpatents

Raj, R.; Baik, S.

1984-12-11

This invention relates to the production of improved high density nitrogen based ceramics by liquid-phase densification of silicon nitride or a compound of silicon-nitrogen-oxygen-metal, e.g. a sialon. In the process and compositions of the invention minor amounts of finely divided silicon are employed together with the conventional liquid phase producing additives to enhance the densification of the resultant ceramic. 4 figs.

Use of free silicon in liquid phase sintering of silicon nitrides and sialons

DOEpatents

Raj, R.; Baik, S.

1985-11-12

This invention relates to the production of improved high density nitrogen based ceramics by liquid-phase densification of silicon nitride or a compound of silicon-nitrogen-oxygen-metal, e.g. a sialon. In the process and compositions of the invention minor amounts of finely divided silicon are employed together with the conventional liquid phase producing additives to enhance the densification of the resultant ceramic. 4 figs.

Use of free silicon in liquid phase sintering of silicon nitrides and sialons

DOEpatents

Raj, Rishi; Baik, Sunggi

1985-11-12

This invention relates to the production of improved high density nitrogen based ceramics by liquid-phase densification of silicon nitride or a compound of silicon-nitrogen-oxygen-metal, e.g. a sialon. In the process and compositions of the invention minor amounts of finely divided silicon are employed together with the conventional liquid phase producing additives to enhance the densification of the resultant ceramic.

Ribosomes are optimized for autocatalytic production

NASA Astrophysics Data System (ADS)

Reuveni, Shlomi; Ehrenberg, Måns; Paulsson, Johan

2017-07-01

Many fine-scale features of ribosomes have been explained in terms of function, revealing a molecular machine that is optimized for error-correction, speed and control. Here we demonstrate mathematically that many less well understood, larger-scale features of ribosomes—such as why a few ribosomal RNA molecules dominate the mass and why the ribosomal protein content is divided into 55-80 small, similarly sized segments—speed up their autocatalytic production.

Drilling fluids and thinners therefor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Allison, G.M. III

1986-10-21

This patent describes an aqueous drilling fluid comprising water, finely divided solids and a first agent and a second agent. The first agent comprises a sulfoalkylated tannin containing no complexing heavy metal. The second agent comprises at least one at least partly water-soluble metal compound comprising tin. The weight ratio of the first agent to the second agent is in the range from about 100;1 to about 1:1.

Making Microscopic Cubes Of Boron

NASA Technical Reports Server (NTRS)

Faulkner, Joseph M.

1993-01-01

Production of finely divided cubes of boron involves vacuum-deposition technology and requires making of template. Template supports pattern of checkered squares 25 micrometers on side, which are etched 25 micrometers into template material. Template coasted uniformly with paralyene or some similar vacuum coating with low coefficient of adhesion. Intended application to solid rocket fuels, explosives, and pyrotechnics; process used for other applications, from manufacture of pharmaceuticals to processing of nuclear materials.

IQ discrepancy differentiates levels of fine motor skills and their relationship in children with autism spectrum disorders

PubMed Central

Yu, Tzu-Ying; Chou, Willy; Chow, Julie Chi; Lin, Chien-Ho; Tung, Li-Chen; Chen, Kuan-Lin

2018-01-01

Purpose We investigated 1) the impact of differences in intelligence quotient discrepancy (IQD) on motor skills of preschool-aged children with autism spectrum disorders (ASD); 2) the relationships between IQD and motor skills in preschool-aged children with ASD. Methods A total of 127 ASD preschool-aged children were divided into three groups according to the size of the IQD: IQD within 1 standard deviation (1SD; EVENIQ; n=81), discrepantly higher verbal intelligence quotient (VIQ; n=22; VIQ>performance intelligence quotient [PIQ] above 1SD [≥15 points]), and discrepantly higher PIQ (n=24; PIQ>VIQ above 1SD [≥15 points]). Children’s IQD and motor skills were determined with the Wechsler Preschool and Primary Scale of Intelligence™ – Fourth Edition and the motor subtests of the Comprehensive Developmental Inventory for Infants and Toddlers (CDIIT), respectively. Results One-way analysis of variance revealed significant group differences for the fine motor domain of the CDIIT and the visual–motor coordination subtest (F=3.37–4.38, p<0.05). Children with discrepantly higher PIQ were associated with better fine motor skills than were children with even IQD and those with discrepantly higher VIQ, and vice versa. IQD (PIQ – VIQ) had significant positive correlations with the fine motor domain and fine motor subtests of the CDIIT (r=0.18–0.29, p<0.05). Conclusion The IQD can identify different levels of fine motor skills in preschool-aged children with ASD. This study suggests important implications for clinicians, therapists, and researchers: discrepantly higher PIQ could be related to better visual–motor coordination, and discrepantly higher VIQ could be related to poor visual–motor coordination. Furthermore, the results support that when therapists are working with preschool-aged children with ASD who are developing fine motor skills or undertaking fine motor tasks related to visual–motor coordination, they may need to pay attention to the children’s IQD. PMID:29503543

IQ discrepancy differentiates levels of fine motor skills and their relationship in children with autism spectrum disorders.

PubMed

Yu, Tzu-Ying; Chou, Willy; Chow, Julie Chi; Lin, Chien-Ho; Tung, Li-Chen; Chen, Kuan-Lin

2018-01-01

We investigated 1) the impact of differences in intelligence quotient discrepancy (IQD) on motor skills of preschool-aged children with autism spectrum disorders (ASD); 2) the relationships between IQD and motor skills in preschool-aged children with ASD. A total of 127 ASD preschool-aged children were divided into three groups according to the size of the IQD: IQD within 1 standard deviation (1SD; EVENIQ; n=81), discrepantly higher verbal intelligence quotient (VIQ; n=22; VIQ>performance intelligence quotient [PIQ] above 1SD [≥15 points]), and discrepantly higher PIQ (n=24; PIQ>VIQ above 1SD [≥15 points]). Children's IQD and motor skills were determined with the Wechsler Preschool and Primary Scale of Intelligence™ - Fourth Edition and the motor subtests of the Comprehensive Developmental Inventory for Infants and Toddlers (CDIIT), respectively. One-way analysis of variance revealed significant group differences for the fine motor domain of the CDIIT and the visual-motor coordination subtest ( F =3.37-4.38, p <0.05). Children with discrepantly higher PIQ were associated with better fine motor skills than were children with even IQD and those with discrepantly higher VIQ, and vice versa. IQD (PIQ - VIQ) had significant positive correlations with the fine motor domain and fine motor subtests of the CDIIT ( r =0.18-0.29, p <0.05). The IQD can identify different levels of fine motor skills in preschool-aged children with ASD. This study suggests important implications for clinicians, therapists, and researchers: discrepantly higher PIQ could be related to better visual-motor coordination, and discrepantly higher VIQ could be related to poor visual-motor coordination. Furthermore, the results support that when therapists are working with preschool-aged children with ASD who are developing fine motor skills or undertaking fine motor tasks related to visual-motor coordination, they may need to pay attention to the children's IQD.

Durability and performance optimization of cathode materials for fuel cells

NASA Astrophysics Data System (ADS)

Colon-Mercado, Hector Rafael

The primary objective of this dissertation is to develop an accelerated durability test (ADT) for the evaluation of cathode materials for fuel cells. The work has been divided in two main categories, namely high temperature fuel cells with emphasis on the Molten Carbonate Fuel Cell (MCFC) cathode current collector corrosion problems and low temperature fuel cells in particular Polymer Electrolyte Fuel Cell (PEMFC) cathode catalyst corrosion. The high operating temperature of MCFC has given it benefits over other fuel cells. These include higher efficiencies (>50%), faster electrode kinetics, etc. At 650°C, the theoretical open circuit voltage is established, providing low electrode overpotentials without requiring any noble metal catalysts and permitting high electrochemical efficiency. The waste heat is generated at sufficiently high temperatures to make it useful as a co-product. However, in order to commercialize the MCFC, a lifetime of 40,000 hours of operation must be achieved. The major limiting factor in the MCFC is the corrosion of cathode materials, which include cathode electrode and cathode current collector. In the first part of this dissertation the corrosion characteristics of bare, heat-treated and cobalt coated titanium alloys were studied using an ADT and compared with that of state of the art current collector material, SS 316. PEMFCs are the best choice for a wide range of portable, stationary and automotive applications because of their high power density and relatively low-temperature operation. However, a major impediment in the commercialization of the fuel cell technology is the cost involved due to the large amount of platinum electrocatalyst used in the cathode catalyst. In an effort to increase the power and decrease the cathode cost in polymer electrolyte fuel cell (PEMFC) systems, Pt-alloy catalysts were developed to increase its activity and stability. Extensive research has been conducted in the area of new alloy development and understanding the mechanisms of ORR. However, a relatively small number of publications are related to the durability of Pt alloys in the PEMFC environment. In the second part of this dissertation an ADT is developed for the evaluation of PEMFC cathode catalysts in a time and cost effective way.

Measurement of Fine Particles From Mobile and Stationary Sources, and Reducing the Air Conditioner Power Consumption in Hybrid Electric Vehicles

NASA Astrophysics Data System (ADS)

Brewer, Eli Henry

We study the PM2.5and ultrafine exhaust emissions from a new natural gas-fired turbine power facility to better understand air pollution in California. To characterize the emissions from new natural gas turbines, a series of tests were performed on a GE LMS100 gas turbine. These tests included PM2.5 and wet chemical tests for SO2/SO 3 and NH3, as well as ultrafine (less than 100 nm in diameter) particulate matter measurements. The turbine exhaust had an average particle number concentration that was 2.3x103 times higher than ambient air. The majority of these particles were nanoparticles; at the 100 nm size, stack particle concentrations were about 20 times higher than ambient, and increased to 3.9x104 times higher on average in the 2.5 - 3 nm particle size range. This study also found that ammonia emissions were higher than expected, but in compliance with permit conditions. This was possibly due to an ammonia imbalance entering the catalyst, some flue gas bypassing the catalyst, or not enough catalyst volume. SO3 accounted for an average of 23% of the total sulfur oxides emissions measured. Some of the SO3 is formed in the combustion process, it is likely that the majority formed as the SO2 in the combustion products passed across the oxidizing CO catalyst and SCR catalyst. The 100 MW turbine sampled in this study emitted particle loadings similar to those previously measured from turbines in the SCAQMD area, however, the turbine exhaust contained far more particles than ambient air. The power consumed by an air conditioner accounts for a significant fraction of the total power used by hybrid and electric vehicles especially during summer. This study examined the effect of recirculation of cabin air on power consumption of mobile air conditioners both in-lab and on-road. Real time power consumption and vehicle mileage were recorded by an On Board Diagnostic monitor and carbon balance method. Vehicle mileage improved with increased cabin air recirculation. The recirculation of cabin air also significantly reduced in-cabin particle concentrations. Recirculation of cabin air is an excellent and immediate solution to increase vehicle mileage and improve cabin air quality.

A correlational method to concurrently measure envelope and temporal fine structure weights: effects of age, cochlear pathology, and spectral shaping.

PubMed

Fogerty, Daniel; Humes, Larry E

2012-09-01

The speech signal may be divided into spectral frequency-bands, each band containing temporal properties of the envelope and fine structure. This study measured the perceptual weights for the envelope and fine structure in each of three frequency bands for sentence materials in young normal-hearing listeners, older normal-hearing listeners, aided older hearing-impaired listeners, and spectrally matched young normal-hearing listeners. The availability of each acoustic property was independently varied through noisy signal extraction. Thus, the full speech stimulus was presented with noise used to mask six different auditory channels. Perceptual weights were determined by correlating a listener's performance with the signal-to-noise ratio of each acoustic property on a trial-by-trial basis. Results demonstrate that temporal fine structure perceptual weights remain stable across the four listener groups. However, a different weighting typography was observed across the listener groups for envelope cues. Results suggest that spectral shaping used to preserve the audibility of the speech stimulus may alter the allocation of perceptual resources. The relative perceptual weighting of envelope cues may also change with age. Concurrent testing of sentences repeated once on a previous day demonstrated that weighting strategies for all listener groups can change, suggesting an initial stabilization period or susceptibility to auditory training.

PROCESS FOR THE RECOVERY OF METALS FROM HIGH-LIME CARNOTITE ORES

DOEpatents

Grinstead, R.R.

1959-01-20

A process is presented for recovering uranium values from a high-lime carnotite ore comprising contacting the ore dispersed in a finely divided state with a concentrated mineral acid, adding an industrial orgnnic solvent containing alkyl ontho or pyro phosphoric acids, alkyl phosphates or alkyl phosphonates so as to effect an organic phase into which the metal value is leached and then recovering the metal value from the organic phase.

Solar selective surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Buskirk, O.R.

1982-01-12

Postformable solar selective coatings are disclosed for use on substrates such as aluminum. The coatings use a finely divided black inherently selective spinel pigment such as Co3O4, CuCr2O4 or CuxCo3-xO4 where X is 0.03 to 0.3 and preferably 0.10 to 0.30. The binders are soluble copolymers of vinylidene fluoride or blends thereof or vinylidene fluoride with a copolymer of methyl methacrylate.

China Report: Science and Technology, No. 209. China Addresses Environmental Issues -- 1/83

DTIC Science & Technology

1983-10-12

determines suc- cess or failure of a plan. The steps in planning can be divided into two stages , preparation and planning. The preparation stage ...Noise Control Legislation Requirements Surveyed (Wen Bobing; FAXUE YANJIU, No 6, 1982)........... 21 System of Two -Fines in...with constant improvement in economic results, it is necessary to adopt the two phase strategic plan of laying a good foundation in the first 10 years

Characterization of off-gases from a small-scale, joule-heated ceramic melter for nuclear waste vitrification. [Ru, Cl, F, /sup 137/Cs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Woolsey, G.B.; Wilhite, E.L.

1980-01-01

This paper confirmed with actual nuclear waste the thermodynamic predictions of the fate of some of the semivolatiles in off-gas. Ruthenium behaves erratically and it is postulated that it migrates as a finely divided solid, rather than as a volatile oxide. Provisions for handling these waste off-gasses will be incorporated in the design of facilities for vitrifying SRP waste.

Bi-axial grown amorphous MoSx bridged with oxygen on r-GO as a superior stable and efficient nonprecious catalyst for hydrogen evolution

PubMed Central

Lee, Cheol-Ho; Yun, Jin-Mun; Lee, Sungho; Jo, Seong Mu; Eom, KwangSup; Lee, Doh C.; Joh, Han-Ik; Fuller, Thomas F.

2017-01-01

Amorphous molybdenum sulfide (MoSx) is covalently anchored to reduced graphene oxide (r-GO) via a simple one-pot reaction, thereby inducing the reduction of GO and simultaneous doping of heteroatoms on the GO. The oxygen atoms form a bridged between MoSx and GO and play a crucial role in the fine dispersion of the MoSx particles, control of planar MoSx growth, and increase of exposed active sulfur sites. This bridging leads to highly efficient (−157 mV overpotential and 41 mV/decade Tafel slope) and stable (95% versus initial activity after 1000 cycles) electrocatalyst for hydrogen evolution. PMID:28106126

Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

NASA Astrophysics Data System (ADS)

Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

2014-12-01

Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications.

Micelle-template synthesis of nitrogen-doped mesoporous graphene as an efficient metal-free electrocatalyst for hydrogen production.

PubMed

Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

2014-12-19

Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications.

Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

PubMed Central

Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

2014-01-01

Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications. PMID:25523276

Reverse micelle synthesis of nanoscale metal containing catalysts. [Nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide nanoscale powders

DOE Office of Scientific and Technical Information (OSTI.GOV)

Darab, J.G.; Fulton, J.L.; Linehan, J.C.

1993-03-01

The need for morphological control during the synthesis of catalyst precursor powders is generally accepted to be important. In the liquefaction of coal, for example, iron-bearing catalyst precursor particles containing individual crystallites with diameters in the 1-100 nanometer range are believed to achieve good dispersion through out the coal-solvent slurry during liquefaction 2 runs and to undergo chemical transformations to catalytically active iron sulfide phases. The production of the nanoscale powders described here employs the confining spherical microdomains comprising the aqueous phase of a modified reverse micelle (MRM) microemulsion system as nanoscale reaction vessels in which polymerization, electrochemical reduction andmore » precipitation of solvated salts can occur. The goal is to take advantage of the confining nature of micelles to kinetically hinder transformation processes which readily occur in bulk aqueous solution in order to control the morphology and phase of the resulting powder. We have prepared a variety of metal, alloy, and metal- and mixed metal-oxide nanoscale powders from appropriate MRM systems. Examples of nanoscale powders produced include Co, Mo-Co, Ni[sub 3]Fe, Ni, and various oxides and oxyhydroxides of iron. Here, we discuss the preparation and characterization of nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide MRM nanoscale powders. We have used extended x-ray absorption fine structure (EXAFS) spectroscopy to study the chemical polymerization process in situ, x-ray diffraction (XRD), scanning and transmission electron microcroscopies (SEM and TEM), elemental analysis and structural modelling to characterize the nanoscale powders produced. The catalytic activity of these powders is currently being studied.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Pingping; Siddiqi, Georges; Vining, William C.

Catalysts for the dehydrogenation of light alkanes were prepared by dispersing Pt on the surface of a calcined hydrotalcite-like support containing indium, Mg(In)(Al)O. Upon reduction in H{sub 2} at temperatures above 673 K, bimetallic particles of PtIn are observed by TEM, which have an average diameter of 1 nm. Analysis of Pt LIII-edge extended X-ray absorption fine structure (EXAFS) data shows that the In content of the bimetallic particles increases with increasing bulk In/Pt ratio and reduction temperature. Pt LIII-edge X-ray absorption near edge structure (XANES) indicates that an increasing donation of electronic charge from In to Pt occurs withmore » increasing In content in the PtIn particles. The activity and selectivity of the Pt/Mg(In)(Al)O catalysts for ethane and propane dehydrogenation reactions are strongly dependent on the bulk In/Pt ratio. For both reactants, maximum activity was achieved for a bulk In/Pt ratio of 0.48, and at this In/Pt ratio, the selectivity to alkene was nearly 100%. Coke deposition was observed after catalyst use for either ethane or propane dehydrogenation, and it was observed that the alloying of Pt with In greatly reduced the amount of coke deposited. Characterization of the deposit by Raman spectroscopy indicates that the coke is present as highly disordered graphite particles <30 nm in diameter. While the amount of coke deposited during ethane and propane dehydrogenation are comparable, the effects on activity are dependent on reactant composition. Coke deposition had no effect on ethane dehydrogenation activity, but caused a loss in propane dehydrogenation activity. This difference is attributed to the greater ease with which coke produced on the surface of PtIn nanoparticles migrates to the support during ethane dehydrogenation versus propane dehydrogenation.« less

An efficient route to selective bio-oxidation catalysts: an iterative approach comprising modeling, diversification, and screening, based on CYP102A1.

PubMed

Seifert, Alexander; Antonovici, Mihaela; Hauer, Bernhard; Pleiss, Jürgen

2011-06-14

Perillyl alcohol is the terminal hydroxylation product of the cheap and readily available terpene, limonene. It has high potential as an anti-tumor substance, but is of limited availability. In principle, cytochrome P450 monooxygenases, such as the self-sufficient CYP102A1, are promising catalysts for the oxidation of limonene or other inert hydrocarbons. The wild-type enzyme converts (4R)-limonene to four different oxidation products; however, terminal hydroxylation at the allylic C7 is not observed. Here we describe a generic strategy to engineer this widely used enzyme to hydroxylate exclusively the exposed, but chemically less reactive, primary C7 in the presence of other reactive positions. The approach presented here turns CYP102A1 into a highly selective catalyst with a shifted product spectra by successive rounds of modeling, the design of small focused libraries, and screening. In the first round a minimal CYP102A1 mutant library was rationally designed. It contained variants with improved or strongly shifted regio-, stereo- and chemoselectivity, compared to wild-type. From this library the variant with the highest perillyl alcohol ratio was fine-tuned by two additional rounds of molecular modeling, diversification, and screening. In total only 29 variants needed to be screened to identify the triple mutant A264V/A238V/L437F that converts (4R)-limonene to perillyl alcohol with a selectivity of 97 %. Focusing mutagenesis on a small number of relevant positions identified by computational approaches is the key for efficient screening for enzyme selectivity. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of dopant distribution on aging of catalytic Cr-doped transition aluminas

NASA Astrophysics Data System (ADS)

Borisevich, Albina; Rashkeev, Sergey; Wang, Sanwu; Glazoff, Michael; Sohlberg, Karl; Pennycook, Stephen; Pantelides, Sokrates

2004-03-01

Metastable (transition) aluminas, in particular γ -Al_2O3 and η -Al_2O_3, are widely used as catalysts as well as supports for different transition metals. When doped with Cr, the two modifications exhibit remarkably different aging behavior: γ -Al_2O_3-supported catalysts degrade two orders of magnitude faster than those based on η -Al_2O_3. Here we use a combination of Z-contrast aberration-corrected scanning transmission electron microscopy (STEM), electron energy loss spectroscopy (EELS), and extended X-ray absorption fine structure (EXAFS) studies with first-principles calculations to determine the origin of this disparity. EXAFS data reveal that the coordination environments of Cr in the two forms are significantly different. STEM and EELS observations demonstrate that on γ -Al_2O3 Cr tends to segregate and form Cr_2O_3, while on η -Al_2O3 Cr is uniformly distributed. The reason for the dissimilarity, as shown by first-principles calculations, lies in the different reconstruction of the preferentially exposed 110 surface. In γ -Al_2O_3, it serves to destabilize the catalytically active Cr sites, at the same time inducing the formation of Cr_2O_3, while in η -Al_2O3 Cr atoms stay dispersed on the surface and catalytically active. This work provides interesting insights in the aging behavior of transition-metal based catalysts. Authors thank Dr. Saeed Alerasool (Engelhard Corp., Beechwood, OH) for providing samples and DOE (Grants DE-AC05-00OR22725 and DE-FC02-01CH11085) and NSF (Grant DMR-0111841) for financial support.

Commercial-scale demonstration of the Liquid Phase Methanol (LPMEOH{trademark}) process. Technical progress report number 6, October 1--December 31, 1995

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1996-12-31

The project involves the construction of an 80,000 gallons per day (260 TPD) methanol unit utilizing coal-derived synthesis gas from Eastman`s integrated coal gasification facility. The new equipment consists of synthesis gas feed preparation and compression facilities, the liquid phase reactor and auxiliaries, product distillation facilities, and utilities. The technology to be demonstrated is the product of a cooperative development effort by Air Products and DOE in a program that started in 1981. Developed to enhance electric power generation using integrated gasification combined cycle (IGCC) technology, the LPMEOH{trademark} process is ideally suited for directly processing gases produced by modern-day coalmore » gasifiers. This liquid phase process suspends fine catalyst particles in an inert liquid, forming a slurry. The slurry dissipates the heat of the chemical reaction away from the catalyst surface protecting the catalyst and allowing the methanol synthesis reaction to proceed at higher rates. At the Eastman complex, the technology will be integrated with existing coal-gasifiers. A carefully developed test plan will allow operations at Eastman to simulate electricity demand load-following in coal-based IGCC facilities. The operations will also demonstrate the enhanced stability and heat dissipation of the conversion process, its reliable on/off operation, and its ability to produce methanol as a clean liquid fuel without additional upgrading. An off-site product testing program will be conducted to demonstrate the suitability of the methanol product as a transportation fuel and as a fuel for stationary applications for small modular electric power generators for distributed power.« less

Size-Controlled Synthesis of Sub-10 nm PtNi3 Alloy Nanoparticles and their Unusual Volcano-Shaped Size Effect on ORR Electrocatalysis.

PubMed

Gan, Lin; Rudi, Stefan; Cui, Chunhua; Heggen, Marc; Strasser, Peter

2016-06-01

Dealloyed Pt bimetallic core-shell catalysts derived from low-Pt bimetallic alloy nanoparticles (e.g, PtNi3 ) have recently shown unprecedented activity and stability on the cathodic oxygen reduction reaction (ORR) under realistic fuel cell conditions and become today's catalyst of choice for commercialization of automobile fuel cells. A critical step toward this breakthrough is to control their particle size below a critical value (≈10 nm) to suppress nanoporosity formation and hence reduce significant base metal (e.g., Ni) leaching under the corrosive ORR condition. Fine size control of the sub-10 nm PtNi3 nanoparticles and understanding their size dependent ORR electrocatalysis are crucial to further improve their ORR activity and stability yet still remain unexplored. A robust synthetic approach is presented here for size-controlled PtNi3 nanoparticles between 3 and 10 nm while keeping a constant particle composition and their size-selected growth mechanism is studied comprehensively. This enables us to address their size-dependent ORR activities and stabilities for the first time. Contrary to the previously established monotonic increase of ORR specific activity and stability with increasing particle size on Pt and Pt-rich bimetallic nanoparticles, the Pt-poor PtNi3 nanoparticles exhibit an unusual "volcano-shaped" size dependence, showing the highest ORR activity and stability at the particle sizes between 6 and 8 nm due to their highest Ni retention during long-term catalyst aging. The results of this study provide important practical guidelines for the size selection of the low Pt bimetallic ORR electrocatalysts with further improved durably high activity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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.

Emissions of sulfur trioxide from coal-fired power plants.

PubMed

Srivastava, R K; Miller, C A; Erickson, C; Jambhekar, R

2004-06-01

Emissions of sulfur trioxide (SO3) are a key component of plume opacity and acid deposition. Consequently, these emissions need to be low enough to not cause opacity violations and acid deposition. Generally, a small fraction of sulfur (S) in coal is converted to SO3 in coal-fired combustion devices such as electric utility boilers. The emissions of SO3 from such a boiler depend on coal S content, combustion conditions, flue gas characteristics, and air pollution devices being used. It is well known that the catalyst used in the selective catalytic reduction (SCR) technology for nitrogen oxides control oxidizes a small fraction of sulfur dioxide in the flue gas to SO3. The extent of this oxidation depends on the catalyst formulation and SCR operating conditions. Gas-phase SO3 and sulfuric acid, on being quenched in plant equipment (e.g., air preheater and wet scrubber), result in fine acidic mist, which can cause increased plume opacity and undesirable emissions. Recently, such effects have been observed at plants firing high-S coal and equipped with SCR systems and wet scrubbers. This paper investigates the factors that affect acidic mist production in coal-fired electric utility boilers and discusses approaches for mitigating emission of this mist.

Towards efficient chemical synthesis via engineering enzyme catalysis in biomimetic nanoreactors.

PubMed

Liu, Jia; Yang, Qihua; Li, Can

2015-09-18

Biocatalysis with immobilized enzymes as catalysts holds enormous promise in developing more efficient and sustainable processes for the synthesis of fine chemicals, chiral pharmaceuticals and biomass feedstocks. Despite the appealing potentials, nowadays the industrial-scale application of biocatalysts is still quite modest in comparison with that of traditional chemical catalysts. A critical issue is that the catalytic performance of enzymes, the sophisticated and vulnerable catalytic machineries, strongly depends on their intracellular working environment; however the working circumstances provided by the support matrix are radically different from those in cells. This often leads to various adverse consequences on enzyme conformation and dynamic properties, consequently decreasing the overall performance of immobilized enzymes with regard to their activity, selectivity and stability. Engineering enzyme catalysis in support nanopores by mimicking the physiological milieu of enzymes in vivo and investigating how the interior microenvironment of nanopores imposes an influence on enzyme behaviors in vitro are of paramount significance to modify and improve the catalytic functions of immobilized enzymes. In this feature article, we have summarized the recent advances in mimicking the working environment and working patterns of intracellular enzymes in nanopores of mesoporous silica-based supports. Especially, we have demonstrated that incorporation of polymers into silica nanopores could be a valuable approach to create the biomimetic microenvironment for enzymes in the immobilized state.

Tailoring the Hydrothermal Synthesis of Stainless Steel Wire Sieve-Supported Ag-Doped ZnO Nanowires to Optimize Their Photo-catalytic Activity

NASA Astrophysics Data System (ADS)

Jing, W. X.; Shi, J. F.; Xu, Z. P.; Jiang, Z. D.; Wei, Z. Y.; Zhou, F.; Wu, Q.; Cui, Q. B.

2018-03-01

Batches of un-doped and Ag-doped ZnO nanowires (ZnONWs) were prepared hydrothermally on stainless steel wire sieves at varied Zn2+ concentrations of the growth solution and at different Ag+ concentrations of the silver nitrate solution. Methylene blue solution was degraded with these as-prepared ZnONWs in the presences of ultraviolet irradiation. It is found that both the processing parameters greatly affect the surface textures, wettability, and photo-activity of the ZnONWs. The latter synthesizing parameter is optimized only after the former one has been finely regulated. The un-doped and Ag-doped ZnONWs at Zn2+ concentration of 75 mM of the growth solution and at Ag+ concentration of3 mM of the silver nitrate solution both produce Gaussian rough surfaces and in each batch are most hydrophilic. Therefore, in the related batch the contacting surface area of the catalyst is the largest, the hydroxyl radicals attached on the top ends of corresponding ZnONWs the most, and the catalytic activity of these catalysts the optimal. Besides these, the latter synthesizing parameter affects the photo-activity of Ag-doped ZnONWs more significantly than the former one does that of un-doped ZnONWs.

Data on PKO biodiesel production using CaO catalyst from Turkey bones.

PubMed

Ayoola, A A; Fayomi, O S I; Usoro, I F

2018-08-01

In this research paper the production of biodiesel from palm kernel oil (PKO) using CaO obtained from waste turkey bones (WTB) and analytical grade calcium oxide was investigated. Treated WTB was reduced to fine particulate size of <150 µm and then calcinated at 800 °C for 3 h to increase its catalytic activity by its conversion from Calcium phosphate hydroxide (Ca 10 P 6 O 26 H 2 ) to CaO. X-ray diffraction (XRD) and X-ray fluorescent (XRF) analysis of the analytical grade CaO, uncalcined and calcined WTB were carried out to establish their elemental chemical composition. The transesterification reaction between the triglyceride of palm kernel oil (PKO) and methanol was carried out at a constant agitation speed of 600 rpm and temperature of 65 °C, with varied methanol to oil molar ratio (8-14), catalyst concentration (1-7 wt/wt%) and the reaction time (1-3 h). Minitab 17 software (using response surface method) was employed for the design of experiment and statistical analysis required in the transesterification process of biodiesel production. The qualities of the biodiesel produced were assessed and the results obtained showed conformity of the biodiesel produced to the ASTM standard for biodiesel.

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.

PubMed

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.

Thermal Emission Spectroscopy of 1 Ceres: Evidence for Olivine

NASA Technical Reports Server (NTRS)

Witteborn, Fred. C.; Roush, Ted L.; Cohen, Martin

1999-01-01

Thermal emission spectra of the largest asteroid, 1 Ceres, obtained from the Kuiper Airborne Observatory display features that may provide information about its surface mineralogy. The emissivity, obtained by dividing the spectra by a standard thermal model, is compared with emissivity spectra of olivines and phyllosilicates deduced via Kirchoff's law from reflectivity measurements. The spectra provide a fairly good match to fine grained olivines (0 to 5 micrometer size range). The smoothness of the spectrum beyond 18 micrometers is an indication of particles smaller than 50 micrometers. While the abrupt rise in emissivity near 8 micrometers matches many silicates, the distinct emissivity minimum centered near 12.8 micrometers is consistant with iron-poor olivines, but not with phyllosilicates. It suggests the presence of opaques and does not exclude a mixture with organics and fine-grained phyllosilicates.

Photocatalytic oxidation of organic compounds via waveguide-supported titanium dioxide films

NASA Astrophysics Data System (ADS)

Miller, Lawrence W.

A photochemical reactor based on titanium dioxide (TiO2)-coated silica optical fibers was constructed to explore the use of waveguide-supported TiO2 films for photocatalytic oxidation of organic compounds. The reactor was used for the photocatalytic oxidation of 4-chlorophenol in water. It was confirmed that TiO2 films could be securely attached to silica optical fibers. The 4-chlorophenol (100 mumol/L in water) was successfully oxidized on the TiO2 surface when UV light (310 nm--380 nm) was propagated through the fibers to the films. Rates of 4-chlorophenol oxidation and UV light flux to the fibers were measured. The quantum efficiency of 4-chlorophenol oxidation [defined as the change in 4-chlorophenol concentration divided by the UV light absorbed by the catalyst] was determined as a function of TiO2 catalyst film thickness and internal incident angle of propagating UV light. A maximum quantum efficiency of 2.8% was measured when TiO2 film thickness was ca. 80 nm and the maximum internal incident angle of propagating light was 84°. Quantum efficiency increased with increasing internal angle of incidence of propagating light and decreased with TiO2 film thickness. UV-Visible internal reflection spectroscopy was used to determine whether UV light propagated through TiO2-coated silica waveguides in an ATR mode. Propagation of UV light in an ATR mode was confirmed by the similarities between internal reflection spectra of phenolphthalein obtained with uncoated and TiO2-coated silica crystals. Planar silica waveguides coated with TiO2 were employed in a photocatalytic reactor for the oxidation of formic acid (833 mumol/L in water). It was shown that the quantum yield of formic acid oxidation [defined as the moles of formic acid oxidized divided by the moles of UV photons absorbed by the catalyst] on the waveguide-supported TiO2 surface is enhanced when UV light propagates through the waveguides in an ATR mode. A maximum quantum yield of 3.9% was found for formic acid oxidation on silica waveguides. The waveguides were coated with 150 nm of TiO2 and activated with UV light (lambdamax = 360 nm) propagating through the waveguides at an internal incident angle of 68°.

Engaging a Diverse Group of Students with a Broad Spectrum of Geological Experience: The CSUN Catalyst Approach and a MARGINS Application

NASA Astrophysics Data System (ADS)

Marsaglia, K. M.; Vazquez, J.; Yule, J. D.; Simila, G.

2007-12-01

Imagine the challenge of teaching a one-unit Geoscience course composed of a diverse mix of first-year graduate majors, senior to freshman majors, and high school students with little earth science background. With the help of Geodiversity grants from NSF (CSUN Catalyst program), we have developed a successful environment for learning and mentorship via a series of short (2-3 week) inquiry-based exercises that emphasize teamwork. Each exercise is organized around research projects headed by Catalyst Faculty members: Northridge Earthquake, San Andreas Fault System, Yellowstone and Long Valley supervolcanoes, and New Zealand MARGIN geology. After participating in the course, students conduct independent research within one of four research groups as part of their MS or BS theses including summer research experiences. One exercise, constructed as a version of "The Oil Game," is meant to familiarize students with MARGINS Source-to-Sink focus (Waipaoa Sedimentary System, North Island) and alternate focus (Bounty Fan, South Island) sites in New Zealand. Students are divided into rival petroleum companies (Tiger Oil and Flower Petroleum) and asked to evaluate offshore areas for an impending government lease sale and to provide the rationale for competitive sealed bids that they recommend in a final presentation to management (Catalyst Faculty). To accomplish this they are supplied with reference materials on onshore geology and known petroleum production, samples of New Zealand rock units and stream sediments, and a limited budget. In addition to geological parameters (source rocks, seals, reservoir rocks, trapping mechanisms) they must also take into account environmental, economic and infrastructure concerns. Other projects included documenting volcanic hazards around Long Valley caldera and evaluating seismic hazards of local high school sites. The tiered structure of the projects perhaps best serves the undergraduate participants, who benefit from being mentored by graduate students as well as serving as mentors for the high school students.

Catalytic and electrocatalytic hydrogenolysis of brominated diphenyl ethers.

PubMed

Bonin, Pascale M L; Edwards, Patrick; Bejan, Dorin; Lo, Chun Chi; Bunce, Nigel J; Konstantinov, Alexandre D

2005-02-01

Polybrominated diphenyl ethers (PBDEs) are ubiquitous environmental contaminants due to their use as additive flame-retardants. Conventional catalytic hydrogenolysis in methanol solution and electrocatalytic hydrogenolysis in aqueous methanol were examined as methods for debrominating mono- and di-bromodiphenyl ethers, as well as a commercial penta-PBDE mixture, in each case using palladium on alumina as the catalyst. Electrocatalytic hydrogenolysis employed a divided flow-through batch cell, with reticulated vitreous carbon cathodes and IrO2/Ti dimensionally stable anodes. Both methods gave efficient sequential debromination, with essentially complete removal of bromine from the PBDEs, but the electrocatalytic method was limited by the poor solubility of PBDEs in aqueous methanol.

Is It Homogeneous or Heterogeneous Catalysis Derived from [RhCp*Cl2]2? In Operando-XAFS, Kinetic and Crucial Kinetic Poisoning Evidence for Subnanometer Rh4 Cluster-Based Benzene Hydrogenation Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bayram, Ercan; Linehan, John C.; Fulton, John L.

2011-11-23

Determining the true, kinetically dominant catalytically active species, in the classic benzene hydrogenation system pioneered by Maitlis and co-workers 34 years ago starting with [RhCp*Cl2]2 (Cp* = [{eta}5-C5(CH3)5]), has proven to be one of the most challenging case studies in the quest to distinguish single-metal-based 'homogeneous' from polymetallic, 'heterogeneous' catalysis. The reason, this study will show, is the previous failure to use the proper combination of (i) operando spectroscopy to determine the dominant form(s) of the precatalyst's mass under catalysis (i.e., operating) conditions, plus then and crucially also (ii) the previous lack of the necessary kinetic studies, catalysis being amore » 'wholly kinetic phenomenon' as J. Halpern long ago noted. An important contribution from this study will be to reveal the power of quantitiative kinetic poisoning experiments for distinguishing single-metal, or in this case subnanometer Rh4 cluster-based catalysis from larger, polymetallic Rh(0)n nanoparticle catalysis, at least under favorable conditions. The combined operando-XAFS (X-ray absorption fine structure) spectroscopy and kinetic evidences provide a compelling case for Rh4-based, with average stoichiometry 'Rh4Cp*2.4Cl4Hc', benzene hydrogenation catalysis in 2-propanol with added Et3N and at 100 C and 50 atm initial H2 pressure. The results also reveal, however, that if even ca. 1.4% of the total soluble Rh(0)n had formed nanoparticles, then those Rh(0)n nanoparticles would have been able to account for all the observed benzene hydrogenation catalytic rate (using commercial, ca. 2 nm, polyethyleneglycol-dodecylether hydrosol stabilized Rh(0)n nanoparticles as a model system). The results 'especially the poisoning methodology developed and employed' are of significant, broader interest since determining the nature of the true catalyst continues to be a central, often vexing issue in any and all catalytic reactions. The results are also of fundamental interest in that they add to a growing body of evidence indicating that certain, appropriately ligated, coordinatively unsaturated, subnanometer M4 transition-metal clusters can be relatively robust catalysts. Also demonstrated herein is that Rh4 clusters are poisoned by Hg(0), demonstrating for the first time that the classic Hg(0) poisoning test of 'homogeneous' vs 'heterogeneous'catalysts cannot distinguish Rh4-based subnanometer catalysts from Rh(0)n nanoparticle catalysts, at least for the present examples of these two specific, Rh-based catalysts.« less

Transport mechanisms of contaminants released from fine sediment in rivers

NASA Astrophysics Data System (ADS)

Cheng, Pengda; Zhu, Hongwei; Zhong, Baochang; Wang, Daozeng

2015-12-01

Contaminants released from sediment into rivers are one of the main problems to study in environmental hydrodynamics. For contaminants released into the overlying water under different hydrodynamic conditions, the mechanical mechanisms involved can be roughly divided into convective diffusion, molecular diffusion, and adsorption/desorption. Because of the obvious environmental influence of fine sediment (D_{90}= 0.06 mm), non-cohesive fine sediment, and cohesive fine sediment are researched in this paper, and phosphorus is chosen for a typical adsorption of a contaminant. Through theoretical analysis of the contaminant release process, according to different hydraulic conditions, the contaminant release coupling mathematical model can be established by the N-S equation, the Darcy equation, the solute transport equation, and the adsorption/desorption equation. Then, the experiments are completed in an open water flume. The simulation results and experimental results show that convective diffusion dominates the contaminant release both in non-cohesive and cohesive fine sediment after their suspension, and that they contribute more than 90 % of the total release. Molecular diffusion and desorption have more of a contribution for contaminant release from unsuspended sediment. In unsuspension sediment, convective diffusion is about 10-50 times larger than molecular diffusion during the initial stages under high velocity; it is close to molecular diffusion in the later stages. Convective diffusion is about 6 times larger than molecular diffusion during the initial stages under low velocity, it is about a quarter of molecular diffusion in later stages, and has a similar level with desorption/adsorption. In unsuspended sediment, a seepage boundary layer exists below the water-sediment interface, and various release mechanisms in that layer mostly dominate the contaminant release process. In non-cohesive fine sediment, the depth of that layer increases linearly with shear stress. In cohesive fine sediment, the range seepage boundary is different from that in non-cohesive sediment, and that phenomenon is more obvious under a lower shear stress.

Improving Attachments of Non-Invasive (Type III) Electronic Data Loggers to Cetaceans

DTIC Science & Technology

2015-09-30

animals in human care will be performed to test and validate this approach. The cadaver trials will enable controlled testing to failure or with both...quantitative metrics and analysis tools to assess the impact of a tag on the animal . Here we will present: 1) the characterization of the mechanical...fine scale motion analysis for swimming animals . 2 APPROACH Our approach is divided into four subtasks: Task 1: Forces and failure modes

Structural wood panels with improved fire resistance

NASA Technical Reports Server (NTRS)

Sawko, P. M. (Inventor)

1980-01-01

Structural wood paneling or other molded wood compositions consisting of finely divided wood chips, flour, or strands are bound together and hot pressed with a modified novolac resin which is the cured product of a prepolymer made from an aralkyl ether or halide with a phenol and a hardening agent such as hexamethylene tetramine. The fire resistance of these articles is further improved by incorporating in the binder certain inorganic fillers, especially a mixture of ammonium oxalate and ammonium phosphate.

A correlational method to concurrently measure envelope and temporal fine structure weights: Effects of age, cochlear pathology, and spectral shaping1

PubMed Central

Fogerty, Daniel; Humes, Larry E.

2012-01-01

The speech signal may be divided into spectral frequency-bands, each band containing temporal properties of the envelope and fine structure. This study measured the perceptual weights for the envelope and fine structure in each of three frequency bands for sentence materials in young normal-hearing listeners, older normal-hearing listeners, aided older hearing-impaired listeners, and spectrally matched young normal-hearing listeners. The availability of each acoustic property was independently varied through noisy signal extraction. Thus, the full speech stimulus was presented with noise used to mask six different auditory channels. Perceptual weights were determined by correlating a listener’s performance with the signal-to-noise ratio of each acoustic property on a trial-by-trial basis. Results demonstrate that temporal fine structure perceptual weights remain stable across the four listener groups. However, a different weighting typography was observed across the listener groups for envelope cues. Results suggest that spectral shaping used to preserve the audibility of the speech stimulus may alter the allocation of perceptual resources. The relative perceptual weighting of envelope cues may also change with age. Concurrent testing of sentences repeated once on a previous day demonstrated that weighting strategies for all listener groups can change, suggesting an initial stabilization period or susceptibility to auditory training. PMID:22978896

Enamel and Dentin Surface Finishing Influence on the Roughness and Microshear Bond Strength of a Lithium Silicate Glass-Ceramic for Laminate Veneers

PubMed Central

Gonzaga, Carla Castiglia; Bravo, Ruth Peggy; Pavelski, Thiago Vinícius; Garcia, Paula Pontes; Correr, Gisele Maria; Leonardi, Denise Piotto; da Cunha, Leonardo Fernandes; Furuse, Adilson Yoshio

2015-01-01

Objectives. This study evaluated the influence of cavity surface finishing with diamond burs of different grit mounted on high-speed turbine and ultrasound on the roughness and microshear bond strength (MBS) of a lithium silicate glass-ceramic to enamel and dentin. Methods. Enamel and dentin specimens were divided into seven groups, according to the type of surface finishing: 1200-grit sandpaper (control), two different brands of medium-grit and fine-grit diamond burs in a high-speed turbine; medium-grit and fine-grit CVD (chemical vapor deposition) tips in an ultrasonic device. Roughness parameters (n = 5) and MSBS to a glass-ceramic (n = 10) were determined. Data were analyzed using ANOVA and Tukey's test (α = 5%). Results. Control group showed lower mean roughness readings and groups that used medium-grit diamond burs showed the highest mean roughness values. Regarding MSBS, there was no statistical difference when comparing the groups gritted with the same brand of medium- and fine-grit burs and tips. Conclusions. Cavity surface finishing influenced the roughness parameters and MSBS of a glass-ceramic to enamel and dentin. Medium-grit diamond burs in high-speed turbine showed the highest mean roughness values. Fine-grit CVD tips in ultrasound presented the highest MSBS values for both enamel and dentin. PMID:27347507

Enamel and Dentin Surface Finishing Influence on the Roughness and Microshear Bond Strength of a Lithium Silicate Glass-Ceramic for Laminate Veneers.

PubMed

Gonzaga, Carla Castiglia; Bravo, Ruth Peggy; Pavelski, Thiago Vinícius; Garcia, Paula Pontes; Correr, Gisele Maria; Leonardi, Denise Piotto; da Cunha, Leonardo Fernandes; Furuse, Adilson Yoshio

2015-01-01

Objectives. This study evaluated the influence of cavity surface finishing with diamond burs of different grit mounted on high-speed turbine and ultrasound on the roughness and microshear bond strength (MBS) of a lithium silicate glass-ceramic to enamel and dentin. Methods. Enamel and dentin specimens were divided into seven groups, according to the type of surface finishing: 1200-grit sandpaper (control), two different brands of medium-grit and fine-grit diamond burs in a high-speed turbine; medium-grit and fine-grit CVD (chemical vapor deposition) tips in an ultrasonic device. Roughness parameters (n = 5) and MSBS to a glass-ceramic (n = 10) were determined. Data were analyzed using ANOVA and Tukey's test (α = 5%). Results. Control group showed lower mean roughness readings and groups that used medium-grit diamond burs showed the highest mean roughness values. Regarding MSBS, there was no statistical difference when comparing the groups gritted with the same brand of medium- and fine-grit burs and tips. Conclusions. Cavity surface finishing influenced the roughness parameters and MSBS of a glass-ceramic to enamel and dentin. Medium-grit diamond burs in high-speed turbine showed the highest mean roughness values. Fine-grit CVD tips in ultrasound presented the highest MSBS values for both enamel and dentin.

The influence of a real job on upper limb performance in motor skill tests: which abilities are transferred?

PubMed

Giangiardi, Vivian Farahte; Alouche, Sandra Regina; de Freitas, Sandra Maria Sbeghen Ferreira; Pires, Raquel Simoni; Padula, Rosimeire Simprini

2018-06-01

To investigate whether the specificities of real jobs create distinctions in the performance of workers in different motor tests for the upper limbs, 24 participants were divided into two groups according to their specific job: fine and repetitive tasks and general tasks. Both groups reproduced tasks related to aiming movements, handling and strength of the upper limbs. There were no significant differences between groups in the dexterity and performance of aiming movements. However, the general tasks group had higher grip strength than the repetitive tasks group, demonstrating differences according to job specificity. The results suggest that a particular motor skill in a specific job cannot improve performance in other tasks with the same motor requirements. The transfer of the fine and gross motor skills from previous experience in a job-specific task is the basis for allocating training and guidance to workers.

Biomass-derived Syngas Utilization for Fuels and Chemicals - Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dayton, David C

2010-03-24

Executive Summary The growing gap between petroleum production and demand, mounting environmental concerns, and increasing fuel prices have stimulated intense interest in research and development (R&D) of alternative fuels, both synthetic and bio-derived. Currently, the most technically defined thermochemical route for producing alternative fuels from lignocellulosic biomass involves gasification/reforming of biomass to produce syngas (carbon monoxide [CO] + hydrogen [H2]), followed by syngas cleaning, Fischer-Tropsch synthesis (FTS) or mixed alcohol synthesis, and some product upgrading via hydroprocessing or separation. A detailed techno-economic analysis of this type of process has recently been published [1] and it highlights the need for technicalmore » breakthroughs and technology demonstration for gas cleanup and fuel synthesis. The latter two technical barrier areas contribute 40% of the total thermochemical ethanol cost and 70% of the production cost, if feedstock costs are factored out. Developing and validating technologies that reduce the capital and operating costs of these unit operations will greatly reduce the risk for commercializing integrated biomass gasification/fuel synthesis processes for biofuel production. The objective of this project is to develop and demonstrate new catalysts and catalytic processes that can efficiently convert biomass-derived syngas into diesel fuel and C2-C4 alcohols. The goal is to improve the economics of the processes by improving the catalytic activity and product selectivity, which could lead to commercialization. The project was divided into 4 tasks: Task 1: Reactor Systems: Construction of three reactor systems was a project milestone. Construction of a fixed-bed microreactor (FBR), a continuous stirred tank reactor (CSTR), and a slurry bubble column reactor (SBCR) were completed to meet this milestone. Task 2: Iron Fischer-Tropsch (FT) Catalyst: An attrition resistant iron FT catalyst will be developed and tested. Task 3: Chemical Synthesis: Promising process routes will be identified for synthesis of selected chemicals from biomass-derived syngas. A project milestone was to select promising mixed alcohol catalysts and screen productivity and performance in a fixed bed micro-reactor using bottled syngas. This milestone was successfully completed in collaboration withour catalyst development partner. Task 4: Modeling, Engineering Evaluation, and Commercial Assessment: Mass and energy balances of conceptual commercial embodiment for FT and chemical synthesis were completed.« less

Synthesis and x-ray characterization of cobalt phosphide (Co₂P) nanorods for the oxygen reduction reaction

DOE PAGES

Doan-Nguyen, Vicky V.T.; Su, Dong; Zhang, Sen; ...

2015-07-14

Low temperature fuel cells are clean, effective alternative fuel conversion technology. Oxygen reduction reaction (ORR) at the fuel cell cathode has required Pt as the electrocatalyst for high activity and selectivity of the four-electron reaction pathway. Targeting a less expensive, earth abundant alternative, we have developed the synthesis of cobalt phosphide (Co₂P) nanorods for ORR. Characterization techniques that include total X-ray scattering and extended X-ray absorption fine structure revealed a deviation of the nanorods from bulk crystal structure with a contraction along the b orthorhombic lattice parameter. The carbon supported nanorods have comparable activity but are remarkably more stable thanmore » conventional Pt catalysts for the oxygen reduction reaction in alkaline environments.« less

Fast Synthesis of Pt Nanocrystals and Pt/Microporous La2O3 Materials Using Acoustic Levitation.

PubMed

Yu, Yinkai; Qu, Shaohua; Zang, Duyang; Wang, Liuding; Wu, Hongjing

2018-02-13

Usually, we must use an appropriate support material to keep the metal species stable and finely dispersed as supported metal nanoparticles for industry application. Therefore, the choice of support material is a key factor in determining the dispersion and particle size of the noble metal species. Here, we report the synthesis of a single-atom Pt material in the solution and supported Pt nanoclusters on microporous La 2 O 3 by a one-step acoustic levitation method without any pretreatment/modification of raw oxide. We have strongly contributed to the synthetic methodology of the surface/interfacial heterogeneous catalysts in this study, and this finding could open another door for synthesis of supported metal nanoparticles on porous materials for environmental catalysis.

Fast Synthesis of Pt Nanocrystals and Pt/Microporous La2O3 Materials Using Acoustic Levitation

NASA Astrophysics Data System (ADS)

Yu, Yinkai; Qu, Shaohua; Zang, Duyang; Wang, Liuding; Wu, Hongjing

2018-02-01

Usually, we must use an appropriate support material to keep the metal species stable and finely dispersed as supported metal nanoparticles for industry application. Therefore, the choice of support material is a key factor in determining the dispersion and particle size of the noble metal species. Here, we report the synthesis of a single-atom Pt material in the solution and supported Pt nanoclusters on microporous La2O3 by a one-step acoustic levitation method without any pretreatment/modification of raw oxide. We have strongly contributed to the synthetic methodology of the surface/interfacial heterogeneous catalysts in this study, and this finding could open another door for synthesis of supported metal nanoparticles on porous materials for environmental catalysis.

Conversion of polymers of methyl- and vinylsilane to Si-C ceramics

NASA Technical Reports Server (NTRS)

Hurwitz, Frances I.; Kacik, Terrance A.; Bu, Xin-Ya; Masnovi, John; Heimann, Paula J.; Beyene, Kassahun

1994-01-01

Poly(methylsilane) and poly(vinylsilane) were synthesized using a titanocene catalyst, and their pyrolytic conversion to ceramics was followed using a combination of thermal analysis and infrared spectroscopy. The two polymers have distinctly different backbone structures, as determined by Si NMR; methylsilane polymerizes to a polysilane, while vinylsilane polymers have predominately polycarbosilane backbone, with some polysilane structure as well. The pyrolysis path and char yield were dependent primarily on backbone structure, with little influence of polymer molecular weight. The majority of the weight loss on conversion occurs below 650 degrees C, although bond rearrangement continues to 1400 degrees C. Poly(vinylsilane) produced a C-rich Si-C ceramic in which the carbon was dispersed on a sufficiently fine level to show resistance to oxidation on heating in air to 1400 degrees C.

Mathematical modeling of atmospheric fine particle-associated primary organic compound concentrations

NASA Astrophysics Data System (ADS)

Rogge, Wolfgang F.; Hildemann, Lynn M.; Mazurek, Monica A.; Cass, Glen R.; Simoneit, Bernd R. T.

1996-08-01

An atmospheric transport model has been used to explore the relationship between source emissions and ambient air quality for individual particle phase organic compounds present in primary aerosol source emissions. An inventory of fine particulate organic compound emissions was assembled for the Los Angeles area in the year 1982. Sources characterized included noncatalyst- and catalyst-equipped autos, diesel trucks, paved road dust, tire wear, brake lining dust, meat cooking operations, industrial oil-fired boilers, roofing tar pots, natural gas combustion in residential homes, cigarette smoke, fireplaces burning oak and pine wood, and plant leaf abrasion products. These primary fine particle source emissions were supplied to a computer-based model that simulates atmospheric transport, dispersion, and dry deposition based on the time series of hourly wind observations and mixing depths. Monthly average fine particle organic compound concentrations that would prevail if the primary organic aerosol were transported without chemical reaction were computed for more than 100 organic compounds within an 80 km × 80 km modeling area centered over Los Angeles. The monthly average compound concentrations predicted by the transport model were compared to atmospheric measurements made at monitoring sites within the study area during 1982. The predicted seasonal variation and absolute values of the concentrations of the more stable compounds are found to be in reasonable agreement with the ambient observations. While model predictions for the higher molecular weight polycyclic aromatic hydrocarbons (PAH) are in agreement with ambient observations, lower molecular weight PAH show much higher predicted than measured atmospheric concentrations in the particle phase, indicating atmospheric decay by chemical reactions or evaporation from the particle phase. The atmospheric concentrations of dicarboxylic acids and aromatic polycarboxylic acids greatly exceed the contributions that are due to direct emissions from primary sources, confirming that these compounds are principally formed by atmospheric chemical reactions.

Treatment feasibility study of osteoporosis using minimal invasive laser needle system

NASA Astrophysics Data System (ADS)

Kang, Dongyeon; Ko, Chang-Yong; Ryu, Yeon-Hang; Park, Sunwook; Kim, Han-Sung; Jung, Byungjo

2010-02-01

Although the mechanism of laser stimulation effect in bone has not completely understood, laser stimulation is recommended in the treatment of osteoporosis due to positive treatment efficacy. In this study, a minimal invasive laser needle system (MILNS) was developed using a fine hollow needle in order to stimulate directly bone site by guiding an optical fiber. In order to evaluate the MILNS as a treatment method, in-vivo animal experiment study was performed using osteopenic mice. Twelve virginal ICR mice were employed and divided two groups: SHAM-group and LASERgroup. SHARM-group was stimulated by only fine hollow needle and LASER-group by fine hollow needle combined with laser stimulation. All mice were served in-vivo micro-CT images before and after treatment. Three dimensional (3D) structural parameters and vBMD (volume bone mineral density, g/cm3) in the trabecular bone were measured. After 2 weeks of stimulation, the vBMD, BV/TV, Tb.Th and Tb.N in LASER-group were significantly higher than those in SHAM-group (p<0.05). Potentially, this study suggested that the MILNS might prevent the bone loss and maintains the bone mineral density of osteopenic mice.

Fine Structure and Host-Virus Relationship of a Marine Bacterium and Its Bacteriophage

PubMed Central

Valentine, Artrice F.; Chapman, George B.

1966-01-01

Valentine, Artrice F. (Georgetown University, Washington, D.C.), and George B. Chapman. Fine structure and host-virus relationship of a marine bacterium and its bacteriophage. J. Bacteriol. 92:1535–1554. 1966.—The fine structure of a gram-negative marine bacterium, Cytophaga marinoflava sp. n., has been revealed by ultrathin sectioning and electron microscopy. Stages in the morphogenesis of the bacterial virus NCMB 385, which has been shown to be highly specific for this organism, were also demonstrated in bacterial cells fixed according to the Kellenberger technique. The bacterium possessed a cell wall, cytoplasmic membrane, and nuclear and cytoplasmic regions typical of bacterial cells. Both the cell wall and the cytoplasmic membrane showed a tripartite structure, i.e., each was composed of two dense layers separated by a low-density zone. Intracytoplasmic membrane systems were also observed, especially in dividing cells and in cells in which new viruses were being formed. As many as 18 hexagonally shaped, empty phage heads (membranes only) were observed in untreated, infected bacterial cells. Phage heads, intermediate in density to empty heads and fully condensed ones, possibly representing stages in the morphological development of the virus, were also seen. Images PMID:5924277

Method of encapsulating solid radioactive waste material for storage

DOEpatents

Bunnell, Lee Roy; Bates, J. Lambert

1976-01-01

High-level radioactive wastes are encapsulated in vitreous carbon for long-term storage by mixing the wastes as finely divided solids with a suitable resin, formed into an appropriate shape and cured. The cured resin is carbonized by heating under a vacuum to form vitreous carbon. The vitreous carbon shapes may be further protected for storage by encasement in a canister containing a low melting temperature matrix material such as aluminum to increase impact resistance and improve heat dissipation.

METHOD FOR PRODUCING ISOTOPIC METHANES AND PARTIALLY HALOGENATED DERIVATIVES THEROF

DOEpatents

Frazer, J.W.

1959-08-18

A method is given for producing isotopic methanes and/ or partially halogenated derivatives. Lithium hydride, deuteride, or tritide is reacted with a halogenated methane or with a halogenated methane in combination with free halogen. The process is conveniently carried out by passing a halogenated methane preferably at low pressures or in an admixture with an inert gas through a fixed bed of finely divided lithium hydride heated initially to temperatures of 100 to 200 deg C depending upon the halogenated methane used.

[Parasternal lymphoscintigraphy in planning the radiation therapy of breast cancer].

PubMed

Bykov, S A; Mironov, E E; Zhdanova, V I

1990-07-01

Altogether 82 breast cancer patients were investigated to determine a possibility of the use of parasternal lymphoscintigraphy with colloid finely divided radiopharmaceuticals 99mTc and 198Au to form individual irradiation fields; 43 patients with fibroadenomatosis were taken as controls. Variants of the localization of parasternal lymph nodes were defined, standard and "optimum" (individual) parasternal irradiation field values were compared. 54.9% of the patients were shown to be in need of correction by increasing a standard irradiation field (5 cm wide).

Fine-Scale Volume Heterogeneity in a Mixed Sand/Mud Sediment Off Fort Walton Beach, FL

DTIC Science & Technology

2010-07-01

by Vaughan et al. [4]. Subsequent to the mud drape, wind-wave activity mobilized sediment and some of the mud layer was resuspended, and sand from...hardening effects, which is a common issue with polychromatic energy sources, such as the HD-500 and medical CT systems. Beam hardening is a process...provides a convenient characterization of levels of heterogeneity. The CV is defined as the standard devi - ation divided by the mean and multiplied by

Powdered Chitin Agar as a Selective Medium for Enumeration of Actinomycetes in Water and Soil1

PubMed Central

Hsu, S. C.; Lockwood, J. L.

1975-01-01

Agar media made with 0.4% colloidal chitin plus mineral salts and adjusted to pH 8.0 was superior to four other commonly used media for the isolation and enumeration of actinomycetes from water samples. More actinomycetes developed on chitin agar, and the development of bacteria and fungi was suppressed. Frozen and vacuum-dried chitin from aqueous colloidal suspensions was finely divided and gave results comparable to those obtained with media prepared from colloidal suspensions. Images PMID:234719

METHOD OF PREPARING URANIUM, THORIUM, OR PLUTONIUM OXIDES IN LIQUID BISMUTH

DOEpatents

Davidson, J.K.; Robb, W.L.; Salmon, O.N.

1960-11-22

A method is given for forming compositions, as well as the compositions themselves, employing uranium hydride in a liquid bismuth composition to increase the solubility of uranium, plutonium and thorium oxides in the liquid bismuth. The finely divided oxide of uranium, plutonium. or thorium is mixed with the liquid bismuth and uranium hydride, the hydride being present in an amount equal to about 3 at. %, heated to about 5OO deg C, agitated and thereafter cooled and excess resultant hydrogen removed therefrom.

Automatic EMC test system

NASA Astrophysics Data System (ADS)

Kasai, R.; Abe, T.; Sano, T.

Automated electromagnetic compatibility (EMC) tests for spacecraft hardware are described. EMC tests are divided into three categories: compensating measurement and calibration errors, comparison of test results with specification, and fine-frequency searching using predictive interference analysis. The automated system features an RF receiver and transmitter, a control system, and antennas. Trials are run with conducted and radiated emissions and conducted and radiated susceptibility over a frequency range of 0.1-40 GHz with narrow, broad and random broad band noise. The system meets military specifications 1541, 461, and 462.

Molecular catalytic coal liquid conversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stock, L.M.; Yang, Shiyong

1995-12-31

This research, which is relevant to the development of new catalytic systems for the improvement of the quality of coal liquids by the addition of dihydrogen, is divided into two tasks. Task 1 centers on the activation of dihydrogen by molecular basic reagents such as hydroxide ion to convert it into a reactive adduct (OH{center_dot}H{sub 2}){sup {minus}} that can reduce organic molecules. Such species should be robust withstanding severe conditions and chemical poisons. Task 2 is focused on an entirely different approach that exploits molecular catalysts, derived from organometallic compounds that are capable of reducing monocyclic aromatic compounds under verymore » mild conditions. Accomplishments and conclusions are discussed.« less

Changes in very fine root respiration and morphology with time since last fire in a boreal forest

NASA Astrophysics Data System (ADS)

Makita, Naoki; Pumpanen, Jukka; Köster, Kajar; Berninger, Frank

2016-04-01

We examined the physiological and morphological responses of individual fine root segments in boreal forests stands with different age since the last fire to determine changes in specific fine root respiration and morphological traits during forest succession. We investigated the respiration of fine roots divided into three diameter classes (<0.5, 0.5-1.0, and 1.0-2.0 mm) in a Finnish boreal Pinus sylvestris L. in forest stands with 5, 45, 63, and 155 years since the last fire. Specific respiration rates of <0.5 mm roots in 155-year-old stands were 74%, 38%, and 31% higher than in 5-, 45-, and 63-year-old stands, respectively. However, the respiration rates of thicker diameter roots did not significantly change among stands with respect to time after fire. Similarly, fire disturbance had a strong impact on morphological traits of <0.5 mm roots, but not on thicker roots. Root respiration rates correlated positively with specific root length (length per unit mass) and negatively with root tissue density (mass per unit volume) in all stand ages. The linear regression lines fitted to the relationships between root respiration and specific root length or root tissue density showed significantly higher intercepts in 63- and 155-year-old than in 5-year-old stands. Significant shifts in the intercept of the common slope of respiration vs. morphology indicate the different magnitude of the changes in physiological performance among the fire age class. Despite a specific small geographic area, we suggest that the recovery of boreal forests following wildfire induces a strategy that favors carbon investment in nutrient and water exploitation efficiency with consequences for higher respiration, length, and lower tissue density of very fine roots.

Surface roughness of zirconia for full-contour crowns after clinically simulated grinding and polishing.

PubMed

Hmaidouch, Rim; Müller, Wolf-Dieter; Lauer, Hans-Christoph; Weigl, Paul

2014-12-01

The aim of this study was to evaluate the effect of controlled intraoral grinding and polishing on the roughness of full-contour zirconia compared to classical veneered zirconia. Thirty bar-shaped zirconia specimens were fabricated and divided into two groups (n=15). Fifteen specimens (group 1) were glazed and 15 specimens (group 2) were veneered with feldspathic ceramic and then glazed. Prior to grinding, maximum roughness depth (Rmax) values were measured using a profilometer, 5 times per specimen. Simulated clinical grinding and polishing were performed on the specimens under water coolant for 15 s and 2 N pressure. For grinding, NTI diamonds burs with grain sizes of 20 µm, 10 µm, and 7.5 µm were used sequentially. The ground surfaces were polished using NTI kits with coarse, medium and fine polishers. After each step, Rmax values were determined. Differences between groups were examined using one-way analysis of variance (ANOVA). The roughness of group 1 was significantly lower than that of group 2. The roughness increased significantly after coarse grinding in both groups. The results after glazing were similar to those obtained after fine grinding for non-veneered zirconia. However, fine-ground veneered zirconia had significantly higher roughness than venerred, glazed zirconia. No significant difference was found between fine-polished and glazed zirconia, but after the fine polishing of veneered zirconia, the roughness was significantly higher than after glazing. It can be concluded that for full-contour zirconia, fewer defects and lower roughness values resulted after grinding and polishing compared to veneered zirconia. After polishing zirconia, lower roughness values were achieved compared to glazing; more interesting was that the grinding of glazed zirconia using the NTI three-step system could deliver smooth surfaces comparable to untreated glazed zirconia surfaces.

Surface roughness of zirconia for full-contour crowns after clinically simulated grinding and polishing

PubMed Central

Hmaidouch, Rim; Müller, Wolf-Dieter; Lauer, Hans-Christoph; Weigl, Paul

2014-01-01

The aim of this study was to evaluate the effect of controlled intraoral grinding and polishing on the roughness of full-contour zirconia compared to classical veneered zirconia. Thirty bar-shaped zirconia specimens were fabricated and divided into two groups (n=15). Fifteen specimens (group 1) were glazed and 15 specimens (group 2) were veneered with feldspathic ceramic and then glazed. Prior to grinding, maximum roughness depth (Rmax) values were measured using a profilometer, 5 times per specimen. Simulated clinical grinding and polishing were performed on the specimens under water coolant for 15 s and 2 N pressure. For grinding, NTI diamonds burs with grain sizes of 20 µm, 10 µm, and 7.5 µm were used sequentially. The ground surfaces were polished using NTI kits with coarse, medium and fine polishers. After each step, Rmax values were determined. Differences between groups were examined using one-way analysis of variance (ANOVA). The roughness of group 1 was significantly lower than that of group 2. The roughness increased significantly after coarse grinding in both groups. The results after glazing were similar to those obtained after fine grinding for non-veneered zirconia. However, fine-ground veneered zirconia had significantly higher roughness than venerred, glazed zirconia. No significant difference was found between fine-polished and glazed zirconia, but after the fine polishing of veneered zirconia, the roughness was significantly higher than after glazing. It can be concluded that for full-contour zirconia, fewer defects and lower roughness values resulted after grinding and polishing compared to veneered zirconia. After polishing zirconia, lower roughness values were achieved compared to glazing; more interesting was that the grinding of glazed zirconia using the NTI three-step system could deliver smooth surfaces comparable to untreated glazed zirconia surfaces. PMID:25059249

MRL and SuperFine+MRL: new supertree methods

PubMed Central

2012-01-01

Background Supertree methods combine trees on subsets of the full taxon set together to produce a tree on the entire set of taxa. Of the many supertree methods, the most popular is MRP (Matrix Representation with Parsimony), a method that operates by first encoding the input set of source trees by a large matrix (the "MRP matrix") over {0,1, ?}, and then running maximum parsimony heuristics on the MRP matrix. Experimental studies evaluating MRP in comparison to other supertree methods have established that for large datasets, MRP generally produces trees of equal or greater accuracy than other methods, and can run on larger datasets. A recent development in supertree methods is SuperFine+MRP, a method that combines MRP with a divide-and-conquer approach, and produces more accurate trees in less time than MRP. In this paper we consider a new approach for supertree estimation, called MRL (Matrix Representation with Likelihood). MRL begins with the same MRP matrix, but then analyzes the MRP matrix using heuristics (such as RAxML) for 2-state Maximum Likelihood. Results We compared MRP and SuperFine+MRP with MRL and SuperFine+MRL on simulated and biological datasets. We examined the MRP and MRL scores of each method on a wide range of datasets, as well as the resulting topological accuracy of the trees. Our experimental results show that MRL, coupled with a very good ML heuristic such as RAxML, produced more accurate trees than MRP, and MRL scores were more strongly correlated with topological accuracy than MRP scores. Conclusions SuperFine+MRP, when based upon a good MP heuristic, such as TNT, produces among the best scores for both MRP and MRL, and is generally faster and more topologically accurate than other supertree methods we tested. PMID:22280525

Music-supported motor training after stroke reveals no superiority of synchronization in group therapy.

PubMed

Van Vugt, Floris T; Ritter, Juliane; Rollnik, Jens D; Altenmüller, Eckart

2014-01-01

Music-supported therapy has been shown to be an effective tool for rehabilitation of motor deficits after stroke. A unique feature of music performance is that it is inherently social: music can be played together in synchrony. The present study explored the potential of synchronized music playing during therapy, asking whether synchronized playing could improve fine motor rehabilitation and mood. Twenty-eight patients in neurological early rehabilitation after stroke with no substantial previous musical training were included. Patients learned to play simple finger exercises and familiar children's songs on the piano for 10 sessions of half an hour. Patients first received three individual therapy sessions and then continued in pairs. The patient pairs were divided into two groups. Patients in one group played synchronously (together group) whereas the patients in the other group played one after the other (in-turn group). To assess fine motor skill recovery the patients performed standard clinical tests such as the nine-hole-pegboard test (9HPT) and index finger-tapping speed and regularity, and metronome-paced finger tapping. Patients' mood was established using the Profile of Mood States (POMS). Both groups showed improvements in fine motor control. In metronome-paced finger tapping, patients in both groups improved significantly. Mood tests revealed reductions in depression and fatigue in both groups. During therapy, patients in the in-turn group rated their partner as more sympathetic than the together-group in a visual-analog scale. Our results suggest that music-supported stroke rehabilitation can improve fine motor control and mood not only individually but also in patient pairs. Patients who were playing in turn rather than simultaneously tended to reveal greater improvement in fine motor skill. We speculate that patients in the former group may benefit from the opportunity to learn from observation.

Microstructure investigation on micropore formation in microporous silica materials prepared via a catalytic sol-gel process by small angle X-ray scattering.

PubMed

Shimizu, Wataru; Hokka, Junsuke; Sato, Takaaki; Usami, Hisanao; Murakami, Yasushi

2011-08-04

The so-called sol-gel technique has been shown to be a template-free, efficient way to create functional porous silica materials having uniform micropores. This appears to be closely linked with a postulation that the formation of weakly branched polymer-like aggregates in a precursor solution is a key to the uniform micropore generation. However, how such a polymer-like structure can precisely be controlled, and further, how the generated low-fractal dimension solution structure is imprinted on the solid silica materials still remain elusive. Here we present fabrication of microporous silica from tetramethyl orthosilicate (TMOS) using a recently developed catalytic sol-gel process based on a nonionic hydroxyacetone (HA) catalyst. Small angle X-ray scattering (SAXS), nitrogen adsorption porosimetry, and transmission electron microscope (TEM) allowed us to observe the whole structural evolution, ranging from polymer-like aggregates in the precursor solution to agglomeration with heat treatment and microporous morphology of silica powders after drying and hydrolysis. Using the HA catalyst with short chain monohydric alcohols (methanol or ethanol) in the precursor solution, polymer-like aggregates having microscopic correlation length (or mesh-size) < 2 nm and low fractal dimensions ∼2, which is identical to that of an ideal coil polymer, can selectively be synthesized, yielding the uniform micropores with diameters <2 nm in the solid materials. In contrast, the absence of HA or substitution of 1-propanol led to considerably different scattering behavior reflecting the particle-like aggregate formation in the precursor solution, which resulted in the formation of mesopores (diameter >2 nm) in the solid product due to apertures between the particle-like aggregates. The data demonstrate that the extremely fine porous silica architecture comes essentially from a gaussian polymer-like nature of the silica aggregates in the precursor having the microscopic mesh-size and their successful imprint on the solid product. The result offers a general but significantly efficient route to creating precisely designed fine porous silica materials under mild condition that serve as low refractive index and efficient thermal insulation materials in their practical applications.

Unique properties of ceria nanoparticles supported on metals: novel inverse ceria/copper catalysts for CO oxidation and the water-gas shift reaction.

PubMed

Senanayake, Sanjaya D; Stacchiola, Dario; Rodriguez, Jose A

2013-08-20

Oxides play a central role in important industrial processes, including applications such as the production of renewable energy, remediation of environmental pollutants, and the synthesis of fine chemicals. They were originally used as catalyst supports and were thought to be chemically inert, but now they are used to build catalysts tailored toward improved selectivity and activity in chemical reactions. Many studies have compared the morphological, electronic, and chemical properties of oxide materials with those of unoxidized metals. Researchers know much less about the properties of oxides at the nanoscale, which display distinct behavior from their bulk counterparts. More is known about metal nanoparticles. Inverse-model catalysts, composed of oxide nanoparticles supported on metal or oxide substrates instead of the reverse (oxides supporting metal nanoparticles), are excellent tools for systematically testing the properties of novel catalytic oxide materials. Inverse models are prepared in situ and can be studied with a variety of surface science tools (e.g. scanning tunneling microscopy, X-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, low-energy electron microscopy) and theoretical tools (e.g. density functional theory). Meanwhile, their catalytic activity can be tested simultaneously in a reactor. This approach makes it possible to identify specific functions or structures that affect catalyst performance or reaction selectivity. Insights gained from these tests help to tailor powder systems, with the primary objective of rational design (experimental and theoretical) of catalysts for specific chemical reactions. This Account describes the properties of inverse catalysts composed of CeOx nanoparticles supported on Cu(111) or CuOx/Cu(111) as determined through the methods described above. Ceria is an important material for redox chemistry because of its interchangeable oxidation states (Ce⁴⁺ and Ce³⁺). Cu(111), meanwhile, is a standard catalyst for reactions such as CO oxidation and the water-gas shift (WGS). This metal serves as an ideal replacement for other noble metals that are neither abundant nor cost effective. To prepare the inverse system we deposited nanoparticles (2-20 nm) of cerium oxide onto the Cu(111) surface. During this process, the Cu(111) surface grows an oxide layer that is characteristic of Cu₂O (Cu¹⁺). This oxide can influence the growth of ceria nanoparticles. Evidence suggests triangular-shaped CeO₂(111) grows on Cu₂O(111) surfaces while rectangular CeO₂(100) grows on Cu₄O₃(111) surfaces. We used the CeOx/Cu₂O/Cu(111) inverse system to study two catalytic processes: the WGS (CO + H₂O → CO₂ + H₂) and CO oxidation (2CO + O₂ → 2CO₂). We discovered that the addition of small amounts of ceria nanoparticles can activate the Cu(111) surface and achieve remarkable enhancement of catalytic activity in the investigated reactions. In the case of the WGS, the CeOx nanoparticle facilitated this process by acting at the interface with Cu to dissociate water. In the CO oxidation case, an enhancement in the dissociation of O₂ by the nanoparticles was a key factor. The strong interaction between CeOx nanoparticles and Cu(111) when preoxidized and reduced in CO resulted in a massive surface reconstruction of the copper substrate with the introduction of microterraces that covered 25-35% of the surface. This constitutes a new mechanism for surface reconstruction not observed before. These microterraces helped to facilitate a further enhancement of activity towards the WGS by opening an additional channel for the dissociation of water. In summary, inverse catalysts of CeOx/Cu(111) and CeO₂/Cu₂O/Cu(111) demonstrate the versatility of a model system to obtain insightful knowledge of catalytic processes. These systems will continue to offer a unique opportunity to probe key catalytic components and elucidate the relationship between structure and reactivity of novel materials and reactions in the future.

Oxidation of diesel soot on binary oxide CuCr(Co)-based monoliths.

PubMed

Soloviev, Sergiy O; Kapran, Andriy Y; Kurylets, Yaroslava P

2015-02-01

Binary oxide systems (CuCr2O4, CuCo2O4), deposited onto cordierite monoliths of honeycomb structure with a second support (finely dispersed Al2O3), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine's gas exhausts (O2, NOx, H2O, CO2) and O3 as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO2. Oxidants used can be arranged with reference to decreasing their activity in a following series: O3≫NO2>H2O>NO>O2>CO2. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O3 occurs intensively (in the presence of copper chromite based catalyst) even at closing to ambient temperatures. Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the "cold start" problem. Copyright © 2014. Published by Elsevier B.V.

Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts† †Electronic supplementary information (ESI) available: Experimental details, material characterization data, catalytic measurement details and crystallographic details. CCDC 1499756. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc05178b Click here for additional data file. Click here for additional data file.

PubMed Central

Searles, Keith; Siddiqi, Georges; Safonova, Olga V.

2017-01-01

Single-site gallium centers on the surface of silica are prepared via grafting of [Ga(OSi(OtBu)3)3(THF)] on SiO2–700 followed by a thermolysis step. The resulting surface species corresponds to well-defined tetra-coordinate gallium single-sites, [( 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 SiO)3Ga(XOSi)] (X = –H or Si) according to IR, X-ray absorption near-edge structure and extended X-ray absorption fine structure analysis. These gallium sites show high activity, selectivity and stability for propane dehydrogenation with an initial turnover frequency of 20 per h per gallium center, propylene selectivity of ≥93% and remarkable stability over 20 h. The stability of the catalyst probably results from site-isolation of the active site on a non-reducible support such as silica, diminishing facile reduction typical of Ga2O3-based catalysts. PMID:28553501

Visible light induced green transformation of primary amines to imines using a silicate supported anatase photocatalyst.

PubMed

Zavahir, Sifani; Zhu, Huaiyong

2015-01-26

Catalytic oxidation of amine to imine is of intense present interest since imines are important intermediates for the synthesis of fine chemicals, pharmaceuticals, and agricultural chemicals. However, considerable efforts have been made to develop efficient methods for the oxidation of secondary amines to imines, while little attention has until recently been given to the oxidation of primary amines, presumably owing to the high reactivity of generated imines of primary amines that are easily dehydrogenated to nitriles. Herein, we report the oxidative coupling of a series of primary benzylic amines into corresponding imines with dioxygen as the benign oxidant over composite catalysts of TiO2 (anatase)-silicate under visible light irradiation of λ > 460 nm. Visible light response of this system is believed to be as a result of high population of defects and contacts between silicate and anatase crystals in the composite and the strong interaction between benzylic amine and the catalyst. It is found that tuning the intensity and wavelength of the light irradiation and the reaction temperature can remarkably enhance the reaction activity. Water can also act as a green medium for the reaction with an excellent selectivity. This report contributes to the use of readily synthesized, environmentally benign, TiO2 based composite photocatalyst and solar energy to realize the transformation of primary amines to imine compounds.

A New Contribution for WYP 2005: The Golden Ratio, Bohr Radius, Planck's Constant, Fine-Structure Constant and g-Factors

NASA Astrophysics Data System (ADS)

Heyrovska, R.; Narayan, S.

2005-10-01

Recently, the ground state Bohr radius (aB) of hydrogen was shown to be divided into two Golden sections, aB,p = aB/ø2 and aB,e = aB/ø at the point of electrical neutrality, where ø = 1.618 is the Golden ratio (R. Heyrovska, Molecular Physics 103: 877-882, and the literature cited therein). The origin of the difference of two energy terms in the Rydberg equation was thus shown to be in the ground state energy itself, as shown below: EH = (1/2)e2/(κaB) = (1/2)(e2/κ) [(1/aB,p - (1/aB,e)] (1). This work brings some new results that 1) a unit charge in vacuum has a magnetic moment, 2) (e2/2κ) in eq. (1) is an electromagnetic condenser constant, 3) the de Broglie wavelengths of the proton and electron correspond to the Golden arcs of a circle with the Bohr radius, 4) the fine structure constant (α) is the ratio of the Planck's constants without and with the interaction of light with matter, 5) the g-factors of the electron and proton, ge/2 and gp/2 divide the Bohr radius at the magnetic center and 6) the ``mysterious'' value (137.036) of α -1 = (360/ø2) - (2/ø3), where (2/ø3) arises from the difference, (gp - ge).

Molecular approaches to the photocatalytic reduction of carbon dioxide for solar fuels.

PubMed

Morris, Amanda J; Meyer, Gerald J; Fujita, Etsuko

2009-12-21

The scientific community now agrees that the rise in atmospheric CO(2), the most abundant green house gas, comes from anthropogenic sources such as the burning of fossil fuels. This atmospheric rise in CO(2) results in global climate change. Therefore methods for photochemically transforming CO(2) into a source of fuel could offer an attractive way to decrease atmospheric concentrations. One way to accomplish this conversion is through the light-driven reduction of carbon dioxide to methane (CH(4(g))) or methanol (CH(3)OH((l))) with electrons and protons derived from water. Existing infrastructure already supports the delivery of natural gas and liquid fuels, which makes these possible CO(2) reduction products particularly appealing. This Account focuses on molecular approaches to photochemical CO(2) reduction in homogeneous solution. The reduction of CO(2) by one electron to form CO(2)(*-) is highly unfavorable, having a formal reduction potential of -2.14 V vs SCE. Rapid reduction requires an overpotential of up to 0.6 V, due at least in part to the kinetic restrictions imposed by the structural difference between linear CO(2) and bent CO(2)(*-). An alternative and more favorable pathway is to reduce CO(2) though proton-assisted multiple-electron transfer. The development of catalysts, redox mediators, or both that efficiently drive these reactions remains an important and active area of research. We divide these reactions into two class types. In Type I photocatalysis, a molecular light absorber and a transition metal catalyst work in concert. We also consider a special case of Type 1 photocatalysis, where a saturated hydrocarbon links the catalyst and the light absorber in a supramolecular compound. In Type II photocatalysis, the light absorber and the catalyst are the same molecule. In these reactions, transition-metal coordination compounds often serve as catalysts because they can absorb a significant portion of the solar spectrum and can promote activation of small molecules. This Account discusses four classes of transition-metal catalysts: (A) metal tetraaza-macrocyclic compounds; (B) supramolecular complexes; (C) metalloporphyrins and related metallomacrocycles; (D) Re(CO)(3)(bpy)X-based compounds where bpy = 2,2'-bipyridine. Carbon monoxide and formate are the primary CO(2) reduction products, and we also propose bicarbonate/carbonate production. For comprehensiveness, we briefly discuss hydrogen formation, a common side reaction that occurs concurrently with CO(2) reduction, though the details of that process are beyond the scope of this Account. It is our hope that drawing attention both to current mechanistic hypotheses and to the areas that are poorly understood will stimulate research that could one day provide an efficient solution to this global problem.

Patterns of cell division, DNA base compositions, and fine structures of some radiation-resistant vegetative bacteria found in food

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanders, S.W.; Maxcy, R.B.

1979-01-01

Representative highly radiation-resistant Moraxella-Acinetobacter (M-A), Pseudomonas radiora, Micrococcus radiodurans, and Micrococcus radiophilus exhibited a wide variety of division systems and cell wall characteristics. However, the more resistant M-A possessed unusually thick cell walls, indicating a possible role of the cell wall in radiation resistance in the M-A. Thick septation was present in most of the bacteria studied, but was absent in P. radiora, thus excluding this as a necessity for high resistance. Reliable determination of the number of division planes of the M-A for use as a taxonomic criterion was achieved by the direct observation of dividing cells. The highlymore » resistant M-A were found to divide in multiple planes and had base compositions of 54.0 to 57.5%, unlike typical Moraxella and/or Acinetobacter species. The taxonomic position of most highly resistant bacteria remains unclear.« less

Surface chemical properties of eutectic and frozen NaCl solutions probed by XPS and NEXAFS.

PubMed

Křepelová, Adéla; Huthwelker, Thomas; Bluhm, Hendrik; Ammann, Markus

2010-12-17

We study the surface of sodium chloride-water mixtures above, at, and below the eutectic temperature using X-ray photoelectron spectroscopy (XPS) and electron-yield near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The NaCl frozen solutions are mimicking sea-salt deposits in ice or snow. Sea-salt particles emitted from the oceans are a major contributor to the global aerosol burden and can act as a catalyst for heterogeneous chemistry or as cloud condensation nuclei. The nature of halogen ions at ice surfaces and their influence on surface melting of ice are of significant current interest. We found that the surface of the frozen solution, depending on the temperature, consists of ice and different NaCl phases, that is, NaCl, NaCl·2H(2)O, and surface-adsorbed water.

Cytochrome P450 monooxygenases: perspectives for synthetic application.

PubMed

Urlacher, Vlada B; Eiben, Sabine

2006-07-01

Cytochrome P450 monooxygenases are versatile biocatalysts that introduce oxygen into a vast range of molecules. These enzymes catalyze diverse reactions in a regio- and stereoselective manner, and their properties have been used for drug development, bioremediation and the synthesis of fine chemicals and other useful compounds. However, the potential of P450 monooxygenases has not been fully exploited; there are some drawbacks limiting the broader implementation of these catalysts for commercial needs. Protein engineering has produced P450 enzymes with widely altered substrate specificities, substantially increased activity and higher stability. Furthermore, electrochemical and enzymatic approaches for the replacement or regeneration of NAD(P)H have been developed, enabling the more cost-effective use of P450 enzymes. In this review, we focus on the aspects relevant to the synthetic applications of P450 enzymes and their optimization for commercial needs.

USD Catalysis Group for Alternative Energy - Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoefelmeyer, James

2014-10-03

I. Project Summary Catalytic processes are a major technological underpinning of modern society, and are essential to the energy sector in the processing of chemical fuels from natural resources, fine chemicals synthesis, and energy conversion. Advances in catalyst technology are enormously valuable since these lead to reduced chemical waste, reduced energy loss, and reduced costs. New energy technologies, which are critical to future economic growth, are also heavily reliant on catalysts, including fuel cells and photo-electrochemical cells. Currently, the state of South Dakota is underdeveloped in terms of research infrastructure related to catalysis. If South Dakota intends to participate inmore » significant economic growth opportunities that result from advances in catalyst technology, then this area of research needs to be made a high priority for investment. To this end, a focused research effort is proposed in which investigators from The University of South Dakota (USD) and The South Dakota School of Mines and Technology (SDSMT) will contribute to form the South Dakota Catalysis Group (SDCG). The multidisciplinary team of the (SDCG) include: (USD) Dan Engebretson, James Hoefelmeyer, Ranjit Koodali, and Grigoriy Sereda; (SDSMT) Phil Scott Ahrenkiel, Hao Fong, Jan Puszynski, Rajesh Shende, and Jacek Swiatkiewicz. The group is well suited to engage in a collaborative project due to the resources available within the existing programs. Activities within the SDCG will be monitored through an external committee consisting of three distinguished professors in chemistry. The committee will provide expert advice and recommendations to the SDCG. Advisory meetings in which committee members interact with South Dakota investigators will be accompanied by individual oral and poster presentations in a materials and catalysis symposium. The symposium will attract prominent scientists, and will enhance the visibility of research in the state of South Dakota. The SDCG requests funding through the Department of Energy (DoE) to establish this multidisciplinary research cluster in the area of catalysis. This long-term approach includes synthesis, characterization, catalyst evaluation, modeling, and scale-up. The project includes plans to acquire instrumentation critical to enabling competitive research. These acquisitions will complement existing resources in the state. The effect of implementation of the proposed efforts will be to significantly enhance state infrastructure in personnel and equipment, and lead to a nationally and internationally recognized research center.« less

Removal of sulfur and nitrogen containing pollutants from discharge gases

DOEpatents

Joubert, James I.

1986-01-01

Oxides of sulfur and of nitrogen are removed from waste gases by reaction with an unsupported copper oxide powder to form copper sulfate. The resulting copper sulfate is dissolved in water to effect separation from insoluble mineral ash and dried to form solid copper sulfate pentahydrate. This solid sulfate is thermally decomposed to finely divided copper oxide powder with high specific surface area. The copper oxide powder is recycled into contact with the waste gases requiring cleanup. A reducing gas can be introduced to convert the oxide of nitrogen pollutants to nitrogen.

METHOD OF PREPARING RADIOACTIVE CESIUM SOURCES

DOEpatents

Quinby, T.C.

1963-12-17

A method of preparing a cesium-containing radiation source with physical and chemical properties suitable for high-level use is presented. Finely divided silica is suspended in a solution containing cesium, normally the fission-product isotope cesium 137. Sodium tetraphenyl boron is then added to quantitatively precipitate the cesium. The cesium-containing precipitate is converted to borosilicate glass by heating to the melting point and cooling. Up to 60 weight percent cesium, with a resulting source activity of up to 21 curies per gram, is incorporated in the glass. (AEC)

In-situ stabilization of radioactive zirconium swarf

DOEpatents

Hess, Clay C.

1999-01-01

The method for treating ignitable cutting swarf in accordance with the present invention involves collecting cutting swarf in a casting mold underwater and injecting a binder mixture comprising vinyl ester styrene into the vessel to fill void volume; and form a mixture comprising swarf and vinyl ester styrene; and curing the mixture. The method is especially useful for stabilizing the ignitable characteristics of radioactive zirconium cutting swarf, and can be used to solidify zirconium swarf, or other ignitable finely divided material, underwater. The process could also be performed out of water with other particulate wastes.

SEPARATION OF PROTACTINIUM FROM CONTAMINANTS

DOEpatents

Malm, J.G.; Fried, S.

1959-07-01

The separation of protactinium by volatilization method is described. According to the invention, neutron irradiated finely divided thorium is reacted with aluminum trichloride or a mixture of aluminum trichloride and chlorine gas at a temperature of preferably between about 200 and 400 deg C. Following the chlorinating step the protactinium chloride along with aluminum chloride is selectively distilled from the mixture at a temperature of approximately 100 deg C. The protactinium chloride may be recovered from the mixture by treatment with sodium hydroxide, which converts the aluminum chloride to a soluble salt and forms insoluble protactinium hydroxide.

Manufacture of silicon carbide using solar energy

DOEpatents

Glatzmaier, Gregory C.

1992-01-01

A method is described for producing silicon carbide particles using solar energy. The method is efficient and avoids the need for use of electrical energy to heat the reactants. Finely divided silica and carbon are admixed and placed in a solar-heated reaction chamber for a time sufficient to cause a reaction between the ingredients to form silicon carbide of very small particle size. No grinding of silicon carbide is required to obtain small particles. The method may be carried out as a batch process or as a continuous process.

A correlation study of diagnostic fine-needle aspiration with histologic diagnosis in cystic neck lesions.

PubMed

Moatamed, Neda A; Naini, Bita V; Fathizadeh, Payman; Estrella, Julie; Apple, Sophia K

2009-10-01

The clinical diagnosis of a mass in the neck region encompasses a wide spectrum of differential diagnosis. Fine-needle aspiration is a quick and safe technique, which can provide useful information for initial assessment and further therapeutic measures. The aim of this retrospective study was to evaluate the performance characteristics of the fine-needle aspiration (FNA) in cystic neck lesions. Of 142 patients with FNA for cystic neck masses during 2002-2007, 92 cases were selected with a follow-up histologic diagnosis, excluding the cystic colloid nodule of the thyroid. The cases were divided into salivary gland cystic neck (37 patients) and non-salivary cystic neck (55 patients) mass groups. False-positive and false-negative diagnoses were applied only to the malignant lesions after confirmation by histopathology. In the first group, nine malignant and 28 benign diagnoses were made by FNA; of which three were false-negative. In the second group, there were nine malignant and 46 benign diagnoses with three false negatives. The overall performance of the FNA showed 76% sensitivity and 100% specificity. In conclusion, FNA of the cystic neck lesions offers an invaluable and highly specific initial diagnostic approach for the management of the patients. (c) 2009 Wiley-Liss, Inc.

Motor skills in Czech children with attention-deficit/hyperactivity disorder and their neurotypical counterparts.

PubMed

Scharoun, S M; Bryden, P J; Otipkova, Z; Musalek, M; Lejcarova, A

2013-11-01

Attention-deficit/hyperactivity disorder (ADHD) is the most commonly diagnosed neurobehavioural disorder. Characterized by recurring problems with impulsiveness and inattention in combination with hyperactivity, motor impairments have also been well documented in the literature. The aim of this study was to compare the fine and gross motor skills of male and female children with ADHD and their neurotypical counterparts within seven skill assessments. This included three fine motor tasks: (1) spiral tracing, (2) dot filling, (3) tweezers and beads; and four gross motor tasks: (1) twistbox, (2) foot tapping, (3) small plate finger tapping, and (4) large plate finger tapping. It was hypothesized that children with ADHD would display poorer motor skills in comparison to neurotypical controls in both fine and gross motor assessments. However, statistically significant differences between the groups only emerged in four of the seven tasks (spiral tracing, dot filling, tweezers and beads and foot tapping). In line with previous findings, the complexity underlying upper limb tasks solidified the divide in performance between children with ADHD and their neurotypical counterparts. In light of similar research, impairments in lower limb motor skill were also observed. Future research is required to further delineate trends in motor difficulties in ADHD, while further investigating the underlying mechanisms of impairment. Copyright © 2013 Elsevier Ltd. All rights reserved.

Perceptual weighting of individual and concurrent cues for sentence intelligibility: Frequency, envelope, and fine structure

PubMed Central

Fogerty, Daniel

2011-01-01

The speech signal may be divided into frequency bands, each containing temporal properties of the envelope and fine structure. For maximal speech understanding, listeners must allocate their perceptual resources to the most informative acoustic properties. Understanding this perceptual weighting is essential for the design of assistive listening devices that need to preserve these important speech cues. This study measured the perceptual weighting of young normal-hearing listeners for the envelope and fine structure in each of three frequency bands for sentence materials. Perceptual weights were obtained under two listening contexts: (1) when each acoustic property was presented individually and (2) when multiple acoustic properties were available concurrently. The processing method was designed to vary the availability of each acoustic property independently by adding noise at different levels. Perceptual weights were determined by correlating a listener’s performance with the availability of each acoustic property on a trial-by-trial basis. Results demonstrated that weights were (1) equal when acoustic properties were presented individually and (2) biased toward envelope and mid-frequency information when multiple properties were available. Results suggest a complex interaction between the available acoustic properties and the listening context in determining how best to allocate perceptual resources when listening to speech in noise. PMID:21361454

Catalytic Conversion of Short-Chain Alcohols on Atomically Dispersed Au and Pd Supported on Nanoscale Metal Oxides

NASA Astrophysics Data System (ADS)

Wang, Chongyang

With the development of technologies for cellulosic biomass conversion to fuels and chemicals, bio-alcohols are among the main alternative feedstocks to fossil fuels. The research pursued in my thesis was the investigation of gold and palladium as catalysts for the application of short aliphatic alcohols to hydrogen generation and value-added chemicals production. Specifically, selective methanol steam reforming and non-oxidative ethanol dehydrogenation to hydrogen and acetaldehyde were investigated in this thesis work. A major aim of the thesis was to develop atomically efficient catalysts with tuned surface chemistry for the desired reactions, using suitable synthesis methods. Methanol steam reforming (SRM) for hydrogen production has recently been investigated on gold catalysts to overcome the drawbacks of copper catalysts (deactivation, pyrophoricity). Previous work at Tufts University has shown that both CeO2 and ZnO are suitable supports for gold. In this thesis, nanoscale composite oxides ZnZrOx were prepared by a carbon hard-template method, which resulted in homogeneous distribution of Zn species in the matrix of ZrO2. Tunable surface chemistry of ZnZrO x was demonstrated by varying the Zn/Zr ratio to suppress the strong Lewis acidity of ZrO2, which leads to undesired production of CO through methanol decomposition. With atomic dispersion of gold, Au/ZnZrO x catalyzes the SRM reaction exclusively via the methanol self-coupling pathway up to 375°C. The activity of Au/ZnZrOx catalysts was compared to Au/TiO2, which is another catalyst system demonstrating atomic dispersion of gold. Similarity in the apparent activation energy of SRM on all the supported gold catalysts studied in this thesis and in the literature further confirms the same single-site Au-Ox-MO centers as active sites for SRM with indirect effects of the supports exploited. With this fundamental understanding of gold-catalyzed C1 alcohol reforming, the Au/ZnZrOx catalyst was evaluated for the dehydrogenation of ethanol. Bare ZnZrOx activate ethanol conversion in the range of 280-300°C and produce undesired ethylene as product of ethanol dehydration, whereas, addition of small amount of gold (<1wt.%) was found to significantly change the product distribution in the low-temperature range (200°C-350°C). As gold passivates the strong Bronsted acid sites of ZrO2 and selectively facilitates the dehydrogenation of ethanol at low-temperature, a wide temperature range was found between the production of acetaldehyde (dehydrogenation products) and ethylene (dehydration product), which can be harnessed for the industrial application. Interestingly, the steam reforming of ethanol did not take place in the low-temperature region, thus the selectivity to acetaldehyde and hydrogen was 100% even in the presence of water. In addition to gold, palladium was also studied in this thesis work on the ZnZrOx composite oxides, and its activity and selectivity were compared to Au/ZnZrOx. Monometallic Pd catalyzes the decomposition of methanol and ethanol, resulting in different product distribution for C 1-C2 alcohol reactions. With ZnZrOx employed as the catalyst support in this thesis work, the finely dispersed ZnO species in ZrO2 were found to alloy with the supported palladium under reduction treatment. Alloying with Zn tunes the chemistry of Pd to catalyze the SRM reaction through the methanol coupling mechanism, shutting off the undesired methanol decomposition pathway. A preliminary study of the Pd/ZnZrO x system for ethanol dehydrogenation also demonstrated the modification of Pd when in the PdZn alloy form. Different from the monometallic Pd catalyst, which primarily catalyzes the C-C bond scission of ethanol, high selectivity to ethanol dehydrogenation products was found on PdZn, over the temperature range of 200-400°C. Formation of the PdZn alloy broadens the application of Pd and potentially other Group VIII metals for selective alcohol conversion reactions. In summary, this thesis work has investigated two noble metals Au and Pd from Group IB and Group VIII, respectively, for methanol and ethanol alcohol reforming reactions employing a novel ZnZrOx composite oxide as a platform catalyst support. Comprehensive study of Au catalyst has deepened our understanding of atomically dispersed Au anchored on various supports through oxygen bonds as the active sites for alcohol reforming reactions, and showed the support effect to be indirect, serving as the carrier and stabilizer of the gold species. For Pd, the Zn species of the composite oxide is necessary to modify the Pd catalyst and the PdZn alloy gives it the desired Au-like properties. Full characterization of the catalysts used here by ICP, XPS, XRD, FTIR and STEM imaging was conducted throughout the thesis to identify the stable species and correlate the catalyst performance with its composition and morphology. Surface acidity titration by isopropanol temperature-programmed desorption/mass spectrometry (IPA-TPD/MS) and pyridine-IR adsorption/desorption was conducted in parallel to temperature-programmed surface reaction (TPSR) studies and products from isothermal steady-state reactions were monitored online by mass spectrometry.

Photo-oxidation catalysts

DOEpatents

Pitts, J Roland [Lakewood, CO; Liu, Ping [Irvine, CA; Smith, R Davis [Golden, CO

2009-07-14

Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

Novel, high-activity hydroprocessing catalysts: Iron group phosphides

NASA Astrophysics Data System (ADS)

Wang, Xianqin

A series of iron, cobalt and nickel transition metal phosphides was synthesized by means of temperature-programmed reduction (TPR) of the corresponding phosphates. The same materials, Fe2P, CoP and NO, were also prepared on a silica (SiO2) support. The phase purity of these catalysts was established by x-ray diffraction (XRD), and the surface properties were determined by N2 BET specific surface area (Sg) measurements and CO chemisorption. The activities of the silica-supported catalysts were tested in a three-phase trickle bed reactor for the simultaneous hydrodenitrogenation (HDN) of quinoline and hydrodesulfurization (HDS) of dibenzothiophene using a model liquid feed at realistic conditions (30 atm, 370°C). The reactivity studies showed that the nickel phosphide (Ni2P/SiO2) was the most active of the catalysts. Compared with a commercial Ni-Mo-S/gamma-Al 2O3 catalyst at the same conditions, Ni2P/silica had a substantially higher HDS activity (100% vs. 76%) and HDN activity (82% vs. 38%). Because of their good hydrotreating activity, an extensive study of the preparation of silica supported nickel phosphides, Ni2P/SiO 2, was carried out. The parameters investigated were the phosphorus content and the weight loading of the active phase. The most active composition was found to have a starting synthesis Ni/P ratio close to 1/2, and the best loading of this sample on silica was observed to be 18 wt.%. Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge spectroscopy (XANES) measurements were employed to determine the structures of the supported samples. The main phase before and after reaction was found to be Ni2P, but some sulfur was found to be retained after reaction. A comprehensive scrutiny of the HDN reaction mechanism was also made over the Ni2P/SiO2 sample (Ni/P = 1/2) by comparing the HDN activity of a series of piperidine derivatives of different structure. It was found that piperidine adsorption involved an alpha-H activation and nitrogen removal proceeded mainly by means of a beta-H activation though an elimination (E2) mechanism. The relative elimination rates depended on the type and number of beta-hydrogen atoms. Elimination of beta-H atoms attached to tertiary carbon atoms occurred faster than those attached to secondary carbon atoms. Also, the greater the number of the beta-H atoms, the higher the elimination rates. The nature of the adsorbed intermediates was probed by Fourier transform infrared spectroscopy (FTIR) and temperature-programmed desorption (TPD) of the probe molecule, ethylamine. This measurement allowed the determination of the likely steps in the hydrodenitrogenation reaction.

The History of Current State of the Art of Propylene Polymerization Catalysts.

ERIC Educational Resources Information Center

Goodall, Brian L.

1986-01-01

Outlines the development of the modern catalysts for propylene polymerization, considering the historical background; structure of titanium chloride catalysts; first-generation catalysts; cocatalysts; second-generation catalysts; catalysts morphology; and third-generation (supported catalysts). (JN)

Preparation of thick silica coatings on carbon fibers with fine-structured silica nanotubes induced by a self-assembly process

PubMed Central

Baumgärtner, Benjamin; Möller, Hendrik; Neumann, Thomas

2017-01-01

A facile method to coat carbon fibers with a silica shell is presented in this work. By immobilizing linear polyamines on the carbon fiber surface, the high catalytic activity of polyamines in the sol–gel-processing of silica precursors is used to deposit a silica coating directly on the fiber’s surface. The surface localization of the catalyst is achieved either by attaching short-chain polyamines (e.g., tetraethylenepentamine) via covalent bonds to the carbon fiber surface or by depositing long-chain polyamines (e.g., linear poly(ethylenimine)) on the carbon fiber by weak non-covalent bonding. The long-chain polyamine self-assembles onto the carbon fiber substrate in the form of nanoscopic crystallites, which serve as a template for the subsequent silica deposition. The silicification at close to neutral pH is spatially restricted to the localized polyamine and consequently to the fiber surface. In case of the linear poly(ethylenimine), silica shells of several micrometers in thickness can be obtained and their morphology is easily controlled by a considerable number of synthesis parameters. A unique feature is the hierarchical biomimetic structure of the silica coating which surrounds the embedded carbon fiber by fibrillar and interconnected silica fine-structures. The high surface area of the nanostructured composite fiber may be exploited for catalytic applications and adsorption purposes. PMID:28685115

Control of Fine Particulate (PM2.5) Emissions from Restaurant Operations.

PubMed

Whynot, Jill; Quinn, Gary; Perryman, Pamela; Votlucka, Peter

1999-09-01

This paper describes efforts to reduce particulate matter (PM) emissions from restaurant operations, including application of an existing control method to a new equipment type. Commercial charbroiling in the South Coast Air Basin results in emissions of approximately 10 tons/day of fine particulate matter ( PM 2.5) and 1.3 tons/day of volatile organic compounds (VOCs). Over a seven-year period, the South Coast Air Quality Management District worked with industry to develop test methods for measuring emissions from various cooking operations, evaluate control technologies, and develop a rule to reduce these emissions. Of the two basic types of charbroilers-chain-driven and underfired-underfired produce four times the emissions when equivalent amounts of product are cooked. Cost-effective control technology is currently available only for chain-driven charbroilers. The application of flameless catalytic oxidizers to chain-driven charbroilers was found to effectively reduce emissions by at least 83% and is cost-effective. The catalysts have been used worldwide at restaurants for several years. Research efforts are underway to identify control options for underfired charbroilers. Implementation of Rule 1138, Control of Emissions from Restaurant Operations, adopted November 14, 1997, will result in reductions of 0.5 tons/day of PM 2.5 and 0.2 tons/day of VOCs. Future rules will result in reductions from underfired charbroilers and possibly other restaurant equipment when cost-effective solutions are available.

Control of fine particulate (PM2.5) emissions from restaurant operations.

PubMed

Whynot, J; Quinn, G; Perryman, P; Votlucka, P

1999-09-01

This paper describes efforts to reduce particulate matter (PM) emissions from restaurant operations, including application of an existing control method to a new equipment type. Commercial charbroiling in the South Coast Air Basin results in emissions of approximately 10 tons/day of fine particulate matter (PM2.5) and 1.3 tons/day of volatile organic compounds (VOCs). Over a seven-year period, the South Coast Air Quality Management District worked with industry to develop test methods for measuring emissions from various cooking operations, evaluate control technologies, and develop a rule to reduce these emissions. Of the two basic types of charbroilers--chain-driven and underfired--underfired produce four times the emissions when equivalent amounts of product are cooked. Cost-effective control technology is currently available only for chain-driven charbroilers. The application of flameless catalytic oxidizers to chain-driven charbroilers was found to effectively reduce emissions by at least 83% and is cost-effective. The catalysts have been used worldwide at restaurants for several years. Research efforts are underway to identify control options for underfired charbroilers. Implementation of Rule 1138, Control of Emissions from Restaurant Operations, adopted November 14, 1997, will result in reductions of 0.5 tons/day of PM2.5 and 0.2 tons/day of VOCs. Future rules will result in reductions from underfired charbroilers and possibly other restaurant equipment when cost-effective solutions are available.

Preparation of thick silica coatings on carbon fibers with fine-structured silica nanotubes induced by a self-assembly process.

PubMed

Baumgärtner, Benjamin; Möller, Hendrik; Neumann, Thomas; Volkmer, Dirk

2017-01-01

A facile method to coat carbon fibers with a silica shell is presented in this work. By immobilizing linear polyamines on the carbon fiber surface, the high catalytic activity of polyamines in the sol-gel-processing of silica precursors is used to deposit a silica coating directly on the fiber's surface. The surface localization of the catalyst is achieved either by attaching short-chain polyamines (e.g., tetraethylenepentamine) via covalent bonds to the carbon fiber surface or by depositing long-chain polyamines (e.g., linear poly(ethylenimine)) on the carbon fiber by weak non-covalent bonding. The long-chain polyamine self-assembles onto the carbon fiber substrate in the form of nanoscopic crystallites, which serve as a template for the subsequent silica deposition. The silicification at close to neutral pH is spatially restricted to the localized polyamine and consequently to the fiber surface. In case of the linear poly(ethylenimine), silica shells of several micrometers in thickness can be obtained and their morphology is easily controlled by a considerable number of synthesis parameters. A unique feature is the hierarchical biomimetic structure of the silica coating which surrounds the embedded carbon fiber by fibrillar and interconnected silica fine-structures. The high surface area of the nanostructured composite fiber may be exploited for catalytic applications and adsorption purposes.

Investigations on solid-solid phase transformation of 5-methyl-2-[(4-methyl-2-nitrophenyl)amino]-3-thiophenecarbonitrile.

PubMed

Li, Hui; Stowell, Joseph G; He, Xiaorong; Morris, Kenneth R; Byrn, Stephen R

2007-05-01

Solid-solid transformation of 5-methyl-2-[(4-methyl-2-nitrophenyl)amino]-3-thiophenecarbonitrile from the dark-red to the red form was investigated. By controlled crystallization, the dark-red form was prepared and the crystals were sieved into fractions: coarse (>250 microm), medium (125-177 microm), and fine (<88 microm). The transformation rate order (fastest to slowest) of the different fractions is coarse > medium > fine. However, milling accelerates the transformation, that is, smaller particles generated by milling transforms faster. Furthermore, ethanol vapor annealing slows both the transformation of the coarse and medium fractions, especially the latter. Therefore, the mechanism of transformation is not directly related to the crystal-size and most likely related to the amount and activity of the defects in the crystals. The three-dimensional (3-D) Avrami-Erofe'ev model, know as "random nucleation and growth" model, fits the kinetics of coarse fraction best. Higher relative humidity accelerates the transformation dramatically even though the compound is highly-hydrophobic. With minimal hydrogen bonding interaction involved, it appears even small amounts of water can serve as a nucleation catalyst by binding to the crystal surface, especially at defect sites, thus increasing the molecular mobility of these sites, promoting the transformation to the second phase and thereby increasing the transformation rate. (c) 2007 Wiley-Liss, Inc. and the American Pharmacists Association.

Probing the influence of the center atom coordination structure in iron phthalocyanine multi-walled carbon nanotube-based oxygen reduction reaction catalysts by X-ray absorption fine structure spectroscopy

NASA Astrophysics Data System (ADS)

Peng, Yingxiang; Li, Zhipan; Xia, Dingguo; Zheng, Lirong; Liao, Yi; Li, Kai; Zuo, Xia

2015-09-01

Three different pentacoordinate iron phthalocyanine (FePc) electrocatalysts with an axial ligand (pyridyl group, Py) anchored to multi-walled carbon nanotubes (MWCNTs) are prepared by a microwave method as high performance composite electrocatalysts (FePc-Py/MWCNTs) for the oxygen reduction reaction (ORR). For comparison, tetracoordinate FePc electrocatalysts without an axial ligand anchored to MWCNTs (FePc/MWCNTs) are assembled in the same way. Ultraviolet-visible spectrophotometry (UV-Vis), Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HRTEM) are used to characterize the obtained electrocatalysts. The electrocatalytic activity of the samples is measured by linear sweep voltammetry (LSV), and the onset potential of all of the FePc-Py/MWCNTs electrocatalysts is found to be more positive than that of their FePc/MWCNTs counterparts. X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy are employed to elucidate the relationship between molecular structure and electrocatalytic activity. XPS indicates that higher concentrations of Fe3+ and pyridine-type nitrogen play critical roles in determining the electrocatalytic ORR activity of the samples. XAFS spectroscopy reveals that the FePc-Py/MWCNTs electrocatalysts have a coordination geometry around Fe that is closer to the square pyramidal structure, a higher concentration of Fe3+, and a smaller phthalocyanine ring radius compared with those of FePc/MWCNTs.

Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: structure-activity relationship

NASA Astrophysics Data System (ADS)

Guo, Yu; Gu, Dong; Jin, Zhao; Du, Pei-Pei; Si, Rui; Tao, Jing; Xu, Wen-Qian; Huang, Yu-Ying; Senanayake, Sanjaya; Song, Qi-Sheng; Jia, Chun-Jiang; Schüth, Ferdi

2015-03-01

Uniform Au nanoparticles (~2 nm) with narrow size-distribution (standard deviation: 0.5-0.6 nm) supported on both hydroxylated (Fe_OH) and dehydrated iron oxide (Fe_O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) showed high homogeneity in the supported Au nanoparticles. The ex situ and in situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reduction by hydrogen (H2-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe_OH < Au/Fe_O) and CD (Au/Fe_OH > Au/Fe_O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe_OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeOx catalysts with very similar structural characteristics in CO oxidation.

Enhanced activity and stability of binuclear iron (III) phthalocyanine on graphene nanosheets for electrocatalytic oxygen reduction in acid

NASA Astrophysics Data System (ADS)

Li, Tengfei; Peng, Yingxiang; Li, Kai; Zhang, Rui; Zheng, Lirong; Xia, Dingguo; Zuo, Xia

2015-10-01

Binuclear iron (III) phthalocyanine (bi-FePc) and iron (III) phthalocyanine (FePc) are synthesized in situ on graphene nanosheets (GNS) by a microwave-assisted method. TEM, ultraviolet-visible spectroscopy and Raman spectroscopy confirm that bi-FePc is supported on GNS through π-π interactions. The catalytic activity of the bi-FePc/GNS and FePc/GNS composites in the oxygen reduction reaction (ORR) is investigated by CV and RDE measurements. The bi-FePc/GNS composite shows a more positive onset potential (0.12 V vs. Hg/Hg2SO4) for the ORR than FePc/GNS (-0.02 V vs. Hg/Hg2SO4), and a four-electron mechanism similar to commercial Pt/C (0.22 V vs. Hg/Hg2SO4). Moreover, bi-FePc/GNS exhibits good stability with 100% retention after 36,000 s, while Pt/C has a retention of only 50% after the same period. Additionally, bi-FePc/GNS shows higher tolerance toward methanol than the Pt/C catalyst. XPS and X-ray absorption fine structure spectroscopy demonstrate that compared with FePc/GNS, bi-FePc/GNS possesses a higher concentration of Fe3+ and smaller skeleton radius of the phthalocyanine ring, which has a square-planar structure that evidently favors the ORR. Thus, bi-FePc/GNS is a promising candidate as a cathode catalyst in direct methanol fuel cells.

A combination of CoO and Co nanoparticles supported on electrospun carbon nanofibers as highly stable air electrodes

NASA Astrophysics Data System (ADS)

Alegre, Cinthia; Busacca, Concetta; Di Blasi, Orazio; Antonucci, Vincenzo; Aricò, Antonino Salvatore; Di Blasi, Alessandra; Baglio, Vincenzo

2017-10-01

Bifunctional materials able to catalyze both the oxygen reduction (ORR) and the oxygen evolution (OER) reactions in alkaline media are still a challenge for the progress of energy conversion and storage devices such as metal-air batteries or unitized regenerative fuel cells. In this work, carbon nanofibers synthesized by electrospinning are modified with a combination of cobalt oxide and metallic cobalt (CoO-Co/CNF) and studied as a bifunctional air electrode for metal-air batteries. The performance of CoO-Co/CNF for both reactions is compared with state-of-the-art catalysts such as Pt/C and IrO2. The combination of cobalt oxide and metallic cobalt, finely distributed on the surface of graphitic carbon nanofibers, leads to a bifunctional catalyst with a half-wave potential for the ORR slightly better than Pt/C and a reversibility (ΔEOER-ORR) of 809 mV. The stability of CoO-Co/CNF is assessed by means of different stress tests: polarizations at high electrochemical potentials (2 V vs. RHE), rapid charge-discharge cycles at ±80 mA cm-2 and long durability tests by charging for 12 h at 60 mA cm-2 and discharging for 8 h at -80 mA cm-2. CoO-Co/CNF shows a remarkable stability, maintaining, at least, an 82% of its performance for the ORR after the stress tests, even when cycled for more than 100 h.

Effect of pretreating of host oil on coprocessing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hajdu, P.E.; Tierney, J.W.; Wender, I.

1995-12-31

The principal objective of this research was to determine if coprocessing performance (i.e., coal conversion and oil yield) could be significantly improved by pretreating the heavy resid prior to reacting it with coal. For this purpose, two petroleum vacuum resids (1000{degrees}F+), one from the Amoco Co. and another from the Citgo Co., were used as such and after they had been pretreated by catalytic hydrogenation and hydrocracking reactions. The pretreatments were aimed at improving the host oil by; (1) converting any aromatic structures in the petroleum to hydroaromatic compounds capable of donating hydrogen, (2) cracking the heavy oil to lowermore » molecular weight material that might serve as a better solvent, (3) reducing the coking propensity of the heavy oil through the hydrogenation of polynuclear aromatic compounds, and (4) removing metals and heteroatoms that might poison a coprocessing catalyst. Highly dispersed catalysts, including fine particle Fe- and Mo-based, and dicobalt octacarbonyl, Co{sub 2}(CO){sub 8}, were used in this study. The untreated and pretreated resids were extensively characterized in order to determine chemical changes brought about by the pretreatments. The modified heavy oils were then coprocessed with an Illinois No. 6 coal as well as with a Wyodak coal, and compared to coprocessing with untreated resids under the same hydroliquefaction conditions. The amount of oil derived from coal was estimated by measuring the level of phenolic oxygen (derived mainly from coal) present in the oil products. Results are presented and discussed.« less

Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: Structure-activity relationship

DOE PAGES

Guo, Yu; Senanayake, Sanjaya; Gu, Dong; ...

2015-01-12

Uniform Au nanoparticles (~2 nm) with narrow size-distribution (standard deviation: 0.5–0.6 nm) supported on both hydroxylated (Fe_OH) and dehydrated iron oxide (Fe_O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. The transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) described the high homogeneity in the supported Au nanoparticles. The ex-situ and in-situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in-situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reductionmore » by hydrogen (H₂-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe_OH < Au/Fe_O) and CD (Au/Fe_OH > Au/Fe_O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe_OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeO x catalysts with very similar structural characteristics in CO oxidation.« less

Hydrogenation of CO 2 to methanol: Importance of metal–oxide and metal–carbide interfaces in the activation of CO 2

DOE PAGES

Rodriguez, José A.; Liu, Ping; Stacchiola, Dario J.; ...

2015-09-30

In this study, the high thermochemical stability of CO 2 makes it very difficult to achieve the catalytic conversion of the molecule into alcohols or other hydrocarbon compounds, which can be used as fuels or the starting point for the generation of fine chemicals. Pure metals and bimetallic systems used for the CO 2 → CH 3OH conversion usually bind CO 2 too weakly and, thus, show low catalytic activity. Here, we discuss a series of recent studies that illustrate the advantages of metal–oxide and metal–carbide interfaces when aiming at the conversion of CO2 into methanol. CeO x/Cu(111), Cu/CeO x/TiOmore » 2(110), and Au/CeO x/TiO 2(110) exhibit an activity for the CO 2 → CH 3OH conversion that is 2–3 orders of magnitude higher than that of a benchmark Cu(111) catalyst. In the Cu–ceria and Au–ceria interfaces, the multifunctional combination of metal and oxide centers leads to complementary chemical properties that open active reaction pathways for methanol synthesis. Efficient catalysts are also generated after depositing Cu and Au on TiC(001). In these cases, strong metal–support interactions modify the electronic properties of the admetals and make them active for the binding of CO 2 and its subsequent transformation into CH 3OH at the metal–carbide interfaces.« less

Oxidation catalyst

DOEpatents

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.

On-site manufacture of propellant oxygen from lunar resources

NASA Technical Reports Server (NTRS)

Rosenberg, Sanders D.

1992-01-01

The Aerojet Carbothermal Process for the manufacture of oxygen from lunar resources has three essential steps: the reduction of silicate with methane to form carbon monoxide and hydrogen; the reduction of carbon monoxide with hydrogen to form methane and water; and the electrolysis of water to form oxygen and hydrogen. This cyclic process does not depend upon the presence of water or water precursors in the lunar materials; it will produce oxygen from silicates regardless of their precise composition and fine structure. Research on the first step of the process was initiated by determining some of the operating conditions required to reduce igneous rock with carbon and silicon carbide. The initial phase of research on the second step is completed; quantitative conversion of carbon monoxide and hydrogen to methane and water was achieved with a nickel-on-kieselguhr catalyst. The equipment used in and the results obtained from these process studies are reported in detail.

Wavelet-based surrogate time series for multiscale simulation of heterogeneous catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Savara, Aditya Ashi; Daw, C. Stuart; Xiong, Qingang

We propose a wavelet-based scheme that encodes the essential dynamics of discrete microscale surface reactions in a form that can be coupled with continuum macroscale flow simulations with high computational efficiency. This makes it possible to simulate the dynamic behavior of reactor-scale heterogeneous catalysis without requiring detailed concurrent simulations at both the surface and continuum scales using different models. Our scheme is based on the application of wavelet-based surrogate time series that encodes the essential temporal and/or spatial fine-scale dynamics at the catalyst surface. The encoded dynamics are then used to generate statistically equivalent, randomized surrogate time series, which canmore » be linked to the continuum scale simulation. As a result, we illustrate an application of this approach using two different kinetic Monte Carlo simulations with different characteristic behaviors typical for heterogeneous chemical reactions.« less

Catalyst effects in heterogeneous nucleation of acicular ferrite

NASA Astrophysics Data System (ADS)

Grong, Ø.; Kluken, A. O.; Nylund, H. K.; Dons, A. L.; Hjelen, J.

1995-03-01

The present investigation is concerned with basic studies of the mechanisms of acicular ferrite (AF)’formation in low-alloy steel weld metal. It is confirmed experimentally that different types of orientation relationships exist between AF and specific cubic inclusion constituent phases (i.e., γ-Al2 MnOAl2O3, and TiN). Since the majority of these falls within the Bain orientation region, it is concluded that the associated reduction of the energy barrier to nucleation is the primary cause for the ferrite nucleus to develop orientation relationships with both the substrate and the austenite. Theoretical calculations show that about 12 pct of the inclusions will contain a cubic phase that lies within the Bain region purely by chance if they are randomly orientated in space. This intrinsic density of heterogeneous nucleation sites is sufficiently high to promote the formation of fine, interlocking AF laths in the weld metal during the y- to- a transformation.

Synthesis of nanoparticles using ethanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jia Xu

The present disclosure relates to methods for producing nanoparticles. The nanoparticles may be made using ethanol as the solvent and the reductant to fabricate noble-metal nanoparticles with a narrow particle size distributions, and to coat a thin metal shell on other metal cores. With or without carbon supports, particle size is controlled by fine-tuning the reduction power of ethanol, by adjusting the temperature, and by adding an alkaline solution during syntheses. The thickness of the added or coated metal shell can be varied easily from sub-monolayer to multiple layers in a seed-mediated growth process. The entire synthesis of designed core-shellmore » catalysts can be completed using metal salts as the precursors with more than 98% yield; and, substantially no cleaning processes are necessary apart from simple rinsing. Accordingly, this method is considered to be a "green" chemistry method.« less

Access to enantioenriched alpha-amino esters via rhodium-catalyzed 1,4-addition/enantioselective protonation.

PubMed

Navarre, Laure; Martinez, Rémi; Genet, Jean-Pierre; Darses, Sylvain

2008-05-14

Conjugate addition of potassium trifluoro(organo)borates 2 to dehydroalanine derivatives 1, mediated by a chiral rhodium catalyst and in situ enantioselective protonation, afforded straightforward access to a variety of protected alpha-amino esters 3 with high yields and enantiomeric excesses up to 95%. Among the tested chiral ligands and proton sources, Binap, in combination with guaiacol (2-methoxyphenol), an inexpensive and nontoxic phenol, afforded the highest asymmetric inductions. Organostannanes have also shown to participate in this reaction. By a fine-tuning of the ester moiety, and using Difluorophos as chiral ligand, increased levels of enantioselectivity, generally close to 95%, were achieved. Deuterium labeling experiments revealed, and DFT calculation supported, an unusual mechanism involving a hydride transfer from the amido substituent to the alpha carbon explaining the high levels of enantioselectivity attained in controlling this alpha chiral center.

Bitumen and heavy oil upgrading in Canada

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chrones, J.; Germain, R.R.

1989-01-01

A review is presented of the heavy oil upgrading industry in Canada. Up to now it has been based on the processing of bitumen extracted from oil sands mining operations at two sites, to produce a residue-free, low sulphur, synthetic crude. Carbon rejection has been the prime process technology with delayed coking being used by Suncor and FLUID COKING at Syncrude. Alternative processes for recovering greater amounts of synthetic crude are examined. These include a variety of hydrogen addition processes and combinations which produce pipelineable materials requiring further processing in downstream refineries with expanded capabilities. The Newgrade Energy Inc. upgradermore » now under construction in Regina, will use fixed-bed, catalytic, atmospheric-residue, hydrogen processing. Two additional projects, also based on hydrogenation, will use ebullated bed catalyst systems; the expansion of Syncrude, now underway, is using the LC Fining Process whereas the announced Husky Bi-Provincial upgrader is based on H-Oil.« less

Bitumen and heavy oil upgrading in Canada

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chrones, J.

1988-06-01

A review is presented of the heavy oil upgrading industry in Canada. Up to now it has been based on the processing of bitumen extracted from oil sands mining operations at two sites, to produce a residue-free, low sulfur, synthetic crude. Carbon rejection has been the prime process technology with delayed coking being used by Suncor and FLUID COKING at Syncrude. Alternative processes for recovering greater amounts of synthetic crude are examined. These include a variety of hydrogen addition processes and combinations which produce pipelineable materials requiring further processing in downstream refineries with expanded capabilities. The Newgrade Energy Inc. upgrader,more » now under construction in Regina, will use fixed-bed, catalytic, atmospheric-residue, hydrogen processing. Two additional products, also based on hydrogenation, will use ebullated bed catalyst systems: the expansion of Syncrude, now underway, is using the LC Fining Process whereas the announced Husky Bi-Provincial upgrader is based on H-Oil.« less

Parallel array of nanochannels grafted with polymer-brushes-stabilized Au nanoparticles for flow-through catalysis.

PubMed

Liu, Jianxi; Ma, Shuanhong; Wei, Qiangbing; Jia, Lei; Yu, Bo; Wang, Daoai; Zhou, Feng

2013-12-07

Smart systems on the nanometer scale for continuous flow-through reaction present fascinating advantages in heterogeneous catalysis, in which a parallel array of straight nanochannels offers a platform with high surface area for assembling and stabilizing metallic nanoparticles working as catalysts. Herein we demonstrate a method for finely modifying the nanoporous anodic aluminum oxide (AAO), and further integration of nanoreactors. By using atomic transfer radical polymerization (ATRP), polymer brushes were successfully grafted on the inner wall of the nanochannels of the AAO membrane, followed by exchanging counter ions with a precursor for nanoparticles (NPs), and used as the template for deposition of well-defined Au NPs. The membrane was used as a functional nanochannel for novel flow-through catalysis. High catalytic performance and instantaneous separation of products from the reaction system was achieved in reduction of 4-nitrophenol.

Parallel array of nanochannels grafted with polymer-brushes-stabilized Au nanoparticles for flow-through catalysis

NASA Astrophysics Data System (ADS)

Liu, Jianxi; Ma, Shuanhong; Wei, Qiangbing; Jia, Lei; Yu, Bo; Wang, Daoai; Zhou, Feng

2013-11-01

Smart systems on the nanometer scale for continuous flow-through reaction present fascinating advantages in heterogeneous catalysis, in which a parallel array of straight nanochannels offers a platform with high surface area for assembling and stabilizing metallic nanoparticles working as catalysts. Herein we demonstrate a method for finely modifying the nanoporous anodic aluminum oxide (AAO), and further integration of nanoreactors. By using atomic transfer radical polymerization (ATRP), polymer brushes were successfully grafted on the inner wall of the nanochannels of the AAO membrane, followed by exchanging counter ions with a precursor for nanoparticles (NPs), and used as the template for deposition of well-defined Au NPs. The membrane was used as a functional nanochannel for novel flow-through catalysis. High catalytic performance and instantaneous separation of products from the reaction system was achieved in reduction of 4-nitrophenol.

Utilization of ethyl cellulose polymer and waste materials for roofing tile production

NASA Astrophysics Data System (ADS)

Sam, Suubitaa Spencer; Ng, ChoonAun; Chee, Swee Yong; Habib, NoorZainab; Nadeem, Humayon; Teoh, Wei Ping

2017-05-01

The aim of this study was to utilize ethyl cellulose, mixture of waste engine oil and waste vegetable oil as a binder in the environmental friendly roofing tile production. The waste engine-vegetable oil wasmix together with ethyl cellulose, fly ash, coarse aggregates, fine aggregatesand a catalyst. The Fourier Transform Infrared (FTIR) analysis showed that the oil mixture added with ethyl cellulose has the relatively high binding effect due to the presence of strong carbonyl group especially after being heat cured at 1900C for 24 hours. The mixed proportion of materials with different amount of ethyl cellulose used was studied in the production of tile specimen. The results showed that the ethyl cellulose composed roofing tile specimens passed the transverse breaking strength, durability, permeabilityand the ultraviolet accelerated test. The shrinkage on the tile can be overcome by adding temperature resistance polymer on the exterior of the tile.

Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rinaldi, Roberto; Jastrzebski, Robin; Clough, Matthew T.

2016-06-17

Lignin is an abundant biopolymer with a high carbon content and high aromaticity. Despite its potential as a raw material for the fuel and chemical industries, lignin remains the most poorly utilised of the lignocellulosic biopolymers. Effective valorisation of lignin requires careful fine-tuning of multiple “upstream” (i.e., lignin bioengineering, lignin isolation and “early-stage catalytic conversion of lignin”) and “downstream” (i.e., lignin depolymerisation and upgrading) process stages, demanding input and understanding from a broad array of scientific disciplines. This review provides a “beginning-to-end” analysis of the recent advances reported in lignin valorisation. Particular emphasis is placed on the improved understanding ofmore » ligninÏs biosynthesis and structure, differences in structure and chemical bonding between native and technical lignins, emerging catalytic valorisation strategies, and the relationships between lignin structure and catalyst performance.« less

Immobilized enzymes: understanding enzyme - surface interactions at the molecular level.

PubMed

Hoarau, Marie; Badieyan, Somayesadat; Marsh, E Neil G

2017-11-22

Enzymes immobilized on solid supports have important and industrial and medical applications. However, their uses are limited by the significant reductions in activity and stability that often accompany the immobilization process. Here we review recent advances in our understanding of the molecular level interactions between proteins and supporting surfaces that contribute to changes in stability and activity. This understanding has been facilitated by the application of various surface-sensitive spectroscopic techniques that allow the structure and orientation of enzymes at the solid/liquid interface to be probed, often with monolayer sensitivity. An appreciation of the molecular interactions between enzyme and surface support has allowed the surface chemistry and method of enzyme attachement to be fine-tuned such that activity and stability can be greatly enhanced. These advances suggest that a much wider variety of enzymes may eventually be amenable to immobilization as green catalysts.

Ruthenium-catalysed alkoxycarbonylation of alkenes with carbon dioxide.

PubMed

Wu, Lipeng; Liu, Qiang; Fleischer, Ivana; Jackstell, Ralf; Beller, Matthias

2014-01-01

Alkene carbonylations represent a major technology for the production of value-added bulk and fine chemicals. Nowadays, all industrial carbonylation processes make use of highly toxic and flammable carbon monoxide. Here we show the application of abundantly available carbon dioxide as C1 building block for the alkoxycarbonylations of industrially important olefins in the presence of a convenient and inexpensive ruthenium catalyst system. In our system, carbon dioxide works much better than the traditional combination of carbon monoxide and alcohols. The unprecedented in situ formation of carbon monoxide from carbon dioxide and alcohols permits an efficient synthesis of carboxylic acid esters, which can be used as detergents and polymer-building blocks. Notably, this transformation allows the catalytic formation of C-C bonds with carbon dioxide as C1 source and avoids the use of sensitive and/or expensive reducing agents (for example, Grignard reagents, diethylzinc or triethylaluminum).

ZnO nanoparticles obtained by ball milling technique: Structural, micro-structure, optical and photo-catalytic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balamurugan, S., E-mail: scandium.chemistry@gmail.com; Joy, Josny; Godwin, M. Anto

The ZnO nanoparticles were obtained by ball milling of commercial grade ZnO powder at 250 rpm for 20 h and studied their structural, micro-structure, optical and photo-catalytic properties. Due to ball milling significant decrease in lattice parameters and average crystalline size is noticed for the as-milled ZnO nano powder. The HRSEM images of the as-milled powder consist of agglomerated fine spherical nanoparticles in the range of ~10-20 nm. The room temperature PL spectrum of as-milled ZnO nano powder excited under 320 nm reveals two emission bands at ~406 nm (violet emission) and ~639 nm (green emission). Interestingly about 98 % of photo degradation of methylene (MB)more » by the ZnO catalyst is achieved at 100 minutes of solar light irradiation.« less

Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis

DOE PAGES

Rinaldi, Roberto; Jastrzebski, Robin; Clough, Matthew T.; ...

2016-06-17

In this study, lignin is an abundant biopolymer with a high carbon content and high aromaticity. Despite its potential as a raw material for the fuel and chemical industries, lignin remains the most poorly utilised of the lignocellulosic biopolymers. Effective valorisation of lignin requires careful fine-tuning of multiple “upstream” (i.e., lignin bioengineering, lignin isolation and “early-stage catalytic conversion of lignin”) and “downstream” (i.e., lignin depolymerisation and upgrading) process stages, demanding input and understanding from a broad array of scientific disciplines. This review provides a “beginning-to-end” analysis of the recent advances reported in lignin valorisation. Particular emphasis is placed on themore » improved understanding of ligninÏs biosynthesis and structure, differences in structure and chemical bonding between native and technical lignins, emerging catalytic valorisation strategies, and the relationships between lignin structure and catalyst performance.« less

A composite material with CeO2-ZrO2 nanocrystallines embedded in SiO2 matrices and its enhanced thermal stability and oxygen storage capacity

NASA Astrophysics Data System (ADS)

Yang, Runnong; Liu, Yumei; Yu, Lin; Zhao, Xiangyun; Yang, Xiaobo; Sun, Ming; Luo, Junyin; Fan, Qun; Xiao, Jianming; Zhao, Yuzhong

2018-06-01

A simple hydrothermal procedure is introduced, which leads to the successful synthesis of a new composite material with fine CeO2-ZrO2 nanocrystallites embedded in amorphous and porous SiO2 matrices. The composite material possesses an extraordinary high thermal stability. After being calcined at 1000 °C, it retains CeO2-ZrO2 nanocrystallites of the size around 5 nm, a BET-specific surface area of 165 m2/g, and an oxygen storage capacity of 468 μmol/g. No phase segregation for CeO2-ZrO2 nanocrystallites is detected and the SiO2 matrices remain not crystallized. The composite material shows a great potential as a support of three-way catalyst, as evidenced in catalytic tests with supported Pt.

Wavelet-based surrogate time series for multiscale simulation of heterogeneous catalysis

DOE PAGES

Savara, Aditya Ashi; Daw, C. Stuart; Xiong, Qingang; ...

2016-01-28

We propose a wavelet-based scheme that encodes the essential dynamics of discrete microscale surface reactions in a form that can be coupled with continuum macroscale flow simulations with high computational efficiency. This makes it possible to simulate the dynamic behavior of reactor-scale heterogeneous catalysis without requiring detailed concurrent simulations at both the surface and continuum scales using different models. Our scheme is based on the application of wavelet-based surrogate time series that encodes the essential temporal and/or spatial fine-scale dynamics at the catalyst surface. The encoded dynamics are then used to generate statistically equivalent, randomized surrogate time series, which canmore » be linked to the continuum scale simulation. As a result, we illustrate an application of this approach using two different kinetic Monte Carlo simulations with different characteristic behaviors typical for heterogeneous chemical reactions.« less

Hydrogen Production by Steam Reforming of Liquefied Natural Gas (LNG) Over Nickel-Phosphorus-Alumina Xerogel Catalyst Prepared by a Carbon-Templating Epoxide-Driven Sol-Gel Method.

PubMed

Bang, Yongju; Park, Seungwon; Han, Seung Ju; Yoo, Jaekyeong; Choi, Jung Ho; Kang, Tae Hun; Lee, Jinwon; Song, In Kyu

2016-05-01

A nickel-phosphorus-alumina xerogel catalyst was prepared by a carbon-templating epoxide-driven sol-gel method (denoted as CNPA catalyst), and it was applied to the hydrogen production by steam reforming of liquefied natural gas (LNG). For comparison, a nickel-phosphorus-alumina xerogel catalyst was also prepared by a similar method in the absence of carbon template (denoted as NPA catalyst). The effect of carbon template addition on the physicochemical properties and catalytic activities of the catalysts in the steam reforming of LNG was investigated. Both CNPA and NPA catalysts showed excellent textural properties with well-developed mesoporous structure. However, CNPA catalyst retained a more reducible nickel aluminate phase than NPA catalyst. XRD analysis of the reduced CNPA and NPA catalysts revealed that nickel sintering on the CNPA catalyst was suppressed compared to that on the NPA catalyst. From H2-TPD and CH4-TPD measurements of the reduced CNPA and NPA catalysts, it was also revealed that CNPA catalyst with large amount of hydrogen uptake and strong hydrogen-binding sites showed larger amount of methane adsorption than NPA catalyst. In the hydrogen production by steam reforming of LNG, CNPA catalyst with large methane adsorption capacity showed a better catalytic activity than NPA catalyst.

Catalyst system comprising a first catalyst system tethered to a supported catalyst

DOEpatents

Angelici, Robert J.; Gao, Hanrong

1998-08-04

The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilation, olefin oxidation, isomerization, hydrocyanation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical.

Catalyst system comprising a first catalyst system tethered to a supported catalyst

DOEpatents

Angelici, R.J.; Gao, H.

1998-08-04

The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilication, olefin oxidation, isomerization, hydrocyanidation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical. 2 figs.

Textured catalysts and methods of making textured catalysts

DOEpatents

Werpy, Todd [West Richland, WA; Frye, Jr., John G.; Wang, Yong [Richland, WA; Zacher, Alan H [Kennewick, WA

2007-03-06

A textured catalyst having a hydrothermally-stable support, a metal oxide and a catalyst component is described. Methods of conducting aqueous phase reactions that are catalyzed by a textured catalyst are also described. The invention also provides methods of making textured catalysts and methods of making chemical products using a textured catalyst.

Music-supported motor training after stroke reveals no superiority of synchronization in group therapy

PubMed Central

Van Vugt, Floris T.; Ritter, Juliane; Rollnik, Jens D.; Altenmüller, Eckart

2014-01-01

Background: Music-supported therapy has been shown to be an effective tool for rehabilitation of motor deficits after stroke. A unique feature of music performance is that it is inherently social: music can be played together in synchrony. Aim: The present study explored the potential of synchronized music playing during therapy, asking whether synchronized playing could improve fine motor rehabilitation and mood. Method: Twenty-eight patients in neurological early rehabilitation after stroke with no substantial previous musical training were included. Patients learned to play simple finger exercises and familiar children's songs on the piano for 10 sessions of half an hour. Patients first received three individual therapy sessions and then continued in pairs. The patient pairs were divided into two groups. Patients in one group played synchronously (together group) whereas the patients in the other group played one after the other (in-turn group). To assess fine motor skill recovery the patients performed standard clinical tests such as the nine-hole-pegboard test (9HPT) and index finger-tapping speed and regularity, and metronome-paced finger tapping. Patients' mood was established using the Profile of Mood States (POMS). Results: Both groups showed improvements in fine motor control. In metronome-paced finger tapping, patients in both groups improved significantly. Mood tests revealed reductions in depression and fatigue in both groups. During therapy, patients in the in-turn group rated their partner as more sympathetic than the together-group in a visual-analog scale. Conclusions: Our results suggest that music-supported stroke rehabilitation can improve fine motor control and mood not only individually but also in patient pairs. Patients who were playing in turn rather than simultaneously tended to reveal greater improvement in fine motor skill. We speculate that patients in the former group may benefit from the opportunity to learn from observation. PMID:24904358

Technology development for cobalt F-T catalysts. Quarterly technical progress report number 10, January 1--March 31, 1995

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singleton, A.H.

1995-06-28

The goal of this project is the development of a commercially-viable, cobalt-based Fischer-Tropsch (F-T) catalyst for use in a slurry bubble column reactor. The major objectives of this work are (1) to develop a cobalt-based F-T catalyst with low (< 5%) methane selectivity, (2) to develop a cobalt-based F-T catalyst with water-gas shift activity, and (3) to combine both these improvements into one catalyst. The project consists of five major tasks: catalyst development; catalyst testing; catalyst reproducibility tests; catalyst aging tests; and preliminary design and cost estimate for a demonstrate scale catalyst production facility. Technical accomplishments during this reporting periodmore » include the following. It appears that the higher activity obtained for the catalysts prepared using an organic solution and reduced directly without prior calcination was the result of higher dispersions obtained under such pretreatment. A Ru-promoted Co catalyst on alumina with 30% Co loading exhibited a 4-fold increase in dispersion and a 2-fold increase in activity in the fixed-bed reactor from that obtained with the non-promoted catalyst. Several reactor runs have again focused on pushing conversion to higher levels. The maximum conversion obtained has been 49.7% with 26g catalyst. Further investigations of the effect of reaction temperature on the performance of Co catalysts during F-T synthesis were started using a low activity catalyst and one of the most active catalysts. The three 1 kg catalyst batches prepared by Calsicat for the reproducibility and aging studies were tested in both the fixed-bed and slurry bubble column reactors under the standard reaction conditions. The effects of adding various promoters to some cobalt catalysts have also been addressed. Results are presented and discussed.« less

Chapter A6. Section 6.7. Turbidity

USGS Publications Warehouse

Anderson, Chauncey W.

2005-01-01

Turbidity is one of the indicators used to assess the environmental health of water bodies. Turbidity is caused by the presence of suspended and dissolved matter, such as clay, silt, finely divided organic matter, plankton and other microscopic organisms, organic acids, and dyes. This section of the National Field Manual (NFM) describes the USGS protocols for determining turbidity in surface and ground waters, including extensive guidance for equipment selection and data reporting. It includes the revised approach to turbidity measurement and reporting that was implemented by the U.S. Geological Survey (USGS) in October 2004 to account for technological advances and consequent measurement complexities.

Peripheral vascular tumors and vascular malformations: imaging (magnetic resonance imaging and conventional angiography), pathologic correlation and treatment options.

PubMed

El-Merhi, Fadi; Garg, Deepak; Cura, Marco; Ghaith, Ola

2013-02-01

Vascular anomalies are classified into vascular tumors (infantile hemangioma) and vascular malformations. Vascular malformations are divided into slow flow and high flow subtypes. Magnetic resonance imaging helps in classification and assessing extent and distribution. Conventional angiography also known as digital subtraction angiography is pivotal in assessment of fine vascular details and treatment planning. Imaging correlates well with histopathology. We review recent development in imaging techniques of various vascular anomalies most of which are affecting the peripheral system which potentially may broaden understanding of their diagnosis, classification and treatment.

Sertoli cell tumour in an Amur tiger.

PubMed

Scudamore, C L; Meredith, A L

2001-01-01

The histological and immunohistochemical characteristics of a malignant Sertoli cell tumour in a 17-year-old Amur tiger (Panthera tigris altaica) are described. Histological examination of the primary lesion in the right testis and metastatic lesions throughout the internal organs showed a variable cellular pattern with an admixture of tubular structures divided by fine stroma filled with fusiform to stellate cells, and sheets of polygonal cells with abundant vacuolated cytoplasm. Immunohistochemical techniques demonstrated strong positive staining for neuron-specific enolase and variable positive staining for vimentin in neoplastic cells, supporting a diagnosis of a tumour of Sertoli cell origin.

METHOD OF MAKING METAL BONDED CARBON BODIES

DOEpatents

Goeddel, W.V.; Simnad, M.T.

1961-09-26

A method of producing carbon bodies having high structural strength and low permeability is described. The method comprises mixing less than 10 wt.% of a diffusional bonding material selected from the group consisting of zirconium, niobium, molybdenum, titanium, nickel, chromium, silicon, and decomposable compounds thereof with finely divided particles of carbon or graphite. While being maintained at a mechanical pressure over 3,000 psi, the mixture is then heated uniformly to a temperature of 1500 deg C or higher, usually for less than one hour. The resulting carbon bodies have a low diffusion constant, high dimensional stability, and high mechanical strength.

In-situ stabilization of radioactive zirconium swarf

DOEpatents

Hess, C.C.

1999-08-31

The method for treating ignitable cutting swarf in accordance with the present invention involves collecting cutting swarf in a casting mold underwater and injecting a binder mixture comprising vinyl ester styrene into the vessel to fill void volume; and form a mixture comprising swarf and vinyl ester styrene; and curing the mixture. The method is especially useful for stabilizing the ignitable characteristics of radioactive zirconium cutting swarf, and can be used to solidify zirconium swarf, or other ignitable finely divided material, underwater. The process could also be performed out of water with other particulate wastes. 6 figs.

PRODUCTION OF URANIUM METAL BY CARBON REDUCTION

DOEpatents

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

1959-09-22

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

Catalyst patterning for nanowire devices

NASA Technical Reports Server (NTRS)

Li, Jun (Inventor); Cassell, Alan M. (Inventor); Han, Jie (Inventor)

2004-01-01

Nanowire devices may be provided that are based on carbon nanotubes or single-crystal semiconductor nanowires. The nanowire devices may be formed on a substrate. Catalyst sites may be formed on the substrate. The catalyst sites may be formed using lithography, thin metal layers that form individual catalyst sites when heated, collapsible porous catalyst-filled microscopic spheres, microscopic spheres that serve as masks for catalyst deposition, electrochemical deposition techniques, and catalyst inks. Nanowires may be grown from the catalyst sites.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

Twelve catalyst test runs were made; ten of these runs used catalysts that contained cobalt as the metal component, while the remaining two runs used catalysts that contained iron as the metal component. Five of the ten cobalt catalyst test runs were made with the catalysts containing one of two different shape selective components (UCC-101 and UCC-108) at two different metal component: shape selective component ratios (1:1 and 3:14). The remaining five cobalt catalyst test runs were made with the catalysts containing different additives incorporated into the cobalt. The five cobalt catalyst test runs using catalysts with different additives showedmore » that these additives had pronounced effects on the catalysts' activity, selectivity, and stability. The most outstanding effect was realized with the additive used in the Run 9 catalyst. This additive greatly improved the stability of the catalyst. While having the same initial activity of an additive-free catalyst, its deactivation rate was only one fourth of that of the additive-free catalyst. Futhermore, this additive improved the quality of the hydrocarbon product, which had a high, stable yield of olefins, and, unlike the product of any other cobalt/UCC-101 catalyst, was free of suspended wax. This lack of suspended wax resulted in jet fuel and diesel oil fractions that had substantially lower pour points than did the fractions produced from an additive-free catalyst.« less

Attrition resistant catalysts and sorbents based on heavy metal poisoned FCC catalysts

DOEpatents

Gangwal, S.; Jothimurugesan, K.

1999-07-27

A heavy metal poisoned, spent FCC catalyst is treated by chemically impregnating the poisoned catalyst with a new catalytic metal or metal salt to provide an attrition resistant catalyst or sorbent for a different catalytic or absorption process, such as catalysts for Fischer-Tropsh Synthesis, and sorbents for removal of sulfur gases from fuel gases and flue-gases. The heavy metal contaminated FCC catalyst is directly used as a support for preparing catalysts having new catalytic properties and sorbents having new sorbent properties, without removing or passivating the heavy metals on the spent FCC catalyst as an intermediate step.

Attrition resistant catalysts and sorbents based on heavy metal poisoned FCC catalysts

DOEpatents

Gangwal, Santosh; Jothimurugesan, Kandaswamy

1999-01-01

A heavy metal poisoned, spent FCC catalyst is treated by chemically impregnating the poisoned catalyst with a new catalytic metal or metal salt to provide an attrition resistant catalyst or sorbent for a different catalytic or absorption processes, such as catalysts for Fischer-Tropsh Synthesis, and sorbents for removal of sulfur gasses from fuel gases and flue-gases. The heavy metal contaminated FCC catalyst is directly used as a support for preparing catalysts having new catalytic properties and sorbents having new sorbent properties, without removing or "passivating" the heavy metals on the spent FCC catalyst as an intermediate step.

Durability testing at one atmosphere of advanced catalysts and catalyst supports for automotive gas turbine engine combustors, part 1

NASA Technical Reports Server (NTRS)

Heck, R. M.; Chang, M.; Hess, H.; Carrubba, R.

1977-01-01

The durability of catalysts and catalyst supports in a combustion environment was experimentally demonstrated. A test of 1000 hours duration was completed with two catalysts, using diesel fuel and operating at catalytically supported thermal combustion conditions. The performance of the catalysts was determined by monitoring emissions throughout the test, and by examining the physical condition of the catalyst core at the conclusion of the test. The test catalysts proved to be capable of low emissions operation after 1000 hours diesel aging, with no apparent physical degradation of the catalyst support.

Summary of Fluidic Thrust Vectoring Research Conducted at NASA Langley Research Center

NASA Technical Reports Server (NTRS)

Deere, Karen A.

2003-01-01

Interest in low-observable aircraft and in lowering an aircraft's exhaust system weight sparked decades of research for fixed geometry exhaust nozzles. The desire for such integrated exhaust nozzles was the catalyst for new fluidic control techniques; including throat area control, expansion control, and thrust-vector angle control. This paper summarizes a variety of fluidic thrust vectoring concepts that have been tested both experimentally and computationally at NASA Langley Research Center. The nozzle concepts are divided into three categories according to the method used for fluidic thrust vectoring: the shock vector control method, the throat shifting method, and the counterflow method. This paper explains the thrust vectoring mechanism for each fluidic method, provides examples of configurations tested for each method, and discusses the advantages and disadvantages of each method.

Textured catalysts, methods of making textured catalysts, and methods of catalyzing reactions conducted in hydrothermal conditions

DOEpatents

Werpy, Todd [West Richland, WA; Wang, Yong [Richland, WA

2003-12-30

A textured catalyst having a hydrothermally-stable support, a metal oxide and a catalyst component is described. Methods of conducting aqueous phase reactions that are catalyzed by a textured catalyst are also described. The invention also provides methods of making textured catalysts and methods of making chemical products using a textured catalyst.

An Overview of Recent Development in Composite Catalysts from Porous Materials for Various Reactions and Processes

PubMed Central

Xie, Zaiku; Liu, Zhicheng; Wang, Yangdong; Yang, Qihua; Xu, Longya; Ding, Weiping

2010-01-01

Catalysts are important to the chemical industry and environmental remediation due to their effective conversion of one chemical into another. Among them, composite catalysts have attracted continuous attention during the past decades. Nowadays, composite catalysts are being used more and more to meet the practical catalytic performance requirements in the chemical industry of high activity, high selectivity and good stability. In this paper, we reviewed our recent work on development of composite catalysts, mainly focusing on the composite catalysts obtained from porous materials such as zeolites, mesoporous materials, carbon nanotubes (CNT), etc. Six types of porous composite catalysts are discussed, including amorphous oxide modified zeolite composite catalysts, zeolite composites prepared by co-crystallization or overgrowth, hierarchical porous catalysts, host-guest porous composites, inorganic and organic mesoporous composite catalysts, and polymer/CNT composite catalysts. PMID:20559508

Near-infrared light controlled photocatalytic activity of carbon quantum dots for highly selective oxidation reaction

NASA Astrophysics Data System (ADS)

Li, Haitao; Liu, Ruihua; Lian, Suoyuan; Liu, Yang; Huang, Hui; Kang, Zhenhui

2013-03-01

Selective oxidation of alcohols is a fundamental and significant transformation for the large-scale production of fine chemicals, UV and visible light driven photocatalytic systems for alcohol oxidation have been developed, however, the long wavelength near infrared (NIR) and infrared (IR) light have not yet fully utilized by the present photocatalytic systems. Herein, we reported carbon quantum dots (CQDs) can function as an effective near infrared (NIR) light driven photocatalyst for the selective oxidation of benzyl alcohol to benzaldehyde. Based on the NIR light driven photo-induced electron transfer property and its photocatalytic activity for H2O2 decomposition, this metal-free catalyst could realize the transformation from benzyl alcohol to benzaldehyde with high selectivity (100%) and conversion (92%) under NIR light irradiation. HO&z.rad; is the main active oxygen specie in benzyl alcohol selective oxidative reaction confirmed by terephthalic acid photoluminescence probing assay (TA-PL), selecting toluene as the substrate. Such metal-free photocatalytic system also selectively converts other alcohol substrates to their corresponding aldehydes with high conversion, demonstrating a potential application of accessing traditional alcohol oxidation chemistry.Selective oxidation of alcohols is a fundamental and significant transformation for the large-scale production of fine chemicals, UV and visible light driven photocatalytic systems for alcohol oxidation have been developed, however, the long wavelength near infrared (NIR) and infrared (IR) light have not yet fully utilized by the present photocatalytic systems. Herein, we reported carbon quantum dots (CQDs) can function as an effective near infrared (NIR) light driven photocatalyst for the selective oxidation of benzyl alcohol to benzaldehyde. Based on the NIR light driven photo-induced electron transfer property and its photocatalytic activity for H2O2 decomposition, this metal-free catalyst could realize the transformation from benzyl alcohol to benzaldehyde with high selectivity (100%) and conversion (92%) under NIR light irradiation. HO&z.rad; is the main active oxygen specie in benzyl alcohol selective oxidative reaction confirmed by terephthalic acid photoluminescence probing assay (TA-PL), selecting toluene as the substrate. Such metal-free photocatalytic system also selectively converts other alcohol substrates to their corresponding aldehydes with high conversion, demonstrating a potential application of accessing traditional alcohol oxidation chemistry. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00092c

Three-dimensional carbon- and binder-free nickel nanowire arrays as a high-performance and low-cost anode for direct hydrogen peroxide fuel cell

NASA Astrophysics Data System (ADS)

Ye, Ke; Guo, Fen; Gao, Yinyi; Zhang, Dongming; Cheng, Kui; Zhang, Wenping; Wang, Guiling; Cao, Dianxue

2015-12-01

A novel three-dimensional carbon- and binder-free nickel nanowire arrays (Ni NAs) electrode is successfully fabricated by a facile galvanostatic electrodeposition method using polycarbonate membrane as the template. The Ni NAs electrode achieves a oxidation current density (divided by the electroactive surface areas of Ni) of 25.1 mA cm-2 in 4 mol L-1 KOH and 0.9 mol L-1 H2O2 at 0.2 V (vs. Ag/AgCl) accompanied with a desirable stability, which is significantly higher than the catalytic activity of H2O2 electro-oxidation achieved previously with precious metals as catalysts. The impressive electrocatalytic performance is largely attributed to the superior 3D open structure and high electronic conductivity, which ensures the high utilization of Ni surfaces and makes the electrode have higher electrochemical activity. The apparent activation energy of H2O2 electro-oxidation on the Ni NAs catalyst is 13.59 kJ mol-1. A direct peroxide-peroxide fuel cell using the Ni NAs as anode exhibits a peak power density of 48.7 mW cm-2 at 20 °C. The electrode displays a great promise as the anode of direct peroxide-peroxide fuel cell due to its low cost, high activity and stability.

Technology for advanced liquefaction processes: Coal/waste coprocessing studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cugini, A.V.; Rothenberger, K.S.; Ciocco, M.V.

1995-12-31

The efforts in this project are directed toward three areas: (1) novel catalyst (supported and unsupported) research and development, (2) study and optimization of major operating parameters (specifically pressure), and (3) coal/waste coprocessing. The novel catalyst research and development activity has involved testing supported catalysts, dispersed catalysts, and use of catalyst testing units to investigate the effects of operating parameters (the second area) with both supported and unsupported catalysts. Several supported catalysts were tested in a simulated first stage coal liquefaction application at 404{degrees}C during this performance period. A Ni-Mo hydrous titanate catalyst on an Amocat support prepared by Sandiamore » National laboratories was tested. Other baseline experiments using AO-60 and Amocat, both Ni-Mo/Al{sub 2}O{sub 3} supported catalysts, were also made. These experiments were short duration (approximately 12 days) and monitored the initial activity of the catalysts. The results of these tests indicate that the Sandia catalyst performed as well as the commercially prepared catalysts. Future tests are planned with other Sandia preparations. The dispersed catalysts tested include sulfated iron oxide, Bayferrox iron oxide (iron oxide from Miles, Inc.), and Bailey iron oxide (micronized iron oxide from Bailey, Inc.). The effects of space velocity, temperature, and solvent-to-coal ratio on coal liquefaction activity with the dispersed catalysts were investigated. A comparison of the coal liquefaction activity of these catalysts relative to iron catalysts tested earlier, including FeOOH-impregnated coal, was made. These studies are discussed.« less

The effect of surface grinding and sandblasting on flexural strength and reliability of Y-TZP zirconia ceramic.

PubMed

Kosmac, T; Oblak, C; Jevnikar, P; Funduk, N; Marion, L

1999-11-01

This study was conducted to evaluate the effect of grinding and sandblasting on the microstructure, biaxial flexural strength and reliability of two yttria stabilized tetragonal zirconia (Y-TZP) ceramics. Two Y-TZP powders were used to produce fine grained and coarse grained microstructures. Sixty discs from each material were randomly divided into six groups of ten. For each group, a different surface treatment was applied: dry grinding, wet grinding, sandblasting, dry grinding + sandblasting, sandblasting + dry grinding and a control group. Biaxial flexural strength was determined and data were analyzed using one-way ANOVA, followed by Tukey's HSD test (p < 0.05). In addition, Weibull statistics was used to analyze the variability of flexural strength. The relative amount of transformed monoclinic zirconia, corresponding transformed zone depth (TZD) and the mean critical defect size Ccr were calculated. There was no difference in mean strength between the as sintered fine and coarse grained Y-TZP. Significant differences (p < 0.05) were found between the control group and ground fine grained material for both wet and dry grinding. Sandblasting significantly increased the strength in fine and coarse grained materials. All surface treatment procedures reduced the Weibull modulus of Y-TZP. For both materials, the highest amount of the monoclinic phase and the largest TZD was found after sandblasting. Lower amounts of the monoclinic phase were obtained after both grinding procedures, where the highest mean critical defect size Ccr was also calculated. Our results indicate that sandblasting may provide a powerful technique for strengthening Y-TZP in clinical practice. In contrast, grinding may lead to substantial strength degradation and reduced reliability of prefabricated zirconia elements, therefore, sandblasting of ground surfaces is suggested.

Late Recovery from Stuttering: The Role of Hand Dominancy, Fine Motor and ‎Inhibition Control

PubMed Central

Mohammadi, Hiwa; Khazaie, Habibolah; Rezaei, Mansour; Joghataei, Mohammad Taghi

2016-01-01

Objective: There are controversial reports about factors that affect recovery from stuttering. In the ‎present study, the effect of hand dominancy, fine motor and inhibition control on late ‎recovery from stuttering was investigated among a group of Kurdish-Persian children who ‎stuttered in Iran.‎ Method: Twenty-two Kurdish-Persian children aged 7-14 years who stuttered were followed for 6 ‎years. Based on the evaluation of three experienced speech therapists and parental judgments, ‎these children were classified into recovered or persistent groups. Data about fine motor ‎control of hand and inhibition control were obtained, using Purdue Pegboard and Victoria ‎Strop Color Word Tests, respectively. Risk factors including sex, age, and family history of ‎stuttering, handedness, inhibitory control and fine motor control of hand were compared ‎between the groups and modeled to predict recovery from stuttering using logistic regression.‎ Results: From the 22 participants, 5 (22.7%) recovered from stuttering. The recovered and persistent ‎groups did not show significant differences in the interference effect. By dividing the scores ‎of the Purdue Pegboard tests to the right and left hand, we created a new Handedness Index ‎‎(HI). HI was significantly higher in the recovered group. The score of right hand was higher ‎than the left in the recovered group, but no difference was found between the two hands in ‎the persistent group. Among the investigated risk factors, only HI could predict the recovery ‎from or persistency of stuttering with 94% sensitivity and 84% specificity.‎ Conclusion: Handedness Index can predict the recovery from stuttering significantly among children who ‎stutter.‎ PMID:27252769

Fluidized bed combustion of high-volatile solid fuels: An assessment of char attrition and volatile matter segregation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chirone, R.; Marzocchella, A.; Salatino, P.

1999-07-01

A simple lumped-parameter model of a bubbling fluidized bed combustor fueled with high-volatile solid fuels is presented. The combustor is divided into three sections: the dense bed, the splashing region and the freeboard. Material balances on fixed carbon, volatile matter and oxygen are set up, taking into account fuel particle fragmentation and attrition, volatile matter segregation as well as postcombustion of both carbon fines and volatiles escaping the bed. A basic assumption of the model is that the combustion pathway that foes from the raw fuel to the combustion products proceeds via the formation of three phases: volatile matter, relativelymore » large non-elutriable char particles and fine char particles of elutriable size. The study is complemented by a simplified thermal balance on the splashing zone taking into account volatiles and elutriated fines postcombustion and radiative and convective heat fluxes to the bed and the freeboard. Results from calculations with either low- or high-volatile solid fuels indicate that low-volatile bituminous coal combustion takes place essentially in the bed mostly via coarse char particles combustion, while high-volatile biomass fuel combustion occurs to comparable extents both in the bed and in the splashing region of the combustor. Depending on the extent of volatile matter segregation with respect to the bed, a significant fraction of the heat is released into the splashing region of the combustor and this results into an increase of temperature in this region. Extensive bed solids recirculation associated to bubble bursting/solids ejection at the bed surface together with effective gas-solids heat transfer promotes thermal feedback from this region to the bed of as much as 90% of the heat release by volatile matter and elutriated fines afterburning.« less

Synthesis H-Zeolite catalyst by impregnation KI/KIO3 and performance test catalyst for biodiesel production

NASA Astrophysics Data System (ADS)

Widayat, W.; Rizky Wicaksono, Adit; Hakim Firdaus, Lukman; Okvitarini, Ndaru

2016-02-01

The objective of this research is to produce H-catalyst catalyst that was impregnated with KI/KIO3. The catalyst was analyzed about surface area, X-Ray Diffraction (XRD) and performance test of catalyst for biodiesel production. An H-Zeolite catalyst was synthesized from natural zeolite with chemical treatment processing, impregnation KI/KIO3 and physical treatment. The results shows that the surface area of the catalyst by 27.236 m2/g at a concentration of 5% KI. XRD analysis shows peak 2-θ at 23.627o indicating that KI was impregnated on H-zeolite catalyst. The catalyst was tested in production of biodiesel using palm oil with conventional methods for 3 hour at temperature of 70-80 oC. The result for conversion Fatty Acid Methyl Ester (FAME) reached maximum value on 87.91% under production process using catalyst 5% KIO3-H zeolite.

Electrochemical catalyst recovery method

DOEpatents

Silva, L.J.; Bray, L.A.

1995-05-30

A method of recovering catalyst material from latent catalyst material solids includes: (a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; (b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; (c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and (d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications. 3 figs.

Electrochemical catalyst recovery method

DOEpatents

Silva, Laura J.; Bray, Lane A.

1995-01-01

A method of recovering catalyst material from latent catalyst material solids includes: a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications.

Zircon Supported Copper Catalysts for the Steam Reforming of Methanol

NASA Astrophysics Data System (ADS)

Widiastri, M.; Fendy, Marsih, I. N.

2008-03-01

Steam reforming of methanol (SRM) is known as one of the most favorable catalytic processes for producing hydrogen. Current research on zirconia, ZrO2 supported copper catalyst revealed that CuO/ZrO2 as an active catalyst for the SRM. Zircon, ZrSiO4 is available from the by-product of tin mining. In the work presented here, the catalytic properties of CuO/ZrSiO4 with various copper oxide compositions ranging from 2.70% (catalyst I), 4.12% (catalyst II), and 7.12%-mass (catalyst III), synthesized by an incipient wetness impregnation technique, were investigated to methanol conversion, selectivity towards CO formation, and effect of ZnO addition (7.83%CuO/8.01%ZnO/ZrSiO4 = catalyst V). The catalytic activity was obtained using a fixed bed reactor and the zircon supported catalyst activity was compared to those of CuO/ZnO/Al2O3 catalyst (catalyst IV) and commercial Kujang LTSC catalyst. An X-ray powder diffraction (XRD) analysis was done to identify the abundant phases of the catalysts. The catalysts topography and particle diameter were measured with scanning electron microscopy (SEM) and composition of the catalysts was measured by SEM-EDX, scanning electron microscope-energy dispersive using X-ray analysis. The results of this research provide information on the possibility of using zircon (ZrSiO4) as solid support for SRM catalysts.

Effect of Oxide Coating on Performance of Copper-Zinc Oxide-Based Catalyst for Methanol Synthesis via Hydrogenation of Carbon Dioxide.

PubMed

Umegaki, Tetsuo; Kojima, Yoshiyuki; Omata, Kohji

2015-11-16

The effect of oxide coating on the activity of a copper-zinc oxide-based catalyst for methanol synthesis via the hydrogenation of carbon dioxide was investigated. A commercial catalyst was coated with various oxides by a sol-gel method. The influence of the types of promoters used in the sol-gel reaction was investigated. Temperature-programmed reduction-thermogravimetric analysis revealed that the reduction peak assigned to the copper species in the oxide-coated catalysts prepared using ammonia shifts to lower temperatures than that of the pristine catalyst; in contrast, the reduction peak shifts to higher temperatures for the catalysts prepared using L(+)-arginine. These observations indicated that the copper species were weakly bonded with the oxide and were easily reduced by using ammonia. The catalysts prepared using ammonia show higher CO₂ conversion than the catalysts prepared using L(+)-arginine. Among the catalysts prepared using ammonia, the silica-coated catalyst displayed a high activity at high temperatures, while the zirconia-coated catalyst and titania-coated catalyst had high activity at low temperatures. At high temperature the conversion over the silica-coated catalyst does not significantly change with reaction temperature, while the conversion over the zirconia-coated catalyst and titania-coated catalyst decreases with reaction time. From the results of FTIR, the durability depends on hydrophilicity of the oxides.

Effect of Oxide Coating on Performance of Copper-Zinc Oxide-Based Catalyst for Methanol Synthesis via Hydrogenation of Carbon Dioxide

PubMed Central

Umegaki, Tetsuo; Kojima, Yoshiyuki; Omata, Kohji

2015-01-01

The effect of oxide coating on the activity of a copper-zinc oxide–based catalyst for methanol synthesis via the hydrogenation of carbon dioxide was investigated. A commercial catalyst was coated with various oxides by a sol-gel method. The influence of the types of promoters used in the sol-gel reaction was investigated. Temperature-programmed reduction-thermogravimetric analysis revealed that the reduction peak assigned to the copper species in the oxide-coated catalysts prepared using ammonia shifts to lower temperatures than that of the pristine catalyst; in contrast, the reduction peak shifts to higher temperatures for the catalysts prepared using L(+)-arginine. These observations indicated that the copper species were weakly bonded with the oxide and were easily reduced by using ammonia. The catalysts prepared using ammonia show higher CO2 conversion than the catalysts prepared using L(+)-arginine. Among the catalysts prepared using ammonia, the silica-coated catalyst displayed a high activity at high temperatures, while the zirconia-coated catalyst and titania-coated catalyst had high activity at low temperatures. At high temperature the conversion over the silica-coated catalyst does not significantly change with reaction temperature, while the conversion over the zirconia-coated catalyst and titania-coated catalyst decreases with reaction time. From the results of FTIR, the durability depends on hydrophilicity of the oxides. PMID:28793674

Methods of making textured catalysts

DOEpatents

Werpy, Todd [West Richland, WA; Frye, Jr., John G.; Wang, Yong [Richland, WA; Zacher, Alan H [Kennewick, WA

2010-08-17

A textured catalyst having a hydrothermally-stable support, a metal oxide and a catalyst component is described. Methods of conducting aqueous phase reactions that are catalyzed by a textured catalyst are also described. The invention also provides methods of making textured catalysts and methods of making chemical products using a textured catalyst.

NOVEL RU-NI-S ELECTRODE CATALYST FOR PEMFC

EPA Science Inventory

The expected results from this project include:

• a new formula and preparation procedures for Ru-Ni-S catalyst;
• demonstration of CO and S tolerance of the new catalyst;
• a small size PEMFC with Ru-Ni-S catalyst and good performance; an...

• Dispersion enhanced metal/zeolite catalysts

  DOEpatents

  Sachtler, W.M.H.; Tzou, M.S.; Jiang, H.J.

  1987-03-31

  Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

• Dispersion enhanced metal/zeolite catalysts

  DOEpatents

  Sachtler, Wolfgang M. H.; Tzou, Ming-Shin; Jiang, Hui-Jong

  1987-01-01

  Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

• Use of aluminum phosphate as the dehydration catalyst in single step dimethyl ether process

  DOEpatents

  Peng, Xiang-Dong; Parris, Gene E.; Toseland, Bernard A.; Battavio, Paula J.

  1998-01-01

  The present invention pertains to a process for the coproduction of methanol and dimethyl ether (DME) directly from a synthesis gas in a single step (hereafter, the "single step DME process"). In this process, the synthesis gas comprising hydrogen and carbon oxides is contacted with a dual catalyst system comprising a physical mixture of a methanol synthesis catalyst and a methanol dehydration catalyst. The present invention is an improvement to this process for providing an active and stable catalyst system. The improvement comprises the use of an aluminum phosphate based catalyst as the methanol dehydration catalyst. Due to its moderate acidity, such a catalyst avoids the coke formation and catalyst interaction problems associated with the conventional dual catalyst systems taught for the single step DME process.

• Platinum and palladium incorporation into phosphate/viologen-phosphonates of zirconium and hafnium: synthesis and characterization

  NASA Astrophysics Data System (ADS)

  Dokoutchaev, Alexandre; Krishnan, Venkatesan V.; Thompson, Mark E.; Balasubramanian, Mahalingam

  1998-10-01

  We have continued previous efforts to synthesize and characterize a microporous metal phosphate/viologen-phosphonate compound, [(ZrF) 2(PO 4)(O 3PCH 2CH 2-4,4'-bipyridinium-CH 2CH 2PO 3)] ṡF·2H 2O, ZrPO PV. A derivative of this material has been shown to be an efficient catalyst for the production of hydrogen peroxide from hydrogen and oxygen. This paper has two objectives—one is to optimize the synthetic routes leading to the preparation of MPO PV (M=zirconium or hafnium) and the second is to characterize MPO PV and the derivatives formed by Pt or Pd incorporation by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray powder diffraction (XRD), inductively coupled plasma-mass spectrometry (ICP-MS) and X-ray absorption fine structure analysis (XAFS). Powder XRD data have shown much higher crystallinity in MPO PV samples prepared by hydrothermal methods than those prepared by reflux methods. In the hydrothermal synthesis, the amount of mineralizer (HF) present controlled the crystallite size (as determined from TEM micrographs). The larger the quantity of HF in the bomb, the larger the size of the crystals but the lower the yield of the MPO PV material. Crystal sizes of about 2.5 μm in length and 0.15 μm in diameter have been made with very large quantities of HF as mineralizer (10 times the required stoichiometric amount). Ion exchange of the material by PdCl 42- has resulted in the incorporation of the PdCl 42- ions in place of X - in the material. This has been confirmed by XAFS studies that demonstrate the oxidation state of Pd is 2+ and show four Cl atoms bound to Pd. Upon reduction it has been confirmed (by XAFS) that the palladium exists as metal with oxidation state of zero. Ion exchange by PdCl 42- and PtCl 42- and subsequent reduction of the material suspension by hydrogen result in the formation of separate Pt and Pd colloids in the close vicinity of the crystallites. TEM micrographs show clearly that the Pt metal obtained after reduction forms much smaller particles in comparison to Pd. These exchanged and reduced materials have also been investigated as catalysts for production of hydrogen peroxide in mixed acetone/water medium. The production of hydrogen peroxide is enhanced by increasing amounts of Pd in the catalyst. Hydrogen peroxide yields are the highest for catalysts containing only Pd as opposed to a mixture of Pt and Pd.

• Experimental research of technology activating catalysts for SCR DeNOx in boiler

  NASA Astrophysics Data System (ADS)

  Zeng, Xi; Yang, Zhengde; Li, Yan; Chen, Donglin

  2018-01-01

  In order to improve activity of the catalysts used in SCR DeNOx system of flue gas, a series of catalysts activated by different activating liquids under varied conditions in boiler directly were conducted. Then these catalysts were characterized by SEM, FT-IR and BET technology. And NO conversions of the activated catalysts were studied and compared with that of inactivated catalyst. The above experiment shows that NO conversion of the activated catalyst can be up to 99%, which 30% higher than that of inactivated catalyst, so activity of catalysts were improved greatly. Furthermore, optimal activating liquid labeled L2 and effective technology parameters were gained in the experiment.

• A Novel Slurry-Based Biomass Reforming Process Final Technical Report

  DOE Office of Scientific and Technical Information (OSTI.GOV)

  Emerson, Sean C.; Davis, Timothy D.; Peles, A.

  2011-09-30

  This project was focused on developing a catalytic means of producing H2 from raw, ground biomass, such as fast growing poplar trees, willow trees, or switch grass. The use of a renewable, biomass feedstock with minimal processing can enable a carbon neutral means of producing H2 in that the carbon dioxide produced from the process can be used in the environment to produce additional biomass. For economically viable production of H2, the biomass is hydrolyzed and then reformed without any additional purification steps. Any unreacted biomass and other byproduct streams are burned to provide process energy. Thus, the development ofmore » a catalyst that can operate in the demanding corrosive environment and presence of potential poisons is vital to this approach. The concept for this project is shown in Figure 1. The initial feed is assumed to be a >5 wt% slurry of ground wood in dilute base, such as potassium carbonate (K2CO3). Base hydrolysis and reforming of the wood is carried out at high but sub-critical pressures and temperatures in the presence of a solid catalyst. A Pd alloy membrane allows the continuous removal of pure , while the retentate, including methane is used as fuel in the plant. The project showed that it is possible to economically produce H2 from woody biomass in a carbon neutral manner. Technoeconomic analyses using HYSYS and the DOE's H2A tool [1] were used to design a 2000 ton day-1 (dry basis) biomass to hydrogen plant with an efficiency of 46% to 56%, depending on the mode of operation and economic assumptions, exceeding the DOE 2012 target of 43%. The cost of producing the hydrogen from such a plant would be in the range of $1/kg H2 to $2/kg H2. By using raw biomass as a feedstock, the cost of producing hydrogen at large biomass consumption rates is more cost effective than steam reforming of hydrocarbons or biomass gasification and can achieve the overall cost goals of the DOE Fuel Cell Technologies Program. The complete conversion of wood to hydrogen, methane, and carbon dioxide was repeatedly demonstrated in batch reactors varying in size from 50 mL to 7.6 L. The different wood sources (e.g., swamp maple, poplar, and commercial wood flour) were converted in the presence of a heterogeneous catalyst and base at relatively low temperatures (e.g., 310°C) at sub-critical pressures sufficient to maintain the liquid phase. Both precious metal and base metal catalysts were found to be active for the liquid phase hydrolysis and reforming of wood. Pt-based catalysts, particularly Pt-Re, were shown to be more selective toward breaking C-C bonds, resulting in a higher selectivity to hydrogen versus methane. Ni-based catalysts were found to prefer breaking C-O bonds, favoring the production of methane. The project showed that increasing the concentration of base (base to wood ratio) in the presence of Raney Ni catalysts resulted in greater selectivity toward hydrogen but at the expense of increasing the production of undesirable organic acids from the wood, lowering the amount of wood converted to gas. It was shown that by modifying Ni-based catalysts with dopants, it was possible to reduce the base concentration while maintaining the selectivity toward hydrogen and increasing wood conversion to gas versus organic acids. The final stage of the project was the construction and testing of a demonstration unit for H2 production. This continuous flow demonstration unit consisted of wood slurry and potassium carbonate feed pump systems, two reactors for hydrolysis and reforming, and a gas-liquid separation system. The technical challenges associated with unreacted wood fines and Raney Ni catalyst retention limited the demonstration unit to using a fixed bed Raney Ni catalyst form. The lower activity of the larger particle Raney Ni in turn limited the residence time and thus the wood mass flow feed rate to 50 g min-1 for a 1 wt% wood slurry. The project demonstrated continuous H2 yields with unmodified, fixed bed Raney Ni, from 63% to 100% with corresponding H2 selectivities of 6% to 21%, for periods of several hours. The fixed bed form of the Raney Ni exhibited signs of deactivation which requires further study.« less

• A modular, energy-based approach to the development of nickel containing molecular electrocatalysts for hydrogen production and oxidation.

  PubMed

  Shaw, Wendy J; Helm, Monte L; DuBois, Daniel L

  2013-01-01

  This review discusses the development of molecular electrocatalysts for H2 production and oxidation based on nickel. A modular approach is used in which the structure of the catalyst is divided into first, second, and outer coordination spheres. The first coordination sphere consists of the ligands bound directly to the metal center, and this coordination sphere can be used to control such factors as the presence or absence of vacant coordination sites, redox potentials, hydride donor abilities and other important thermodynamic parameters. The second coordination sphere includes functional groups such as pendent acids or bases that can interact with bound substrates such as H2 molecules and hydride ligands, but that do not form strong bonds with the metal center. These functional groups can play diverse roles such as assisting the heterolytic cleavage of H2, controlling intra- and intermolecular proton transfer reactions, and providing a physical pathway for coupling proton and electron transfer reactions. By controlling both the hydride donor ability of the catalysts using the first coordination sphere and the proton donor abilities of the functional groups in the second coordination sphere, catalysts can be designed that are biased toward H2 production, oxidation, or bidirectional (catalyzing both H2 oxidation and production). The outer coordination sphere is defined as that portion of the catalytic system that is beyond the second coordination sphere. This coordination sphere can assist in the delivery of protons and electrons to and from the catalytically active site, thereby adding another important avenue for controlling catalytic activity. Many features of these simple catalytic systems are good models for enzymes, and these simple systems provide insights into enzyme function and reactivity that may be difficult to probe in enzymes. This article is part of a Special Issue entitled: Metals in Bioenergetics and Biomimetics Systems. Copyright © 2013 Elsevier B.V. All rights reserved.

• Alkene metathesis: the search for better catalysts.

  PubMed

  Deshmukh, Prashant H; Blechert, Siegfried

  2007-06-28

  Alkene metathesis catalyst development has made significant progress over recent years. Research in metathesis catalyst design has endeavoured to tackle three key issues: those of (i) catalyst efficiency and activity, (ii) substrate scope and selectivity--particularly stereoselective metathesis reactions--and (iii) the minimization of metal impurities and catalyst recycling. This article describes a brief history of metathesis catalyst development, followed by a survey of more recent research, with a particular emphasis on ruthenium catalysts.

• Synthetic catalysts that separate CO.sub.2 from the atmosphere and gas mixtures

  DOEpatents

  Lightstone, Felice C; Wong, Sergio E; Lau, Edmond Y; Satcher, Jr., Joe H; Aines, Roger D

  2015-02-24

  The creation of a catalyst that can be used for a wide variety of applications including the steps of developing preliminary information regarding the catalyst, using the preliminary information to produce a template of the catalyst, and using the template of the catalyst to produce the catalyst.

• Nano-Structured Bio-Inorganic Hybrid Material for High Performing Oxygen Reduction Catalyst.

  PubMed

  Jiang, Rongzhong; Tran, Dat T; McClure, Joshua P; Chu, Deryn

  2015-08-26

  In this study, we demonstrate a non-Pt nanostructured bioinorganic hybrid (BIH) catalyst for catalytic oxygen reduction in alkaline media. This catalyst was synthesized through biomaterial hemin, nanostructured Ag-Co alloy, and graphene nano platelets (GNP) by heat-treatment and ultrasonically processing. This hybrid catalyst has the advantages of the combined features of these bio and inorganic materials. A 10-fold improvement in catalytic activity (at 0.8 V vs RHE) is achieved in comparison of pure Ag nanoparticles (20-40 nm). The hybrid catalyst reaches 80% activity (at 0.8 V vs RHE) of the state-of-the-art catalyst (containing 40% Pt and 60% active carbon). Comparable catalytic stability for the hybrid catalyst with the Pt catalyst is observed by chronoamperometric experiment. The hybrid catalyst catalyzes 4-electron oxygen reduction to produce water with fast kinetic rate. The rate constant obtained from the hybrid catalyst (at 0.6 V vs RHE) is 4 times higher than that of pure Ag/GNP catalyst. A catalytic model is proposed to explain the oxygen reduction reaction at the BIH catalyst.

• Reducing fischer-tropsch catalyst attrition losses in high agitation reaction systems

  DOEpatents

  Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

  2001-01-01

  A method for reducing catalyst attrition losses in hydrocarbon synthesis processes conducted in high agitation reaction systems; a method of producing an attrition-resistant catalyst; a catalyst produced by such method; a method of producing an attrition-resistant catalyst support; and a catalyst support produced by such method. The inventive method of reducing catalyst attrition losses comprises the step of reacting a synthesis gas in a high agitation reaction system in the presence of a catalyst. In one aspect, the catalyst preferably comprises a .gamma.-alumina support including an amount of titanium effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a .gamma.-alumina support which has been treated, after calcination, with an acidic, aqueous solution. The acidic aqueous solution preferably has a pH of not more than about 5. In another aspect, the catalyst preferably comprises cobalt on a .gamma.-alumina support wherein the cobalt has been applied to the .gamma.-alumina support by totally aqueous, incipient wetness-type impregnation. In another aspect, the catalyst preferably comprises cobalt on a .gamma.-alumina support with an amount of a lanthana promoter effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a .gamma.-alumina support produced from boehmite having a crystallite size, in the 021 plane, in the range of from about 30 to about 55 .ANG.ngstrons. In another aspect, the inventive method of producing an attrition-resistant catalyst comprises the step of treating a .gamma.-alumina support, after calcination of and before adding catalytic material to the support, with an acidic solution effective for increasing the attrition resistance of the catalyst. In another aspect, the inventive method of producing an attrition-resistant catalyst support comprises the step of treating calcined .gamma.-alumina with an acidic, aqueous solution effective for increasing the attrition resistance of the .gamma.-alumina.

• Highly Stable and Active Catalyst for Sabatier Reactions

  NASA Technical Reports Server (NTRS)

  Hu, Jianli; Brooks, Kriston P.

  2012-01-01

  Highly active Ru/TiO2 catalysts for Sabatier reaction have been developed. The catalysts have shown to be stable under repeated shutting down/startup conditions. When the Ru/TiO2 catalyst is coated on the engineered substrate Fe-CrAlY felt, activity enhancement is more than doubled when compared with an identically prepared engineered catalyst made from commercial Degussa catalyst. Also, bimetallic Ru-Rh/TiO2 catalysts show high activity at high throughput.